CN106816603A - A kind of three-dimensional grapheme aeroge carries sulphur composite and its preparation method and application - Google Patents
A kind of three-dimensional grapheme aeroge carries sulphur composite and its preparation method and application Download PDFInfo
- Publication number
- CN106816603A CN106816603A CN201710137439.2A CN201710137439A CN106816603A CN 106816603 A CN106816603 A CN 106816603A CN 201710137439 A CN201710137439 A CN 201710137439A CN 106816603 A CN106816603 A CN 106816603A
- Authority
- CN
- China
- Prior art keywords
- sulphur
- composite
- carries
- preparation
- dimensional grapheme
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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
-
- 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
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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
-
- 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
Sulphur composite and its preparation method and application is carried the invention discloses a kind of three-dimensional grapheme aeroge, the composite is mainly and first forms hydrogel precursor by sulphur and graphene oxide, then hydrazine hydrate is recycled to be reduced, the graphene coated sulphur composite of the three-dimensional net structure communicated with inside for obtaining.Relative to prior art, present invention gained composite shows the cyclical stability and high rate performance high of advantage as the positive electrode of lithium-sulfur cell.
Description
Technical field
Sulphur composite and its preparation method and application is carried the invention discloses a kind of three-dimensional grapheme aeroge, belongs to lithium
Sulphur cell positive electrode electrode field of material technology.
Background technology
The energy and environmental problem are the two large problems of current mankind's urgent need to resolve.In fossil energy, increasingly exhausted, environment is dirty
Increasingly serious, today of global warming is contaminated, sought to substitute the renewable green energy resource of traditional fossil energy, sought people and ring
The harmony in border seems particularly urgent.New regenerative resource, for example utilization of wind energy and solar energy etc., electric automobile, mixing
The progressively marketization of power electric motor car, the fast development of various portable power devices is required to efficient, practical, " green " (zero
Pollution or low stain) energy storage system.Chemical energy storage occupies extremely important status in new energy field.New power supply
System, particularly secondary cell or ultracapacitor are current important " green " chemical energy storage devices.In the change sought
In learning energy storage system, lithium ion battery has that operating voltage is high, energy density big (lightweight), memory-less effect, cycle life
Long and pollution-free the advantages of, the fields such as mobile electronic device and electric automobile have been widely used in it.However, at present lithium from
Sub- battery is due to the limitation of its own theoretical capacity, it is difficult to meet the market demand, so being badly in need of exploitation height ratio capacity of future generation, length
The novel secondary battery of cycle life, high safety performance.
Lithium-sulfur cell has theoretical specific capacity (1675mAh g highS -1) and theoretical energy density (2600Wh kg-1), and
And elemental sulfur is widespread in nature, price is low, environment-friendly, therefore, it is considered as current most promising secondary
One of battery system.But, it is to be overcome that lithium-sulfur cell has that some have in commercial applications.First, sulphur and electric discharge
The electric conductivity of product lithium sulfide is poor, and (electrical conductivity is respectively 5 × 10-30S cm-1With 3.6 × 10-7S cm-1)；Second, elemental sulfur
It is larger with the density difference of its complete discharging product lithium sulfide that (density is respectively 2.03g cm-3With 1.67g cm-3), in charge and discharge
Obvious volumetric expansion (about 80%) occurs in electric cyclic process, makes the easy pink blossom of positive electrode even from plus plate current-collecting body
Come off；3rd, during the intermediate product that sulphur is produced in charge and discharge process is readily dissolved in organic electrolyte solution, cause " to shuttle and imitate
Should ".The presence of these problems will cause the utilization rate of positive active material low, and the capacity attenuation of battery is fast, and cycle performance is poor, fills
The low problem of discharging efficiency.
In recent years, people have carried out many beneficial in terms of the Nomenclature Composition and Structure of Complexes of positive electrode is designed etc. to lithium-sulfur cell
Explore, achieve larger progress.It is that carrier using conductive carbon material as sulphur is constituted sulphur carbon and is combined to be used in research most
Positive electrode.The inspiration that these researchs give people is, with excellent electric conductivity, good structural stability and loose structure
Nano-carbon material, such as activated carbon, mesoporous carbon, extra small microporous carbon, multilevel hierarchy porous carbon, hollow carbon sphere, hollow carbon fiber, carbon
Nanotube, Graphene etc., fully meet requirement of the lithium sulfur battery anode material to carbon base body.
But, presently relevant technology is still present some defects, and such as preparation technology is complicated, and heat-treatment process power consumption is high,
And there is sulphur volatilization, and causing wastage of material, transformation efficiency is low；Additionally, resulting materials electric conductivity is not ideal enough, cycle performance
It is poor with high rate performance etc..
