CN103632845A - Graphene/organic thin film composite current collector, preparation method thereof, electrochemical electrode and electrochemical battery or capacitor - Google Patents
Graphene/organic thin film composite current collector, preparation method thereof, electrochemical electrode and electrochemical battery or capacitor Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 142
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 126
- 239000002131 composite material Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000003990 capacitor Substances 0.000 title claims abstract description 18
- 239000010409 thin film Substances 0.000 title abstract 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000725 suspension Substances 0.000 claims abstract description 35
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 18
- 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 abstract description 17
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 14
- 239000010439 graphite Substances 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 9
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Natural products CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 11
- 239000007772 electrode material Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 5
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052493 LiFePO4 Inorganic materials 0.000 claims description 2
- 229920006289 polycarbonate film Polymers 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 16
- 238000000034 method Methods 0.000 abstract description 9
- 239000011149 active material Substances 0.000 abstract description 7
- 239000007788 liquid Substances 0.000 abstract description 5
- 238000003825 pressing Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 2
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 238000005260 corrosion Methods 0.000 abstract 1
- 230000007797 corrosion Effects 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- 238000002791 soaking Methods 0.000 abstract 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 13
- 229910001416 lithium ion Inorganic materials 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000014759 maintenance of location Effects 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 229920002799 BoPET Polymers 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- -1 1-ethyl-3-methylimidazole tetrafluoro boric acid Chemical compound 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005492 condensed matter physics Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007614 solvation 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)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a graphene/organic thin film composite current collector and a preparation method thereof. The method comprises the steps that graphite oxide is taken and added into a solvent; after ultrasonic dispersion, graphene oxide suspension liquid is acquired; pH is adjusted to 10 to 11; a hydrazine hydrate solution is added; after reaction, filtration is carried out to acquire graphene; the graphene is added into an organic solvent to acquire graphene suspension liquid; the graphene suspension liquid is coated on an organic thin film; after drying is carried out, roller pressing is repeatedly carried out; and after the soaking of the mixed solution of acetone and isopropyl alcohol, roller pressing is repeatedly carried out, so as to acquire the graphene/organic thin film composite current collector. According to the method, the process is simple; the use of an adhesive is not needed; the prepared graphene/organic thin film composite current collector has the advantages of light quality, strong electrical conductivity, corrosion resistance and small contact resistance with a battery active material; and the power density and the cycle life of the electrochemical battery or capacitor can be improved. The invention further provides an electrochemical electrode and the electrochemical battery or capacitor employing the electrode.
Description
Technical field
The present invention relates to the synthetic preparation field of new material, particularly relate to a kind of Graphene/organic film composite current collector and preparation method thereof and electrochemical electrode.The invention still further relates to a kind of electrochemical cell or capacitor.
Background technology
Collector is a kind of structure or part that collects electric current, major function is that the electric current that cell active materials is produced collects, electron channel is provided, accelerating electric charge shifts, improve and discharge and recharge a coulomb efficiency, as collector, need to meet the features such as conductivity is high, good mechanical property, quality is light, internal resistance is little.
Graphene is a kind of Two-dimensional Carbon atomic crystal of the discoveries such as the strong K sea nurse of the peace moral of Univ Manchester UK in 2004 (Andre K.Geim), because its unique structure and photoelectric property become the study hotspot in the fields such as material with carbon element, nanometer technology, Condensed Matter Physics and functional material, many scientific workers have been attracted.Graphene has good conduction, heat conductivility and low thermal coefficient of expansion, can be used for electrode material, composite material etc.
At present, what generally use is metal collector, plus plate current-collecting body generally adopts aluminium foil, negative current collector adopts Copper Foil, but because the density of metal collector is larger, quality is heavier, the weight of general collector accounts for 20 ~ 25% of whole battery, the weight ratio that electrode material accounts for is reduced, thereby cause the energy density of energy storage device lower; Meanwhile, metal material is easily corroded, and then has affected the useful life of energy storage device.
Therefore, be badly in need of seeking that a kind of quality is light, conductivity strong, be difficult for being corroded, have the collector of excellent compatibility with electrode active material.
Summary of the invention
For addressing the above problem, the present invention aims to provide a kind of preparation method of Graphene/organic film composite current collector, Graphene/organic film composite current collector that the method makes, quality is light, conductivity is strong, with between battery active material to contact internal resistance little, thereby can reduce the internal resistance of electrochemical cell or capacitor, improve its power density, and Graphene is difficult for being corroded, thus cyclical stability and the life-span that can improve electrochemical cell or capacitor.The present invention also provides a kind of electrochemical electrode and a kind of electrochemical cell or capacitor that uses this electrode.
