CN103825000B - Based on mesoporous carbon-loaded sulphur/selenium flexible electrode and preparation method thereof and the application of three-dimensional grapheme self supporting structure - Google Patents
Based on mesoporous carbon-loaded sulphur/selenium flexible electrode and preparation method thereof and the application of three-dimensional grapheme self supporting structure Download PDFInfo
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- CN103825000B CN103825000B CN201410076977.1A CN201410076977A CN103825000B CN 103825000 B CN103825000 B CN 103825000B CN 201410076977 A CN201410076977 A CN 201410076977A CN 103825000 B CN103825000 B CN 103825000B
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 47
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000011669 selenium Substances 0.000 title claims abstract description 41
- 229910052711 selenium Inorganic materials 0.000 title claims abstract description 41
- 239000005864 Sulphur Substances 0.000 title claims abstract description 40
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 56
- 239000006260 foam Substances 0.000 claims description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 22
- 239000002131 composite material Substances 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
- 238000002156 mixing Methods 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
- 235000019441 ethanol Nutrition 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
- 229910052799 carbon Inorganic materials 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
- 239000002184 metal Substances 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 229910021389 graphene Inorganic materials 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
- 239000007833 carbon precursor Substances 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
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 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
- 230000007935 neutral effect Effects 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
- 230000015572 biosynthetic process Effects 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
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- MBLUWALPEKUVHJ-UHFFFAOYSA-N [Se].[C] Chemical compound [Se].[C] MBLUWALPEKUVHJ-UHFFFAOYSA-N 0.000 claims 1
- 239000008367 deionised water Substances 0.000 claims 1
- 229910021641 deionized water Inorganic materials 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 abstract description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 8
- ZVSWQJGHNTUXDX-UHFFFAOYSA-N lambda1-selanyllithium Chemical compound [Se].[Li] ZVSWQJGHNTUXDX-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052744 lithium Inorganic materials 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- RSDUJIHCDSYTBB-UHFFFAOYSA-N [S].[Se].[Li] Chemical compound [S].[Se].[Li] RSDUJIHCDSYTBB-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 16
- 238000000034 method Methods 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 5
- 239000006258 conductive agent Substances 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000011149 active material Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 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
- 239000007772 electrode material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 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
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- ZQRRBZZVXPVWRB-UHFFFAOYSA-N [S].[Se] Chemical compound [S].[Se] ZQRRBZZVXPVWRB-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000001802 infusion 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
- 239000012071 phase Substances 0.000 description 1
- 125000003748 selenium group Chemical group *[Se]* 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
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
- H01M4/13—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
-
- 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
-
- 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
- H01M4/36—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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses the flexible electrode of the mesoporous carbon-loaded sulphur/selenium based on three-dimensional grapheme self supporting structure.The preparation method also disclosing above-mentioned electrode of the present invention.The flexible electrode that the invention also discloses based on the mesoporous carbon-loaded sulphur/selenium of three-dimensional grapheme self supporting structure is preparing the application in lithium rechargeable battery.The invention also discloses and a kind ofly comprise the lithium-sulfur cell of this electrode and a kind of lithium selenium cell.The flexible electrode of the mesoporous carbon-loaded selenium based on three-dimensional grapheme self supporting structure provided by the invention adopts the structure of self-supporting, there is good mechanical property and electric property, effectively can promote the specific energy density of electric level, lithium sulphur (selenium) battery of above-mentioned electrode fabrication is adopted to have volume little, capacity is high, life-span is long, the advantage that efficiency is high, possesses very high application potential and commercial value.
