CN103825000A - Mesoporous carbon loaded sulfur/selenium flexible electrode based on three-dimensional graphite alkene self-supporting structure as well as preparation method and application thereof - Google Patents
Mesoporous carbon loaded sulfur/selenium flexible electrode based on three-dimensional graphite alkene self-supporting structure as well as preparation method and application thereof Download PDFInfo
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- CN103825000A CN103825000A CN201410076977.1A CN201410076977A CN103825000A CN 103825000 A CN103825000 A CN 103825000A CN 201410076977 A CN201410076977 A CN 201410076977A CN 103825000 A CN103825000 A CN 103825000A
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- dimensional grapheme
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- sulphur
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910052711 selenium Inorganic materials 0.000 title claims abstract description 54
- 239000011669 selenium Substances 0.000 title claims abstract description 54
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 title claims abstract description 53
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 10
- 239000010439 graphite Substances 0.000 title claims abstract description 10
- 229910052717 sulfur Inorganic materials 0.000 title abstract description 7
- 239000011593 sulfur Substances 0.000 title abstract description 7
- -1 graphite alkene Chemical class 0.000 title abstract 4
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 62
- 239000005864 Sulphur Substances 0.000 claims description 43
- 239000006260 foam Substances 0.000 claims description 29
- 239000000463 material Substances 0.000 claims description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 21
- 239000002131 composite material Substances 0.000 claims description 19
- 235000019441 ethanol Nutrition 0.000 claims description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 16
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 239000003708 ampul Substances 0.000 claims description 12
- 238000003763 carbonization Methods 0.000 claims description 12
- 239000010453 quartz Substances 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 229920000428 triblock copolymer Polymers 0.000 claims description 12
- 238000010792 warming Methods 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 8
- 239000007833 carbon precursor Substances 0.000 claims description 8
- 229910052744 lithium Inorganic materials 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 239000005011 phenolic resin Substances 0.000 claims description 8
- 229920001568 phenolic resin Polymers 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 238000005844 autocatalytic reaction Methods 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 229910021389 graphene Inorganic materials 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 6
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 238000010276 construction Methods 0.000 claims description 2
- 238000001802 infusion Methods 0.000 claims description 2
- ZVSWQJGHNTUXDX-UHFFFAOYSA-N lambda1-selanyllithium Chemical compound [Se].[Li] ZVSWQJGHNTUXDX-UHFFFAOYSA-N 0.000 abstract description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 3
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 3
- 239000000126 substance Substances 0.000 description 9
- 239000006258 conductive agent Substances 0.000 description 5
- 239000011149 active material Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229920001021 polysulfide Polymers 0.000 description 2
- 239000005077 polysulfide Substances 0.000 description 2
- 150000008117 polysulfides Polymers 0.000 description 2
- 150000003346 selenoethers Chemical class 0.000 description 2
- ZQRRBZZVXPVWRB-UHFFFAOYSA-N [S].[Se] Chemical compound [S].[Se] ZQRRBZZVXPVWRB-UHFFFAOYSA-N 0.000 description 1
- RSDUJIHCDSYTBB-UHFFFAOYSA-N [S].[Se].[Li] Chemical compound [S].[Se].[Li] RSDUJIHCDSYTBB-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 230000010412 perfusion Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 125000003748 selenium group Chemical group *[Se]* 0.000 description 1
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/387—Tin or alloys based on tin
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Abstract
The invention discloses a mesoporous carbon loaded sulfur/selenium flexible electrode based on a three-dimensional graphite alkene self-supporting structure. The invention further discloses a preparation method of the electrode, and application of the mesoporous carbon loaded sulfur/selenium flexible electrode based on the three-dimensional graphite alkene self-supporting structure in preparing a lithium ion secondary battery. The invention further discloses a lithium-sulfur battery and a lithium-selenium battery both comprising the electrode. The mesoporous carbon loaded sulfur/selenium flexible electrode based on the three-dimensional graphite alkene self-supporting structure, provided by the invention, has good mechanical performance and electrical performance, can effectively improve the specific energy intensity of the electrode; the lithium-sulfur(selenium) battery manufactured by adopting the electrode has the advantages of small size, high capacity, long service life and high efficiency, and has very high application potential and commercial value.
