CN103482620A - Graphene oxide or reduced graphene base mesh material and preparation method thereof - Google Patents
Graphene oxide or reduced graphene base mesh material and preparation method thereof Download PDFInfo
- Publication number
- CN103482620A CN103482620A CN201310412740.1A CN201310412740A CN103482620A CN 103482620 A CN103482620 A CN 103482620A CN 201310412740 A CN201310412740 A CN 201310412740A CN 103482620 A CN103482620 A CN 103482620A
- Authority
- CN
- China
- Prior art keywords
- reduced graphene
- filter paper
- oxidation
- graphene
- paper
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Abstract
The invention relates to a graphene oxide or reduced graphene base mesh material, which is characterized in that a plurality of meshes are distributed on a graphene oxide or reduced graphene base macroscopic material, the graphene oxide or reduced graphene base macroscopic material has a thickness of 200 nm-200 mum, a length of 2 cm-20 m, and a width of 2 cm-20 m, the mesh size is 0.1-1 mm, and a distance between the meshes is 1-5 mm. The preparation method comprises that: a graphene oxide or reduced graphene base composite solution is poured into a suction filtration device having double layer filtration paper to be subjected to suction filtration, wherein mesh formation can be completed through one-step suction filtration by adding a hole preparation fitting to the conventional suction filtration device, or suction filtration is performed to form graphene oxide or reduced graphene paper, and then a special hole preparation mold is adopted to mold meshes. According to the present invention, the key problems that graphene paper or graphene oxide paper and other two-dimensional macroscopic composite materials have characteristics of small effective electrochemistry activity specific surface area, low effective utilization rate, impermeability and the like are well solved, and obstacles are cleared for large-scale production of graphene and composite materials and practical applications in various fields.
Description
Technical field
The present invention relates to new carbon and preparation method thereof, particularly a kind of graphene-based grid material and industrialized process for preparing thereof.
Background technology
Graphene (Graphene) is a kind ofly by carbon atom, with the sp2 hybridized orbital, to form the flat film that hexangle type is the honeycomb lattice, only has the two-dimensional material of a carbon atom thickness.Graphene is not only the nano material of the thinnest intensity maximum in the world, and it also has numerous excellent properties, as superelevation transparence (only absorbing 2.3%); High thermal conductivity (5300W/mK), under high normal temperature, its electronic mobility surpasses 15000cm
2/ Vs, electrical and thermal conductivity is all higher than carbon nanotube and diamond, and resistivity only approximately 10
-6Ω cm, lower than copper or silver, be the current material of resistivity minimum in the world.
Oxidation or reduced graphene paper [Graphene (oxide) paper] are successively to pile up self-assembly and the two dimension macroscopic view Graphene novel material for preparing by individual layer or multilayer oxidation or reduced graphene.The Thickness Ratio paper of oxidation or reduced graphene paper is thin, and the light intensity of quality is high, and has outstanding snappiness, and environmental protection and renewable.In view of the large characteristic of the light intensity of Graphene papery, this material can be used for replacing traditional steel and aluminium, is expected at first obtain application in automobile making and aircraft industry field.Compare traditional aircraft and automobile, the light intensity of the automobile made from this novel material and aircraft weight is high, thereby can directly realize energy-saving and emission-reduction, and intensity is higher, safer, also greatly reduces electronic or design hybrid vehicle of Future New Energy Source simultaneously and promote the power of electrical source of power and the requirement of energy density.
Simultaneously, due to its excellent conduction and heat conductivility, and special nanostructure and surface interface characteristic, Graphene and with the application in energy storage and conversion field of the Composite Paper of excessive metallic compound be all one of emphasis of Graphene area research all the time.The Graphene paper that for example researchist of U.S. Rensselaer Polytech Inst will process through the flash of light of laser or camera flashlamp is made the anode material of lithium ion battery, due to its unique pore space structure, to ionogen, wetting and lithium ion migration provides high-speed channel, thereby its chemical property compares generally fast 10 times of the graphite anode charge or discharge speed used, can drive power truck future.In addition, Graphene and Sn or SnO
x, Si, the composite graphite alkene paper of the compositions such as Ge has higher lithium ion storage capacity, and than pure metal and oxide compound thereof, composite graphite alkene paper possesses volume energy density and the safety performance of more excellent cycle performance and Geng Gao.The Graphene Composite Paper is also by extensive as should to be used in the electric chemical super capacitor field.
Because oxidation or reduced graphene paper have special high-density and high-intensity layered nano-structure and derivative special mechanics, physical and chemical performance thus, thereby oxidation or reduced graphene paper has broad application prospects, but ultralow effective electrochemically active specific surface area that its high-density stratiform nanostructure causes and impenetrability be equally also restriction its in rechargeable battery and the storage of ultracapacitor equal energy source with prepare one of the crucial barrier of the large-scale practical application in the fields such as high performance composite as two-dimentional wild phase.Existing patent documentation is mainly also for the preparation of oxidation or reduced graphene and film thereof and the novel process of modification, the Graphene of usining prepares various functional matrix materials as conductive additive, is being difficult to solution aspect ultralow effective electrochemically active specific surface area and impenetrability.