Description
Technical field
The invention belongs to battery material scientific domain, be specifically related to the mesoporous carbon-loaded sulphur/selenium flexible electrode and preparation method thereof based on three-dimensional grapheme self supporting structure 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 ressource are abundant, environmental friendliness, low price; Lithium-selenium cell has the volume and capacity ratio (3253mAh/cm3) similar to lithium-sulfur cell, 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 is many problems in actual applications in lithium sulphur and lithium selenium cell, 2 wherein relatively more outstanding points: one is, due to the ionic conductivity of sulphur and electron conduction all very low, cause that the chemical property of sulphur in electrode is not good and utilance is low, and although elemental selenium has relatively high conductance, still need by realizing the object of high power charging-discharging with the effective compound of conductive agent; Two are, because lithium sulphur and lithium selenium cell electrode also exist the phenomenon of active material dissolving and effect of shuttling back and forth in charge and discharge process, cause 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 of simple self-supporting negative pole-electrolyte and membrane layer-self-supporting positive pole to design, owing to eliminating collector, box hat and a large amount of organic electrolyte poured into, 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 adopting mesoporous carbon-loaded sulphur, inhibits the dissolving of active material polysulfide and effect of shuttling back and forth preferably; Chinese patent CN103178246A discloses a kind of method adopting mesoporous carbon-loaded selenium, inhibits the dissolving of the many selenides of active material and effect of shuttling back and forth preferably.The result of above-mentioned patent illustrates that mesoporous carbon structure can suppress the dissolving of polysulfide or many selenides effectively, thus 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 and is used as electrode use.Above-mentioned operation needs to control fully and accurate mixing, and simultaneously due to conductive agent, adding of binding agent and collector, the energy density of electrode is significantly cut down.
Summary of the invention
Goal of the invention: for above-mentioned existing scheme Problems existing and deficiency, 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, excellent electrochemical performance, energy density are high.
The second object of the present invention is to provide the preparation method of above-mentioned electrode.
The flexible electrode that the third object of the present invention is to provide the mesoporous carbon-loaded sulphur/selenium with three-dimensional grapheme self supporting structure is preparing the application in lithium rechargeable battery.
The fourth object of the present invention is to provide and a kind ofly comprises the lithium-sulfur cell of this electrode and a kind of lithium selenium cell.
Technical scheme: for achieving the above object, technical scheme of the present invention is as follows: a kind of flexible electrode of the sulphur/selenium of the mesoporous carbon-loaded based on three-dimensional grapheme self supporting structure, and described electrode is sulphur/selenium carbon electrode that the flexible mesoporous carbon-loaded sulphur/selenium with three-dimensional grapheme self supporting structure obtains.
Wherein, above-mentioned three-dimensional grapheme self supporting structure is that template obtains with foam metal.
Wherein, above-mentioned three-dimensional grapheme self supporting structure is the Graphene-mesoporous carbon composite construction obtained by infusion process and heat treating process.
The preparation method of the flexible electrode of above-mentioned a kind of sulphur/selenium of the mesoporous carbon-loaded based on three-dimensional grapheme self supporting structure, comprises the following steps:
1) preparation of three-dimensional graphene framework: by foam metal cleaned for EtOH Sonicate, 700-1000 DEG C is warming up in inertia or reducing atmosphere, pass into hydrogen and ethanol gas, under foam metal autocatalysis, Graphene layer structure is in foam metal superficial growth, the three-dimensional foam metal-graphite alkene obtained puts into 10-100ml red fuming nitric acid (RFNA), soaks 5-24 hour; Spend ion-cleaning to solution for neutral, then use ethanol successively, ether embathes, and takes out rear 20-80 DEG C of vacuumize 6 ~ 10 hours, namely obtains three-dimensional grapheme self-supporting material;
2) synthesis of mesoporous carbon precursor solution: by triblock copolymer and phenolic resins Homogeneous phase mixing, be dissolved in a certain amount of absolute ethyl alcohol, obtain yellow solution;
3) preparation of three-dimensional grapheme-mesoporous carbon composite material: be impregnated into by mesoporous carbon precursor solution 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 DEG C; Sample puts into tubular heater after taking out, and in nitrogen atmosphere, is warming up to 700-950 DEG C of carbonization 0.5-2h, is cooled to room temperature after carbonization completes in nitrogen atmosphere, can obtain three-dimensional grapheme-mesoporous carbon composite material;
4) based on the preparation of the flexibility mesoporous sulphur/selenium carbon electrode of three-dimensional grapheme self supporting structure: take a certain amount of sulphur or selenium puts into quartz ampoule together with three-dimensional grapheme-mesoporous carbon composite material, being inserted by quartz ampoule is full of in the tube furnace of inert atmosphere, is heated to 300-800 DEG C of insulation 5-10h and namely obtains flexibility mesoporous sulphur/selenium 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 DEG C, 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 sulphur/selenium of the mesoporous carbon-loaded based on three-dimensional grapheme self supporting structure is preparing the application in lithium rechargeable battery.
