CN106816603B - A kind of three-dimensional grapheme aeroge carries sulphur composite material and preparation method and application - Google Patents
A kind of three-dimensional grapheme aeroge carries sulphur composite material and preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of three-dimensional grapheme aeroges to carry sulphur composite material and preparation method and application, the composite material is mainly first to form hydrogel precursor by sulphur and graphene oxide, then hydrazine hydrate is recycled to be restored, what is obtained has the graphene coated sulphur composite material of the internal three-dimensional net structure communicated.Compared with the existing technology, positive electrode of the present invention gained composite material as lithium-sulfur cell, shows the cyclical stability and high high rate performance of advantage.
Description
Technical field
The invention discloses a kind of three-dimensional grapheme aeroges to carry sulphur composite material and preparation method and application, belongs to lithium
Sulphur cell positive electrode electrode field of material technology.
Background technique
Energy and environmental problem is the two large problems of current mankind's urgent need to resolve.In fossil energy, increasingly exhaustion, environment are dirty
Dye get worse, today of global warming, seek substitute traditional fossil energy renewable green energy resource, seek people and ring
The harmony in border seems especially urgent.Novel renewable energy, for example utilization of wind energy and solar energy etc., electric car, mixing
The gradually marketization, the fast development of various portable power devices of power electric motor car are required to efficient, practical, " green " (zero
Pollution or low pollution) energy storage system.Chemical energy storage occupies extremely important status in new energy field.Novel power supply
System, especially secondary cell or supercapacitor are current important " green " chemical energy storage devices.In the change sought
It learns in energy storage system, lithium ion battery has operating voltage height, energy density big (light-weight), memory-less effect, cycle life
The advantages that long and pollution-free, has been widely used in the fields such as mobile electronic device and electric car.However, at present lithium from
Limitation of the sub- battery due to its own theoretical capacity, it is difficult to meet the market demand, so being badly in need of developing next-generation height ratio capacity, length
Cycle life, the new secondary battery of high safety performance.
Lithium-sulfur cell has high theoretical specific capacity (1675mAh gS -1) and theoretical energy density (2600Wh kg-1), and
And elemental sulfur is widespread in nature, price is low, and environmental-friendly, therefore, it is considered current most promising secondary
One of battery system.But lithium-sulfur cell there is a problem of in commercial applications it is some have it is to be overcome.First, sulphur and electric discharge
The electric conductivity of product lithium sulfide is poor, and (conductivity is respectively 5 × 10-30S cm-1With 3.6 × 10-7S cm-1)；Second, elemental sulfur
Larger (density is respectively 2.03g cm with the density difference of its complete discharging product lithium sulfide-3With 1.67g cm-3), in charge and discharge
It will appear apparent volume expansion (about 80%) in electric cyclic process, positive electrode made to be easy pink blossom even from plus plate current-collecting body
It falls off；Third, the intermediate product that sulphur generates in charge and discharge process are readily dissolved in organic electrolyte solution, cause " to shuttle and imitate
It answers ".The utilization rate that the presence of these problems will lead to positive active material is low, and the capacity attenuation of battery is fast, and poor circulation is filled
The problems such as discharging efficiency is low.
In recent years, people have carried out lithium-sulfur cell from the Nomenclature Composition and Structure of Complexes of positive electrode design etc. many beneficial
It explores, makes great progress.Use that most to be that carrier using conductive carbon material as sulphur is constituted sulphur carbon compound in research
Positive electrode.These researchs are to the inspiration of people, with excellent electric conductivity, good structural stability and porous structure
Nano-carbon material, such as activated carbon, mesoporous carbon, extra small microporous carbon, multilevel structure porous carbon, hollow carbon sphere, hollow carbon fiber, carbon
Nanotube, graphene etc. sufficiently meet requirement of the lithium sulfur battery anode material to carbon base body.
But presently relevant technology still has some defects, such as preparation process complexity, heat-treatment process energy consumption is high,
And there are sulphur volatilizations, lead to wastage of material, transformation efficiency is low；In addition, resulting materials electric conductivity is not ideal enough, cycle performance
With high rate performance difference etc..