The preparation method of Graphene/organic film composite current collector provided by the invention, comprises the following steps:
Get graphite oxide, join in solvent, after ultrasonic dispersion 0.5 ~ 1h, obtain graphene oxide suspension, the pH value of described graphene oxide suspension is adjusted to 10 ~ 11, add hydrazine hydrate solution, at 80 ~ 120 ℃ of temperature, react 12 ~ 24 hours, suction filtration, obtains Graphene, described Graphene is joined in organic solvent, obtain graphene suspension;
Described graphene suspension is evenly coated on clean organic film, dry after 6 ~ 12 hours at 80 ~ 100 ℃, repeatedly pair roller compacting, soaks after 10 ~ 60min with acetone and isopropyl alcohol mixture, continue again repeatedly pair roller compacting, obtain Graphene/organic film composite current collector.
Preferably, organic film is PETG (PET) film, PEN (PEN) film, Merlon (PC) film or polymethyl methacrylate (PMMA) film.
Organic film can carry out following clean operation: with the HCL of 1mol/L, soak, then with ethanol, clean 2 ~ 3 times.
Preferably, the thickness of organic film is 6 ~ 50 μ m.
Preferably, solvent is deionized water, ethanol, isopropyl alcohol or n-butanol.
Preferably, the concentration of graphene oxide suspension is 0.25 ~ 1mg/mL.
Preferably, organic solvent is dimethyl sulfoxide (DMSO) (DMSO), DMF (DMF), DMA (DMAc), 1-METHYLPYRROLIDONE (NMP).
Preferably, organic solvent accounts for 10 ~ 30% of described graphene suspension gross mass.
Wherein, the pH value of graphene oxide suspension is adjusted to 10 ~ 11, can adopts the sodium hydroxide solution, ammonia spirit or the potassium hydroxide solution that slowly add 0.1mol/L to realize.
Adding of hydrazine hydrate solution, graphene oxide can be reduced into Graphene.
Preferably, with N
2h
4quality meter, the mass concentration of described hydrazine hydrate solution is 85%, described hydrazine hydrate solution is pressed N
2h
4with the mass ratio of described graphite oxide be that 1 ~ 7:10 adds.
After reduction reaction, in the reactant liquor obtaining, contain the complete hydrazine hydrate of unreacted, suction filtration operation can be removed, and obtains Graphene.The Graphene of gained after suction filtration is joined in organic solvent, just obtain graphene suspension.
Graphene suspension is coated on organic film, at 80 ~ 100 ℃, is dried 6 ~ 12 hours, it is dry that graphene suspension obtains part, repeatedly pair roller compacting, then soak after 10 ~ 60min with acetone and isopropyl alcohol mixture, more repeatedly pair roller is suppressed.Wherein, acetone has been into and has turned use into isopropyl alcohol mixture immersion Main Function, and the molecular structure in solvation relief graphene layer is further adjusted, to obtain the more graphene layer of rock-steady structure.Preferably, the thickness of graphene layer is 3 ~ 10 μ m.Repeatedly pair roller pressing operation, can make Graphene and organic film have better combination, thereby effectively prevents the generation of dry linting phenomenon.The number of times of described pair roller compacting is not limit, and can be applicable to as required the compacting of number of times, preferably, suppresses 2 ~ 3 times.
At roll squeezer, carry out in the operating process of pair roller compacting, the surface that part Graphene particle is pressed into organic film by mechanical pressure by force finally forms graphene layer, another part is pressed in the internal structure of organic film, be uniformly distributed in organic film inside, so just obtain having Graphene/organic film composite current collector of composite construction.In this Graphene/organic film composite current collector, the combination between Graphene and organic film is tight, has larger peel strength, is difficult for producing dry linting phenomenon.Conventionally binding agent add the reduction that membership causes collector conductivity, in the present invention, between Graphene and organic film, do not use binding agent, and Graphene has high conductivity, so this Graphene/organic film composite current collector has stronger electric conductivity.Like this, Graphene can strengthen the compatibility of collector and electrode active material as conductive layer, reduces the interface contact resistance of collector and electrode active material, thereby reduces the internal resistance of electrochemical cell or capacitor, effectively improves its power density.Meanwhile, Graphene is difficult for being corroded, thereby can extend the useful life of electrochemical cell or capacitor.
