CN105591076A - A preparing method of a graphene sulfo-based composite material - Google Patents
A preparing method of a graphene sulfo-based composite material Download PDFInfo
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- CN105591076A CN105591076A CN201410567985.6A CN201410567985A CN105591076A CN 105591076 A CN105591076 A CN 105591076A CN 201410567985 A CN201410567985 A CN 201410567985A CN 105591076 A CN105591076 A CN 105591076A
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Abstract
A preparing method of a graphene sulfo-based composite material is provided. Electrical conductivity of the composite material can be effectively enhanced by in-situ addition of graphene, the electronic conductivity can be increased by one or two orders of magnitudes, and the graphene as a three-dimensional current collector of the composite material effectively relieves agglomeration in a cyclic process, and therefore cyclic stability and rate capability of the composite material when the composite material is adopted as an electrode material are obviously improved.
Description
Technical field
The present invention relates to serondary lithium battery technical field, relate to particularly the synthetic technology of preparing of Graphene electrodes composite.
Background technology
The serondary lithium battery of high-energy-density is the emphasis of field of chemical power source research and development. Sulphur is as the extremely potential positive pole material of secondary lithium battery of one, while doing electrode with lithium metal, there is high theoretical energy density and specific capacity, and have the advantages such as aboundresources, with low cost and environmental friendliness, relevant secondary lithium-sulfur cell has become important research direction with critical material.
Graphene be a kind of by monolayer carbon atom with sp2The cellular Two-dimensional Carbon material of hydridization composition, the advantageous property revealing because of its unique two-dimension single layer structural table has obtained strong interest in field widely. Particularly excellent electron conduction, higher reference area, preferably chemical stability and very wide these performances of electrochemical window make it be favored especially in electrochemical energy storage application aspect.
Summary of the invention
The technical problem that the present invention solves is: the preparation method that a kind of Graphene sulfenyl composite is provided.
The technical scheme that the present invention realizes goal of the invention employing is: a kind of preparation method of Graphene sulfenyl composite, it is characterized in that, and comprise the following steps:
A. natural graphite powder is that raw material is prepared graphene oxide;
B. graphene oxide is dispersed in water and obtains graphene oxide aqueous dispersions, after add acrylonitrile monemer and azodiisobutyronitrile heating water bath under nitrogen protection to carry out home position polymerization reaction, until polymerization obtains the graphene composite material dispersion liquid of grey after stopping, after vacuum drying, obtain graphene composite material;
C. after the graphene composite material making being mixed with elemental sulfur, put into quartz ampoule, under slumpability atmosphere, be heated to 250-350 DEG C, insulation 1～10h, obtains Graphene sulfenyl composite.
Preferably, the concrete steps of described step a are first natural graphite powder to be carried out to pre-oxidation step, and then be oxidized by force strip step.
Preferably, in described step a, the step of pre-oxidation is for respectively by K2S2O8And P2O5Mass ratio by 1 to 1 slowly adds in the concentrated sulfuric acid successively, to completely dissolve, after natural graphite powder is added wherein, after constant temperature 7-8h, obtain navy blue suspension, be cooled to clean after room temperature to pH value and be about till 7, obtained the graphite powder of the pre-oxidation of black after dry.
Preferably, in described step a, being oxidized by force strip step is the concentrated sulfuric acid of the graphite powder of pre-oxidation being put into ice-water bath, after dispersed with stirring is even, adds KMnO4, and temperature control is below 20 DEG C. Stir 3h at 30-40 DEG C after, obtain cyan suspension, add deionized water, obtain the suspension of brown, then add H2O2Solution, obtains glassy yellow suspension, obtains graphene oxide after centrifugal treating.
In the present invention, the original position of Graphene adds the effectively electric conductivity of reinforced composite, electronic conductivity can improve one to two order of magnitude, Graphene has effectively been alleviated its reunion in cyclic process as the three-dimensional collector of composite, and cyclical stability and high rate performance that therefore composite uses as electrode material all significantly improve.
Brief description of the drawings
Fig. 1, embodiment adds the Graphene of different content on the datagram that affects of Graphene sulfenyl composite electronic conductivity.
Detailed description of the invention
Below, with specific embodiments and the drawings describes the present invention.
