CN103971945A - Preparation method for graphene-ionic liquid composite materials and preparation method for supercapacitor - Google Patents
Preparation method for graphene-ionic liquid composite materials and preparation method for supercapacitor Download PDFInfo
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- CN103971945A CN103971945A CN201310032152.5A CN201310032152A CN103971945A CN 103971945 A CN103971945 A CN 103971945A CN 201310032152 A CN201310032152 A CN 201310032152A CN 103971945 A CN103971945 A CN 103971945A
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- Y02E60/13—Energy storage using capacitors
Abstract
The invention provides a preparation method for graphene-ionic liquid composite materials. The preparation method comprises the steps that graphite is pressed on a stainless steel current collector to be used as a working electrode, a lead plate is used as a counter electrode, Hg/Hg2SO4 is used as a reference electrode, an intercalator is used as an electrolyte, the working electrode, the counter electrode and the reference electrode are placed into the electrolyte and react for 1 hour to 20 hours at the indoor temperature with the current density ranging from 5 mA/cm<2> to 100 mA/cm<2>, the electrolyte is filtered, and intercalation graphite is obtained after cleaning and drying; the intercalation graphite is placed at the temperature ranging from -252 DEG C to -170 DEG C to be frozen and processed for 0.5 min to 5 min and then is taken out; the cooled intercalation graphite is transferred to ionic liquid at the temperature ranging from 200 DEG C to 300 DEG C when stirred and is kept in the ionic liquid for 10 min to 300 min, the mixture is cooled to be at the indoor temperature, and the graphene-ionic liquid composite materials are obtained, wherein the massic volume ratio of the intercalation graphite to the ionic liquid is 1 g: 10 mL to 100 mL. The intercalation graphite obtained through electrolysis is processed on the quick heating and cooling conditions to obtain the graphene-ionic liquid composite materials good in energy accumulation performance. In addition, the invention further provides a preparation method for a supercapacitor.
Description
Technical field
The present invention relates to the preparation method of graphene composite material field, particularly graphene-ionic liquid composite material and ultracapacitor.
Background technology
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), has excellent character, as high-specific surface area, and high conductivity, the toughness of high mechanical properties and excellence etc.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 worker's extensive concerns are attracted.Graphene can be used for electrode material, composite material etc. because of its good electric conductivity.
The preparation method of traditional Graphene mainly contains mechanical stripping, epitaxial growth, epitaxy method and chemical method.Because chemical method synthetic system is easy and simple to handle, output is large, and the product form of Graphene colloidal sol is also convenient to further processing, the moulding of material simultaneously, and therefore the general chemical method that adopts of industry is prepared Graphene.Conventional in chemical method have graphite oxide reducing process or a pyrolysis carbon source method, and its preparation technology is simply controlled, but can cause the destruction of graphene-structured, thereby affects the energy-storage property of graphene composite material.
Summary of the invention
Based on this, be necessary to provide the preparation method of the good graphene-ionic liquid composite material of a kind of energy-storage property and ultracapacitor.
A preparation method for graphene-ionic liquid composite material, comprising:
Graphite is suppressed on stainless steel collector as work electrode, taking stereotype as to electrode, Hg/Hg
2sO
4for reference electrode, intercalator is electrolyte, by described work electrode, electrode and reference electrode are placed in to described electrolyte, is 5 ~ 100mA/cm in current density
2, react 1 ~ 20 hour under room temperature, filter reacted electrolyte, obtain intercalated graphite through cleaning, after dry;
Described intercalated graphite is placed at the temperature of-252 ~-170 DEG C and carries out freezing processing 0.5 ~ 5 minute; And
Intercalated graphite after freezing processing be transferred to temperature under stirring condition and be in the ionic liquid of 200 ~ 300 DEG C and keep 10 ~ 300 minutes, then be cooled to room temperature, obtain graphene-ionic liquid composite material, wherein, the mass volume ratio of described intercalated graphite and described ionic liquid is 1g:10mL ~ 100mL.
In an embodiment, described intercalator is at least one in formic acid, acetic acid, propionic acid, nitric acid and nitromethane therein.
Therein in an embodiment, described intercalated graphite is placed in to the step of freezing processing at the temperature of-252 ~-170 DEG C for described intercalated graphite is placed in to liquid nitrogen, liquid argon or liquid hydrogen.
Therein in an embodiment, described ionic liquid is 1-ethyl-3-methylimidazole bromine salt (EtMeImBr), 1-ethyl-3-methylimidazole villaumite (EtMeImCl), 1-ethyl-3-methylimidazole salt compounded of iodine (EtMeImI), 1-ethyl-2,3-methylimidazole fluoroform sulphonate (1-Et-2,3-Me
2imCF
3sO
3), 1,2-diethyl-3-methylimidazole fluoroform sulphonate (1,2-Et
2-3-MeImCF
3sO
3), 1,2-dimethyl-3-ethyl imidazol(e) bromine salt (1,2-Me
2-3-EtImBr), 1,2-dimethyl-3-ethyl imidazol(e) villaumite (1,2-Me
2-3-EtImCl), 1,2-dimethyl-3-ethyl imidazol(e) tetrafluoroborate (1,2-Me
2-3-EtImBF
4) at least one.
In an embodiment, described being dried at 60 ~ 80 DEG C in vacuum drying chamber processed 12 ~ 24 hours therein.