The content of the invention
Goal of the invention：For above-mentioned technical problem, simple, cheap, energy-conservation, ring are prepared present invention aim at one kind is provided
Border close friend and the preparation method of the anode composite material of lithium sulfur battery being produced on a large scale, with conventional melting diffusion method sulfurizing not
Together, sulphur and graphene oxide are formed hydrogel precursor by the method at room temperature, it is to avoid in traditional sulfur electrode preparation technology
The high energy consumption of complicated heat-treatment process and thus issuable sulphur volatilization, are more convenient to large-scale production.It is prepared
Graphene coated sulphur composite there is the internal three-dimensional net structure for communicating, can be raw in charge and discharge process by sulfur electrode
Into polysulfide be effectively limited in three-dimensional grapheme network, this structure is conducive to the infiltration and diffusion of electrolyte, together
When improve the electric conductivity of material, so as to ensure that prepared three-dimensional grapheme aeroge carries sulphur composite in charge and discharge process
In show good cycle performance and high rate performance.
Technical scheme：Sulphur composite is carried the invention provides a kind of three-dimensional grapheme aeroge, it is mainly first by sulphur
Hydrogel precursor is formed with graphene oxide, then recycles hydrazine hydrate to be reduced, communicated with inside three for obtaining
Tie up the graphene coated sulphur composite of network structure.
The invention provides the preparation method that the three-dimensional grapheme aeroge carries sulphur composite, comprise the following steps：
(1) graphene oxide and sublimed sulfur are dispersed in distilled water, at room temperature, using the chitosan/acetic acid aqueous solution
Hydrogel precursor is made, so that three-dimensional graphite oxide aerogel is obtained carries sulphur (S/GO) composite；
(2) product for obtaining step (1) is disperseed with distilled water, is reduced using hydrazine hydrate in aqueous ammonia medium, cold
It is lyophilized dry, obtain final product described three-dimensional grapheme aeroge and carry sulphur (S/rGO) composite.
It is preferred that, comprise the following steps：
(1) three-dimensional graphite oxide aerogel carries the preparation of sulphur (S/GO) composite：By appropriate graphene oxide and
Sublimed sulfur is dispersed in distilled water, adds the appropriate chitosan/acetic acid aqueous solution while stirring under room temperature (25 DEG C), and stirring is extremely
In hydrogel, then standing carries out freeze-drying after 4-8 hours at room temperature, so that three-dimensional graphite oxide aerogel is obtained carries sulphur
(S/GO) composite；
(2) three-dimensional grapheme aeroge carries the preparation of sulphur (S/rGO) composite：The product that step (1) is obtained is used suitable
The distilled water dispersion of amount, adds a certain amount of ammoniacal liquor and hydrazine hydrate at moderate temperatures, reacts appropriate time, suction filtration and with distilling
Collected solid, in neutrality, is carried out freeze-drying by water washing to filtrate, is obtained described three-dimensional grapheme aeroge and is carried sulphur
(S/rGO) composite.
It is preferred that, in step (1), the shitosan relative molecular weight is 5~150,000；The body of acetic acid and water in aqueous acetic acid
Product is than being 5:95.
It is preferred that, in step (1), after graphene oxide and sublimed sulfur are dispersed in distilled water, the concentration of graphene oxide is 5
~20mg mL-1, the concentration of sublimed sulfur is 5~80mg mL-1。
It is preferred that, in step (1), the mass ratio of the graphene oxide and shitosan is (5~20):1.
It is preferred that, in step (2), after the product that step (1) is obtained is disperseed with distilled water, graphite oxide aerogel carries sulphur
The concentration of composite is 10~50mg mL-1。
It is preferred that, in step (2), the ammonia concn for being added is 15~30wt%, and the concentration of hydrazine hydrate is 40~80wt%.
It is preferred that, proper temperature described in step (2) is 10~80 DEG C, and the appropriate reaction time is 1~3 hour.
Sulphur composite is carried as lithium sulfur battery anode material present invention also offers the three-dimensional grapheme aeroge
Using.
Graphene, as a kind of two-dimensional slice structural material, the electrical conductivity with superelevation, larger specific surface area and excellent
Mechanical property.Its lamellar structure is conducive to building three-dimensional net structure, can not only store sulphur active material, and can also
Alleviate the Volume Changes that sulphur occurs in charge and discharge process, so as to ensure that positive electrode has lasting structural intergrity.Additionally,
The superior electric conductivity of Graphene constructs conductive network skeleton high, so that it is guaranteed that the good electronics in charge and discharge process of sulphur is led
Electrically.