Description
Technical field
The invention belongs to battery material scientific domain, be specifically related to mesoporous carbon-loaded sulphur/selenium flexible electrode based on three-dimensional grapheme self supporting structure and preparation method thereof and application.
Background technology
Lithium sulphur and lithium selenium cell are two kinds that academic circles at present and industrial quarters just have higher energy density in the lithium rechargeable battery system of joint development, are representative and the direction of high-energy-density performance secondary cell.Compare with other battery, lithium-sulfur cell has the advantages such as energy density high (the theoretical volume specific capacity of elemental sulfur is 3467mAh/cm3), sulphur aboundresources, environmental friendliness, low price; Lithium-selenium cell has the volume and capacity ratio similar to lithium-sulfur cell (3253mA h/cm3), and the conductivity of selenium and electro-chemical activity are all far away higher than sulphur, therefore have very high application potential and commercial value.
But, still there are in actual applications many problems in lithium sulphur and lithium selenium cell, wherein 2 relatively more outstanding points: the one,, because ionic conductivity and the electron conduction of sulphur are all very low, cause that the chemical property of sulphur in electrode is not good and utilance is low, and although simple substance selenium has relatively high conductance, still need by with the effectively compound object that realizes high power charging-discharging of conductive agent; The 2nd,, because lithium sulphur and lithium selenium cell electrode exist in charge and discharge process, active material dissolves and the phenomenon of the effect of shuttling back and forth, and causes the capacity attenuation of battery very fast.
The flexibility design of lithium rechargeable battery has also been subject to the extensive concern of academia.This battery adopts the interlayer sandwich structure design of simple self-supporting negative pole-electrolyte and membrane layer-self-supporting positive pole, owing to having saved the organic electrolyte of collector, box hat and a large amount of perfusions, the specific energy density of battery and fail safe are greatly improved and application becomes more extensive.
Chinese patent CN103050669A discloses a kind of method that adopts mesoporous carbon-loaded sulphur, has suppressed preferably the dissolving of active material polysulfide and the effect of shuttling back and forth; Chinese patent CN103178246A discloses a kind of method that adopts mesoporous carbon-loaded selenium, has suppressed preferably the dissolving of the many selenides of active material and the effect of shuttling back and forth.The presentation of results mesoporous carbon structure of above-mentioned patent can suppress the dissolving of polysulfide or many selenides effectively, thereby delays the capacity attenuation of battery, promotes the life-span of battery; But above-mentioned mesoporous sulphur (selenium) material with carbon element still needs and conductive agent, binding agent mixes, and is coated on collector, to be used as electrode and to use.Above-mentioned operation needs to control fully and accurate mixing, and simultaneously due to conductive agent, the adding of binding agent and collector, the energy density of electrode is significantly cut down.
Summary of the invention
Goal of the invention: the problem and shortage existing for above-mentioned existing scheme, the flexible electrode of the mesoporous carbon-loaded sulphur/selenium of the three-dimensional grapheme self supporting structure that the first mechanical property of the present invention is good, chemical property is good, energy density is high.
The second object of the present invention is to provide the preparation method of above-mentioned electrode.
The flexible electrode that the 3rd object of the present invention is to provide the mesoporous carbon-loaded sulphur/selenium with three-dimensional grapheme self supporting structure is in the application of preparing in lithium rechargeable battery.
The 4th object of the present invention is to provide a kind of lithium-sulfur cell and a kind of lithium selenium cell that comprises this electrode.