In an embodiment, the speed of described stirring is 100 ~ 1000 revs/min therein.
In an embodiment, described graphite is natural scale graphite or Delanium therein.
A preparation method for ultracapacitor, comprising:
Prepare graphene-ionic liquid composite material according to above-mentioned preparation method;
Described graphene-ionic liquid composite material is placed in to mould, described graphene-ionic liquid composite material is applied constant pressure and keeps pressure to described graphene-ionic liquid composite material to be cooled to room temperature, obtain Graphene-ionic liquid compound electric pole piece; And
After barrier film is immersed in ionic liquid, take out, obtain the barrier film that contains ionic liquid; Stack gradually assembling according to the order of described Graphene-ionic liquid compound electric pole piece, the barrier film that contains ionic liquid and Graphene-ionic liquid compound electric pole piece and obtain battery core, and at described battery core outer cladding housing, obtain ultracapacitor.
Therein in an embodiment, described ionic liquid is 1-ethyl-3-methylimidazole bromine salt, 1-ethyl-3-methylimidazole villaumite, 1-ethyl-3-methylimidazole salt compounded of iodine, 1-ethyl-2,3-methylimidazole fluoroform sulphonate, 1,2-diethyl-3-methylimidazole fluoroform sulphonate, 1,2-dimethyl-3-ethyl imidazol(e) bromine salt, 1, at least one in 2-dimethyl-3-ethyl imidazol(e) villaumite and 1,2-dimethyl-3-ethyl imidazol(e) tetrafluoroborate.
In an embodiment, described pressure is 20 ~ 30MP therein.
In the preparation method of above-mentioned graphene-ionic liquid composite material and ultracapacitor, first prepare intercalated graphite, again intercalated graphite is processed and obtained graphene-ionic liquid composite material under rapid heat cycle condition, make the graphene-ionic liquid composite material obtaining keep higher stored energy ratio capacity, there is good energy-storage property, the simultaneous reactions time is short, and preparation technology is simple, is easy to realize industrialization.
Brief description of the drawings
Fig. 1 is the preparation method's of the graphene-ionic liquid composite material of an execution mode flow chart;
Fig. 2 is the preparation method's of the ultracapacitor of an execution mode flow chart.
Embodiment
Below in conjunction with execution mode and accompanying drawing, the preparation method of graphene-ionic liquid composite material and ultracapacitor is described in further detail.
Refer to Fig. 1, the graphene-ionic liquid composite material of an execution mode comprises the following steps:
S101, suppresses on stainless steel collector graphite as work electrode, taking stereotype as to electrode, and Hg/Hg
2sO
4for reference electrode, intercalator is electrolyte, by work electrode, electrode and reference electrode are placed in to described electrolyte, is 5 ~ 100mA/cm in current density
2, react 1 ~ 20 hour under room temperature, filter reacted electrolyte, obtain intercalated graphite through cleaning, after dry.
Wherein, taking stainless steel as collector, graphite is suppressed and on collector, formed 75 × 40 × 7mm
3the graphite flake of (about 2g) is as work electrode.In other embodiment, also can be pressed into as required the graphite flake of different size.In cleaning process, can directly adopt deionized water to do cleaning fluid, clean and be stained with the intercalator covering, realize a step cleaning and put in place, not introduce other impurity, simplify the operation course.Dry actual conditions can be for to process 12 ~ 24 hours in vacuum drying chamber at 60 ~ 80 DEG C.By the dry deionized water of removing in intercalated graphite, obtain dry intercalated graphite.
In the present embodiment, graphite can be natural scale graphite or Delanium.Intercalator can be at least one in formic acid, acetic acid, propionic acid, nitric acid and nitromethane.Because graphite is laminar structured, every one deck carbon atom with sp2 hydridization in conjunction with forming plane reticular large molecule, between lamella with very weak Van der Waals force combination, therefore, under certain condition, atom or the molecule of Cucumber (as acid, alkali, halogen) etc. can enter in the space between lamella.Thereby obtain intercalated graphite.
S102, is placed in described intercalated graphite at the temperature of-252 ~-170 DEG C and carries out freezing processing 0.5 ~ 5 minute.
In the present embodiment, intercalated graphite is cooled down rapidly at low temperature environment.Refrigerant in low temperature environment can be liquid nitrogen, liquid argon or liquid hydrogen.In other embodiments, also can select other can for can cooling intercalated graphite as the refrigerant such as liquid oxygen, liquid helium.
S103, the intercalated graphite after freezing processing to be transferred to temperature under the condition stirring be in the ionic liquid of 200 ~ 300 DEG C and keep 10 ~ 300 minutes, is then cooled to room temperature, obtains graphene-ionic liquid composite material; Wherein, the mass volume ratio of intercalated graphite and ionic liquid is 1g:10 ~ 100mL.