Summary of the invention
Goal of the invention: in view of the above technical problems, simple, cheap, energy saving, ring is prepared it is an object of that present invention to provide a kind of
The preparation method of border close friend and the anode composite material of lithium sulfur battery being produced on a large scale, not with conventional melting diffusion method sulfurizing
Together, which forms hydrogel precursor for sulphur and graphene oxide at room temperature, avoids in traditional sulfur electrode preparation process
The high energy consumption of complicated heat-treatment process and thus issuable sulphur volatilization, it is more convenient in large-scale production.It is prepared
Graphene coated sulphur composite material there is the internal three-dimensional net structure communicated, can be raw in charge and discharge process by sulfur electrode
At 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, to guarantee that prepared three-dimensional grapheme aeroge carries sulphur composite material in charge and discharge process
In show good cycle performance and high rate performance.
Technical solution: the present invention provides a kind of three-dimensional grapheme aeroges to carry sulphur composite material, mainly first by sulphur
Hydrogel precursor is formed with graphene oxide, then hydrazine hydrate is recycled to be restored, what is obtained has internal three communicated
Tie up the graphene coated sulphur composite material of network structure.
The present invention provides the preparation methods that the three-dimensional grapheme aeroge carries sulphur composite material, comprising the following steps:
(1) graphene oxide and sublimed sulfur are dispersed in distilled water, at room temperature, utilize chitosan/acetic acid aqueous solution
Hydrogel precursor is made, so that three-dimensional graphite oxide aerogel, which is made, carries sulphur (S/GO) composite material；
(2) product for obtaining step (1) distillation water dispersion, is restored in aqueous ammonia medium using hydrazine hydrate, cold
It is lyophilized dry to get described three-dimensional grapheme aeroge load sulphur (S/rGO) composite material.
It is preferred that, comprising the following steps:
(1) three-dimensional graphite oxide aerogel carries the preparation of sulphur (S/GO) composite material: by suitable graphene oxide and
Sublimed sulfur is dispersed in distilled water, suitable chitosan/acetic acid aqueous solution is added while stirring under room temperature (25 DEG C), stirring is extremely
It is freeze-dried in hydrogel, then after standing 4-8 hours at room temperature, so that three-dimensional graphite oxide aerogel, which is made, carries sulphur
(S/GO) composite material；
(2) three-dimensional grapheme aeroge carries the preparation of sulphur (S/rGO) composite material: the product that step (1) is obtained is used suitable
The distillation water dispersion of amount, is added a certain amount of ammonium hydroxide and hydrazine hydrate at moderate temperatures, reacts appropriate time, filters and with distilling
Water washing to filtrate is in neutrality, and collected solid is freeze-dried, and obtains the three-dimensional grapheme aeroge and carries sulphur
(S/rGO) composite material.
It is preferred that the chitosan relative molecular weight is 5~150,000 in step (1)；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 the mass ratio of the graphene oxide and chitosan is (5~20): 1 in step (1).
It is preferred that after the product distillation water dispersion for obtaining step (1), graphite oxide aerogel carries sulphur in step (2)
The concentration of composite material is 10~50mg mL-1。
It is preferred that the ammonia concn being added is 15~30wt% in step (2), the concentration of hydrazine hydrate is 40~80wt%.
It is preferred that proper temperature described in step (2) is 10~80 DEG C, the appropriate reaction time is 1~3 hour.
The present invention also provides the three-dimensional grapheme aeroges to carry sulphur composite material as lithium sulfur battery anode material
Using.
Graphene, as a kind of two-dimensional slice structural material, the conductivity with superelevation, biggish specific surface area and excellent
Mechanical property.Its lamellar structure is conducive to construct three-dimensional net structure, not only can store sulphur active material, but also can be with
Alleviate the volume change that sulphur occurs in charge and discharge process, to guarantee that positive electrode has lasting structural intergrity.In addition,
The superior electric conductivity of graphene constructs high conductive network skeleton, so that it is guaranteed that sulphur good electronics in charge and discharge process is led
Electrically.
Technical effect: compared with the existing technology, present invention has the advantage that
(1) present invention prepares three-dimensional grapheme aeroge using easy method and carries sulphur composite material.With conventional melting
Diffusion method sulfurizing prepares sulphur composite electrode difference, which forms hydrogel forerunner for sulphur and graphene oxide at room temperature
Body avoids the high energy consumption of heat-treatment process complicated in traditional sulfur electrode preparation process and thus issuable sulphur is waved
Hair, it is more convenient in large-scale production.
(2) the three-dimensional grapheme aeroge prepared by the present invention, which carries sulphur composite material, has the internal three-dimensional network knot communicated
The polysulfide that sulfur electrode generates in charge and discharge process can be effectively limited in three-dimensional grapheme network by structure, thus
Inhibit the shuttle of polysulfide, alleviates volume change positive in charge and discharge process；This structure also helps the infiltration of electrolyte
It thoroughly and spreads, while improving the electric conductivity of material, to improve the cyclical stability and high rate performance of positive electrode.