Summary of the invention
The technical problem to be solved in the present invention is to provide that a kind of effective electrochemically active specific surface area is large, utilization ratio is high and permeable oxidation or reduced graphene base net grid material, and its industrialized low cost production method also is provided simultaneously.
In order to solve the problems of the technologies described above, the invention provides a kind of oxidation or reduced graphene base net grid material, be distributed with a plurality of grids on graphene-based macroscopic material; Described graphene-based macroscopic material is of a size of: thickness: 200nm – 200 μ m, length: 2cm – 20m, width: 2cm – 20m; Described size of mesh opening: 0.1mm-1mm; Mesh spacing: 1mm-5mm.
In described graphene-based grid material, compound interpolation is carbon nanomaterial mutually, or is transition metal or transistion metal compound, or is one or more in nano-silicon, or is high molecule nano material; The content of compound interpolation in oxidation or reduced graphene base paper is 0 to 70wt%, when content is 0, is the pure phase grid material that oxidation or reduced graphene form.
Described mesh shape is circular, or oval, or trilateral, or Polygons.
The present invention also provides the preparation method of a kind of oxidation or reduced graphene base net grid material, is preparation method A or B;
Described method A is:
Adopt vacuum apparatus, filter funnel is arranged on it, the funnel size range is: 2cm * 2cm～20m * 20m, or be 2cm or be～20m for diameter; Be provided with double-deck filter paper in described filter funnel, above described double-deck filter paper, be provided with the drilling accessory; Described drilling accessory is provided with stainless steel column array, the steel column spacing of described stainless steel column array: 1-5mm, and the steel column shape of cross section is trilateral or circle or Polygons; Steel column cross-sectional diameter or size dimension scope: 0.1mm-1mm; The thick porous carbon film of 100 μ m – 1000 μ m that described double-deck filter paper is Mierocrystalline cellulose qualitative filter paper and surface deposition thereof;
Oxidation or reduced graphene base composite solution are poured in the suction filtration device with double-deck filter paper, and put into the drilling accessory, described steel column end is conflicted on described double-deck filter paper, then carry out suction filtration, after completing, suction filtration formed graphene-based grid paper on double-deck filter paper surface, by its oven dry, peel off, obtaining thickness is the graphene mesh ruled paper of 200nm – 200 μ m, its size of mesh opening is that 0.1mm-1mm, mesh spacing are 1mm-5mm;
Described method B is:
Oxidation or reduced graphene base composite solution are poured in the suction filtration device with individual layer filter paper or double-deck filter paper and carried out suction filtration, and the filter funnel size range of suction filtration device is: 2cm * 2cm～20m * 20m, or be 2cm or be～20m for diameter; The thick porous carbon film of 100 μ m – 1000 μ m that described double-deck filter paper is Mierocrystalline cellulose qualitative filter paper and surface deposition thereof; After completing, suction filtration formed oxidation or reduced graphene base paper at individual layer filter paper or double-deck filter paper surface;
Oxidation or the paper conversion of reduced graphene base are gone out to a plurality of through holes, and it is oxidation or the reduced graphene base net grid material that 0.1mm-1mm, mesh spacing are 1mm-5mm that formation has size of mesh opening.
In the preparation method of described oxidation or reduced graphene base net grid material:
Described oxidation or the paper conversion of reduced graphene base are gone out to a plurality of through holes, the method adopted is: adopt punching die to carry out the porous processing, described punching die consists of the die cooperatively interacted and punch, described die is the stainless steel plate with porous array, pitch of holes: 1-5mm, the hole shape of cross section is trilateral or circle, or Polygons; The hole cross section length of side or diameter dimension are 0.1mm-1mm; Described punch is provided with the corresponding insertion one by one of above-mentioned porous array, also can produces the stainless steel column array of punching effect; Oxidation or reduced graphene base paper are placed in the die upper surface with porous array, with the corresponding die of the punch with stainless steel post array, carry out punching.
In the preparation method of described oxidation or reduced graphene base net grid material:
Described method A or/and the preparation method of the double-deck filter paper in method B be:
The double-deck filter paper that adopts following steps to make: by the one dimension carbon nanotube or/and carbon nanofiber is ultrasonic is scattered in organic solvent; Then be deposited on Mierocrystalline cellulose qualitative filter paper surface by the vacuum filtration method, form the thick porous carbon film of 100 μ m – 1000 μ m, thereby make the double-deck filter paper of Mierocrystalline cellulose qualitative filter paper/porous nano carbon film.