In the present embodiment, ionic liquid can be 1-ethyl-3-methylimidazole bromine salt, 1-ethyl-3-methylimidazole villaumite, 1-ethyl-3-methylimidazole salt compounded of iodine, 1-ethyl-2,3-methylimidazole fluoroform sulphonate, 1,2-diethyl-3-methylimidazole fluoroform sulphonate, 1,2-dimethyl-3-ethyl imidazol(e) bromine salt, 1, at least one in 2-dimethyl-3-ethyl imidazol(e) villaumite and 1,2-dimethyl-3-ethyl imidazol(e) tetrafluoroborate.The speed stirring can 100 ~ 1000 revs/min, under rapid stirring, can prevent that intercalated graphite from reuniting in ionic liquid.Concrete steps can be: get the dried intercalated graphite of 100g and be placed in the container that liquid nitrogen, liquid argon or liquid hydrogen are housed, soak 0.5 ~ 5 minute, after intercalated graphite is completely cooling, take out, under the condition of rapid stirring, join 1000 ~ 10000ml temperature and be in the ionic liquid of 200 ~ 300 DEG C.And then proceed in the relatively good ionic liquid of temperature, intercalated graphite is peeled off the Graphene of formation in ion body fluid, Graphene can well be dispersed between ionic liquid, can effectively avoid Graphene to reunite, and is conducive to improve effective energy storage surface of Graphene.Meanwhile, in the time that graphene-ionic liquid composite material is made capacitor during for the preparation of electrode slice, ionic liquid can also serve as electrolyte.
In the preparation method of above-mentioned graphene-ionic liquid composite material, first prepare intercalated graphite, again intercalated graphite is processed and obtained graphene-ionic liquid composite material under rapid heat cycle condition, the course of reaction time is relatively short, the graphene-ionic liquid composite material obtaining has kept higher energy-storage property, adopt intercalated graphite to prepare in the process of Graphene except having used the ionic liquid that can be used for doing electrolyte, substantially do not need to use other chemical reagent, realize green non-pollution preparation, raw material sources are wide simultaneously, cost is low, preparation technology is simple, be easy to realize industrialization.
Refer to Fig. 2, the preparation method of the ultracapacitor of an execution mode comprises the following steps:
S201, prepares graphene-ionic liquid composite material according to above-mentioned preparation method.
S202, is placed in mould by graphene-ionic liquid composite material, and graphene-ionic liquid composite material is applied constant pressure and keeps pressure to graphene-ionic liquid composite material to be cooled to room temperature, obtains Graphene-ionic liquid compound electric pole piece.
In the present embodiment, the length and width specification of mould can be 50mm × 30mm, in other embodiment, also can be arranged to as required the mould size of different size.The size of pressure is 20MPa ~ XX.Cover in the motion process towards mold bottom and can produce heat at condition of high voltage bed die, until die cover no longer after mold bottom motion, also continues maintenance this pressure to graphene-ionic liquid composite material temperature and is reduced to room temperature.Because graphene-ionic liquid composite material contains ionic liquid, after ionic liquid is cooling, can serve as binding agent and electrolyte, therefore Graphene-ionic liquid compound electric pole piece does not need to add binding agent, is conducive to the raising of capacity.
S203, is immersed in rear taking-up in ionic liquid by barrier film, obtains the barrier film that contains ionic liquid; Stack gradually assembling according to the order of Graphene-ionic liquid compound electric pole piece, the barrier film that contains ionic liquid and Graphene-ionic liquid compound electric pole piece and obtain battery core; And at battery core outer cladding housing, obtain ultracapacitor.
In the present embodiment, ionic liquid is 1-ethyl-3-methylimidazole bromine salt, 1-ethyl-3-methylimidazole villaumite, 1-ethyl-3-methylimidazole salt compounded of iodine, 1-ethyl-2,3-methylimidazole fluoroform sulphonate, 1,2-diethyl-3-methylimidazole fluoroform sulphonate, 1,2-dimethyl-3-ethyl imidazol(e) bromine salt, 1, at least one in 2-dimethyl-3-ethyl imidazol(e) villaumite and 1,2-dimethyl-3-ethyl imidazol(e) tetrafluoroborate.
In the preparation method of above-mentioned ultracapacitor, taking the graphene-ionic liquid composite material that contains ionic liquid as raw material, make Graphene-ionic liquid compound electric pole piece by mould molding, after ionic liquid is cooling, can serve as binding agent and electrolyte, therefore in ultracapacitor, do not need to add binding agent, be conducive to the raising of capacity.Meanwhile, use Graphene-ionic liquid compound electric pole piece as electrode, do not need to use collector, can reduce costs, and reduced size mixing, the technology for preparing electrode such as batch mixing, coating, do not need the techniques such as fluid injection, further optimize capacitor manufacturing process.Whole preparation process is simple, operate controlled, be applicable to large-scale industrial production.
Describe below in conjunction with specific embodiment.
Embodiment 1
(1) adopt stainless steel substrates as collector, natural scale graphite is pressed into 75 × 40 × 7mm
3the graphite flake of (quality is 2g) is as work electrode, using stereotype as to electrode, and Hg/Hg
2sO
4as reference electrode, intercalator formic acid, as electrolyte, is fully immersed in three electrodes in electrolyte, at 5mA/cm
2current density, room temperature under react 20 hours, can obtain formic acid intercalated graphite.Obtain pure intercalated graphite in 60 DEG C after dry 24 hours through washed with de-ionized water, vacuum drying chamber.
(2) get the dried intercalated graphite of 100g and put in the container that liquid nitrogen is housed, at the temperature of-170 DEG C, soak 5 minutes, after intercalated graphite is completely cooling, take out.
