CN103880003A - Graphene material prepared from biological calcium carbonate source and application thereof - Google Patents
Graphene material prepared from biological calcium carbonate source and application thereof Download PDFInfo
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- CN103880003A CN103880003A CN201410140813.0A CN201410140813A CN103880003A CN 103880003 A CN103880003 A CN 103880003A CN 201410140813 A CN201410140813 A CN 201410140813A CN 103880003 A CN103880003 A CN 103880003A
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- carbonate source
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 120
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 60
- 239000000463 material Substances 0.000 title claims abstract description 59
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims description 21
- 239000007772 electrode material Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000011260 aqueous acid Substances 0.000 claims description 9
- 239000003990 capacitor Substances 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- 238000000498 ball milling Methods 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 4
- 102000002322 Egg Proteins Human genes 0.000 claims description 3
- 108010000912 Egg Proteins Proteins 0.000 claims description 3
- 241000371997 Eriocheir sinensis Species 0.000 claims description 3
- 241000287828 Gallus gallus Species 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000010406 cathode material Substances 0.000 claims description 3
- 210000004027 cell Anatomy 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 229910001416 lithium ion Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 210000004681 ovum Anatomy 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000004966 Carbon aerogel Substances 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 claims description 2
- 229910021385 hard carbon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 13
- 239000000126 substance Substances 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 8
- 238000007599 discharging Methods 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- -1 poly(vinylidene fluoride) Polymers 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000407 epitaxy Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- 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
-
- 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
- Y02E60/13—Energy storage using capacitors
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- Carbon And Carbon Compounds (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a method for preparing a graphene material from a biological calcium carbonate source, which comprises the following steps: (1) heating a biological calcium carbonate source to 400-550 DEG C to remove organic substances, thereby obtaining biological calcium carbonate; (2) adding the obtained biological calcium carbonate and a metallic reducing agent in a mass ratio of 1:(0.01-2.4) into a high-temperature furnace in different modes, heating to 600-750 DEG C to react for 0.5-8 hours in an inert atmosphere, and cooling to room temperature; and (3) reacting the obtained black product with a 0.5-6M acid water solution for 0.5-12 hours, filtering and drying to obtain the graphene. The method for preparing the graphene material from the biological calcium carbonate source has the advantages of lower preparation cost, wider and more abundant sources, and lower requirements for preparation conditions and preparation equipment.
Description
Technical field
The present invention relates to one and prepare grapheme material and application, relate in particular to a kind of prepare taking biological calcium carbonate source as raw material grapheme material and application.
Background technology
Graphene is the bi-dimensional cellular two dimensional structure forming with the carbon atom of sp2 hybrid bond combination, and this special two-dirnentional structure makes Graphene show physics, machinery and the character such as chemical of many excellences.Except single-layer graphene, grapheme material also comprises bilayer, minority layer and multi-layer graphene, and they have application very widely in fields such as electronics, information and the energy.In energy storage application, because the specific surface area of single-layer graphene material reaches 2630m2/g, make it have larger advantage than other energy storage electrode materials: the both sides that lithium ion can be stored in monolithic Graphene form LiC
3structure, its theoretical capacity can reach 744 mAh/g, is the twice of conventional graphite electrode theory capacity (372 mAh/g).Have compared with the grapheme material of perfect structure and can obtain by methods such as mechanically peel high order pyrolytic graphite, chemical vapour deposition, epitaxy and CNT (carbon nano-tube) expansion, but above method is difficult for realizing the preparation in macroscopic quantity of grapheme material.Grapheme material also can obtain by redox graphene.Conventionally, graphene oxide can utilize the preparation of the pharmaceutical chemicals such as potassium permanganate and vitriol oil graphite oxide by hummers method or improved hummers method.The method of reduction comprises high temperature annealing reduction, microwave reduction, photo catalytic reduction and chemical reagent reduction etc.Wherein, chemical reagent reduction method, because the reductive condition requirement of needs is lower, can be prepared grapheme material more in a large number.But the method also exists environmental protection and safety problem.The Graphene product carbon-to-oxygen ratio obtaining by the method is lower, causes electric conductivity lower.As Chinese invention patent " preparing the method for Graphene taking Wingdale as raw material ", application number is 201210082281.0, discloses a kind of Wingdale that utilizes and within the scope of 800～1100 DEG C, has reacted a kind of method of grapheme material of obtaining with magnesium powder for raw material.The above-mentioned method preparation temperature of preparing Graphene is higher, requires also higher to preparation condition.
Summary of the invention
For the technical problem of above-mentioned existence, the object of the invention is: proposed a kind of method of preparing grapheme material taking biological calcium carbonate source as raw material prepared by sustainability at a lower temperature.