A kind of lithium sulphur/lithium selenium cell, comprises the flexible electrode of the above-mentioned sulphur/selenium of the mesoporous carbon-loaded based on three-dimensional grapheme self supporting structure.
Beneficial effect: compared with prior art, the flexible electrode with the mesoporous carbon-loaded sulphur/selenium of three-dimensional grapheme self supporting structure provided by the invention effectively can promote the specific energy density of electric level and have good pliability, adopt the lithium of above-mentioned electrode fabrication sulphur/selenium cell have 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 sulphur battery electrode preparation technology based on carbon tube bank is simple, with low cost, this electrode adopts the method sulfur materials load of liquid phase growth in situ 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 to have the flexible electrode film of certain mechanical strength, the flexibility of electrode can be realized well and improve the chemical property of sulfur materials, there is the advantage that mechanical property is good, excellent electrochemical performance, energy density are high.
Specifically, the present invention has following outstanding advantage relative to prior art:
(1) flexible electrode of the sulphur/selenium of the mesoporous carbon-loaded based on three-dimensional grapheme self supporting structure provided by the invention has that pliability is high, specific area is large, substantially increases mechanical property and the chemical property of self-supporting electrode.
(2) the present invention is by the load of mesoporous carbon realization to sulphur/selenium, ensures the close contact between sulphur/selenium and carbon nanometer skeleton; Control the pattern of sulphur/selenium, the distance that shortening lithium ion and electronics spread in electrode material simultaneously, thus improve lithium ion and electronics transporting in electrode material.
(3) stripping in the electrolytic solution of sulphur/selenium 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, effectively can suppress the decay of lithium sulphur or lithium selenium cell capacity, extend the life-span of lithium-sulfur cell.
(4) this flexible electrode can be directly used in the assembling of lithium rechargeable battery, and do not need again in cell fabrication processes and conductive agent, binding agent mixes, and is coated on collector is used as electrode uses.Save operation, ensure that effective 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 adopts the cycle performance that the present invention is based on the lithium-sulfur cell of the flexible electrode of the mesoporous carbon-loaded sulphur of three-dimensional grapheme self supporting structure;
Fig. 4 is the cycle performance adopting the present invention to have the lithium selenium cell of the flexible electrode of the mesoporous carbon-loaded selenium of three-dimensional grapheme self supporting structure.