(3) under the condition of rapid stirring, joining 1000mL temperature is, in the 1-ethyl-3-methylimidazole bromine salt of 200 DEG C, to keep being cooled to room temperature after 100 minutes, just obtains graphene-ionic liquid composite material.
Embodiment 2
(1) adopt stainless steel substrates as collector, Delanium is pressed into 75 × 40 × 7mm
3the graphite flake of (quality is 2g) is as work electrode, using stereotype as to electrode, and Hg/Hg
2sO
4as reference electrode, intercalator acetic acid, as electrolyte, is fully immersed in three electrodes in electrolyte, at 20mA/cm
2current density, room temperature under react 1 hour, can obtain acetic acid intercalated graphite.Obtain pure intercalated graphite in 70 DEG C after dry 20 hours through washed with de-ionized water, vacuum drying chamber; .
(2) get the dried intercalated graphite of 100g and put in the container that liquid argon is housed, at the temperature of-180 DEG C, soak 3 minutes, after intercalated graphite is completely cooling, take out.
(3) under the condition of rapid stirring, joining 2000mL temperature is, in the 1-ethyl-3-methylimidazole villaumite of 220 DEG C, to keep being cooled to room temperature after 200 minutes, just obtains graphene-ionic liquid composite material.
Embodiment 3
(1) adopt stainless steel substrates as collector, natural scale graphite is pressed into 75 × 40 × 7mm
3the graphite flake of (quality is 2g) is as work electrode, using stereotype as to electrode, and Hg/Hg
2sO
4as reference electrode, intercalator propionic acid, as electrolyte, is fully immersed in three electrodes in electrolyte, at 50mA/cm
2current density, room temperature under react 2 hours, can obtain propionic acid intercalated graphite.Obtain pure intercalated graphite in 80 DEG C after dry 12 hours through washed with de-ionized water, vacuum drying chamber; .
(2) get the dried intercalated graphite of 100g and put in the container that liquid hydrogen is housed, at the temperature of-230 DEG C, soak 1 minute, after intercalated graphite is completely cooling, take out.
(3) under the condition of rapid stirring, joining 5000mL temperature is, in the 1-ethyl-3-methylimidazole salt compounded of iodine of 250 DEG C, to keep being cooled to room temperature after 300 minutes, just obtains graphene-ionic liquid composite material.
Embodiment 4
(1) adopt stainless steel substrates as collector, Delanium is pressed into 75 × 40 × 7mm
3the graphite flake of (quality is 2g) is as work electrode, using stereotype as to electrode, and Hg/Hg
2sO
4as reference electrode, the nitric acid of intercalator 68%, as electrolyte, is fully immersed in three electrodes in electrolyte, at 100mA/cm
2current density, room temperature under react 5 hours, can obtain 68% nitric acid intercalated graphite.Obtain pure intercalated graphite in 75 DEG C after dry 15 hours through washed with de-ionized water, vacuum drying chamber; .
(2) get the dried intercalated graphite of 100g and put in the container that liquid argon is housed, at the temperature of-252 DEG C, soak 0.5 minute, after intercalated graphite is completely cooling, take out.
(3) under the condition of rapid stirring, joining 8000mL temperature is 1-ethyl-2 of 300 DEG C, in 3-methylimidazole fluoroform sulphonate, keeps being cooled to room temperature after 10 minutes, just obtains graphene-ionic liquid composite material.
Embodiment 5
(1) adopt stainless steel substrates as collector, natural scale graphite is pressed into 75 × 40 × 7mm
3the graphite flake of (quality is 2g) is as work electrode, using stereotype as to electrode, and Hg/Hg
2sO
4as reference electrode, intercalator formic acid, as electrolyte, is fully immersed in three electrodes in electrolyte, at 80mA/cm
2current density, room temperature under react 10 hours, can obtain formic acid intercalated graphite.Obtain pure intercalated graphite in 65 DEG C after dry 18 hours through washed with de-ionized water, vacuum drying chamber; .
(2) get the dried intercalated graphite of 100g and put in the container that liquid nitrogen is housed, at the temperature of-240 DEG C, soak 1 minute, after intercalated graphite is completely cooling, take out.
(3) under the condition of rapid stirring, join 10000mL temperature be 220 DEG C 1, in 2-diethyl-3-methylimidazole fluoroform sulphonate, keep being cooled to room temperature after 50 minutes, just obtain graphene-ionic liquid composite material.
Embodiment 6
(1) adopt stainless steel substrates as collector, Delanium is pressed into 75 × 40 × 7mm
3the graphite flake of (quality is 2g) is as work electrode, using stereotype as to electrode, and Hg/Hg
2sO
4as reference electrode, intercalator nitromethane, as electrolyte, is fully immersed in three electrodes in electrolyte, at 40mA/cm
2current density, room temperature under react 15 hours, can obtain nitromethane intercalated graphite.Obtain pure intercalated graphite in 60 DEG C after dry 20 hours through washed with de-ionized water, vacuum drying chamber.
(2) get the dried intercalated graphite of 100g and put in the container that liquid argon is housed, at the temperature of-210 DEG C, soak 2 minutes, after intercalated graphite is completely cooling, take out.
(3) under the condition of rapid stirring, join 5000mL temperature be 250 DEG C 1, in 2-dimethyl-3-ethyl imidazol(e) bromine salt, keep being cooled to room temperature after 80 minutes, just obtain graphene-ionic liquid composite material.