Technique effect：Relative to prior art, the present invention has the advantage that：
(1) present invention prepares three-dimensional grapheme aeroge and carries sulphur composite using easy method.With conventional melting
Diffusion method sulfurizing prepares sulphur composite electrode difference, and sulphur and graphene oxide are formed hydrogel forerunner by the method at room temperature
Body, it is to avoid the high energy consumption of complicated heat-treatment process and thus issuable sulphur is waved in traditional sulfur electrode preparation technology
Hair, is more convenient to large-scale production.
(2) the three-dimensional grapheme aeroge prepared by the present invention carries sulphur composite has the internal three-dimensional network knot for communicating
, effectively can be limited in the polysulfide that sulfur electrode is generated in charge and discharge process in three-dimensional grapheme network by structure, so that
Suppress the shuttle of polysulfide, alleviate the Volume Changes of positive pole in charge and discharge process；This structure also helps oozing for electrolyte
Saturating and diffusion, while the electric conductivity of material is improved, so as to improve the cyclical stability and high rate performance of positive electrode.
Brief description of the drawings
Fig. 1 is the X ray diffracting spectrum of S/rGO composites obtained in embodiment 1.
Fig. 2 is the thermal multigraph of S/rGO composites obtained in embodiment 1.
Fig. 3 is the scanning electron microscope (SEM) photograph of S/GO and S/rGO composites obtained in embodiment 1.
Fig. 4 is the charging and discharging curve of S/rGO composites (a) obtained in embodiment 1 and bright sulfur (b).
Fig. 5 is the charge-discharge performance figure of S/rGO composites obtained in embodiment 1 and bright sulfur.
Fig. 6 is the charge-discharge magnification performance map of S/rGO composites obtained in embodiment 1 and bright sulfur.
Specific embodiment
Below in conjunction with the accompanying drawings and instantiation, the present invention is furture elucidated, it should be understood that these examples are merely to illustrate this hair
Bright rather than limitation the scope of the present invention.
Embodiment 1
(1) three-dimensional graphite oxide aerogel carries the preparation of sulphur (S/GO) composite：By the graphene oxide of 50mg and
50mg sublimed sulfurs are dispersed in 5mL distilled water, and 0.5mL 10mgmL are added under room temperature (25 DEG C)-1(molecular weight is 15 to shitosan
Ten thousand) (acetic acid is 5 with the volume ratio of water to/aqueous acetic acid:95), stirring is to formation hydrogel, then stands 6 hours at room temperature,
Freeze-drying, so that three-dimensional graphite oxide aerogel is obtained carries sulphur (S/GO) composite.
(2) three-dimensional grapheme aeroge carries the preparation of sulphur (S/rGO) composite：The product 105mg that step (1) is obtained
Disperseed with the distilled water of 5mL, ammoniacal liquor (25wt%) and 0.2mL hydrazine hydrates (50wt%) reaction 1.5 of 0.3mL is added at 60 DEG C
Hour, suction filtration is simultaneously washed with distilled water to filtrate in neutrality, and collected solid is carried out into freeze-drying, obtains described three-dimensional
Graphene aerogel carries sulphur (S/rGO) composite.
Fig. 1 is the X ray diffracting spectrum of the S/GO and S/rGO composites of the present embodiment synthesis.As seen from the figure, S/GO and
Sulphur in S/rGO composites is present with rhombic sulfur (JCPDS No.08-0247) crystalline phase.
Fig. 2 is the thermogravimetric analysis figure of the S/rGO composites of the present embodiment synthesis.It can be calculated that S/rGO is multiple from figure
The content of S is 50wt% in condensation material.
Fig. 3 is the S/GO (Fig. 3 a, b) of the present embodiment synthesis and the stereoscan photograph of S/rGO (Fig. 3 c, d) composite.
From Fig. 3 a and Fig. 3 b, the size heterogeneity of sublimed sulfur, graphene oxide is uniformly coated on the surface of sulfur granules, shape
Into three-dimensional net structure.After hydrazine hydrate reduction, product still maintains original size and pattern (Fig. 3 c, d), these structures
Characteristic is all conducive to the composite positive pole to show preferably to store up lithium performance.
Fig. 4 is the S/rGO composites of the present embodiment synthesis and the charging and discharging curve of bright sulfur.From discharge curve, S/
RGO composites and bright sulfur all show typical Double tabletop curve, and many lithium sulfides are converted into corresponding to sulphur, are eventually converted into sulphur
Change lithium；Compared with bright sulfur, second platform contribution capacity of S/rGO composites is more.