Embodiment
Can explain the present invention in more detail 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 nickel foam cleaned for EtOH Sonicate, 900 DEG C are warming up in nitrogen atmosphere, pass into hydrogen and ethanol gas, under nickel foam autocatalysis, Graphene layer structure in foam metal superficial growth, the three-dimensional foam nickel-graphite alkene of acquisition put into mass fraction be 65% 100ml red fuming nitric acid (RFNA) soak 24 hours; Spend ion-cleaning to solution for neutral, using ethanol successively, ether embathes, and takes out rear 50 DEG C of vacuumizes 8 hours; Namely three-dimensional grapheme self-supporting material is obtained;
2., by triblock copolymer F127 and phenolic resins and absolute ethyl alcohol 1:1:1 mixing in mass ratio, whipping temp is 50 DEG C, and mixing time is 8h, after stirring, obtains yellow solution;
3. mesoporous carbon precursor solution is impregnated in three-dimensional grapheme self-supporting material, after at room temperature placing 8h, baking oven heat treatment 12h sample being put into 100 DEG C obtains sample, sample puts into tubular heater after taking out, in nitrogen atmosphere, be warming up to 700 DEG C of carbonization 2h, after carbonization completes, in nitrogen atmosphere, be cooled to room temperature, three-dimensional grapheme-mesoporous carbon composite material can be obtained;
4. take a certain amount of elemental sulfur and put into quartz ampoule together with three-dimensional grapheme-mesoporous carbon composite material (sulphur and material with carbon element mass ratio are 5:1).Being inserted by quartz ampoule is full of in the tube furnace of blanket of nitrogen, is heated to the flexible electrode that namely 350 DEG C of insulation 5h obtain 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 remains the structure of nickel foam.
As shown in Figure 2, three-dimensional grapheme-mesoporous carbon composite material shows 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 1200mAhg after being assembled into battery
-1specific capacity and cycle performance is excellent.
Embodiment 2:
1, by nickel foam cleaned for EtOH Sonicate, in nitrogen atmosphere, be warming up to 900 DEG C, pass into hydrogen and ethanol gas.Under nickel foam autocatalysis, Graphene layer 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 puts into mass fraction; Spend ion-cleaning to solution for neutral, using ethanol successively, ether embathes, and takes out rear 20 DEG C of vacuumizes 10 hours, namely 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 DEG C, and mixing time is 15h, after stirring, obtains yellow solution;
3, mesoporous carbon precursor solution is impregnated in three-dimensional grapheme self-supporting material, after at room temperature placing 8h, sample is put into the baking oven heat treatment 12h of 100 DEG C.Sample puts into tubular heater after taking out, and in nitrogen atmosphere, is warming up to 700 DEG C of carbonization 2h, is cooled to room temperature after carbonization completes in nitrogen atmosphere;
4, take a certain amount of elemental selenium and put into quartz ampoule together with three-dimensional grapheme-mesoporous carbon composite material (selenium and material with carbon element mass ratio are 8:1).Being inserted by quartz ampoule is full of in the tube furnace of nitrogen atmosphere, is heated to the flexible electrode that namely 600 DEG C of insulation 5h obtain 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 650-500mAhg after being assembled into battery
-1specific capacity and cycle performance is excellent.
Embodiment 3
1, by foamed iron cleaned for EtOH Sonicate, in argon gas atmosphere, be warming up to 700 DEG C, pass into hydrogen and ethanol gas.Under foamed iron autocatalysis, Graphene layer structure in foamed iron superficial growth, the three-dimensional foam iron-graphite alkene of acquisition put into mass fraction be 66% 55ml red fuming nitric acid (RFNA) soak 15 hours; Spend ion-cleaning to solution for neutral, using ethanol successively, ether embathes, and takes out rear 80 DEG C of vacuumizes 6 hours, namely 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 DEG C, and mixing time is 1h, after stirring, obtains yellow solution;
3, mesoporous carbon precursor solution is impregnated in three-dimensional grapheme self-supporting material, after at room temperature placing 12h, sample is put into the baking oven heat treatment 12h of 120 DEG C.Sample puts into tubular heater after taking out, and in nitrogen atmosphere, is warming up to 950 DEG C of carbonization 0.5h, is cooled to room temperature after carbonization completes 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 and material with carbon element mass ratio are 1:1).Being inserted by quartz ampoule is full of in the tube furnace of blanket of nitrogen, is heated to the flexible electrode that namely 300 DEG C of insulation 10h obtain 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 1500mAhg after being assembled into battery
-1specific capacity and cycle performance is excellent.