Embodiment 7
(1) adopt stainless steel substrates as collector, natural scale graphite is pressed into 75 × 40 × 7mm
3the graphite flake of (quality is 2g) is as work electrode, using stereotype as to electrode, and Hg/Hg
2sO
4as reference electrode, the acetic acid-nitromethane intercalator that is 1:1 using volume ratio, as electrolyte, is fully immersed in three electrodes in electrolyte, at 10mA/cm
2current density, room temperature under react 6 hours, can obtain nitromethane intercalated graphite.Obtain pure intercalated graphite in 80 DEG C after dry 12 hours through washed with de-ionized water, vacuum drying chamber.
(2) get the dried intercalated graphite of 100g and put in the container that liquid hydrogen is housed, at the temperature of-180 DEG C, soak 4 minutes, after intercalated graphite is completely cooling, take out.
(3) under the condition of rapid stirring, join 3000mL temperature be 280 DEG C 1, in 2-dimethyl-3-ethyl imidazol(e) villaumite, keep being cooled to room temperature after 150 minutes, just obtain graphene-ionic liquid composite material.
Embodiment 8
(1) adopt stainless steel substrates as collector, Delanium is pressed into 75 × 40 × 7mm
3the graphite flake of (quality is 2g) is as work electrode, using stereotype as to electrode, and Hg/Hg
2sO
4as reference electrode, the nitric acid intercalator of formic acid-68% that is 4:1 using volume ratio, as electrolyte, is fully immersed in three electrodes in electrolyte, at 30mA/cm
2current density, room temperature under react 8 hours, can obtain nitromethane intercalated graphite.Obtain pure intercalated graphite in 70 DEG C after dry 15 hours through washed with de-ionized water, vacuum drying chamber.
(2) get the dried intercalated graphite of 100g and put in the container that liquid argon is housed, at the temperature of-170 DEG C, soak 5 minutes, after intercalated graphite is completely cooling, take out.
(3) under the condition of rapid stirring, join 2000mL temperature be 300 DEG C 1, in 2-dimethyl-3-ethyl imidazol(e) tetrafluoroborate, keep being cooled to room temperature after 250 minutes, just obtain graphene-ionic liquid composite material.
Embodiment 9
(1) adopt stainless steel substrates as collector, natural scale graphite is pressed into 75 × 40 × 7mm
3the graphite flake of (quality is 2g) is as work electrode, using stereotype as to electrode, and Hg/Hg
2sO
4as reference electrode, the nitric acid intercalator of propionic acid-68% that is 1:2 using volume ratio, as electrolyte, is fully immersed in three electrodes in electrolyte, at 5mA/cm
2current density, room temperature under react 15 hours, can obtain nitromethane intercalated graphite.Obtain pure intercalated graphite in 80 DEG C after dry 20 hours through washed with de-ionized water, vacuum drying chamber.
(2) get the dried intercalated graphite of 100g and put in the container that liquid nitrogen is housed, at the temperature of-200 DEG C, soak 3 minutes, after intercalated graphite is completely cooling, take out.
(3) under the condition of rapid stirring, joining 1000mL temperature is, in the 1-ethyl-3-methylimidazole bromine salt of 200 DEG C, to keep being cooled to room temperature after 200 minutes, just obtains graphene-ionic liquid composite material.
Embodiment 10
(1) adopt stainless steel substrates as collector, Delanium is pressed into 75 × 40 × 7mm
3the graphite flake of (quality is 2g) is as work electrode, using stereotype as to electrode, and Hg/Hg
2sO
4as reference electrode, intercalator acetic acid, as electrolyte, is fully immersed in three electrodes in electrolyte, at 100mA/cm
2current density, room temperature under react 12 hours, can obtain nitromethane intercalated graphite.Obtain pure intercalated graphite in 60 DEG C after dry 18 hours through washed with de-ionized water, vacuum drying chamber.
(2) get the dried intercalated graphite of 100g and put in the container that liquid argon is housed, at the temperature of-230 DEG C, soak 2 minutes, after intercalated graphite is completely cooling, take out.
(3) under the condition of rapid stirring, joining 2500mL temperature is, in the 1-ethyl-3-methylimidazole villaumite of 210 DEG C, to keep being cooled to room temperature after 10 minutes, just obtains graphene-ionic liquid composite material.
Embodiment 11
(1) adopt stainless steel substrates as collector, Delanium is pressed into 75 × 40 × 7mm
3the graphite flake of (quality is 2g) is as work electrode, using stereotype as to electrode, and Hg/Hg
2sO
4as reference electrode, intercalator nitromethane, as electrolyte, is fully immersed in three electrodes in electrolyte, at 50mA/cm
2current density, room temperature under react 1 hour, can obtain nitromethane intercalated graphite.Obtain pure intercalated graphite in 80 DEG C after dry 20 hours through washed with de-ionized water, vacuum drying chamber.
(2) get the dried intercalated graphite of 100g and put in the container that liquid hydrogen is housed, at the temperature of-252 DEG C, soak 0.5 minute, after intercalated graphite is completely cooling, take out.
(3) under the condition of rapid stirring, joining 6000mL temperature is, in the 1-ethyl-3-methylimidazole salt compounded of iodine of 230 DEG C, to keep being cooled to room temperature after 300 minutes, just obtains graphene-ionic liquid composite material.