Detailed description of the invention
Fig. 1 is the X ray diffracting spectrum of S/rGO composite material made from embodiment 1.
Fig. 2 is the thermal multigraph of S/rGO composite material made from embodiment 1.
Fig. 3 is the scanning electron microscope (SEM) photograph of S/GO and S/rGO composite material made from embodiment 1.
Fig. 4 is the charging and discharging curve of S/rGO composite material (a) and bright sulfur (b) made from embodiment 1.
Fig. 5 is the charge-discharge performance figure of S/rGO composite material and bright sulfur made from embodiment 1.
Fig. 6 is the charge-discharge magnification performance map of S/rGO composite material and bright sulfur made from embodiment 1.
Specific embodiment
With reference to the accompanying drawing and specific example, the present invention is furture elucidated, it should be understood that these examples are merely to illustrate this hair
It is bright rather than limit the scope of the invention.
Embodiment 1
(1) three-dimensional graphite oxide aerogel carries the preparation of sulphur (S/GO) composite material: by the graphene oxide of 50mg and
50mg sublimed sulfur is dispersed in 5mL distilled water, and 0.5mL 10mgmL is added under room temperature (25 DEG C)-1Chitosan (molecular weight 15
Ten thousand)/aqueous acetic acid (volume ratio of acetic acid and water is 5:95), stirring to formation hydrogel, then 6 hours are stood at room temperature,
Freeze-drying, so that three-dimensional graphite oxide aerogel, which is made, carries sulphur (S/GO) composite material.
(2) three-dimensional grapheme aeroge carries the preparation of sulphur (S/rGO) composite material: the product 105mg that step (1) is obtained
With the distillation water dispersion of 5mL, ammonium hydroxide (25wt%) and 0.2mL hydrazine hydrate (50wt%) reaction 1.5 of 0.3mL are added at 60 DEG C
Hour, it filters and is washed with distilled water to filtrate and be in neutrality, collected solid is freeze-dried, obtain the three-dimensional
Graphene aerogel carries sulphur (S/rGO) composite material.
Fig. 1 is the X ray diffracting spectrum of the S/GO and S/rGO composite material of the present embodiment synthesis.As seen from the figure, S/GO and
Sulphur in S/rGO composite material is all with the presence of rhombic sulfur (JCPDS No.08-0247) crystalline phase.
Fig. 2 is the thermogravimetric analysis figure of the S/rGO composite material 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 material.
By Fig. 3 a and Fig. 3 b as it can be seen that the size of sublimed sulfur is inhomogenous, graphene oxide is uniformly coated on the surface of sulfur granules, shape
At three-dimensional net structure.After hydrazine hydrate reduction, product still maintains original size and shape (Fig. 3 c, d), these structures
Characteristic is all conducive to the composite positive pole and shows preferably to store up lithium performance.
Fig. 4 is the S/rGO composite material of the present embodiment synthesis and the charging and discharging curve of bright sulfur.By discharge curve as it can be seen that S/
RGO composite material and bright sulfur all show typical Double tabletop curve, are converted into more lithium sulfides corresponding to sulphur, are eventually converted into sulphur
Change lithium；It is compared with bright sulfur, second platform contribution capacity of S/rGO composite material is more.
Fig. 5 is the S/rGO composite material 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 composite material is 711mAh g-1, higher than putting for bright sulfur
Electric specific capacity (573mAh g-1)；After 300 charge and discharge cycles, the specific discharge capacity of S/rGO composite material is still up to
421mAh g-1, higher than specific discharge capacity (the 173mAh g of bright sulfur-1), show superior cycle performance and higher specific volume
Amount.
Fig. 6 is the S/rGO composite material 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 is restored to 560mAh g-1, all higher than bright sulfur
Specific capacity, this illustrates the high rate performance that S/rGO composite material has had, and 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 material: by the graphene oxide of 25mg and
50mg sublimed sulfur is dispersed in 5mL distilled water, and 0.5mL 10mgmL is added under room temperature (25 DEG C)-1Chitosan (molecular weight 15
Ten thousand)/aqueous acetic acid (volume ratio of acetic acid and water is 5:95), stirring to formation hydrogel, then 6 hours are stood at room temperature,
Freeze-drying, so that three-dimensional graphite oxide aerogel, which is made, carries sulphur (S/GO) composite material.