Fig. 5 is the S/rGO composites of the present embodiment synthesis and the charge-discharge performance figure of bright sulfur.As seen from the figure, exist
Under the charging and discharging currents density of 0.1C, the first circle specific discharge capacity of S/rGO composites is 711mAh g-1, higher than putting for bright sulfur
Electric specific capacity (573mAh g-1)；By after 300 charge and discharge cycles, the specific discharge capacity of S/rGO composites is still up to
421mAh g-1, higher than specific discharge capacity (the 173mAh g of bright sulfur-1), show superior cycle performance and specific volume higher
Amount.
Fig. 6 is the S/rGO composites of the present embodiment synthesis and the charge-discharge magnification performance map of bright sulfur.As seen from the figure, when
When current density is 0.1,0.2,0.5 and 1C, the averaged discharge specific capacity of product respectively may be about 680,560,420 and 320mAh
g-1；When current density returns to 0.1C from 1C, the averaged discharge specific capacity of product returns to 560mAh g-1, all higher than bright sulfur
Specific capacity, the high rate performance that this explanation S/rGO composite has had, is expected to realize the business on lithium sulphur power battery anode
Change application.
Embodiment 2
(1) three-dimensional graphite oxide aerogel carries the preparation of sulphur (S/GO) composite：By the graphene oxide of 25mg and
50mg sublimed sulfurs are dispersed in 5mL distilled water, and 0.5mL 10mgmL are added under room temperature (25 DEG C)-1(molecular weight is 15 to shitosan
Ten thousand) (acetic acid is 5 with the volume ratio of water to/aqueous acetic acid:95), stirring is to formation hydrogel, then stands 6 hours at room temperature,
Freeze-drying, so that three-dimensional graphite oxide aerogel is obtained carries sulphur (S/GO) composite.
(2) three-dimensional grapheme aeroge carries the preparation of sulphur (S/rGO) composite：The product 80mg that step (1) is obtained
Disperseed with the distilled water of 5mL, add ammoniacal liquor (30wt%) and 0.2mL hydrazine hydrates (40wt%) reaction 2 of 0.3mL small at 50 DEG C
When, suction filtration is simultaneously washed with distilled water to filtrate in neutrality, and collected solid is carried out into freeze-drying, obtains described three-dimensional stone
Black alkene aeroge carries sulphur (S/rGO) composite.
Prepared three-dimensional grapheme aeroge is carried sulphur composite carry out similar to the dependence test in embodiment 1 and
Characterize, conclusion is similar to embodiment 1.
Embodiment 3
(1) three-dimensional graphite oxide aerogel carries the preparation of sulphur (S/GO) composite：By the graphene oxide of 50mg and
100mg sublimed sulfurs are dispersed in 5mL distilled water, and 0.5mL 10mgmL are added under room temperature (25 DEG C)-1(molecular weight is 15 to shitosan
Ten thousand) (acetic acid is 5 with the volume ratio of water to/aqueous acetic acid:95), stirring is to formation hydrogel, then stands 6 hours at room temperature,
Freeze-drying, so that three-dimensional graphite oxide aerogel is obtained carries sulphur (S/GO) composite.
(2) three-dimensional grapheme aeroge carries the preparation of sulphur (S/rGO) composite：The product 155mg that step (1) is obtained
Disperseed with the distilled water of 10mL, ammoniacal liquor (15wt%) and 0.2mL hydrazine hydrates (50wt%) reaction of 0.3mL are added at 70 DEG C
1.2 hours, suction filtration was simultaneously washed with distilled water to filtrate in neutrality, and collected solid is carried out into freeze-drying, obtained described
Three-dimensional grapheme aeroge carries sulphur (S/rGO) composite.
Prepared three-dimensional grapheme aeroge is carried sulphur composite carry out similar to the dependence test in embodiment 1 and
Characterize, conclusion is similar to embodiment 1.
Embodiment 4
(1) three-dimensional graphite oxide aerogel carries the preparation of sulphur (S/GO) composite：By the graphene oxide of 100mg and
250mg sublimed sulfurs are dispersed in 5mL distilled water, and 1mL 5mgmL are added under room temperature (25 DEG C)-1(molecular weight is 15 to shitosan
Ten thousand) (acetic acid is 5 with the volume ratio of water to/aqueous acetic acid:95), stirring is to formation hydrogel, then stands 4 hours at room temperature,
Freeze-drying, so that three-dimensional graphite oxide aerogel is obtained carries sulphur (S/GO) composite.