Embodiment 12
The preparation of Graphene-ionic liquid compound electric pole piece:
(1) graphene-ionic liquid composite material that provides embodiment 1 to obtain.
(2) provide the mould with die cover, get in the mould that 20g graphene-ionic liquid composite material is placed in 50mm × 30mm, add die cover, to the constant pressure that applies 20MPa of mould, until die cover is no longer after mold bottom motion, and keep this pressure until Graphene-1-ethyl-3-methylimidazole bromine salt composite cools down, to room temperature, is opened mould, take out the sample in mould, just obtain blocky graphite alkene-ionic liquid compound electric pole piece.
(3) after barrier film being immersed in ionic liquid, take out, obtain the barrier film that contains ionic liquid; Stack gradually assembling according to the order of Graphene-ionic liquid compound electric pole piece, the barrier film that contains ionic liquid and Graphene-ionic liquid compound electric pole piece and obtain battery core; At battery core outer cladding housing, obtain ultracapacitor.
Embodiment 13
(1) graphene-ionic liquid composite material that provides embodiment 2 to obtain.
(2) provide the mould with die cover, get in the mould that 30g graphene-ionic liquid composite material is placed in 50mm × 30mm, add die cover, to the constant pressure that applies 30MPa of mould, until die cover is no longer after mold bottom motion, and keep this pressure until Graphene-1-ethyl-3-methylimidazole bromine salt composite cools down, to room temperature, is opened mould, take out the sample in mould, just obtain blocky graphite alkene-ionic liquid compound electric pole piece.
(3) after barrier film being immersed in ionic liquid, take out, obtain the barrier film that contains ionic liquid; Stack gradually assembling according to the order of Graphene-ionic liquid compound electric pole piece, the barrier film that contains ionic liquid and Graphene-ionic liquid compound electric pole piece and obtain battery core; At battery core outer cladding housing, obtain ultracapacitor.
Embodiment 14
(1) graphene-ionic liquid composite material that provides embodiment 3 to obtain.
(2) provide the mould with die cover, get in the mould that 50g graphene-ionic liquid composite material is placed in 50mm × 30mm, add die cover, to the constant pressure that applies 20MPa of mould, until die cover is no longer after mold bottom motion, and keep this pressure until Graphene-1-ethyl-3-methylimidazole bromine salt composite cools down, to room temperature, is opened mould, take out the sample in mould, just obtain blocky graphite alkene-ionic liquid compound electric pole piece.
(3) after barrier film being immersed in ionic liquid, take out, obtain the barrier film that contains ionic liquid; Stack gradually assembling according to the order of Graphene-ionic liquid compound electric pole piece, the barrier film that contains ionic liquid and Graphene-ionic liquid compound electric pole piece and obtain battery core; At battery core outer cladding housing, obtain ultracapacitor.
Embodiment 15
(1) graphene-ionic liquid composite material that provides embodiment 4 to obtain.
(2) provide the mould with die cover, get in the mould that 10g graphene-ionic liquid composite material is placed in 50mm × 30mm, add die cover, to the constant pressure that applies 30MPa of mould, until die cover is no longer after mold bottom motion, and keep this pressure until Graphene-1-ethyl-3-methylimidazole bromine salt composite cools down, to room temperature, is opened mould, take out the sample in mould, just obtain blocky graphite alkene-ionic liquid compound electric pole piece.
(3) after barrier film being immersed in ionic liquid, take out, obtain the barrier film that contains ionic liquid; Stack gradually assembling according to the order of Graphene-ionic liquid compound electric pole piece, the barrier film that contains ionic liquid and Graphene-ionic liquid compound electric pole piece and obtain battery core; At battery core outer cladding housing, obtain ultracapacitor.
Embodiment 16
(1) graphene-ionic liquid composite material that provides embodiment 5 to obtain.
(2) provide the mould with die cover, get in the mould that 5g graphene-ionic liquid composite material is placed in 50mm × 30mm, add die cover, to the constant pressure that applies 20MPa of mould, until die cover is no longer after mold bottom motion, and keep this pressure until Graphene-1-ethyl-3-methylimidazole bromine salt composite cools down, to room temperature, is opened mould, take out the sample in mould, just obtain blocky graphite alkene-ionic liquid compound electric pole piece.
(3) after barrier film being immersed in ionic liquid, take out, obtain the barrier film that contains ionic liquid; Stack gradually assembling according to the order of Graphene-ionic liquid compound electric pole piece, the barrier film that contains ionic liquid and Graphene-ionic liquid compound electric pole piece and obtain battery core; At battery core outer cladding housing, obtain ultracapacitor.
Embodiment 17
(1) graphene-ionic liquid composite material that provides embodiment 6 to obtain.
(2) provide the mould with die cover, get in the mould that 25g graphene-ionic liquid composite material is placed in 50mm × 30mm, add die cover, to the constant pressure that applies 20MPa of mould, until die cover is no longer after mold bottom motion, and keep this pressure until Graphene-1-ethyl-3-methylimidazole bromine salt composite cools down, to room temperature, is opened mould, take out the sample in mould, just obtain blocky graphite alkene-ionic liquid compound electric pole piece.