Technical scheme: for achieving the above object, technical scheme of the present invention is as follows: a kind of flexible electrode of the mesoporous carbon-loaded sulphur/selenium based on three-dimensional grapheme self supporting structure, described electrode is sulphur/selenium carbon electrode that the flexible mesoporous carbon-loaded sulphur with three-dimensional grapheme self supporting structure/selenium obtains.
Wherein, above-mentioned three-dimensional grapheme self supporting structure is to make take foam metal as template.
Wherein, above-mentioned three-dimensional grapheme self supporting structure is the Graphene-mesoporous carbon composite construction making by infusion process and heat treating process.
The preparation method of the flexible electrode of above-mentioned a kind of mesoporous carbon-loaded sulphur/selenium based on three-dimensional grapheme self supporting structure, comprises the following steps:
1) preparation of three-dimensional grapheme skeleton: by the foam metal of ethanol ultrasonic cleaning, in inertia or reducing atmosphere, be warming up to 700-1000 ℃, pass into hydrogen and ethanol gas, under foam metal autocatalysis, Graphene stratiform structure is in foam metal superficial growth, the three-dimensional foam metal-graphite alkene obtaining is put into 10-100ml red fuming nitric acid (RFNA), soaks 5-24 hour; Spending ion-cleaning to solution is neutrality, then uses successively ethanol, and ether embathes, and takes out rear 20-80 ℃ of vacuumize 6～10 hours, obtains three-dimensional grapheme self-supporting material;
2) mesoporous carbon precursor solution is synthetic: triblock copolymer and phenolic resins are evenly mixed, be dissolved in a certain amount of absolute ethyl alcohol, obtain yellow solution;
3) preparation of three-dimensional grapheme-mesoporous carbon composite material: mesoporous carbon precursor solution is impregnated in three-dimensional grapheme self-supporting material, obtains sample after at room temperature placing 8-12h, sample is put into the baking oven heat treatment 12-24h of 100-120 ℃; Sample is put into tubular heater after taking out, and in nitrogen atmosphere, is warming up to 700-950 ℃ of carbonization 0.5-2h, after carbonization completes, is cooled to room temperature in nitrogen atmosphere, can obtain three-dimensional grapheme-mesoporous carbon composite material;
4) preparation of the mesoporous sulphur/selenium of the flexibility based on three-dimensional grapheme self supporting structure carbon electrode: take a certain amount of sulphur or selenium and put into quartz ampoule together with three-dimensional grapheme-mesoporous carbon composite material, quartz ampoule is inserted in the tube furnace that is full of inert atmosphere, be heated to 300-800 ℃ of insulation 5-10h and obtain the mesoporous sulphur/selenium of the flexibility carbon electrode based on three-dimensional grapheme self supporting structure.
Wherein, in step 1), foam metal is nickel, iron, copper, cobalt or its alloy; Inertia or reducing atmosphere are nitrogen, argon gas or ammonia etc.; The mass fraction of described red fuming nitric acid (RFNA) is 65%-68%.
Wherein, step 2) in triblock copolymer be F127 or P123, the mass ratio of described triblock copolymer and phenolic resins is 3:1～1:3; The mass ratio of triblock copolymer and absolute ethyl alcohol is 5:1～1:5; Whipping temp is 20-80 ℃, and mixing time is 1-15h.
Wherein, the mass ratio 1:1～10:1 of elemental sulfur or selenium and three-dimensional grapheme-mesoporous carbon composite material in step 4).
The flexible electrode of above-mentioned a kind of mesoporous carbon-loaded sulphur/selenium based on three-dimensional grapheme self supporting structure is in the application of preparing in lithium rechargeable battery.
A kind of lithium sulphur/lithium selenium cell, the flexible electrode that comprises the above-mentioned mesoporous carbon-loaded sulphur/selenium based on three-dimensional grapheme self supporting structure.