Embodiment 4
1, by foam copper cleaned for EtOH Sonicate, in ammonia atmosphere, be warming up to 1000 DEG C, pass into hydrogen and ethanol gas.Under foam copper autocatalysis, Graphene layer 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 puts into mass fraction; Spend ion-cleaning to solution for neutral, using ethanol successively, ether embathes, and takes out rear 70 DEG C of vacuumizes 7 hours, namely 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 DEG C, and mixing time is 10h, after stirring, obtains yellow solution;
3, mesoporous carbon precursor solution is impregnated in three-dimensional grapheme self-supporting material, after at room temperature placing 10h, sample is put into the baking oven heat treatment 24h of 110 DEG C, sample puts into tubular heater after taking out, in nitrogen atmosphere, be warming up to 800 DEG C of carbonization 1h, after carbonization completes, in nitrogen atmosphere, be cooled to room temperature, three-dimensional grapheme-mesoporous carbon composite material can be obtained;
4, take a certain amount of elemental selenium and put into quartz ampoule together with three-dimensional grapheme-mesoporous carbon composite material (selenium and material with carbon element mass ratio are 10:1), being inserted by quartz ampoule is full of in the tube furnace of ammonia atmosphere, is heated to the flexible electrode that namely 800 DEG C of insulation 5h obtain 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 800mAhg after being assembled into battery
-1specific capacity and cycle performance is excellent.
In sum, tool provided by the invention is based on the structure of the flexible electrode employing self-supporting of the mesoporous carbon-loaded selenium of three-dimensional grapheme self supporting structure, effectively can promote the specific energy density of electric level, lithium sulphur (selenium) battery of above-mentioned electrode fabrication is adopted to have volume little, capacity is high, life-span is long, the advantage that efficiency is high, possesses very high application potential and commercial value.
Claims (4)
1., based on a preparation method for the flexible electrode of the mesoporous carbon-loaded sulphur/selenium of three-dimensional grapheme self supporting structure, it is characterized in that: comprise the following steps:
1) preparation of three-dimensional graphene framework: by foam metal cleaned for EtOH Sonicate, 700-1000 DEG C is warming up in inertia or reducing atmosphere, pass into hydrogen and ethanol gas, under foam metal autocatalysis, Graphene layer structure is in foam metal superficial growth, obtain three-dimensional foam metal-graphite alkene, put into 10-100ml red fuming nitric acid (RFNA), soak 5-24 hour; Spend deionized water to neutral, then use ethanol successively, ether embathes, and after taking-up, 20-80 DEG C of vacuumize 6 ~ 10 hours, namely obtains three-dimensional graphene framework;
2) synthesis of mesoporous carbon precursor solution: by triblock copolymer and phenolic resins Homogeneous phase mixing, be dissolved in a certain amount of absolute ethyl alcohol, obtain yellow solution;
3) preparation of three-dimensional grapheme-mesoporous carbon composite material: be impregnated into by mesoporous carbon precursor solution 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 DEG C; Sample puts into tubular heater after taking out, and in nitrogen atmosphere, is warming up to 700-950 DEG C of carbonization 0.5-2h, is cooled to room temperature after carbonization completes in nitrogen atmosphere, can obtain three-dimensional grapheme-mesoporous carbon composite material;
4) based on the preparation of the flexibility mesoporous sulphur/selenium carbon electrode of three-dimensional grapheme self supporting structure: take a certain amount of sulphur or selenium puts into quartz ampoule together with three-dimensional grapheme-mesoporous carbon composite material, being inserted by quartz ampoule is full of in the tube furnace of inert atmosphere, is heated to 300-800 DEG C of insulation 5-10h and namely obtains the mesoporous sulphur of flexibility based on three-dimensional grapheme self supporting structure or selenium carbon electrode.
2. preparation method according to claim 1, 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; The mass fraction of described red fuming nitric acid (RFNA) is 65%-68%.
3. preparation method according to claim 1, 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 DEG C, and mixing time is 1-15h.
4. preparation method according to claim 1, 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).
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