The preparation method of the present embodiment Graphene sulfenyl composite comprises the following steps:
A. natural graphite powder is that raw material is prepared graphene oxide; Concrete steps are:
Respectively by 5gK2S2O8And 5gP2O5Slowly add in the 50mL concentrated sulfuric acid successively, be heated to 80 DEG C, constant temperature, to dissolving completely, makes settled solution. Then 10g natural graphite powder is added wherein, after constant temperature 6h, obtain navy blue suspension. After being cooled to room temperature, use deionized water eccentric cleaning, until pH value is about 7. Finally products therefrom dry 12h in 80 DEG C of baking ovens is obtained to the pre-oxidation graphite powder of black.
The graphite powder of pre-oxidation is put into the 230mL concentrated sulfuric acid of ice-water bath, after dispersed with stirring is even, added 30gKMnO4, and temperature control is below 20 DEG C. Stir 3h at 35 DEG C after, obtain cyan suspension. Add 800mL deionized water, obtain the suspension of brown. Add again 50mL30%H2O2, obtain glassy yellow suspension. Then by suspension centrifugal treating, remove impurity, collect slurry. Finally the graphene oxide slurry obtaining is dialysed to remove metal ion and acid ion, after centrifugal treating, can obtain pure graphene oxide.
B. the preparation of graphene composite material: be scattered in 100mL deionized water ultrasonic 0.1gGO in flask, make the graphene oxide aqueous dispersions of brown. Add acrylonitrile monemer (AN) liquid of 1g clear, continue ultrasonic agitation 30min, so that AN fully mixes with GO. Then add 0.05g azodiisobutyronitrile (AIBN). Full nitrogen in flask subsequently, continues after 20min, flask sealing to be transferred in water-bath. Vigorous stirring under 65 DEG C of water-baths, carries out home position polymerization reaction. After 3h, shift out water-bath, polymerization stops, and obtains the aqueous dispersions of grey. Add 1mL hydrazine hydrate as reducing agent after stirring 10min in above-mentioned dispersion liquid and seal, be placed in 80 DEG C of baking ovens and be incubated 10h, obtain the graphene composite material aqueous dispersions of black. Finally by product with after ethanol filtration and washing at 80 DEG C vacuum drying obtain graphene composite material. The composite of different GNS content makes by the input mass ratio of controlling raw material.
C. the preparation of Graphene sulfenyl composite: after the graphene composite material making is mixed in certain mass ratio with elemental sulfur, put into quartz ampoule, under slumpability atmosphere, be heated to 300 DEG C, insulation 1～10h, obtains Graphene sulfenyl composite after naturally cooling.
Fig. 1 is the affect datagram of Graphene on Graphene sulfenyl composite electronic conductivity that adds different content. As can be seen from the figure,, along with having the adding of Graphene of high conductivity, the electronic conductivity of pPAN-S composite is from 10-4Scm-1Promoted one to two order of magnitude, the electronic conductivity that really can obviously improve composite that adds of Graphene is described, this is more prone to transmit electronics just can make it as electrode material time.
The original position of preparing in the present embodiment adds the Graphene sulfenyl composite (pPAN-S/GNS) obtaining after Graphene to demonstrate more stable cycle performance:
(1) method that adopts in-situ polymerization to add subsequent heat treatment is prepared Graphene sulfenyl composite, can realize almost each independent pPAN-S particle and Graphene and keep stable close contact, make Graphene in composite, give full play to the effect of its high conducting medium as the nanometer collector of three-dimensional structure, improve the electric conductivity of composites;
(2) in composite, Graphene can be used as the fulcrum of the pPAN-S particle of dispersion, suppress reunion and the growth of pPAN-S nano particle in cyclic process, keep the stable of composite microstructure, weaken the electronics and the ion Diffusion Barrier that therefore cause;
(3) from another angle, because pPAN-S nano particle is dispersed in the surface of Graphene uniformly, and can keep stable contact, so the dispersant that pPAN-S nano particle also can be used as between graphene film exists, prevent again laminating and reuniting of Graphene self, therefore can keep the reference area of its super large, ensure effective contact area larger between electrode and electrolyte.
In the present embodiment, the original position of Graphene adds the effectively electric conductivity of reinforced composite, electronic conductivity can improve one to two order of magnitude, Graphene has effectively been alleviated its reunion in cyclic process as the three-dimensional collector of composite, and cyclical stability and high rate performance that therefore composite uses as electrode material all significantly improve.