(2) three-dimensional grapheme aeroge carries the preparation of sulphur (S/rGO) composite material: the product 80mg that step (1) is obtained
With the distillation water dispersion of 5mL, ammonium hydroxide (30wt%) and 0.2mL hydrazine hydrate (40wt%) reaction 2 that 0.3mL is added at 50 DEG C are small
When, it filters and is washed with distilled water to filtrate and be in neutrality, collected solid is freeze-dried, obtain the three-dimensional stone
Black alkene aeroge carries sulphur (S/rGO) composite material.
To prepared three-dimensional grapheme aeroge carry sulphur composite material carry out the dependence test being similar in embodiment 1 and
Characterization, conclusion are similar to embodiment 1.
Embodiment 3
(1) three-dimensional graphite oxide aerogel carries the preparation of sulphur (S/GO) composite material: by the graphene oxide of 50mg and
100mg sublimed sulfur is dispersed in 5mL distilled water, and 0.5mL 10mgmL is added under room temperature (25 DEG C)-1Chitosan (molecular weight 15
Ten thousand)/aqueous acetic acid (volume ratio of acetic acid and water is 5:95), stirring to formation hydrogel, then 6 hours are stood at room temperature,
Freeze-drying, so that three-dimensional graphite oxide aerogel, which is made, carries sulphur (S/GO) composite material.
(2) three-dimensional grapheme aeroge carries the preparation of sulphur (S/rGO) composite material: the product 155mg that step (1) is obtained
With the distillation water dispersion of 10mL, ammonium hydroxide (15wt%) and 0.2mL hydrazine hydrate (50wt%) reaction of 0.3mL are added at 70 DEG C
It 1.2 hours, filters and is washed with distilled water to filtrate and be in neutrality, collected solid is freeze-dried, obtain described
Three-dimensional grapheme aeroge carries sulphur (S/rGO) composite material.
To prepared three-dimensional grapheme aeroge carry sulphur composite material carry out the dependence test being similar in embodiment 1 and
Characterization, conclusion are similar to embodiment 1.
Embodiment 4
(1) three-dimensional graphite oxide aerogel carries the preparation of sulphur (S/GO) composite material: by the graphene oxide of 100mg and
250mg sublimed sulfur is dispersed in 5mL distilled water, and 1mL 5mgmL is added under room temperature (25 DEG C)-1Chitosan (molecular weight 15
Ten thousand)/aqueous acetic acid (volume ratio of acetic acid and water is 5:95), stirring to formation hydrogel, then 4 hours are stood at room temperature,
Freeze-drying, so that three-dimensional graphite oxide aerogel, which is made, carries sulphur (S/GO) composite material.
(2) three-dimensional grapheme aeroge carries the preparation of sulphur (S/rGO) composite material: the product 355mg that step (1) is obtained
With the distillation water dispersion of 10mL, ammonium hydroxide (30wt%) and 0.2mL hydrazine hydrate (80wt%) reaction 1 of 0.3mL are added at 80 DEG C
Hour, it filters and is washed with distilled water to filtrate and be in neutrality, collected solid is freeze-dried, obtain the three-dimensional
Graphene aerogel carries sulphur (S/rGO) composite material.
To prepared three-dimensional grapheme aeroge carry sulphur composite material carry out the dependence test being similar in embodiment 1 and
Characterization, conclusion are similar to embodiment 1.
Embodiment 5
(1) three-dimensional graphite oxide aerogel carries the preparation of sulphur (S/GO) composite material: by the graphene oxide of 100mg and
25mg sublimed sulfur is dispersed in 5mL distilled water, and 1mL 5mg mL is added under room temperature (25 DEG C)-1Chitosan (molecular weight 15
Ten thousand)/aqueous acetic acid (volume ratio of acetic acid and water is 5:95), stirring to formation hydrogel, then 8 hours are stood at room temperature,
Freeze-drying, so that three-dimensional graphite oxide aerogel, which is made, carries sulphur (S/GO) composite material.
(2) three-dimensional grapheme aeroge carries the preparation of sulphur (S/rGO) composite material: the product 130mg that step (1) is obtained
With the distillation water dispersion of 5mL, ammonium hydroxide (30wt%) and 0.2mL hydrazine hydrate (80wt%) reaction 1.5 of 0.3mL are added at 60 DEG C
Hour, it filters and is washed with distilled water to filtrate and be in neutrality, collected solid is freeze-dried, obtain the three-dimensional
Graphene aerogel carries sulphur (S/rGO) composite material.