Beneficial effect: compared with prior art, the flexible electrode of the mesoporous carbon-loaded sulphur/selenium with three-dimensional grapheme self supporting structure provided by the invention can effectively promote the specific energy density of electricity level and have good pliability, adopt the lithium sulphur/selenium cell of above-mentioned electrode fabrication to there is volume little, capacity is high, life-span is long, the advantage that efficiency is high, possesses very high application potential and commercial value.Flexible lithium-sulfur cell technology for preparing electrode based on carbon tube bank is simple, with low cost, this electrode adopts the method sulfur materials of liquid phase growth in situ to load on the carbon nano tube network of high conductivity and coated with conductive polymer thereon, utilize the feature of carbon nano-tube and conducting polymer compound system to prepare the flexible electrode film with certain mechanical strength, can realize well the flexibility of electrode and improve the chemical property of sulfur materials, have advantages of that mechanical property is good, chemical property is good, energy density is high.
Particularly, the present invention has following outstanding advantage with respect to prior art:
(1) flexible electrode of the mesoporous carbon-loaded sulphur/selenium based on three-dimensional grapheme self supporting structure provided by the invention has that pliability is high, specific area is large, has greatly improved mechanical property and the chemical property of self-supporting electrode.
(2) the present invention realizes the load to sulphur/selenium by mesoporous carbon, guarantees the close contact between sulphur/selenium and carbon nanometer skeleton; Control the pattern of sulphur/selenium simultaneously, shorten the distance that lithium ion and electronics spread in electrode material, thereby improve lithium ion and electronics transporting in electrode material.
(3) stripping of sulphur/selenium in electrolyte is one of the key factor in restriction lithium-sulfur cell life-span, and the present invention adopts the method for mesoporous carbon confinement to suppress the stripping of sulphur/selenium, can effectively suppress the decay of lithium sulphur or lithium selenium cell capacity, the life-span of prolongation lithium-sulfur cell.
(4) this flexible electrode can be directly used in the assembling of lithium rechargeable battery, does not need in battery manufacturing process and conductive agent again, and binding agent mixes, and is coated on collector, to be used as electrode and to use.Saved operation, guaranteed the effectively compound of active material and conductive agent, the energy density of electrode is obviously promoted simultaneously.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph of three-dimensional grapheme self-supporting material;
Fig. 2 is the stereoscan photograph of three-dimensional grapheme-mesoporous carbon composite material;
Fig. 3 is the cycle performance that adopts the lithium-sulfur cell of the flexible electrode of the mesoporous carbon-loaded sulphur that the present invention is based on three-dimensional grapheme self supporting structure;
Fig. 4 adopts the present invention to have the cycle performance of the lithium selenium cell of the flexible electrode of the mesoporous carbon-loaded selenium of three-dimensional grapheme self supporting structure.
Embodiment
Can explain in more detail the present invention by the following examples, disclose object of the present invention and be intended to protect all changes and improvements in the scope of the invention, the present invention is not limited to the following examples.
Embodiment 1:
1. by the nickel foam of ethanol ultrasonic cleaning, in nitrogen atmosphere, be warming up to 900 ℃, pass into hydrogen and ethanol gas, under nickel foam autocatalysis, Graphene stratiform structure is in foam metal superficial growth, and it is that 65% 100ml red fuming nitric acid (RFNA) soaks 24 hours that the three-dimensional foam nickel-graphite alkene of acquisition is put into mass fraction; It is neutral spending ion-cleaning to solution, is using successively ethanol, and ether embathes, and takes out rear 50 ℃ of vacuumizes 8 hours; Obtain three-dimensional grapheme self-supporting material;
2. by triblock copolymer F127 and phenolic resins and absolute ethyl alcohol 1:1:1 mixing in mass ratio, whipping temp is 50 ℃, and mixing time is 8h, after stirring, obtains yellow solution;
3. mesoporous carbon precursor solution is impregnated in three-dimensional grapheme self-supporting material, at room temperature place after 8h, the baking oven heat treatment 12h that sample is put into 100 ℃ obtains sample, sample is put into tubular heater after taking out, in nitrogen atmosphere, be warming up to 700 ℃ of carbonization 2h, after carbonization completes, in nitrogen atmosphere, be cooled to room temperature, can obtain three-dimensional grapheme-mesoporous carbon composite material;
4. take a certain amount of elemental sulfur and put into quartz ampoule together with three-dimensional grapheme-mesoporous carbon composite material (sulphur is 5:1 with material with carbon element mass ratio).Quartz ampoule is inserted in the tube furnace that is full of blanket of nitrogen, be heated to 350 ℃ of insulation 5h and obtain the flexible electrode of the mesoporous carbon-loaded sulphur with three-dimensional grapheme self supporting structure.