The foregoing is only preferred embodiment of the present invention, in order to limit the present invention, within the spirit and principles in the present invention not all, any amendment of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (4)
1. a preparation method for Graphene sulfenyl composite, is characterized in that, comprise withLower step:
A. natural graphite powder is that raw material is prepared graphene oxide;
B. graphene oxide is dispersed in water and obtains graphene oxide aqueous dispersions, after addIt is anti-that acrylonitrile monemer and azodiisobutyronitrile heating water bath under nitrogen protection carries out in-situ polymerizationShould, until polymerization obtains the graphene composite material dispersion liquid of grey after stopping, after vacuum dryingObtain graphene composite material;
C. after the graphene composite material making being mixed with elemental sulfur, put into quartz ampoule,Under slumpability atmosphere, be heated to 250-350 DEG C, insulation 1～10h, obtains graphiteAlkenylthio group composite.
2. the preparation method of Graphene sulfenyl composite according to claim 1, itsBe characterised in that: the concrete steps of described step a are first natural graphite powder to be carried out to pre-oxidation stepSuddenly, and then be by force oxidized strip step.
3. the preparation method of Graphene sulfenyl composite according to claim 2, itsBe characterised in that: in described step a, the step of pre-oxidation is for respectively by K2S2O8And P2O5By 1Slowly add successively in the concentrated sulfuric acid than 1 mass ratio, to dissolving completely, after by natural graphite powderAdd wherein, after constant temperature 7-8h, obtain navy blue suspension, be cooled to after room temperature clearBe washed till pH value and be about till 7, after being dried, obtain the graphite powder of the pre-oxidation of black.
4. the preparation method of Graphene sulfenyl composite according to claim 2, itsBe characterised in that: in described step a, being oxidized by force strip step is that the graphite powder of pre-oxidation is put intoIn the concentrated sulfuric acid of ice-water bath, after dispersed with stirring is even, add KMnO4, and temperature control 20 DEG C withUnder. Stir 3h at 30-40 DEG C after, obtain cyan suspension, add deionized water,Obtain the suspension of brown, then add H2O2Solution, obtains glassy yellow suspension, centrifugal treatingAfter obtain graphene oxide.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150303457A1 (en) * | 2012-11-30 | 2015-10-22 | Shanghai Jiaotong University | Cathode Material for a Li-S Battery and the Method for Preparing the Same, a Cathode Made of the Cathode Material and a Li-S Battery Comprising the Cathode |
| CN107032343A (en) * | 2017-05-24 | 2017-08-11 | 北京服装学院 | The preparation method of wet spinning graphene oxide solution and graphene fiber |
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| CN102504145A (en) * | 2011-11-15 | 2012-06-20 | 苏州大学 | Preparation method for polymer grafted graphene oxide |
| CN103178242A (en) * | 2013-03-25 | 2013-06-26 | 中国科学院上海硅酸盐研究所 | Graphene-sulfur composite material used as positive material of lithium-sulfur battery and preparation method of graphene-sulfur composite material |
| CN103515608A (en) * | 2012-06-27 | 2014-01-15 | 海洋王照明科技股份有限公司 | Graphene/sulfur composite material and preparation method thereof, battery positive electrode and preparation method thereof, and battery |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102504145A (en) * | 2011-11-15 | 2012-06-20 | 苏州大学 | Preparation method for polymer grafted graphene oxide |
| CN103515608A (en) * | 2012-06-27 | 2014-01-15 | 海洋王照明科技股份有限公司 | Graphene/sulfur composite material and preparation method thereof, battery positive electrode and preparation method thereof, and battery |
| CN103178242A (en) * | 2013-03-25 | 2013-06-26 | 中国科学院上海硅酸盐研究所 | Graphene-sulfur composite material used as positive material of lithium-sulfur battery and preparation method of graphene-sulfur composite material |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150303457A1 (en) * | 2012-11-30 | 2015-10-22 | Shanghai Jiaotong University | Cathode Material for a Li-S Battery and the Method for Preparing the Same, a Cathode Made of the Cathode Material and a Li-S Battery Comprising the Cathode |
| US9773581B2 (en) * | 2012-11-30 | 2017-09-26 | Robert Bosch Gmbh | Cathode material for a Li—S battery and the method for preparing the same, a cathode made of the cathode material and a Li—S battery comprising the cathode |
| CN107032343A (en) * | 2017-05-24 | 2017-08-11 | 北京服装学院 | The preparation method of wet spinning graphene oxide solution and graphene fiber |
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