(2) three-dimensional grapheme aeroge carries the preparation of sulphur (S/rGO) composite：The product 355mg that step (1) is obtained
Disperseed with the distilled water of 10mL, ammoniacal liquor (30wt%) and 0.2mL hydrazine hydrates (80wt%) reaction 1 of 0.3mL is added at 80 DEG C
Hour, suction filtration is simultaneously washed with distilled water to filtrate in neutrality, and collected solid is carried out into freeze-drying, obtains described three-dimensional
Graphene aerogel carries sulphur (S/rGO) composite.
Prepared three-dimensional grapheme aeroge is carried sulphur composite carry out similar to the dependence test in embodiment 1 and
Characterize, conclusion is similar to embodiment 1.
Embodiment 5
(1) three-dimensional graphite oxide aerogel carries the preparation of sulphur (S/GO) composite：By the graphene oxide of 100mg and
25mg sublimed sulfurs are dispersed in 5mL distilled water, and 1mL 5mg mL are added under room temperature (25 DEG C)-1(molecular weight is 15 to shitosan
Ten thousand) (acetic acid is 5 with the volume ratio of water to/aqueous acetic acid:95), stirring is to formation hydrogel, then stands 8 hours at room temperature,
Freeze-drying, so that three-dimensional graphite oxide aerogel is obtained carries sulphur (S/GO) composite.
(2) three-dimensional grapheme aeroge carries the preparation of sulphur (S/rGO) composite：The product 130mg that step (1) is obtained
Disperseed with the distilled water of 5mL, ammoniacal liquor (30wt%) and 0.2mL hydrazine hydrates (80wt%) reaction 1.5 of 0.3mL is added at 60 DEG C
Hour, suction filtration is simultaneously washed with distilled water to filtrate in neutrality, and collected solid is carried out into freeze-drying, obtains described three-dimensional
Graphene aerogel carries sulphur (S/rGO) composite.
Prepared three-dimensional grapheme aeroge is carried sulphur composite carry out similar to the dependence test in embodiment 1 and
Characterize, conclusion is similar to embodiment 1.
Embodiment 6
(1) three-dimensional graphite oxide aerogel carries the preparation of sulphur (S/GO) composite：By the graphene oxide of 100mg and
400mg sublimed sulfurs are dispersed in 5mL distilled water, and 1mL 10mg mL are added under room temperature (25 DEG C)-1(molecular weight is 5 to shitosan
Ten thousand) (acetic acid is 5 with the volume ratio of water to/aqueous acetic acid:95), stirring is to formation hydrogel, then places 6 hours at room temperature,
Freeze-drying, so that three-dimensional graphite oxide aerogel is obtained carries sulphur (S/GO) composite.
(2) three-dimensional grapheme aeroge carries the preparation of sulphur (S/rGO) composite：The product 510mg that step (1) is obtained
Disperseed with the distilled water of 10.2mL, ammoniacal liquor (30wt%) and 0.2mL hydrazine hydrates (80wt%) reaction of 0.3mL are added at 60 DEG C
1.5 hours, suction filtration was simultaneously washed with distilled water to filtrate in neutrality, and collected solid is carried out into freeze-drying, obtained described
Three-dimensional grapheme aeroge carries sulphur (S/rGO) composite.
Prepared three-dimensional grapheme aeroge is carried sulphur composite carry out similar to the dependence test in embodiment 1 and
Characterize, conclusion is similar to embodiment 1.
Embodiment 7
(1) three-dimensional graphite oxide aerogel carries the preparation of sulphur (S/GO) composite：By the graphene oxide of 50mg and
50mg sublimed sulfurs are dispersed in 5mL distilled water, and 0.5mL 10mg mL are added under room temperature (25 DEG C)-1(molecular weight is 5 to shitosan
Ten thousand) (acetic acid is 5 with the volume ratio of water to/aqueous acetic acid:95), stirring is to formation hydrogel, then stands 6 hours at room temperature,
Freeze-drying, so that three-dimensional graphite oxide aerogel is obtained carries sulphur (S/GO) composite.
(2) three-dimensional grapheme aeroge carries the preparation of sulphur (S/rGO) composite：The product 105mg that step (1) is obtained
Disperseed with the distilled water of 5mL, ammoniacal liquor (25wt%) and 0.2mL hydrazine hydrates (50wt%) reaction 1.5 of 0.3mL is added at 60 DEG C
Hour, suction filtration is simultaneously washed with distilled water to filtrate in neutrality, and collected solid is carried out into freeze-drying, obtains described three-dimensional
Graphene aerogel carries sulphur (S/rGO) composite.
Prepared three-dimensional grapheme aeroge is carried sulphur composite carry out similar to the dependence test in embodiment 1 and
Characterize, conclusion is similar to embodiment 1.