As shown in Figure 1, the three-dimensional grapheme self-supporting material of gained has retained the structure of nickel foam.
As shown in Figure 2, three-dimensional grapheme-mesoporous carbon composite material has shown the pattern different from three-dimensional grapheme self-supporting material.
As shown in Figure 3, the flexible electrode of the mesoporous carbon-loaded sulphur of three-dimensional grapheme self supporting structure has 1200mAh g being assembled into after battery
-1specific capacity and cycle performance good.
Embodiment 2:
1, by the nickel foam of ethanol ultrasonic cleaning, in nitrogen atmosphere, be warming up to 900 ℃, pass into hydrogen and ethanol gas.Under nickel foam autocatalysis, Graphene stratiform structure is in nickel foam superficial growth, and it is that 10ml68% red fuming nitric acid (RFNA) soaks 5 hours that the three-dimensional foam nickel-graphite alkene of acquisition is put into mass fraction; It is neutral spending ion-cleaning to solution, is using successively ethanol, and ether embathes, and takes out rear 20 ℃ of vacuumizes 10 hours, obtains three-dimensional grapheme self-supporting material;
2, by triblock copolymer F127 and phenolic resins and absolute ethyl alcohol 1:1:1 mixing in mass ratio, whipping temp is 20 ℃, and mixing time is 15h, after stirring, obtains yellow solution;
3, mesoporous carbon precursor solution is impregnated in three-dimensional grapheme self-supporting material, at room temperature places after 8h, sample is put into the baking oven heat treatment 12h of 100 ℃.Sample is put into tubular heater after taking out, and in nitrogen atmosphere, is warming up to 700 ℃ of carbonization 2h, after carbonization completes, is cooled to room temperature in nitrogen atmosphere;
4, take a certain amount of simple substance selenium and put into quartz ampoule together with three-dimensional grapheme-mesoporous carbon composite material (selenium is 8:1 with material with carbon element mass ratio).Quartz ampoule is inserted in the tube furnace that is full of nitrogen atmosphere, be heated to 600 ℃ of insulation 5h and obtain the flexible electrode of the mesoporous carbon-loaded selenium with three-dimensional grapheme self supporting structure.
As shown in Figure 4, the flexible electrode of the mesoporous carbon-loaded selenium of three-dimensional grapheme self supporting structure has 650-500mAh g being assembled into after battery
-1specific capacity and cycle performance good.