To prepared three-dimensional grapheme aeroge carry sulphur composite material carry out the dependence test being similar in embodiment 1 and
Characterization, conclusion are similar to embodiment 1.
Embodiment 6
(1) three-dimensional graphite oxide aerogel carries the preparation of sulphur (S/GO) composite material: by the graphene oxide of 100mg and
400mg sublimed sulfur is dispersed in 5mL distilled water, and 1mL 10mg mL is added under room temperature (25 DEG C)-1Chitosan (molecular weight 5
Ten thousand)/aqueous acetic acid (volume ratio of acetic acid and water is 5:95), stirring to formation hydrogel, then place 6 hours at room temperature,
Freeze-drying, so that three-dimensional graphite oxide aerogel, which is made, carries sulphur (S/GO) composite material.
(2) three-dimensional grapheme aeroge carries the preparation of sulphur (S/rGO) composite material: the product 510mg that step (1) is obtained
With the distillation water dispersion of 10.2mL, ammonium hydroxide (30wt%) and 0.2mL hydrazine hydrate (80wt%) reaction of 0.3mL are added at 60 DEG C
It 1.5 hours, filters and is washed with distilled water to filtrate and be in neutrality, collected solid is freeze-dried, obtain described
Three-dimensional grapheme aeroge carries sulphur (S/rGO) composite material.
To prepared three-dimensional grapheme aeroge carry sulphur composite material carry out the dependence test being similar in embodiment 1 and
Characterization, conclusion are similar to embodiment 1.
Embodiment 7
(1) three-dimensional graphite oxide aerogel carries the preparation of sulphur (S/GO) composite material: by the graphene oxide of 50mg and
50mg sublimed sulfur is dispersed in 5mL distilled water, and 0.5mL 10mg mL is added under room temperature (25 DEG C)-1Chitosan (molecular weight 5
Ten thousand)/aqueous acetic acid (volume ratio of acetic acid and water is 5:95), stirring to formation hydrogel, then 6 hours are stood at room temperature,
Freeze-drying, so that three-dimensional graphite oxide aerogel, which is made, carries sulphur (S/GO) composite material.
(2) three-dimensional grapheme aeroge carries the preparation of sulphur (S/rGO) composite material: the product 105mg that step (1) is obtained
With the distillation water dispersion of 5mL, ammonium hydroxide (25wt%) and 0.2mL hydrazine hydrate (50wt%) reaction 1.5 of 0.3mL are added at 60 DEG C
Hour, it filters and is washed with distilled water to filtrate and be in neutrality, collected solid is freeze-dried, obtain the three-dimensional
Graphene aerogel carries sulphur (S/rGO) composite material.
To prepared three-dimensional grapheme aeroge carry sulphur composite material carry out the dependence test being similar in embodiment 1 and
Characterization, conclusion are similar to embodiment 1.
Embodiment 8
(1) three-dimensional graphite oxide aerogel carries the preparation of sulphur (S/GO) composite material: by the graphene oxide of 50mg and
50mg sublimed sulfur is dispersed in 5mL distilled water, and 0.5mL 10mg mL is added under room temperature (25 DEG C)-1Chitosan (molecular weight 15
Ten thousand)/aqueous acetic acid (volume ratio of acetic acid and water is 5:95), stirring to formation hydrogel, then 6 hours are stood at room temperature,
Freeze-drying, so that three-dimensional graphite oxide aerogel, which is made, carries sulphur (S/GO) composite material.
(2) three-dimensional grapheme aeroge carries the preparation of sulphur (S/rGO) composite material: the product 105mg that step (1) is obtained
With the distillation water dispersion of 5mL, ammonium hydroxide (25wt%) and 0.2mL hydrazine hydrate (50wt%) reaction 3 that 0.3mL is added at 10 DEG C are small
When, it filters and is washed with distilled water to filtrate and be in neutrality, collected solid is freeze-dried, obtain the three-dimensional stone
Black alkene aeroge carries sulphur (S/rGO) composite material.
To prepared three-dimensional grapheme aeroge carry sulphur composite material carry out the dependence test being similar in embodiment 1 and
Characterization, conclusion are similar to embodiment 1.