Second aspect, the invention provides a kind of Graphene/organic film composite current collector being prepared by above-mentioned preparation method.
The third aspect, the invention provides a kind of electrochemical electrode, this electrochemical electrode comprises described Graphene/organic film composite current collector that second aspect present invention provides, and the electrode material of preparation on this Graphene/organic film composite current collector, this electrode material comprises that mass ratio is LiFePO4, Kynoar binding agent and the conductive black Super P of 92:3:5.
Fourth aspect, the invention provides a kind of electrochemical cell or capacitor, the described electrochemical electrode that the electrode of this electrochemical cell or capacitor adopts third aspect present invention to provide.
Graphene/organic film composite current collector provided by the invention and preparation method thereof, has following beneficial effect:
(1) the present invention suppresses the Graphene/organic film composite current collector that uses the method for mechanical pressure to make by pair roller, and preparation technology is simple, and cost is low, is easy to realize large-scale industrial and produces;
(2) Graphene/organic film composite current collector making by preparation method of the present invention, graphene layer is combined with organic film closely, dry linting not, and between Graphene and organic film, do not use binding agent, Graphene has strengthened the compatibility of collector and battery active material as conductive layer, reduce the interface contact resistance of collector and active material, thereby reduced the internal resistance of electrochemical cell or capacitor, effectively improved its power density;
(3) Graphene is difficult for being corroded, thereby can extend the useful life of electrochemical cell or capacitor.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the prepared Graphene/organic film of the embodiment of the present invention one composite current collector.
Embodiment
The following stated is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
Embodiment mono-
A preparation method for Graphene/organic film composite current collector, comprises the following steps:
(1) providing thickness is the PET film of 6 μ m, with the HCL of 1mol/L, soaks, and then with ethanol, cleans three times;
(2) get graphite oxide, join in deionized water, ultrasonic dispersion 0.5h, obtaining concentration is the graphene oxide suspension of 0.25mg/mL, then slowly adds the sodium hydroxide solution of 0.1mol/L to regulate PH to 10, subsequently, adds hydrazine hydrate solution (with N
2h
4quality meter, mass concentration is 85%), at 120 ℃ of temperature, reacting 12 hours, suction filtration, obtains Graphene, and described Graphene is joined in DMSO, obtains graphene suspension;
Wherein, hydrazine hydrate solution is pressed N
2h
4with the mass ratio of graphite oxide be that 1:10 adds; DMSO solvent accounts for 10% of described graphene suspension gross mass;
(3) graphene suspension is evenly coated on PET film, dry after 12 hours at 80 ℃, pair roller compacting 3 times, soaks after 10min with acetone and isopropyl alcohol mixture, then pair roller compacting 3 times, obtains Graphene/organic film composite current collector.Wherein, the thickness of graphene layer is 3 μ m.
Fig. 1 is the SEM figure of the prepared Graphene/organic film of the embodiment of the present invention one composite current collector.As can be seen from Figure 1, organic film matrix surface is attached with the grapheme material of a lamellar.
The preparation of electrochemical electrode
Take 9.2g LiFePO4,0.5g conductive black Super P and 0.3g PVDF, and add 20g NMP, fully stir and make it to become the slurry mixing.Then by its blade coating on the present embodiment gained Graphene/organic film composite current collector cleaning through ethanol, under the vacuum of 0.01MPa, 80 ℃ are dried to constant weight, and are pressed into iron phosphate lithium electrode in 10 ~ 15MPa pressure lower roll, and are cut into positive plate.Equally, take 4.6g graphite, 0.25g conductive black Super P and 0.15g PVDF, and add 10g NMP, fully stir and make it to become the slurry mixing, then by its blade coating on another Graphene/organic film composite current collector of the present embodiment gained cleaning through ethanol, be pressed into negative plate.
The preparation of electrochemical cell
By above-mentioned positive plate, celgard2000 barrier film, above-mentioned negative plate in order stack of laminations dress up battery core, use again battery housing seal battery core, toward the 1-ethyl-3-methylimidazole tetrafluoro boric acid electrolyzed saline solution liquid that injects 0.5mol/L in battery container, sealing liquid injection port, obtains lithium ion battery.
With CHI660A electrochemical workstation, the lithium ion battery assembling in the present embodiment is carried out to constant current charge-discharge test, the internal resistance that records this lithium ion battery is 3m Ω, power density is 7.0kw/g, carry out after 1200 charge and discharge cycles, capability retention is 93%, and 180 ° of peel strengths that record electrode slice with peel strength tester are 5N.