Embodiment 8
(1) three-dimensional graphite oxide aerogel carries the preparation of sulphur (S/GO) composite：By the graphene oxide of 50mg and
50mg sublimed sulfurs are dispersed in 5mL distilled water, and 0.5mL 10mg mL are added under room temperature (25 DEG C)-1(molecular weight is 15 to shitosan
Ten thousand) (acetic acid is 5 with the volume ratio of water to/aqueous acetic acid:95), stirring is to formation hydrogel, then stands 6 hours at room temperature,
Freeze-drying, so that three-dimensional graphite oxide aerogel is obtained carries sulphur (S/GO) composite.
(2) three-dimensional grapheme aeroge carries the preparation of sulphur (S/rGO) composite：The product 105mg that step (1) is obtained
Disperseed with the distilled water of 5mL, add ammoniacal liquor (25wt%) and 0.2mL hydrazine hydrates (50wt%) reaction 3 of 0.3mL small at 10 DEG C
When, suction filtration is simultaneously washed with distilled water to filtrate in neutrality, and collected solid is carried out into freeze-drying, obtains described three-dimensional stone
Black alkene aeroge carries sulphur (S/rGO) composite.
Prepared three-dimensional grapheme aeroge is carried sulphur composite carry out similar to the dependence test in embodiment 1 and
Characterize, conclusion is similar to embodiment 1.
Embodiment 9
(1) three-dimensional graphite oxide aerogel carries the preparation of sulphur (S/GO) composite：By the graphene oxide of 50mg and
50mg sublimed sulfurs are dispersed in 5mL distilled water, and 0.5mL 10mg mL are added under room temperature (25 DEG C)-1(molecular weight is 10 to shitosan
Ten thousand) (acetic acid is 5 with the volume ratio of water to/aqueous acetic acid:95), stirring is to formation hydrogel, then stands 6 hours at room temperature,
Freeze-drying, so that three-dimensional graphite oxide aerogel is obtained carries sulphur (S/GO) composite.
(2) three-dimensional grapheme aeroge carries the preparation of sulphur (S/rGO) composite：The product 105mg that step (1) is obtained
Disperseed with the distilled water of 5mL, ammoniacal liquor (25wt%) and 0.2mL hydrazine hydrates (50wt%) reaction 1.5 of 0.3mL is added at 60 DEG C
Hour, suction filtration is simultaneously washed with distilled water to filtrate in neutrality, and collected solid is carried out into freeze-drying, obtains described three-dimensional
Graphene aerogel carries sulphur (S/rGO) composite.
Prepared three-dimensional grapheme aeroge is carried sulphur composite carry out similar to the dependence test in embodiment 1 and
Characterize, conclusion is similar to embodiment 1.
Claims (10)
1. a kind of three-dimensional grapheme aeroge carries sulphur composite, it is characterised in that it is mainly first by sulphur and graphene oxide
Hydrogel precursor is formed, then recycles hydrazine hydrate to be reduced, the three-dimensional net structure communicated with inside for obtaining
Graphene coated sulphur composite.
2. three-dimensional grapheme aeroge described in claim 1 carries the preparation method of sulphur composite, it is characterised in that including following
Step：
(1) graphene oxide and sublimed sulfur are dispersed in distilled water, at room temperature, are made using the chitosan/acetic acid aqueous solution
Hydrogel precursor, so that three-dimensional graphite oxide aerogel is obtained carries sulphur (S/GO) composite；
(2) product for obtaining step (1) is disperseed with distilled water, is reduced using hydrazine hydrate in aqueous ammonia medium, and freezing is dry
It is dry, obtain final product described three-dimensional grapheme aeroge and carry sulphur (S/rGO) composite.
3. three-dimensional grapheme aeroge according to claim 2 carries the preparation method of sulphur composite, it is characterised in that bag
Include following steps：
(1) three-dimensional graphite oxide aerogel carries the preparation of sulphur (S/GO) composite：By appropriate graphene oxide and distillation
Sulphur content is dispersed in distilled water, adds the appropriate chitosan/acetic acid aqueous solution while stirring under room temperature (25 DEG C), and stirring is in water
Gel, then standing carries out freeze-drying after 4-8 hours at room temperature, so that three-dimensional graphite oxide aerogel is obtained carries sulphur (S/
GO) composite；
(2) three-dimensional grapheme aeroge carries the preparation of sulphur (S/rGO) composite：The product that step (1) is obtained is with appropriate
Distilled water disperses, and a certain amount of ammoniacal liquor and hydrazine hydrate are added at moderate temperatures, reacts appropriate time, and suction filtration is simultaneously washed with distillation
Wash to filtrate in neutrality, collected solid is carried out into freeze-drying, obtain described three-dimensional grapheme aeroge and carry sulphur (S/
RGO) composite.