Embodiment 9
(1) three-dimensional graphite oxide aerogel carries the preparation of sulphur (S/GO) composite material: by the graphene oxide of 50mg and
50mg sublimed sulfur is dispersed in 5mL distilled water, and 0.5mL 10mg mL is added under room temperature (25 DEG C)-1Chitosan (molecular weight 10
Ten thousand)/aqueous acetic acid (volume ratio of acetic acid and water is 5:95), stirring to formation hydrogel, then 6 hours are stood at room temperature,
Freeze-drying, so that three-dimensional graphite oxide aerogel, which is made, carries sulphur (S/GO) composite material.
(2) three-dimensional grapheme aeroge carries the preparation of sulphur (S/rGO) composite material: the product 105mg that step (1) is obtained
With the distillation water dispersion of 5mL, ammonium hydroxide (25wt%) and 0.2mL hydrazine hydrate (50wt%) reaction 1.5 of 0.3mL are added at 60 DEG C
Hour, it filters and is washed with distilled water to filtrate and be in neutrality, collected solid is freeze-dried, obtain the three-dimensional
Graphene aerogel carries sulphur (S/rGO) composite material.
To prepared three-dimensional grapheme aeroge carry sulphur composite material carry out the dependence test being similar in embodiment 1 and
Characterization, conclusion are similar to embodiment 1.
Claims (9)
1. a kind of three-dimensional grapheme aeroge for lithium sulfur battery anode material carries the preparation method of sulphur composite material, feature
It is, comprising the following steps:
(1) three-dimensional graphite oxide aerogel carries the preparation of sulphur composite material: suitable graphene oxide and sublimed sulfur are dispersed
In distilled water, suitable chitosan/acetic acid aqueous solution is added while stirring at 25 DEG C of room temperature, stirring is extremely in hydrogel, then
It is freeze-dried after standing 4-8 hours at room temperature, so that three-dimensional graphite oxide aerogel, which is made, carries sulphur composite material；
(2) product for obtaining step (1) distillation water dispersion, is restored in aqueous ammonia medium using hydrazine hydrate, freezing is dry
It is dry to carry sulphur composite material to get the three-dimensional grapheme aeroge.
2. the preparation method that three-dimensional grapheme aeroge according to claim 1 carries sulphur composite material, which is characterized in that packet
Include following steps:
(1) three-dimensional graphite oxide aerogel carries the preparation of sulphur composite material: suitable graphene oxide and sublimed sulfur are dispersed
In distilled water, suitable chitosan/acetic acid aqueous solution is added while stirring at 25 DEG C of room temperature, stirring is extremely in hydrogel, then
It is freeze-dried after standing 4-8 hours at room temperature, so that three-dimensional graphite oxide aerogel, which is made, carries sulphur composite material；
(2) three-dimensional grapheme aeroge carries the preparation of sulphur composite material: the suitable distillation moisture of the product that step (1) is obtained
It dissipates, a certain amount of ammonium hydroxide and hydrazine hydrate is added at moderate temperatures, react appropriate time, filter and be washed with distilled water to filtrate
It is in neutrality, collected solid is freeze-dried, obtain the three-dimensional grapheme aeroge and carry sulphur composite material.
3. three-dimensional grapheme aeroge according to claim 1 or 2 carries the preparation method of sulphur composite material, feature exists
In in step (1), the chitosan relative molecular weight is 5~150,000；The volume ratio of acetic acid and water is 5 in aqueous acetic acid:
95。
4. three-dimensional grapheme aeroge according to claim 1 or 2 carries the preparation method of sulphur composite material, 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。
5. three-dimensional grapheme aeroge according to claim 1 or 2 carries the preparation method of sulphur composite material, feature exists
In in step (1), the mass ratio of the graphene oxide and chitosan is (5~20): 1.
6. three-dimensional grapheme aeroge according to claim 1 or 2 carries the preparation method of sulphur composite material, feature exists
In in step (2), after the product distillation water dispersion that step (1) is obtained, graphite oxide aerogel carries sulphur composite material
Concentration is 10~50mg mL-1。
7. three-dimensional grapheme aeroge according to claim 1 or 2 carries the preparation method of sulphur composite material, feature exists
In in step (2), the ammonia concn being added is 15~30wt%, and the concentration of hydrazine hydrate is 40~80wt%.
8. the preparation method that three-dimensional grapheme aeroge according to claim 2 carries sulphur composite material, which is characterized in that step
Suddenly proper temperature described in (2) is 10~80 DEG C, and the appropriate reaction time is 1~3 hour.
9. three-dimensional grapheme aeroge obtained by preparation method described in claim 1 carry sulphur composite material as lithium-sulfur cell just
The application of pole material.
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| 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 |
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