Embodiment bis-
A preparation method for Graphene/organic film composite current collector, comprises the following steps:
(1) providing thickness is the PEN film of 6 μ m, with the HCL of 1mol/L, soaks, and then with ethanol, cleans three times;
(2) get graphite oxide, join in ethanol, ultrasonic dispersion 0.5h, obtaining concentration is the graphene oxide suspension of 1mg/mL, then slowly adds the ammonia spirit of 0.1mol/L to regulate PH to 11, subsequently, adds hydrazine hydrate solution (with N
2h
4quality meter, mass concentration is 85%), at 90 ℃ of temperature, reacting 18 hours, suction filtration, obtains Graphene, and described Graphene is joined in 1-METHYLPYRROLIDONE (NMP), obtains graphene suspension;
Wherein, hydrazine hydrate solution is pressed N
2h
4with the mass ratio of graphite oxide be that 5:10 adds; Nmp solvent accounts for 20% of described graphene suspension gross mass;
(3) graphene suspension is evenly coated on PEN film, dry after 10 hours at 80 ℃, pair roller compacting 2 times, soaks after 10min with acetone and isopropyl alcohol mixture, then pair roller compacting 2 times, obtains Graphene/organic film composite current collector.Wherein, the thickness of graphene layer is 6 μ m.
The present embodiment gained Graphene/organic film composite current collector is prepared into electrochemical electrode according to the method for embodiment mono-, and be assembled into lithium ion battery, with CHI660A electrochemical workstation, the lithium ion battery assembling in the present embodiment is carried out to constant current charge-discharge test, the internal resistance that records this lithium ion battery is 5m Ω, power density is 3.0kw/kg, carry out after 1200 charge and discharge cycles, capability retention is 95%.180 ° of peel strengths that record electrode slice with peel strength tester are 4N.
Embodiment tri-
A preparation method for Graphene/organic film composite current collector, comprises the following steps:
(1) providing thickness is the PC film of 20 μ m, with the HCL of 1mol/L, soaks, and then with ethanol, cleans 2 times;
(2) get graphite oxide, join in n-butanol, ultrasonic dispersion 1h, obtaining concentration is the graphene oxide suspension of 0.5mg/mL, then slowly adds the potassium hydroxide solution of 0.1mol/L to regulate PH to 11, subsequently, adds hydrazine hydrate solution (with N
2h
4quality meter, mass concentration is 85%), at 100 ℃ of temperature, reacting 12 hours, suction filtration, obtains Graphene, and described Graphene is joined in DMF (DMF), obtains graphene suspension;
Wherein, hydrazine hydrate solution is pressed N
2h
4with the mass ratio of graphite oxide be that 7:10 adds; DMF solvent accounts for 30% of described graphene suspension gross mass;
(3) graphene suspension is evenly coated on PC film, dry after 6 hours at 100 ℃, pair roller compacting 2 times, soaks after 60min with acetone and isopropyl alcohol mixture, then pair roller compacting 2 times, obtains Graphene/organic film composite current collector.Wherein, the thickness of graphene layer is 10 μ m.
The present embodiment gained Graphene/organic film composite current collector is prepared into electrochemical electrode according to the method for embodiment mono-, and be assembled into lithium ion battery, with CHI660A electrochemical workstation, the lithium ion battery assembling in the present embodiment is carried out to constant current charge-discharge test, the internal resistance that records this lithium ion battery is 4m Ω, power density is 6.3kw/kg, carry out after 1200 charge and discharge cycles, capability retention is 94%.180 ° of peel strengths that record electrode slice with peel strength tester are 8N.
Embodiment tetra-
A preparation method for Graphene/organic film composite current collector, comprises the following steps:
(1) providing thickness is the PMMA film of 50 μ m, with the HCL of 1mol/L, soaks, and then with ethanol, cleans three times;
(2) get graphite oxide, join in isopropyl alcohol, ultrasonic dispersion 1h, obtaining concentration is the graphene oxide suspension of 0.8mg/mL, then slowly adds the sodium hydroxide solution of 0.1mol/L to regulate PH to 10, subsequently, adds hydrazine hydrate solution (with N
2h
4quality meter, mass concentration is 85%), at 80 ℃ of temperature, reacting 24 hours, suction filtration, obtains Graphene, and described Graphene is joined in DMF (DMF), obtains graphene suspension;
Wherein, hydrazine hydrate solution is pressed N
2h
4with the mass ratio of graphite oxide be that 5:10 adds; DMF solvent accounts for 25% of described graphene suspension gross mass;
(3) graphene suspension is evenly coated on PMMA film, dry after 6 hours at 90 ℃, pair roller compacting 3 times, soaks after 40min with acetone and isopropyl alcohol mixture, then pair roller compacting 3 times, obtains Graphene/organic film composite current collector.Wherein, the thickness of graphene layer is 8 μ m.