Technical solution of the present invention is achieved in that a kind of method of preparing grapheme material taking biological calcium carbonate source as raw material, comprises the following steps:
(1) biological calcium carbonate source is heated to 400～550 DEG C, removes organism, obtain biological calcium carbonate;
(2) be the ratio of 1:0.01～2.4 in mass ratio by the biological calcium carbonate and the metallic reducing agent that obtain, be positioned over differently in High Temperature Furnaces Heating Apparatus, under inert atmosphere, be heated to 600～750 DEG C, react after 0.5～8 hour, be cooled to room temperature;
(3) the black product obtaining is reacted after 0.5～12 hour with the aqueous acid of 0.5～6M, filter, dry, obtain Graphene.
Preferably, in described step (2), modes of emplacement is that biological calcium carbonate mixes with metallic reducing agent, after ball milling or grinding evenly, mixture is placed in High Temperature Furnaces Heating Apparatus.
Preferably, in described step (2), modes of emplacement is the both sides that biological calcium carbonate and metallic reducing agent are placed on respectively reaction vessel, after sealing, reaction vessel is placed in High Temperature Furnaces Heating Apparatus.
Preferably, described biological calcium carbonate source is the wherein a kind of or combination of Ovum crusta Gallus domesticus, Carapax Eriocheir sinensis or shell.
Preferably, described inert atmosphere is argon gas, helium or hydrogen-argon-mixed one or combination.
Preferably, described metallic reducing agent is lithium, magnesium, potassium, aluminium or sodium one or combination.
Preferably, described grapheme material is directly used in the negative material of lithium-ion secondary cell; Mix as ion secondary battery cathode material lithium with other negative materials, when mixing, the consumption of grapheme material is not less than 5% of electrode gross activity material mass.
Preferably, described other negative materials comprise graphite-based carbon, hard carbon material, silicon and stannic oxide.
Preferably, described grapheme material is directly used in electrode material for super capacitor; Mix as electrode material for super capacitor with other electrode material for super capacitor, when mixing, the consumption of grapheme material is not less than 5% of electrode gross activity material mass.
Preferably, described other electrode material for super capacitor comprise activated carbon and carbon aerogels.
Due to the utilization of technique scheme, the present invention compared with prior art has following advantages:
(1) the renewable and sustainability resource of prepared using, cost is cheaper, and source is more extensively and abundant.
(2) temperature of reaction reduces, thereby the requirement of synthesis condition, equipment is reduced.
(3) grapheme material of preparing is better than conventional electrode materials performance as electrode materials.
Brief description of the drawings
Below in conjunction with accompanying drawing, technical solution of the present invention is described further:
The Raman spectrogram of the grapheme material that accompanying drawing 1 is prepared for embodiment 1;
The transmission electron microscope picture of the first representative grapheme material that accompanying drawing 2 is prepared for embodiment 1;
The transmission electron microscope picture of the second representative grapheme material that accompanying drawing 3 is prepared for embodiment 1;
The transmission electron microscope picture of the third generation table grapheme material that accompanying drawing 4 is prepared for embodiment 1;
Accompanying drawing 5 is for the grapheme material prepared by embodiment 1 is as the circulation preserving property figure of ion secondary battery cathode material lithium.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1:
A method of preparing grapheme material taking biological calcium carbonate source as raw material, comprises the following steps:
(1) biological calcium carbonate source is heated to 500 DEG C, removes organism, obtain biological calcium carbonate;
(2) be the ratio of 1:1 in mass ratio by the biological calcium carbonate and the metallic reducing agent that obtain, described biological calcium carbonate and metallic reducing agent are placed on respectively the both sides of reaction vessel, after sealing, reactor is placed in High Temperature Furnaces Heating Apparatus, under inert atmosphere, be heated to 700 DEG C, react after 5 hours, be cooled to room temperature;
(3) the black product obtaining is reacted after 12 hours with the aqueous acid of 2M, filter, dry, obtain Graphene.
The Raman collection of illustrative plates that accompanying drawing 1 is the material that obtains, confirm that the material obtaining is grapheme material, and crystallinity is better, and accompanying drawing 2, accompanying drawing 3, accompanying drawing 4 are transmission electron microscope pictures of three kinds of representative grapheme materials obtaining.The material that obtains has Graphene stratiform structure.
By synthetic grapheme material, conductive agent acetylene black with and poly(vinylidene fluoride) (PVDF) in mass ratio 8:1:1 mix, obtain slurry, and be coated on copper current collector, after 120 DEG C of vacuum-drying, be pressed into cathode pole piece, taking the EC/DMC/DMC organic solution of the LiPF6 of 1M as electrolytic solution, taking metal lithium sheet as to electrode, be assembled into button cell.Under 100 mA/g charging and discharging currents, after 100 charge and discharge cycles, its reversible capacity can keep 640 mAh/g, and coulomb efficiency is greater than 98%, and performance is good.
Embodiment 2:
A method of preparing grapheme material taking biological calcium carbonate source as raw material, comprises the following steps:
(1) biological calcium carbonate source is heated to 400 DEG C, removes organism, obtain biological calcium carbonate;
(2) be the ratio of 1:0.06 in mass ratio by the biological calcium carbonate and the metallic reducing agent that obtain, mix, ball milling or grinding evenly, are placed in mixture in High Temperature Furnaces Heating Apparatus, under inert atmosphere, are heated to 600 DEG C, react after 8 hours, are cooled to room temperature;
(3) the black product obtaining is reacted after 0.5 hour with the aqueous acid of 6M, filter, dry, obtain Graphene.
Grapheme material, tetrafluoroethylene, acetylene black are mixed by weight 8:1:1, form slurry, be rolled into thin slice, be cut into the disk of diameter 12 mm, under the pressure of 10 MPa, be compressed on nickel foam collector.Choose two pole pieces that quality is close, taking NKK TF4840 as barrier film, 6M concentration hydrogen potassium oxide is assembled into electrical condenser as electrolytic solution.Under the charging and discharging currents of 1000 mA/g, it is 210 F/g than electric capacity.
Embodiment 3:
(1) biological calcium carbonate source is heated to 550 DEG C, removes organism, obtain biological calcium carbonate;
(2) be the ratio of 1:2.4 in mass ratio by the biological calcium carbonate and the metallic reducing agent that obtain, mix, ball milling or grinding evenly, are placed in mixture in High Temperature Furnaces Heating Apparatus, under inert atmosphere, are heated to 750 DEG C, react after 0.5 hour, are cooled to room temperature;
(3) the black product obtaining is reacted after 6 hours with the aqueous acid of 3M, filter, dry, obtain Graphene.
The grapheme material of acquisition is made to pole piece by the step in example 1, be assembled into battery, carry out charge-discharge test, under charging and discharging currents 200 mA/g, discharging and recharging by voltage range is 10mV-3.0V, after 30 times discharge and recharge, more than its charge/discharge capacity can keep 480 mAh/g, performance is good.
Embodiment 4:
(1) biological calcium carbonate source is heated to 500 DEG C, removes organism, obtain biological calcium carbonate;
(2) be the ratio of 1:1 in mass ratio by the biological calcium carbonate and the metallic reducing agent that obtain, described biological calcium carbonate and metallic reducing agent are placed on respectively the both sides of reaction vessel, after sealing, reactor is placed in High Temperature Furnaces Heating Apparatus, under inert atmosphere, be heated to 700 DEG C, react after 5 hours, be cooled to room temperature;
(3) the black product obtaining is reacted after 12 hours with the aqueous acid of 2M, filter, dry, obtain Graphene.
Grapheme material is assembled to electrical condenser by embodiment 2, and under the charging and discharging currents of 1000 mA/g, its specific capacitance can reach 205 F/g.
Embodiment 5～16: with reference to implementing 1～4, amendment above-mentioned parameter, as shown in the table:
| ? | The Heating temperature in biological calcium carbonate source (DEG C) | The mass ratio of biological calcium carbonate and metallic reducing agent | Heating temperature (DEG C) | Reaction times (hour) | The concentration (M) of aqueous acid | Reaction times (hour) |
| Embodiment 5 | 475 | 1:0.01 | 600 | 0.5 | 0.5 | 0.5 |
| Embodiment 6 | 550 | 1:0.01 | 600 | 0.5 | 0.5 | 0.5 |
| Embodiment 7 | 400 | 1:1.205 | 600 | 0.5 | 0.5 | 0.5 |
| Embodiment 8 | 400 | 1:2.4 | 600 | 0.5 | 0.5 | 0.5 |
| Embodiment 9 | 400 | 1:0.01 | 675 | 0.5 | 0.5 | 0.5 |
| Embodiment 10 | 400 | 1:0.01 | 750 | 0.5 | 0.5 | 0.5 |
| Embodiment 11 | 400 | 1:0.01 | 600 | 4.25 | 0.5 | 0.5 |
| Embodiment 12 | 400 | 1:0.01 | 600 | 8 | 0.5 | 0.5 |
| Embodiment 13 | 400 | 1:0.01 | 600 | 0.5 | 3.25 | 0.5 |
| Embodiment 14 | 400 | 1:0.01 | 600 | 0.5 | 6 | 0.5 |
| Embodiment 15 | 400 | 1:0.01 | 600 | 0.5 | 0.5 | 6.25 |
| Embodiment 16 | 400 | 1:0.01 | 600 | 0.5 | 0.5 | 12 |
In above-described embodiment, described biological calcium carbonate source is the wherein a kind of or combination of Ovum crusta Gallus domesticus, Carapax Eriocheir sinensis or shell.
In above-described embodiment, described inert atmosphere is argon gas, helium or hydrogen-argon-mixed one or combination.
In above-described embodiment, described metallic reducing agent is lithium, magnesium, potassium, aluminium or sodium one or combination.
The present invention program's the method for preparing grapheme material taking biological calcium carbonate source as raw material, because biological calcium carbonate source is a kind of sustainability and renewable resources, makes this preparation method's preparation cost cheaper, and source is more extensively with abundant; Because the temperature of reaction in biological calcium carbonate source is lower, this preparation method is reduced to the requirement of preparation condition and Preparation equipment again.
The present invention program's the method for preparing grapheme material taking biological calcium carbonate source as raw material, when be placed on respectively the both sides of reaction vessel with biological calcium carbonate and metallic reducing agent, after sealing, when reactor is placed in High Temperature Furnaces Heating Apparatus to prepared by this distributing style, biological calcium carbonate source is decomposed into the Graphene product of by product calcium oxide and acquisition not at same position, more easily separated, this by product directly can be utilized (as reacted and obtain calcium hydroxide with water, as the sorbent material of carbonic acid gas around, obtain again calcium carbonate, can reuse), in the time removing the impurity in Graphene product with aqueous acid, owing to need not removing calcium oxide, the consumption of aqueous acid has obtained greatly reducing, greatly reduce preparation cost.
The present invention program's the method for preparing grapheme material taking biological calcium carbonate source as raw material, when be placed on respectively the both sides of reaction vessel with biological calcium carbonate and metallic reducing agent, after sealing, when reactor is placed in High Temperature Furnaces Heating Apparatus to prepared by this distributing style, on tube wall, there is the grapheme material of square form, can be used for the storage of the gas such as carbonic acid gas and hydrogen.
Above-described embodiment is only explanation technical conceive of the present invention and feature; its object is to allow person skilled in the art can understand content of the present invention and be implemented; can not limit the scope of the invention with this; all equivalences that spirit is done according to the present invention change or modify, and all should be encompassed in protection scope of the present invention.
Claims (10)
1. a method of preparing grapheme material taking biological calcium carbonate source as raw material, is characterized in that comprising the following steps:
(1) biological calcium carbonate source is heated to 400～550 DEG C, removes organism, obtain biological calcium carbonate;
(2) be the ratio of 1:0.01～2.4 in mass ratio by the biological calcium carbonate and the metallic reducing agent that obtain, be positioned over differently in High Temperature Furnaces Heating Apparatus, under inert atmosphere, be heated to 600～750 DEG C, react after 0.5～8 hour, be cooled to room temperature;
(3) the black product obtaining is reacted after 0.5～12 hour with the aqueous acid of 0.5～6M, filter, dry, obtain Graphene.
2. the method for preparing Graphene taking biological calcium carbonate source as raw material according to claim 1, it is characterized in that: in described step (2), modes of emplacement is that biological calcium carbonate mixes with metallic reducing agent, after ball milling or grinding evenly, mixture is placed in High Temperature Furnaces Heating Apparatus.
3. the method for preparing grapheme material taking biological calcium carbonate source as raw material according to claim 1, it is characterized in that: in described step (2), modes of emplacement is the both sides that biological calcium carbonate and metallic reducing agent are placed on respectively reaction vessel, after sealing, reaction vessel is placed in High Temperature Furnaces Heating Apparatus.
4. the method for preparing grapheme material taking biological calcium carbonate source as raw material according to claim 3, is characterized in that: described biological calcium carbonate source is the wherein a kind of or combination of Ovum crusta Gallus domesticus, Carapax Eriocheir sinensis or shell.
5. the method for preparing grapheme material taking biological calcium carbonate source as raw material according to claim 4, is characterized in that: described inert atmosphere is argon gas, helium or hydrogen-argon-mixed one or combination.
6. the method for preparing grapheme material taking biological calcium carbonate source as raw material according to claim 5, is characterized in that: described metallic reducing agent is lithium, magnesium, potassium, aluminium or sodium one or combination.
7. the method for preparing Graphene taking biological calcium carbonate source as raw material as described in claim 1～6 any one claim, is characterized in that: described grapheme material is directly used in the negative material of lithium-ion secondary cell; Mix as ion secondary battery cathode material lithium with other negative materials, when mixing, the consumption of grapheme material is not less than 5% of electrode gross activity material mass.
8. the method for preparing Graphene taking biological calcium carbonate source as raw material according to claim 7, is characterized in that: described other negative materials comprise graphite-based carbon, hard carbon material, silicon and stannic oxide.
9. the method for preparing Graphene taking biological calcium carbonate source as raw material as described in claim 1～6 any one claim, is characterized in that: described grapheme material is directly used in electrode material for super capacitor; Mix as electrode material for super capacitor with other electrode material for super capacitor, when mixing, the consumption of grapheme material is not less than 5% of electrode gross activity material mass.
10. the method for preparing Graphene taking biological calcium carbonate source as raw material according to claim 9, is characterized in that: described other electrode material for super capacitor comprise activated carbon and carbon aerogels.
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| CN104370285A (en) * | 2014-10-23 | 2015-02-25 | 北京大学 | Method for macroscopically preparing high-quality graphene by using bio-mineralized material |
| CN107123550A (en) * | 2017-05-16 | 2017-09-01 | 郭家林 | A kind of egg shell derives the preparation method of three-dimensional honeycomb shape carbon material |
| CN107565103A (en) * | 2017-07-20 | 2018-01-09 | 广东东岛新能源股份有限公司 | A kind of porous silicon/graphene composite material and its production and use |
| CN109455699A (en) * | 2017-09-06 | 2019-03-12 | 哈尔滨工业大学 | A kind of graphene and its preparation method and application prepared using shell or eggshell waste |
| CN109980167A (en) * | 2019-03-07 | 2019-07-05 | 浙江工业大学 | Polyvinylidene difluoride film and its preparation and the application for having bionical three periods minimal surface structure |
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| CN102583357A (en) * | 2012-03-26 | 2012-07-18 | 方大炭素新材料科技股份有限公司 | Method for preparing graphene from limestone |
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| CN102583357A (en) * | 2012-03-26 | 2012-07-18 | 方大炭素新材料科技股份有限公司 | Method for preparing graphene from limestone |
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| CN104370285A (en) * | 2014-10-23 | 2015-02-25 | 北京大学 | Method for macroscopically preparing high-quality graphene by using bio-mineralized material |
| CN107123550A (en) * | 2017-05-16 | 2017-09-01 | 郭家林 | A kind of egg shell derives the preparation method of three-dimensional honeycomb shape carbon material |
| CN107565103A (en) * | 2017-07-20 | 2018-01-09 | 广东东岛新能源股份有限公司 | A kind of porous silicon/graphene composite material and its production and use |
| CN109455699A (en) * | 2017-09-06 | 2019-03-12 | 哈尔滨工业大学 | A kind of graphene and its preparation method and application prepared using shell or eggshell waste |
| CN109455699B (en) * | 2017-09-06 | 2020-10-02 | 哈尔滨工业大学 | A kind of graphene prepared by utilizing shell or eggshell waste and its preparation method and application |
| CN109980167A (en) * | 2019-03-07 | 2019-07-05 | 浙江工业大学 | Polyvinylidene difluoride film and its preparation and the application for having bionical three periods minimal surface structure |
| CN109980167B (en) * | 2019-03-07 | 2021-12-07 | 浙江工业大学 | Polyvinylidene fluoride film with bionic three-cycle minimum curved surface structure and preparation and application thereof |
| CN110416545A (en) * | 2019-08-07 | 2019-11-05 | 东北林业大学 | A method for preparing porous hollow carbon nanorod lithium ion battery negative electrode material using crab shell as template |
| CN114628651A (en) * | 2021-09-27 | 2022-06-14 | 万向一二三股份公司 | Preparation method and application of a high first-efficiency and long-cycle SiO/C composite negative electrode material |
| CN116332164A (en) * | 2023-03-28 | 2023-06-27 | 湛江市南澜珍珠生物科技有限公司 | A kind of continuous preparation graphene process and its continuous reaction equipment |
| CN116835563A (en) * | 2023-06-15 | 2023-10-03 | 浙江工业大学 | A method for synthesizing carbon materials by reacting magnesium powder or calcium powder with carbonate |
| CN116947019A (en) * | 2023-08-03 | 2023-10-27 | 华南师范大学 | A method for preparing biomass carbon materials as negative electrodes for lithium, potassium, and sodium ion batteries |
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