(3) after barrier film being immersed in ionic liquid, take out, obtain the barrier film that contains ionic liquid; Stack gradually assembling according to the order of Graphene-ionic liquid compound electric pole piece, the barrier film that contains ionic liquid and Graphene-ionic liquid compound electric pole piece and obtain battery core; At battery core outer cladding housing, obtain ultracapacitor.
Embodiment 18
(1) graphene-ionic liquid composite material that provides embodiment 7 to obtain.
(2) provide the mould with die cover, get in the mould that 15g graphene-ionic liquid composite material is placed in 50mm × 30mm, add die cover, to the constant pressure that applies 28MPa of mould, until die cover is no longer after mold bottom motion, and keep this pressure until Graphene-1-ethyl-3-methylimidazole bromine salt composite cools down, to room temperature, is opened mould, take out the sample in mould, just obtain blocky graphite alkene-ionic liquid compound electric pole piece.
(3) after barrier film being immersed in ionic liquid, take out, obtain the barrier film that contains ionic liquid; Stack gradually assembling according to the order of Graphene-ionic liquid compound electric pole piece, the barrier film that contains ionic liquid and Graphene-ionic liquid compound electric pole piece and obtain battery core; At battery core outer cladding housing, obtain ultracapacitor.
Embodiment 19
(1) graphene-ionic liquid composite material that provides embodiment 8 to obtain.
(2) provide the mould with die cover, get in the mould that 40g graphene-ionic liquid composite material is placed in 50mm × 30mm, add die cover, to the constant pressure that applies 25MPa of mould, until die cover is no longer after mold bottom motion, and keep this pressure until Graphene-1-ethyl-3-methylimidazole bromine salt composite cools down, to room temperature, is opened mould, take out the sample in mould, just obtain blocky graphite alkene-ionic liquid compound electric pole piece.
(3) after barrier film being immersed in ionic liquid, take out, obtain the barrier film that contains ionic liquid; Stack gradually assembling according to the order of Graphene-ionic liquid compound electric pole piece, the barrier film that contains ionic liquid and Graphene-ionic liquid compound electric pole piece and obtain battery core; At battery core outer cladding housing, obtain ultracapacitor.
Embodiment 20
(1) graphene-ionic liquid composite material that provides embodiment 9 to obtain.
(2) provide the mould with die cover, get in the mould that 30g graphene-ionic liquid composite material is placed in 50mm × 30mm, add die cover, to the constant pressure that applies 20MPa of mould, until die cover is no longer after mold bottom motion, and keep this pressure until Graphene-1-ethyl-3-methylimidazole bromine salt composite cools down, to room temperature, is opened mould, take out the sample in mould, just obtain blocky graphite alkene-ionic liquid compound electric pole piece.
(3) after barrier film being immersed in ionic liquid, take out, obtain the barrier film that contains ionic liquid; Stack gradually assembling according to the order of Graphene-ionic liquid compound electric pole piece, the barrier film that contains ionic liquid and Graphene-ionic liquid compound electric pole piece and obtain battery core; At battery core outer cladding housing, obtain ultracapacitor.
Embodiment 21
(1) graphene-ionic liquid composite material that provides embodiment 10 to obtain.
(2) provide the mould with die cover, get in the mould that 20g graphene-ionic liquid composite material is placed in 50mm × 30mm, add die cover, to the constant pressure that applies 20MPa of mould, until die cover is no longer after mold bottom motion, and keep this pressure until Graphene-1-ethyl-3-methylimidazole bromine salt composite cools down, to room temperature, is opened mould, take out the sample in mould, just obtain blocky graphite alkene-ionic liquid compound electric pole piece.
(3) after barrier film being immersed in ionic liquid, take out, obtain the barrier film that contains ionic liquid; Stack gradually assembling according to the order of Graphene-ionic liquid compound electric pole piece, the barrier film that contains ionic liquid and Graphene-ionic liquid compound electric pole piece and obtain battery core; At battery core outer cladding housing, obtain ultracapacitor.
Embodiment 22
(1) graphene-ionic liquid composite material that provides embodiment 11 to obtain.
(2) provide the mould with die cover, get in the mould that 50g graphene-ionic liquid composite material is placed in 50mm × 30mm, add die cover, to the constant pressure that applies 30MPa of mould, until die cover is no longer after mold bottom motion, and keep this pressure until Graphene-1-ethyl-3-methylimidazole bromine salt composite cools down, to room temperature, is opened mould, take out the sample in mould, just obtain blocky graphite alkene-ionic liquid compound electric pole piece.
(3) after barrier film being immersed in ionic liquid, take out, obtain the barrier film that contains ionic liquid; Stack gradually assembling according to the order of Graphene-ionic liquid compound electric pole piece, the barrier film that contains ionic liquid and Graphene-ionic liquid compound electric pole piece and obtain battery core; At battery core outer cladding housing, obtain ultracapacitor.
Comparative example 23
The present embodiment is the Graphene prepared by the conventional method ultracapacitor as electrode slice
(1) provide the mould with die cover, get 45g Graphene, 5g PVDF is uniformly mixed in the mould that is placed on 50mm × 30mm, add die cover, to the constant pressure that applies 20MPa of mould, until die cover is no longer after mold bottom motion, and keep this pressure drying to constant weight, open mould, take out the sample in mould, just obtain blocky graphite alkene electrode slice.