The present embodiment gained Graphene/organic film composite current collector is prepared into electrochemical electrode according to the method for embodiment mono-, and be assembled into lithium ion battery, with CHI660A electrochemical workstation, the lithium ion battery assembling in the present embodiment is carried out to constant current charge-discharge test, the internal resistance that records this lithium ion battery is 3m Ω, power density is 6.7kw/kg, carry out after 1200 charge and discharge cycles, capability retention is 93%.180 ° of peel strengths that record electrode slice with peel strength tester are 6N.
Graphene/organic film the composite current collector making by preparation method of the present invention, quality is light, the associativity of organic film and Graphene is good, dry linting not, and between Graphene and organic film, do not use binding agent, Graphene has strengthened the compatibility of collector and battery active material as conductive layer, has reduced the interface contact resistance of collector and active material, thereby reduced the internal resistance of electrochemical cell or capacitor, effectively improved its power density; Meanwhile, Graphene is difficult for being corroded, thereby can extend the useful life of electrochemical cell or capacitor.The lithium ion battery that uses this Graphene/organic film composite current collector simultaneously to make as anodal and negative current collector, the capability retention after 1200 times that circulates reaches more than 93%.
The above is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
Claims (10)
1. a preparation method for Graphene/organic film composite current collector, is characterized in that, comprises the following steps:
Get graphite oxide, join in solvent, after ultrasonic dispersion 0.5 ~ 1h, obtain graphene oxide suspension, the pH value of described graphene oxide suspension is adjusted to 10 ~ 11, add hydrazine hydrate solution, at 80 ~ 120 ℃ of temperature, react 12 ~ 24 hours, suction filtration, obtains Graphene, described Graphene is joined in organic solvent, obtain graphene suspension;
Described graphene suspension is evenly coated on clean organic film, dry after 6 ~ 12 hours at 80 ~ 100 ℃, repeatedly pair roller compacting, soaks after 10 ~ 60min with acetone and isopropyl alcohol mixture, continue again repeatedly pair roller compacting, obtain Graphene/organic film composite current collector.
2. the preparation method of Graphene/organic film composite current collector as claimed in claim 1, it is characterized in that, described organic film is pet film, PEN film, polycarbonate film or polymethyl methacrylate film.
3. the preparation method of Graphene/organic film composite current collector as claimed in claim 1, is characterized in that, the thickness of described organic film is 6 ~ 50 μ m.
4. the preparation method of Graphene/organic film composite current collector as claimed in claim 1, is characterized in that, described solvent is deionized water, ethanol, isopropyl alcohol or n-butanol, and the concentration of described graphene oxide suspension is 0.25 ~ 1mg/mL.
5. the preparation method of Graphene/organic film composite current collector as claimed in claim 1, is characterized in that, described organic solvent is dimethyl sulfoxide (DMSO), DMF, DMA or 1-METHYLPYRROLIDONE.
6. the preparation method of Graphene/organic film composite current collector as claimed in claim 1, is characterized in that, described organic solvent accounts for 10 ~ 30% of described graphene suspension gross mass
7. the preparation method of Graphene/organic film composite current collector as claimed in claim 1, is characterized in that, with N
2h
4quality meter, the mass concentration of described hydrazine hydrate solution is 85%, described hydrazine hydrate solution is pressed N
2h
4with the mass ratio of described graphite oxide be that 1 ~ 7:10 adds.
8. Graphene/organic film composite current collector, is characterized in that, this collector is made by the arbitrary described preparation method of claim 1 to 7.
9. an electrochemical electrode, it is characterized in that, this electrochemical electrode comprises Graphene/organic film composite current collector claimed in claim 8, and the electrode material of preparation on this Graphene/organic film composite current collector, this electrode material comprises that mass ratio is LiFePO4, Kynoar binding agent and the conductive black Super P of 92:3:5.
10. electrochemical cell or a capacitor, is characterized in that, the electrode of this electrochemical cell or capacitor adopts electrochemical electrode claimed in claim 9.
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