Embodiment 3
1, by the foam iron of ethanol ultrasonic cleaning, in argon gas atmosphere, be warming up to 700 ℃, pass into hydrogen and ethanol gas.Under the autocatalysis of foam iron, Graphene stratiform structure is in foam iron surface growth, and it is that 66% 55ml red fuming nitric acid (RFNA) soaks 15 hours that the three-dimensional foam iron-graphite alkene of acquisition is put into mass fraction; It is neutral spending ion-cleaning to solution, is using successively ethanol, and ether embathes, and takes out rear 80 ℃ of vacuumizes 6 hours, obtains three-dimensional grapheme self-supporting material;
2, by triblock copolymer P123 and phenolic resins and absolute ethyl alcohol 15:5:3 mixing in mass ratio, whipping temp is 80 ℃, and mixing time is 1h, after stirring, obtains yellow solution;
3, mesoporous carbon precursor solution is impregnated in three-dimensional grapheme self-supporting material, at room temperature places after 12h, sample is put into the baking oven heat treatment 12h of 120 ℃.Sample is put into tubular heater after taking out, and in nitrogen atmosphere, is warming up to 950 ℃ of carbonization 0.5h, after carbonization completes, is cooled to room temperature in argon gas atmosphere, can obtain three-dimensional grapheme-mesoporous carbon composite material;
4, take a certain amount of elemental sulfur and put into quartz ampoule together with three-dimensional grapheme-mesoporous carbon composite material (sulphur is 1:1 with material with carbon element mass ratio).Quartz ampoule is inserted in the tube furnace that is full of blanket of nitrogen, be heated to 300 ℃ of insulation 10h and obtain the flexible electrode of the mesoporous carbon-loaded sulphur with three-dimensional grapheme self supporting structure.
The flexible electrode of the mesoporous carbon-loaded sulphur of three-dimensional grapheme self supporting structure has 1500mAh g being assembled into after battery
-1specific capacity and cycle performance good.
Embodiment 4
1, by the foam copper of ethanol ultrasonic cleaning, in ammonia atmosphere, be warming up to 1000 ℃, pass into hydrogen and ethanol gas.Under foam copper autocatalysis, Graphene stratiform structure is in foam copper superficial growth, and it is that 67%50ml red fuming nitric acid (RFNA) soaks 20 hours that the three-dimensional foam copper-graphite alkene of acquisition is put into mass fraction; It is neutral spending ion-cleaning to solution, is using successively ethanol, and ether embathes, and takes out rear 70 ℃ of vacuumizes 7 hours,, obtain three-dimensional grapheme self-supporting material;
2, by triblock copolymer F127 and phenolic resins and absolute ethyl alcohol 1:3:5 mixing in mass ratio, whipping temp is 60 ℃, and mixing time is 10h, after stirring, obtains yellow solution;
3, mesoporous carbon precursor solution is impregnated in three-dimensional grapheme self-supporting material, at room temperature place after 10h, sample is put into the baking oven heat treatment 24h of 110 ℃, sample is put into tubular heater after taking out, in nitrogen atmosphere, be warming up to 800 ℃ of carbonization 1h, after carbonization completes, in nitrogen atmosphere, be cooled to room temperature, can obtain three-dimensional grapheme-mesoporous carbon composite material;
4, take a certain amount of simple substance selenium and put into quartz ampoule together with three-dimensional grapheme-mesoporous carbon composite material (selenium is 10:1 with material with carbon element mass ratio), quartz ampoule is inserted in the tube furnace that is full of ammonia atmosphere, be heated to 800 ℃ of insulation 5h and obtain the flexible electrode of the mesoporous carbon-loaded selenium with three-dimensional grapheme self supporting structure.
The flexible electrode of the mesoporous carbon-loaded selenium of three-dimensional grapheme self supporting structure has 800mAh g being assembled into after battery
-1specific capacity and cycle performance good.
In sum, the flexible electrode of the mesoporous carbon-loaded selenium of tool provided by the invention based on three-dimensional grapheme self supporting structure adopts the structure of self-supporting, can effectively promote the specific energy density of electricity level, adopt lithium sulphur (selenium) battery of above-mentioned electrode fabrication to there is volume little, capacity is high, life-span is long, and the advantage that efficiency is high possesses very high application potential and commercial value.
Claims (9)
1. a flexible electrode for the mesoporous carbon-loaded sulphur/selenium based on three-dimensional grapheme self supporting structure, is characterized in that: described electrode is sulphur/selenium carbon electrode that the flexible mesoporous carbon-loaded sulphur with three-dimensional grapheme self supporting structure/selenium obtains.