4. the three-dimensional grapheme aeroge according to Claims 2 or 3 carries the preparation method of sulphur composite, and its feature exists
In in step (1), the shitosan relative molecular weight is 5~150,000；Acetic acid and the volume ratio of water are 5 in aqueous acetic acid:
95。
5. the three-dimensional grapheme aeroge according to Claims 2 or 3 carries the preparation method of sulphur composite, and its feature exists
In in step (1), after graphene oxide and sublimed sulfur are dispersed in distilled water, the concentration of graphene oxide is 5~20mg mL-1, the concentration of sublimed sulfur is 5~80mg mL-1。
6. the three-dimensional grapheme aeroge according to Claims 2 or 3 carries the preparation method of sulphur composite, and its feature exists
In in step (1), the mass ratio of the graphene oxide and shitosan is (5~20):1.
7. the three-dimensional grapheme aeroge according to Claims 2 or 3 carries the preparation method of sulphur composite, and its feature exists
In in step (2), after the product that step (1) is obtained is disperseed with distilled water, graphite oxide aerogel carries sulphur composite
Concentration is 10~50mg mL-1。
8. the three-dimensional grapheme aeroge according to Claims 2 or 3 carries the preparation method of sulphur composite, and its feature exists
In in step (2), the ammonia concn for being added is 15~30wt%, and the concentration of hydrazine hydrate is 40~80wt%.
9. three-dimensional grapheme aeroge according to claim 3 carries the preparation method of sulphur composite, it is characterised in that step
Suddenly proper temperature described in (2) is 10~80 DEG C, and the appropriate reaction time is 1~3 hour.
10. three-dimensional grapheme aeroge described in claim 1 carries application of the sulphur composite as lithium sulfur battery anode material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710137439.2A CN106816603B (en) | 2017-03-09 | 2017-03-09 | A kind of three-dimensional grapheme aeroge carries sulphur composite material and preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710137439.2A CN106816603B (en) | 2017-03-09 | 2017-03-09 | A kind of three-dimensional grapheme aeroge carries sulphur composite material and preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106816603A true CN106816603A (en) | 2017-06-09 |
| CN106816603B CN106816603B (en) | 2019-10-18 |
Family
ID=59116130
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710137439.2A Active CN106816603B (en) | 2017-03-09 | 2017-03-09 | A kind of three-dimensional grapheme aeroge carries sulphur composite material and preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106816603B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107910536A (en) * | 2017-12-27 | 2018-04-13 | 东北师范大学 | A kind of selenium/graphene nanocomposite material prepares and its application |
| CN108232135A (en) * | 2017-12-18 | 2018-06-29 | 襄阳华虹高科新材料有限公司 | A kind of lithium sulfur battery anode material and preparation method thereof |
| CN108461732A (en) * | 2018-03-16 | 2018-08-28 | 北京理工大学 | A kind of flexibility sodium metal battery negative material and preparation method thereof |
| CN109103436A (en) * | 2018-08-29 | 2018-12-28 | 四川大学 | A kind of lithium sulfur battery anode material and preparation method thereof |
| CN111668460A (en) * | 2019-03-08 | 2020-09-15 | 新奥科技发展有限公司 | Positive electrode material and preparation method thereof, positive electrode piece and ion battery |
| CN111740091A (en) * | 2020-07-08 | 2020-10-02 | 中国科学院山西煤炭化学研究所 | Carbon aerogel @ sulfur composite material for lithium-sulfur battery positive electrode and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102718210A (en) * | 2012-07-03 | 2012-10-10 | 新疆大学 | Method for preparing graphene oxide three-dimensional self-assembled aerogel and application of graphene oxide three-dimensional self-assembled aerogel |
| CN104401977A (en) * | 2014-10-28 | 2015-03-11 | 同济大学 | Preparation method of graphene aerogel and graphene-carbon nanotube aerogel |
| CN105037820A (en) * | 2015-07-14 | 2015-11-11 | 广东海洋大学 | Chitosan low-temperature hydrogel and preparation method thereof |
-
2017
- 2017-03-09 CN CN201710137439.2A patent/CN106816603B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102718210A (en) * | 2012-07-03 | 2012-10-10 | 新疆大学 | Method for preparing graphene oxide three-dimensional self-assembled aerogel and application of graphene oxide three-dimensional self-assembled aerogel |
| CN104401977A (en) * | 2014-10-28 | 2015-03-11 | 同济大学 | Preparation method of graphene aerogel and graphene-carbon nanotube aerogel |