(2) electrolyte adopts 1M LiPF
6, barrier film adopts PE barrier film; Stack gradually assembling according to the order of Graphene electrodes sheet, barrier film and Graphene electrodes sheet and obtain battery core; At battery core outer cladding housing, and inject electrolyte, after sealing, obtain ultracapacitor.
Ultracapacitor to assembling in embodiment 12 ~ 22 and comparative example 23 carries out charge-discharge test.The voltage window of its test is 4V, and current density is 0.5A/g.Test result is as shown in table 1.
Table 1 embodiment 12 ~ 22 and comparative example's ultracapacitor charge-discharge test result
As shown in Table 1, embodiment 12 ~ embodiment 22 is the ultracapacitors that utilize graphene-ionic liquid composite material to prepare, and the specific capacity under 0.5A/g current density is up to 221F/g.And Graphene prepared by traditional method is only 126F/g as the ultracapacitor of electrode slice specific capacity under the same conditions.The energy-storage property that further illustrates graphene-ionic liquid composite material is better.
The above embodiment has only expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection range of patent of the present invention should be as the criterion with claims.
Claims (10)
1. a preparation method for graphene-ionic liquid composite material, is characterized in that, comprising:
Graphite is suppressed on stainless steel collector as work electrode, taking stereotype as to electrode, Hg/Hg
2sO
4for reference electrode, intercalator is electrolyte, by described work electrode, electrode and reference electrode are placed in to described electrolyte, is 5 ~ 100mA/cm in current density
2, react 1 ~ 20 hour under room temperature, filter reacted electrolyte, obtain intercalated graphite through cleaning, after dry;
Described intercalated graphite is placed at the temperature of-252 ~-170 DEG C and carries out freezing processing 0.5 ~ 5 minute; And
Intercalated graphite after freezing processing be transferred to temperature under stirring condition and be in the ionic liquid of 200 ~ 300 DEG C and keep 10 ~ 300 minutes, then be cooled to room temperature, obtain graphene-ionic liquid composite material, wherein, the mass volume ratio of described intercalated graphite and described ionic liquid is 1g:10mL ~ 100mL.
2. the preparation method of graphene-ionic liquid composite material according to claim 1, is characterized in that, described intercalator is at least one in formic acid, acetic acid, propionic acid, nitric acid and nitromethane.
3. the preparation method of graphene-ionic liquid composite material according to claim 1, is characterized in that, described intercalated graphite is placed in to the step of freezing processing at the temperature of-252 ~-170 DEG C for described intercalated graphite is placed in to liquid nitrogen, liquid argon or liquid hydrogen.
4. the preparation method of graphene-ionic liquid composite material according to claim 1, it is characterized in that, described ionic liquid is 1-ethyl-3-methylimidazole bromine salt, 1-ethyl-3-methylimidazole villaumite, 1-ethyl-3-methylimidazole salt compounded of iodine, 1-ethyl-2,3-methylimidazole fluoroform sulphonate, 1,2-diethyl-3-methylimidazole fluoroform sulphonate, 1,2-dimethyl-3-ethyl imidazol(e) bromine salt, 1, at least one in 2-dimethyl-3-ethyl imidazol(e) villaumite and 1,2-dimethyl-3-ethyl imidazol(e) tetrafluoroborate.
5. the preparation method of graphene-ionic liquid composite material according to claim 1, is characterized in that, described being dried at 60 ~ 80 DEG C in vacuum drying chamber processed 12 ~ 24 hours.
6. the preparation method of graphene-ionic liquid composite material according to claim 1, is characterized in that, the speed of described stirring is 100 ~ 1000 revs/min.
7. the preparation method of graphene-ionic liquid composite material according to claim 1, is characterized in that, described graphite is natural scale graphite or Delanium.
8. a preparation method for ultracapacitor, is characterized in that, comprising:
Prepare graphene-ionic liquid composite material according to preparation method claimed in claim 1;
Described graphene-ionic liquid composite material is placed in to mould, described graphene-ionic liquid composite material is applied to constant pressure to described graphene-ionic liquid composite material and be cooled to room temperature, obtain Graphene-ionic liquid compound electric pole piece; And
After barrier film is immersed in ionic liquid, take out, obtain the barrier film that contains ionic liquid; Stack gradually assembling according to the order of described Graphene-ionic liquid compound electric pole piece, the barrier film that contains ionic liquid and Graphene-ionic liquid compound electric pole piece and obtain battery core, and at described battery core outer cladding housing, obtain ultracapacitor.
9. the preparation method of ultracapacitor according to claim 8, it is characterized in that, described ionic liquid is 1-ethyl-3-methylimidazole bromine salt, 1-ethyl-3-methylimidazole villaumite, 1-ethyl-3-methylimidazole salt compounded of iodine, 1-ethyl-2,3-methylimidazole fluoroform sulphonate, 1,2-diethyl-3-methylimidazole fluoroform sulphonate, 1,2-dimethyl-3-ethyl imidazol(e) bromine salt, 1, at least one in 2-dimethyl-3-ethyl imidazol(e) villaumite and 1,2-dimethyl-3-ethyl imidazol(e) tetrafluoroborate.
10. the preparation method of ultracapacitor according to claim 8, is characterized in that, described pressure is 20 ~ 30MPa.
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