2. the flexible electrode of a kind of mesoporous carbon-loaded sulphur/selenium based on three-dimensional grapheme self supporting structure according to claim 1, is characterized in that: described three-dimensional grapheme self supporting structure is to make take foam metal as template.
3. the flexible electrode of a kind of mesoporous carbon-loaded sulphur/selenium based on three-dimensional grapheme self supporting structure according to claim 1, is characterized in that: described three-dimensional grapheme self supporting structure is the Graphene-mesoporous carbon composite construction making by infusion process and heat treating process.
4. the preparation method of the flexible electrode of a kind of mesoporous carbon-loaded sulphur/selenium based on three-dimensional grapheme self supporting structure claimed in claim 1, is characterized in that: comprise the following steps:
1) preparation of three-dimensional grapheme skeleton: by the foam metal of ethanol ultrasonic cleaning, in inertia or reducing atmosphere, be warming up to 700-1000 ℃, pass into hydrogen and ethanol gas, under foam metal autocatalysis, Graphene stratiform structure is in foam metal superficial growth, the three-dimensional foam metal-graphite alkene obtaining is put into 10-100ml red fuming nitric acid (RFNA), soaks 5-24 hour; Spending ion-cleaning to solution is neutrality, then uses successively ethanol, and ether embathes, and takes out rear 20-80 ℃ of vacuumize 6～10 hours, obtains three-dimensional grapheme self-supporting material;
2) mesoporous carbon precursor solution is synthetic: triblock copolymer and phenolic resins are evenly mixed, be dissolved in a certain amount of absolute ethyl alcohol, obtain yellow solution;
3) preparation of three-dimensional grapheme-mesoporous carbon composite material: mesoporous carbon precursor solution is impregnated in three-dimensional grapheme self-supporting material, obtains sample after at room temperature placing 8-12h, sample is put into the baking oven heat treatment 12-24h of 100-120 ℃; Sample is put into tubular heater after taking out, and in nitrogen atmosphere, is warming up to 700-950 ℃ of carbonization 0.5-2h, after carbonization completes, is cooled to room temperature in nitrogen atmosphere, can obtain three-dimensional grapheme-mesoporous carbon composite material;
4) preparation of the mesoporous sulphur/selenium of the flexibility based on three-dimensional grapheme self supporting structure carbon electrode: take a certain amount of sulphur or selenium and put into quartz ampoule together with three-dimensional grapheme-mesoporous carbon composite material, quartz ampoule is inserted in the tube furnace that is full of inert atmosphere, be heated to 300-800 ℃ of insulation 5-10h and obtain the mesoporous sulphur/selenium of the flexibility carbon electrode based on three-dimensional grapheme self supporting structure.
5. preparation method according to claim 4, is characterized in that: in described step 1), foam metal is nickel, iron, copper, cobalt or its alloy; Inertia or reducing atmosphere are nitrogen, argon gas or ammonia etc.; The mass fraction of described red fuming nitric acid (RFNA) is 65%-68%.
6. preparation method according to claim 4, is characterized in that: described step 2) in triblock copolymer be F127 or P123, the mass ratio of described triblock copolymer and phenolic resins is 3:1～1:3; The mass ratio of triblock copolymer and absolute ethyl alcohol is 5:1～1:5; Whipping temp is 20-80 ℃, and mixing time is 1-15h.
7. preparation method according to claim 4, is characterized in that: the mass ratio 1:1～10:1 of elemental sulfur or selenium and three-dimensional grapheme-mesoporous carbon composite material in described step 4).
8. the flexible electrode of a kind of mesoporous carbon-loaded sulphur/selenium based on three-dimensional grapheme self supporting structure described in claim 1～3 any one is in the application of preparing in lithium rechargeable battery.
9. lithium sulphur/lithium selenium cell, is characterized in that, the flexible electrode that comprises the mesoporous carbon-loaded sulphur/selenium based on three-dimensional grapheme self supporting structure claimed in claim 1.
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