| CN105037820A (en) * | 2015-07-14 | 2015-11-11 | 广东海洋大学 | Chitosan low-temperature hydrogel and preparation method thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108232135A (en) * | 2017-12-18 | 2018-06-29 | 襄阳华虹高科新材料有限公司 | A kind of lithium sulfur battery anode material and preparation method thereof |
| CN107910536A (en) * | 2017-12-27 | 2018-04-13 | 东北师范大学 | A kind of selenium/graphene nanocomposite material prepares and its application |
| CN108461732A (en) * | 2018-03-16 | 2018-08-28 | 北京理工大学 | A kind of flexibility sodium metal battery negative material and preparation method thereof |
| CN109103436A (en) * | 2018-08-29 | 2018-12-28 | 四川大学 | A kind of lithium sulfur battery anode material and preparation method thereof |
| CN111668460A (en) * | 2019-03-08 | 2020-09-15 | 新奥科技发展有限公司 | Positive electrode material and preparation method thereof, positive electrode piece and ion battery |
| CN111740091A (en) * | 2020-07-08 | 2020-10-02 | 中国科学院山西煤炭化学研究所 | Carbon aerogel @ sulfur composite material for lithium-sulfur battery positive electrode and preparation method thereof |
| CN111740091B (en) * | 2020-07-08 | 2022-05-17 | 中国科学院山西煤炭化学研究所 | Carbon aerogel @ sulfur composite material for lithium-sulfur battery positive electrode and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106816603B (en) | 2019-10-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Han et al. | Clean utilization of palm kernel shell: sustainable and naturally heteroatom-doped porous activated carbon for lithium–sulfur batteries | |
| CN106816603B (en) | A kind of three-dimensional grapheme aeroge carries sulphur composite material and preparation method and application | |
| Zhang et al. | Constructing ultra-thin Ni-MOF@ NiS2 nanosheets arrays derived from metal organic frameworks for advanced all-solid-state asymmetric supercapacitor | |
| Zhang et al. | Synthesis of core-shell covalent organic frameworks/multi-walled carbon nanotubes nanocomposite and application in lithium-sulfur batteries | |
| CN106784819B (en) | A kind of lithium sulfur battery anode material and preparation method thereof | |
| CN104466134B (en) | The preparation method of self-supporting graphene/carbon nano-tube hybrid foam support amino anthraquinones base polymer | |
| CN105762360A (en) | Graphene-silicon-coated composite negative electrode material and preparing method and application thereof | |
| CN104201380A (en) | Preparation method of nano Ni3S2 material with lamellar structure | |
| CN106252096A (en) | A kind of ultracapacitor | |
| CN103208625A (en) | Preparation method of ferroferric-oxide-based high-performance negative electrode material for lithium ion battery | |
| CN103000864A (en) | Sulfur composite cathode material and preparation method thereof | |
| CN104176783B (en) | The preparations and applicatio method of the coated manganese dioxide nanowire of a kind of nitrogen carbon material | |
| CN110459755A (en) | A kind of sulphur/polypyrrole/graphene/carbon nano-tube coextruded film, preparation method and applications | |
| CN107611411A (en) | A kind of preparation method and application of the classifying porous nitrogen-doped carbon bag silicon composite of three-dimensional | |
| CN106252628A (en) | The preparation method of a kind of manganese oxide/graphene nanocomposite material, lithium ion battery negative, lithium ion battery | |
| CN106876682A (en) | A kind of manganese oxide with loose structure/nickel micron ball and its preparation and application | |
| CN110165185A (en) | A kind of preparation method and application of lithium sulfur battery anode material | |
| CN106710885A (en) | Nickel selenide/carbon nanotube composite nanometer material and preparation and application thereof | |
| CN112410849B (en) | Preparation method and application of defect black phosphorus alkene carbon nanotube composite material | |
| CN108054020A (en) | A kind of preparation method and application of nitrogen-doped carbon particle/graphitized carbon nitrogen composite material | |
| CN110078053A (en) | A kind of porous carbon materials and its preparation method and application applied to battery diaphragm coating | |
| CN107742701A (en) | Graphene titania aerogel composite and its preparation and application | |
| CN105161690B (en) | The method that molybdenum disulfide charge and discharge cycles ability is improved by doped graphene and titanium dioxide | |
| CN106356555B (en) | The preparation method of the sulphur composite positive pole of the dual modification of carbon nano tube/conducting polymer | |
| CN106098396B (en) | It is a kind of for upright opening carbon compound film of ultracapacitor and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |