CN106683904A - Preparation method for high-nitrogen-boron-doped three-dimensional graphene thin film used for flexible lithium ion hybrid capacitor - Google Patents
Preparation method for high-nitrogen-boron-doped three-dimensional graphene thin film used for flexible lithium ion hybrid capacitor Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 164
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 96
- 239000010409 thin film Substances 0.000 title claims abstract description 40
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 36
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000003990 capacitor Substances 0.000 title claims abstract description 24
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 64
- 239000010439 graphite Substances 0.000 claims abstract description 64
- 239000000463 material Substances 0.000 claims abstract description 62
- TZHYBRCGYCPGBQ-UHFFFAOYSA-N [B].[N] Chemical compound [B].[N] TZHYBRCGYCPGBQ-UHFFFAOYSA-N 0.000 claims abstract description 51
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims description 98
- 230000007547 defect Effects 0.000 claims description 77
- 238000000034 method Methods 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 238000005516 engineering process Methods 0.000 claims description 10
- 238000002525 ultrasonication Methods 0.000 claims description 10
- 239000010408 film Substances 0.000 claims description 9
- 235000010378 sodium ascorbate Nutrition 0.000 claims description 9
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 claims description 9
- 229960005055 sodium ascorbate Drugs 0.000 claims description 9
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 claims description 9
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- 235000010323 ascorbic acid Nutrition 0.000 claims description 3
- 239000011668 ascorbic acid Substances 0.000 claims description 3
- 229960005070 ascorbic acid Drugs 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- 238000010008 shearing Methods 0.000 claims description 3
- 241000446313 Lamella Species 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- -1 Nitrogen boron compound Chemical class 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000001117 sulphuric acid Substances 0.000 claims description 2
- 235000011149 sulphuric acid Nutrition 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 abstract description 16
- 238000010438 heat treatment Methods 0.000 abstract description 15
- 238000004146 energy storage Methods 0.000 abstract description 9
- 238000003825 pressing Methods 0.000 abstract description 2
- 238000003475 lamination Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 1
- 238000005119 centrifugation Methods 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 239000006228 supernatant Substances 0.000 description 6
- 150000001336 alkenes Chemical group 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000004575 stone Substances 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 238000005411 Van der Waals force Methods 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910002986 Li4Ti5O12 Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000012983 electrochemical energy storage Methods 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
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- 239000002994 raw material Substances 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229930003268 Vitamin C Natural products 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
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- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000006192 thin film tablet Substances 0.000 description 1
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- 235000019154 vitamin C Nutrition 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
-
- 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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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Carbon And Carbon Compounds (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
Abstract
The invention discloses a preparation method for a high-nitrogen-boron-doped three-dimensional graphene thin film used for a flexible lithium ion hybrid capacitor. The preparation method comprises the following steps of mixing a graphite oxide solution and an acid based on proportion, washing and then performing lamination peeling, then mixing with a reducing agent solution, and heating for 1-12h to obtain a three-dimensional graphene block material; mixing the three-dimensional graphene block material with a nitrogen-boron compound water solution, heating at a temperature of 50-150 DEG C for 3-12h to obtain a graphene block material; and taking the material out and washing, and pressing at 5-40MPa, and then drying to finally obtain the high-nitrogen-boron-doped three-dimensional graphene thin film with thickness of 0.01-0.1mm. B adoption of the preparation method, the doping amount of N and B on the graphene structure can be greatly improved; and meanwhile, the graphene flexible three-dimensional structure is maintained, so that the negative electrode rate capability and the energy storage performance of the lithium ion hybrid capacitor are improved.
Description
Technical field
The three-dimensional grapheme thin film the present invention relates to a kind of high nitrogen boron of flexible lithium ion mixed capacitor negative material adulterates
Preparation method, belong to field of new material preparation.
Background technology
Ultracapacitor has the advantages that power density is high, has extended cycle life as a kind of model electrochemical energy-storage units,
Extensive promotion and application are obtained in fields such as portable electric appts, stand-by power supply and electric automobiles.With consumption electricity
, towards the development of high integration, the research of flexible super capacitor energy storage technology is also like a raging fire, and achieves numerous for sub- product
Break through, obtain the extensive concern of researcher.
Due to the energy density that symmetric form ultracapacitor is limited, for the research of lithium ion hybrid super capacitor becomes
In burning hot.Wherein for negative material, there are multiple choices, the such as titanium oxide (TiO of nanostructured2, Li4Ti5O12Deng), other
Metal-oxide, graphite etc., respectively there is excellent summary.Titanium oxide (the TiO of nanostructured2, Li4Ti5O12Deng) have prepare it is simple, can
The advantages such as large-scale production, environmental friendliness, quick lithium ion intercalation speed, but its of a relatively high reaction potential
(＞ 1.5V vs Li/Li+) cause plenary capacitance system running voltage low, cause unnecessary energy density to lose, this is that it is obtained
To the biggest obstacle further applied；The fake capacitance storage electric charge produced using metal oxide surface redox reaction, compared with
The lithium ion intercalation of diffusion control has higher reaction rate, it will be appreciated, however, that due to the electricity of metal-oxide
Conductance is extremely low, has a strong impact on itself chemical property, compound with the material with carbon element of high conductivity as needing during active material, ability
Improve electro-chemical activity；In addition, graphite is at present using most successful lithium ion battery negative material, with of a relatively high electricity
Conductance, low cost, low (the 0.1V vs Li/Li of voltage platform+), the advantages of suitable theoretical capacity, but its is relatively low
Lithium ion diffusibility have impact on the high rate performance of lithium ion battery.Meanwhile, existing negative material is difficult to meet flexible lithium ion
The requirement of hybrid super capacitor.
Used as a kind of brand-new material, Graphene (Graphene) has high conductivity, high-specific surface area~2630m2/ g, height
Carrier transport rate~200000cm2The excellent performances such as/Vs, wide electrochemical window.Therefore, Graphene is for negative pole material
The selection of material embodies irreplaceable advantage.Graphene powder material in actual application, due to the suction of Van der Waals force
Draw, Graphene is easy to reunite, affect its corresponding performance.Graphene powder is assembled into into flexible 3 D thin film, both may be used
The performance for keeping Graphene itself excellent, can meet requirement of the flexible energy storage device to electrode material again.Although three-dimensional grapheme
Thin film has higher lithium ion transport ability relative to other materials, if further improving the biography of lithium ion by a kind of method
Conductance, then can greatly improve the high rate performance of battery.In addition, (fast charging and discharging) at higher current densities is had proven at present,
Graphenic surface redox reaction is favourable for lithium ion battery high-power output performance, and chemical doping is for adjusting function
One of most effective approach of material electrochemical performance, compared to unadulterated Graphene, nitrogen-doped graphene possesses more work
Property region, be so more beneficial for the generation of the embedding lithium on its surface/de- lithium；In boron doped graphene, due to boron atom ratio carbon atom
The few electronics of outer layer, in p-type doping, compares Graphene and has more preferable energy-storage property, and Boron contents are higher, its electrochemistry
Can be better.There is now pertinent literature and report and adulterate to improve the chemical property of Graphene using heterogeneous element N, B, improve lithium from
The energy-storage property of sub- battery, but at present, the doping of heterogeneous element N, B is but to limit its master for further optimizing energy-storage property
Want factor.At present N, B doped graphene synthetic method is more, such as chemical vapor deposition (CVD) method, plasma discharge method, electric arc
Electric discharge etc., and these methods have the problems such as preparation condition is harsh, doping is low, production cost is high.Therefore, in preparation technology
Simply, the doping that heterogeneous element N, B how are improved on the premise of low production cost is that the mixing of graphene-based flexible lithium ion is super
Level one new research direction of capacitor area.In view of this, in the case where three-dimensional grapheme film microstructure is not changed,
It is necessary further to improve graphene film heterogeneous element N, B doping by a kind of method, to reach its electrochemistry is improved
The purpose of energy, while being capable of achieving large-scale production, this will produce material impact in electrochemical energy storage field and wide application will be front
Scape.
The content of the invention
The purpose of the present invention be easily reunite for graphene powder present in current technology, lithium ion conductivity is low, make
High rate performance for flexible lithium ion mixed type super capacitor anode is low, and heterogeneous element N, B doping is low, and flexible lithium from
A kind of the problems such as sub- mixed type super capacitor anode high rate performance and not high energy-storage property, there is provided flexible lithium ion mixing electric capacity
Device with high nitrogen boron adulterate three-dimensional grapheme thin film preparation method.The method is by regulating and controlling graphene oxide defect, assemble in situ
Into graphene three-dimensional structure, and doping and thin film post-treating and other steps after N, B heterogeneous element, obtain flexible lithium ion mixed type
Super capacitor anode material high nitrogen boron doping three-dimensional grapheme thin film, regulates and controls simultaneously, according to scarce in three-dimensional grapheme defect
Doping N/B is fallen into, N/B dopings are improved, to reach the purpose for improving capacity and high rate performance.The present invention can increase substantially graphite
The doping of N, B in alkene structure, while keeping Graphene flexible 3 D structure, to reach lithium ion hybrid super electric capacity is improved
The purpose of device negative pole high rate performance and energy-storage property.
The technical scheme is that：
A kind of flexible lithium ion mixed capacitor is adulterated the preparation method of three-dimensional grapheme thin film with high nitrogen boron, including following
Step:
(1) preparation of rich defect graphite oxide solution：Graphite oxide solution is mixed in proportion with acid, at 50-150 DEG C
Heating 2-8h, is obtained the graphite oxide solution of structure richness defect；Be centrifuged washing again, until obtain pH value=7,
Concentration is the graphite oxide solution of the structure richness defect of 0.5-20mg/mL；
Wherein, the concentration of graphite oxide is 0.5-30mg/mL；The mass percentage concentration of acid is 10%-90%；Volume ratio is
Graphite oxide solution：Acid=15：1-5：1；
(2) preparation of rich defect graphene oxide solution：The graphite oxide solution of the structure for obtaining richness defect is carried out into piece
Layer is peeled off, and obtains structure richness defect graphene oxide solution；The concentration of structure richness defect graphene oxide solution is 0.5-20mg/
mL；
(3) preparation of rich defect three-dimensional grapheme block materials：By structure richness defect graphene oxide solution and reducing agent
Solution mixes, and heats 1-12h at 50-150 DEG C, it is scrubbed after, obtain rich defect three-dimensional grapheme block materials；
Wherein, volume ratio graphene oxide solution：Reductant solution=20：1-5：1；The concentration of reductant solution is 0.1-
10mol/L；
(4) preparation of high nitrogen boron doping three-dimensional grapheme thin film：By rich defect three-dimensional grapheme block materials and nitrogen boronation
The aqueous solution of compound, at 50-150 DEG C 3-12h is heated, the high nitrogen boron doped graphene block materials for obtaining, after taking-up
It is scrubbed, suppress under 5-40MPa, then after drying is processed, finally give the thick high nitrogen boron doping of 0.01mm-0.1mm three-dimensional
Graphene film；Wherein, mass ratio is three-dimensional grapheme block materials：Nitrogen boron compound aqueous solution=0.5：1-10：1；
It is 0.001%-1% that the concentration of the aqueous solution of described nitrogen boron compound is mass percent.
Acid-specific in described step (1) is hydrogen peroxide, sulphuric acid, nitric acid or phosphoric acid.
In described step (2), structure richness defect graphene oxide is few layer graphite oxide, and the graphene oxide number of plies is 1-
10 layers.
Lift-off technology in described step (2) is that the shearing machine in solution is peeled off or ultrasonication stripping means.
Reducing agent is preferably ascorbic acid, sodium ascorbate or hydrazine hydrate in described step (3).
In described step (4), nitrogen boron compound is preferably NH3BF3、C6H8BNO2, or NH4B(OH)4。
In described step (1), defect refers mainly to the carbon room in graphene film Rotating fields；Graphite oxide solution is with stone
Powdered ink body is raw material, according to graphite oxide solution obtained in traditional or improved Hummers methods, or for commercially available oxygen
Graphite solution.
In described step (3), Graphene block materials are the Graphene that graphene oxide becomes after reduction, due to
Van der Waals force attracts, and forms the Graphene macroscopic view block materials of the loose structure of self assembly.
Beneficial effects of the present invention are：
The problem that the present invention easily reunites for graphene powder, is assembled into three-dimensional block materials, both by Graphene first
Prevent Graphene to reunite, the excellent performance of Graphene is maintained again.Meanwhile, it is on this basis different using defect control technique
Prime element provides more rooms, and so as to prepare high nitrogen boron element doped graphene, both technologies combine the highly doped of gained
Graphene has higher electrical conductivity and electro-chemical activity.Compare simple doping N, B heterogeneous element material, it is of the invention then in this base
On plinth, two kinds of technologies are combined, i.e., fill up vacancy defect using heterogeneous element N, B, the presence in room is remarkably improved Graphene
N, B doping, therefore can improve lithium ion storage capacity and the high rate performance as negative material, energy density and circulation longevity
Life.Finally, highly doped three-dimensional grapheme block is pressed into by flexible thin-film material by post processing, can be mixed as flexible lithium ion
Close capacitor anode to use, under the electric current density of 1A/g, its specific discharge capacity can reach 1000mAh/g, will be above report at present
The utilization Graphene hydrogel in road make lithium ion battery negative specific discharge capacity (under the electric current density of 1A/g, its specific capacity
Reach 500-600mAh/g), the requirement of following high-performance flexible lithium-ion mixture super capacitor device can be met, with important
Theoretical and practical significance.
Description of the drawings
The specific embodiment of the present invention is described in further detail below in conjunction with the accompanying drawings.
Fig. 1 is the photomacrograph of the high nitrogen boron doping three-dimensional grapheme thin film in embodiment 3.
Fig. 2 is the XPS collection of illustrative plates of the high nitrogen boron doping three-dimensional grapheme thin film in embodiment 3.
Fig. 3 is the SEM figures of the high nitrogen boron doping three-dimensional grapheme thin film in embodiment 3.
Fig. 4 is that the high nitrogen boron doping three-dimensional grapheme thin film in embodiment 3 makees flexible lithium ion hybrid super capacitor
The high rate performance curve of negative pole.
Specific embodiment
The present invention is further described to combine preferred implementation below against accompanying drawing.
The preparation method of three-dimensional grapheme thin film the invention provides a kind of high nitrogen boron adulterates, including：(1) rich defect oxidation
The preparation of graphite solution：By certain density graphite oxide solution, according to a certain volume example uniformly mixes with certain density acid,
At a certain temperature heating a period of time, the graphite oxide solution that structure has abundant defect is obtained.By the graphite oxide for obtaining
Solution is washed, and to remove impurity element in solution, finally obtains the graphite oxide solution of the structure richness defect of pH value of solution=7；
In step (1), described defect refers mainly to the carbon room in graphene film Rotating fields；Graphite oxide solution is to be with graphite composite powder
Raw material, it is according to graphite oxide solution obtained in traditional or improved Hummers methods or molten for commercially available graphite oxide
Liquid；The concentration range of graphite oxide is 0.5-30mg/mL；The mass percentage concentration scope (solute concentration) of acid is 10%-90%；
Graphite oxide solution is 15 with the volume range of acid：1-5：1.Heating temperature range is 50-150 DEG C；Heat time heating time, scope was
2-8h.(2) preparation of rich defect graphene oxide solution：The structure for obtaining richness defect graphite oxide solution is carried out into lamella stripping
From to obtain structure richness defect graphene oxide solution；In step (2), the graphene oxide of structure richness defect is few layer oxygen
Graphite, the graphene oxide number of plies is 1-10 layers；Lift-off technology can be that the shearing machine in solution is peeled off or ultrasonication is peeled off
Method.(3) preparation of rich defect three-dimensional grapheme block materials：By certain density structure richness defect graphene oxide solution with
Reducing agent uniformly mixes according to a certain volume, under the conditions of uniform temperature heating a period of time, it is scrubbed after, obtain rich defect three
Dimension Graphene block materials；In step (3), Graphene block materials become Graphene for graphene oxide after reduction,
Because Van der Waals force attracts, the Graphene macroscopic view block materials of the loose structure of self assembly are formed；Graphene oxide concentration range
For 0.5-20mg/mL；Reducing agent is the compound with reducing power, preferably ascorbic acid, sodium ascorbate, hydrazine hydrate；
The concentration of reductant solution is 0.1-10mol/L；Graphene oxide solution is 20 with the volume range of reducing agent：1-5：1；Plus
Hot temperature range is 50-150 DEG C；Heat time heating time, scope was 1-12h.(4) preparation of high nitrogen boron doping three-dimensional grapheme thin film：Press
According to certain mass than by three-dimensional grapheme block materials and at least containing a kind of aqueous solution of nitrogen boron compound, in a constant temperature
Degree lower heating a period of time, the Graphene block materials for obtaining are taken out, it is scrubbed, suppress under a certain pressure, then drying
After process, high nitrogen boron doping three-dimensional grapheme thin film is finally given；In step (4), nitrogen boron compound is preferably NH3BF3、
C6H8BNO2、NH4B(OH)4；Heating temperature range is 50-150 DEG C；Heat time heating time, scope was 3-12h.Pressing pressure scope is 5-
40MPa；Thin film is the stratified material with 0.01mm-0.1mm thickness that block materials are formed through compacting；It is three-dimensional usually grand
See three dimensional structure.
For a better understanding of the present invention, describe the present invention below in conjunction with specific embodiment, but should recognize
It is that the present invention is illustrated to know these embodiments, and the unrestricted present invention.Compound used in following examples
Or reagent is commercially available, or can be prepared by conventional method well known by persons skilled in the art；The experiment for being used
Instrument can be buied by commercial sources.
Embodiment 1：Graphite oxide solution (graphite oxide solution, the following examples obtained in Hummers methods of 2mg/mL
1h is peeled off in ultrasonication together), and ultrasonic power is 500W, centrifugation, and rotating speed 4000rpm, centrifugation time 30min take upper liquid
Body, obtains the graphene oxide solution of 2mg/mL；The graphene oxide solution of the 2mg/mL for obtaining, the Vitamin C with 1mol/L
Sour sodium reduction agent is with 10：1 uniform mixing, heats 2h at 100 DEG C, it is scrubbed after, obtain three-dimensional grapheme block materials；To obtain
Graphene block materials take out, it is scrubbed, under 5MPa pressure suppress, then drying process after, finally give thickness and be about
The three-dimensional grapheme thin film of 0.04mm.
Embodiment 2：1h is peeled off in the graphite oxide solution ultrasonication of 2mg/mL, and ultrasonic power is 500W, and centrifugation turns
Fast 4000rpm, centrifugation time 30min, takes supernatant liquid, obtains the graphene oxide solution of 2mg/mL；The 2mg/mL for obtaining
Graphene oxide solution, with the sodium ascorbate reducing agent of 1mol/L with 10：1 uniform mixing, at 100 DEG C 2h is heated, and Jing is washed
After washing, three-dimensional grapheme block materials are obtained；It is 0.47% by the three-dimensional grapheme block materials of acquirement and mass percent
NH3BF3Aqueous solution is with 5：4 mass ratio mixing, at 100 DEG C 4h is heated, and the Graphene block materials for obtaining are taken out, and Jing is washed
Wash, suppress under 5MPa pressure, then after drying is processed, finally give the nitrogen boron doping three-dimensional grapheme that thickness is about 0.04mm
Thin film.
Embodiment 3：The graphite oxide solution of 2mg/mL and the H that mass percent is 30%2O2Solution is with 10：1 volume ratio is equal
Even mixing, heats 4h under 100 DEG C of environment, and, finally obtains the knot of pH value of solution=7 with 10000rpm rotating speeds centrifuge washing repeatedly
The graphite oxide solution (the graphite oxide solution concentration for obtaining structure richness defect is 2mg/mL) of structure richness defect, by the structure for obtaining
1h is peeled off in the ultrasonication in the case where ultrasonic power is 500W of the graphite oxide solution of rich defect, is then centrifuged for separating, rotating speed
4000rpm, centrifugation time 30min, takes supernatant liquid, obtains the graphene oxide solution of rich defect of 2mg/mL (in solution
Structure richness defect graphene oxide is few layer graphite oxide, and the graphene oxide number of plies is 1-10 layers.Following examples are same)；Obtain
The graphene oxide solution of the rich defect of the 2mg/mL for arriving, with the sodium ascorbate reducing agent of 1mol/L with volume ratio 10：1 is uniform
Mixing, 100 DEG C heat 2h, it is scrubbed after, obtain rich defect three-dimensional grapheme block materials；By the rich defect three-dimensional stone for obtaining
Black alkene block materials and the NH that mass percent is 0.47%3BF3Aqueous solution is with 5：4 mass ratio mixing, heats at 100 DEG C
4h, the Graphene block materials for obtaining are taken out, scrubbed, are suppressed under 5MPa pressure, then after drying is processed, are finally given
Thickness is about the high nitrogen boron doping three-dimensional grapheme thin film of 0.04mm.
Embodiment 4：The graphite oxide solution of 2mg/mL and the H that mass percent is 30%2O2Solution is with 15：1 volume ratio is equal
Even mixing, heats 4h under 100 DEG C of environment, and, finally obtains the knot of pH value of solution=7 with 10000rpm rotating speeds centrifuge washing repeatedly
The graphite oxide solution (the graphite oxide solution concentration for obtaining is 2mg/mL) of structure richness defect；By the oxygen of the structure for obtaining richness defect
1h is peeled off in the ultrasonication in the case where ultrasonic power is 500W of graphite solution, is then centrifuged for separating, rotating speed 4000rpm, centrifugation time
30min, takes supernatant liquid, obtains the graphene oxide solution of the rich defect of 2mg/mL；The rich defect of the 2mg/mL for obtaining
Graphene oxide solution, with the sodium ascorbate reducing agent of 1mol/L with 10：1 volume ratio uniformly mixes, in 100 DEG C of heating
2h, it is scrubbed after, obtain rich defect three-dimensional grapheme block materials；By the rich defect three-dimensional grapheme block materials for obtaining and matter
Amount percentage ratio is 0.47% NH3BF3Aqueous solution is with 5：4 mass ratio mixing, heats 4h, by the Graphene for obtaining at 100 DEG C
Block materials take out, scrubbed, suppress under 5MPa pressure, then after drying is processed, finally give thickness and be about 0.04mm's
High nitrogen boron doping three-dimensional grapheme thin film.
Embodiment 5：The graphite oxide solution of 2mg/mL and the H that mass percent is 30%2O2Solution is with 10：1 volume ratio is equal
Even mixing, heats 4h under 100 DEG C of environment, and, finally obtains the knot of pH value of solution=7 with 10000rpm rotating speeds centrifuge washing repeatedly
The graphite oxide solution (the graphite oxide solution concentration for obtaining is 2mg/mL) of structure richness defect；By the oxygen of the structure for obtaining richness defect
1h is peeled off in the ultrasonication in the case where ultrasonic power is 500W of graphite solution, is then centrifuged for separating, rotating speed 4000rpm, centrifugation time
30min, takes supernatant liquid, obtains the graphene oxide solution of the rich defect of 2mg/mL；The rich defect of the 2mg/mL for obtaining
Graphene oxide solution, with the sodium ascorbate reducing agent of 1mol/L with 10：1 volume ratio uniformly mixes, in 100 DEG C of heating
2h, it is scrubbed after, obtain rich defect three-dimensional grapheme block materials；By the rich defect three-dimensional grapheme block materials for obtaining and matter
Amount percentage ratio is 0.47% NH3BF3Aqueous solution is with 5：4 mass ratio mixing, heats 4h, by the Graphene for obtaining at 70 DEG C
Block materials take out, scrubbed, suppress under 5MPa pressure, then after drying is processed, finally give thickness and be about 0.04mm's
High nitrogen boron doping three-dimensional grapheme thin film.
Embodiment 6：The graphite oxide solution of 2mg/mL and the H that mass percent is 30%2O2Solution is with 10：1 volume ratio is equal
Even mixing, heats 4h under 100 DEG C of environment, and, finally obtains the knot of pH value of solution=7 with 10000rpm rotating speeds centrifuge washing repeatedly
The graphite oxide solution (the graphite oxide solution concentration for obtaining is 2mg/mL) of structure richness defect；By the oxygen of the structure for obtaining richness defect
1h is peeled off in the ultrasonication in the case where ultrasonic power is 500W of graphite solution, is then centrifuged for separating, rotating speed 4000rpm, centrifugation time
30min, takes supernatant liquid, obtains the graphene oxide solution of the rich defect of 2mg/mL；The rich defect of the 2mg/mL for obtaining
Graphene oxide solution, with the sodium ascorbate reducing agent of 1mol/L with 10：1 volume ratio uniformly mixes, in 100 DEG C of heating
2h, it is scrubbed after, obtain rich defect three-dimensional grapheme block materials；By the rich defect three-dimensional grapheme block materials for obtaining and matter
Amount percentage ratio is 0.47% C6H8BNO2Aqueous solution is with 5：4 mass ratio mixing, heats 4h, by the graphite for obtaining at 120 DEG C
Alkene block materials take out, scrubbed, suppress under 5MPa pressure, then after drying is processed, finally give thickness and be about 0.04mm
High nitrogen boron doping three-dimensional grapheme thin film.
Embodiment 7：The graphite oxide solution of 2mg/mL and the H that mass percent is 30%2O2Solution is with 10：1 volume ratio is equal
Even mixing, heats 4h under 100 DEG C of environment, and, finally obtains the knot of pH value of solution=7 with 10000rpm rotating speeds centrifuge washing repeatedly
The graphite oxide solution (the graphite oxide solution concentration for obtaining is 2mg/mL) of structure richness defect；By the oxygen of the structure for obtaining richness defect
1h is peeled off in the ultrasonication in the case where ultrasonic power is 500W of graphite solution, is then centrifuged for separating, rotating speed 4000rpm, centrifugation time
30min, takes supernatant liquid, obtains the graphene oxide solution of the rich defect of 2mg/mL；The rich defect of the 2mg/mL for obtaining
Graphene oxide solution, with the sodium ascorbate reducing agent of 1mol/L with 10：1 volume ratio uniformly mixes, in 100 DEG C of heating
2h, it is scrubbed after, obtain rich defect three-dimensional grapheme block materials；By the rich defect three-dimensional grapheme block materials for obtaining and matter
Amount percentage ratio is 0.47% NH4B(OH)4Aqueous solution is with 5：4 mass ratio mixing, heats 2h, by the stone for obtaining at 100 DEG C
Black alkene block materials take out, scrubbed, suppress under 5MPa pressure, then after drying is processed, finally give thickness and be about
The high nitrogen boron doping three-dimensional grapheme thin film of 0.04mm.
The preparation and performance test of electrode：By obtained high nitrogen boron doping three-dimensional grapheme thin film tablet machine with 5MPa pressures
To on Copper Foil, metal lithium sheet is that to electrode, CELGARD 2400 is barrier film, LiPF6For electrolyte, group in Ar glove boxs is being full of
Button cell is dressed up, constant current is carried out using new prestige battery test system (BTS-5V20mA, Shenzhen Neware Co.Ltd.)
Charge-discharge test.Charging/discharging voltage scope is 0.01-3V, and electric current density is 1A/g, and performance is as shown in table 1.
Table 1
The embodiment 1,2,3 characterized by XPS in table 1 can be analyzed by regulating and controlling Graphene defect, reach regulation and control nitrogen
The purpose of boron doping amount.Embodiment 1 (zero defect and undope) and embodiment 2 (zero defect, doping) compare and show without lacking
In the case of falling into, nitrogen boron can be doped in Graphene, but the doping of nitrogen boron is a relatively low numerical value；By embodiment 2
The comparison of (zero defect, doping) and embodiment 3 (defective, doping), the doping of nitrogen boron is substantially than flawless in embodiment 3
Nitrogen boron doping amount in embodiment 2 is much higher, and the specific capacity of the embodiment 3 under same current density (1A/g) compares embodiment
2 is high, illustrates that the energy-storage property that high nitrogen boron doping three-dimensional grapheme thin film makees flexible lithium ion mixed capacitor negative material is good.
The present invention reaches the purpose of regulation and control nitrogen boron doping amount by regulating and controlling Graphene defect level, is illustrated in figure 1 flexible height
The photomacrograph of nitrogen boron doping three-dimensional graphite thin film.Fig. 2 is that flexible high nitrogen boron adulterates the XPS collection of illustrative plates of three-dimensional graphite thin film, can be with
Find out the appearance of nitrogen boron doping characteristic peak.Fig. 3 is the SEM figures of flexible high nitrogen boron doping three-dimensional graphite thin film, it can be observed that stone
Black alkene fexible film Cross Section Morphology is stratiform three dimensional structure.Fig. 4 is that initial three-dimensional graphene film mixes with lithium ion after doping
The test result of capacitor anode high rate performance, the high rate performance after as can be seen from the figure adulterating substantially is increased substantially, and is shown
Advantage of the high nitrogen boron doping three-dimensional grapheme thin film in negative pole aspect of performance is shown.
Above content is to combine specific preferred implementation further description made for the present invention, it is impossible to assert
Being embodied as of the present invention is confined to these explanations, and one of ordinary skill in the art should be understood that without departing from the principle of the invention
On the premise of, it be all by possible that can also do various replacements, change and modifications.Therefore, the present invention should not be limited to optimal reality
Apply example and accompanying drawing disclosure of that.
Unaccomplished matter of the present invention is known technology.
Claims (6)
1. a kind of flexible lithium ion mixed capacitor with high nitrogen boron adulterate three-dimensional grapheme thin film preparation method, it is characterized by should
Method is comprised the following steps:
（1）The preparation of rich defect graphite oxide solution：Graphite oxide solution is mixed in proportion with acid, is added at 50-150 DEG C
Hot 2-8 h, are obtained the graphite oxide solution of structure richness defect；Washing is centrifuged again, until obtaining pH value=7, dense
Spend the graphite oxide solution of the structure richness defect for 0.5-20 mg/mL；
Wherein, the concentration of graphite oxide is 0.5-30 mg/mL；The mass percentage concentration of acid is 10 %-90 %；Volume ratio is oxygen
Graphite solution：Acid=15：1-5：1；
（2）The preparation of rich defect graphene oxide solution：The graphite oxide solution of the structure for obtaining richness defect is carried out into lamella stripping
From obtaining structure richness defect graphene oxide solution；The concentration of structure richness defect graphene oxide solution is 0.5-20 mg/mL；
（3）The preparation of rich defect three-dimensional grapheme block materials：By structure richness defect graphene oxide solution and reductant solution
Mixing, at 50-150 DEG C heat 1-12 h, it is scrubbed after, obtain rich defect three-dimensional grapheme block materials；
Wherein, volume ratio graphene oxide solution：Reductant solution=20：1-5：1；The concentration of reductant solution is 0.1- 10
mol/L；
（4）The preparation of high nitrogen boron doping three-dimensional grapheme thin film：By rich defect three-dimensional grapheme block materials and nitrogen boron compound
Aqueous solution, at 50-150 DEG C heat 3-12 h, the high nitrogen boron doped graphene block materials for obtaining, Jing after taking-up
Washing, suppresses under 5-40 MPa, then after drying is processed, finally gives the thick high nitrogen boron doping three of the mm of 0.01 mm- 0.1
Dimension graphene film；Wherein, mass ratio is three-dimensional grapheme block materials：Nitrogen boron compound aqueous solution=0.5：1-10：1；
It is the % of 0.001 %- 1 that the concentration of the aqueous solution of described nitrogen boron compound is mass percent.
2. the flexibility lithium ion mixed capacitor as claimed in claim 1 preparation side of high nitrogen boron doping three-dimensional grapheme thin film
Method, it is characterized by described step（1）In acid-specific be hydrogen peroxide, sulphuric acid, nitric acid or phosphoric acid.
3. the flexibility lithium ion mixed capacitor as claimed in claim 1 preparation side of high nitrogen boron doping three-dimensional grapheme thin film
Method, it is characterized by described step（2）In, structure richness defect graphene oxide is few layer graphite oxide, the graphene oxide number of plies
For 1-10 layers.
4. the flexibility lithium ion mixed capacitor as claimed in claim 1 preparation side of high nitrogen boron doping three-dimensional grapheme thin film
Method, it is characterized by described step（2）In lift-off technology be solution in shearing machine peel off or ultrasonication stripping means.
5. the flexibility lithium ion mixed capacitor as claimed in claim 1 preparation side of high nitrogen boron doping three-dimensional grapheme thin film
Method, it is characterized by described step（3）Middle reducing agent is preferably ascorbic acid, sodium ascorbate or hydrazine hydrate.
6. the flexibility lithium ion mixed capacitor as claimed in claim 1 preparation side of high nitrogen boron doping three-dimensional grapheme thin film
Method, it is characterized by described step（4）In, nitrogen boron compound is preferably NH3BF3、C6H8BNO2Or NH4B(OH)4 。
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108630459A (en) * | 2018-05-10 | 2018-10-09 | 河北工业大学 | A kind of preparation method of all solid state multilevel hierarchy transparent flexible ultracapacitor of low cost |
| CN110136967A (en) * | 2018-02-02 | 2019-08-16 | 中国科学院苏州纳米技术与纳米仿生研究所 | Three-dimensional ternary doping hollow graphene hydrogel and its preparation method and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130216894A1 (en) * | 2012-02-16 | 2013-08-22 | Yanbo Wang | Inorganic nano sheet-enabled lithium-exchanging surface-mediated cells |
| CN103633333A (en) * | 2012-08-24 | 2014-03-12 | 海洋王照明科技股份有限公司 | Nitrogen-doped or boron-doped graphene/aluminum foil composite current collector, preparation method thereof, electrochemical electrode and electrochemical cell or capacitor |
| CN104245578A (en) * | 2012-03-09 | 2014-12-24 | 巴斯夫欧洲公司 | Aerogel based on doped graphene |
-
2016
- 2016-11-18 CN CN201611014462.4A patent/CN106683904B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130216894A1 (en) * | 2012-02-16 | 2013-08-22 | Yanbo Wang | Inorganic nano sheet-enabled lithium-exchanging surface-mediated cells |
| CN104245578A (en) * | 2012-03-09 | 2014-12-24 | 巴斯夫欧洲公司 | Aerogel based on doped graphene |
| CN103633333A (en) * | 2012-08-24 | 2014-03-12 | 海洋王照明科技股份有限公司 | Nitrogen-doped or boron-doped graphene/aluminum foil composite current collector, preparation method thereof, electrochemical electrode and electrochemical cell or capacitor |
Non-Patent Citations (1)
| Title |
|---|
| C.N.R.RAO ET AL.: "Synthesis, properties and applications of graphene doped with boron, nitrogen and other elements", 《NANO TODAY》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110136967A (en) * | 2018-02-02 | 2019-08-16 | 中国科学院苏州纳米技术与纳米仿生研究所 | Three-dimensional ternary doping hollow graphene hydrogel and its preparation method and application |
| CN108630459A (en) * | 2018-05-10 | 2018-10-09 | 河北工业大学 | A kind of preparation method of all solid state multilevel hierarchy transparent flexible ultracapacitor of low cost |
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