In the preparation method of described oxidation or reduced graphene base net grid material:
The preparation concrete steps of described double-deck filter paper are:
The carbon nanotube of the about 5-100nm of diameter or carbon nanofiber are joined in the mixing solutions by the sulfuric acid of 1～3:1 volume ratio and nitric acid, and carbon nanotube or the carbon nanofiber concentration in mixed acid solution is 0.01～0.05g/ml;
At 50-100 ℃ of lower back flow reaction 2-10 hour, with after the deionized water dilution, with deionized water and dehydrated alcohol, clean respectively three times again, then add corresponding dehydrated alcohol, the ultrasonic suspension that disperses to obtain after 5-60 minute carbon nanotube or carbon nanofiber of carbon nanotube in add the ratio that 0.7-1.3 rises than 1g carbon nanotube or carbon nanofiber;
To be installed in funnel with the corresponding Mierocrystalline cellulose qualitative filter paper of funnel size, subsequently carbon nanotube or nanofiber suspension are joined in funnel, just obtain the double-deck filter paper of described Mierocrystalline cellulose filter paper/porous carbon nanotube or carbon nanofiber membrane after vacuum filtration completes.
In the preparation method of described oxidation or reduced graphene base net grid material:
In described method A, described funnel is divided into upper and lower two portions, be filled with the filtrate chamber of porous core or porous aluminium sheet in the funnel bottom is divided into, on top, filtrate chamber shrouding 11, have filter pore 111, filtrate chamber sidewall is communicated in vaccum-pumping equipment by a bleeding point 12; The tubular that funnel upper part 20 is upper lower open mouth or frame shape, its underpart is connected with 10 pressure seals of funnel lower part, and top removably is provided with described drilling accessory; And described double-deck filter paper is between the funnel upper and lower half is divided.
In the preparation method of described oxidation or reduced graphene base net grid material:
The oxidation that described oxidation or reduced graphene base composite solution are 0.1～15mg/ml or reduced graphene solution or compound interpolation is distributed to mutually to described oxidation or the reduced graphene base composite solution made in this oxidation or reduced graphene solution; Compound interpolation is carbon nanomaterial mutually, or is transition metal or transistion metal compound, or is one or more in nano-silicon, or is high molecule nano material.
In the preparation method of described oxidation or reduced graphene base net grid material:
Be graphite oxide thiazolinyl composite solution when what adopt, make described graphene oxide base net grid material; be handled as follows: under 250 ℃ of argon shield atmosphere, annealing is 2 hours; high temperature reduction 5 hours under 400～800 ℃ of argon shields more subsequently, final reduced graphene grid material highly reduced that obtains.
Compared with prior art, it is little that oxidation of the present invention or reduced graphene base composite gridding material and efficient preparation technology have well solved the effective electrochemically active specific surface areas of two-dimentional macrocomposite such as Graphene paper or graphene oxide paper, effective rate of utilization is low, and the key issue such as impermeable, for oxidation or reduced graphene and matrix material scale operation thereof and cleared away obstacle in the practical application in each field.
At first, this oxidation or reduced graphene or its composite gridding material are except the performances such as the excellent mechanics with conventional oxidation or reduced graphene and laminated film thereof, conductive and heat-conductive, compare and also possess superior especially chemical property, can be used as high-performance lithium/Magnesium ion battery, lithium-air battery and electrode of super capacitor.Oxidation or reduced graphene or its compound two-dimensional film are carried out to the porous processing, greatly improved oxidation or reduced graphene macroscopic material effective electrochemical surface area, increased the effective rate of utilization of effective Graphene and matrix material thereof, also can be used as two-dimentional wild phase, in order to substitute carbon fibre material, for the preparation of high-performance oxidation or reduced graphene grid, strengthen the organic or inorganic matrix material.Macroscopical oxidation that high-performance size of the present invention is controlled or reduced graphene or its composite gridding material can meet each field application demand, filled up the blank of grapheme material technology in this field, to promote oxidation or reduced graphene, and the large-scale practical application of carbon nanotube and carbon fiber.
Secondly, the present invention can utilize novel evacuated filtration unit, by oxidation or reduced graphene and composite solution one step filtration preparation thereof; Also can utilize suction filtration device commonly used, first by oxidation or reduced graphene and the preparation of composite solution suction filtration thereof from oxidation or reduced graphene or its laminated film, then by specially designed grinding tool, carry out porous and process to prepare.This grid material shape of a mesh and size can realize by designing corresponding suction filtration device and punching grinding tool.Technique of the present invention is simple, is easy to industrialization.
The accompanying drawing explanation
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail:
The suction filtration device that Fig. 1 a is embodiment 1 and the schematic perspective view of drilling accessory.
The suction filtration device that Fig. 1 b is embodiment 1 and the structure cross-sectional schematic of drilling accessory.
Fig. 2 is the graphene mesh grid material that obtains of embodiment 2 and the first charge-discharge graphic representation of electrode in lithium ion battery of self-supporting soft graphite alkene paper.Wherein, X-coordinate means that the every gram of specific storage/MAH, ordinate zou mean voltage/volt.
The charging and discharging curve of electrode in lithium ion battery of the graphene/carbon nanotube composite gridding that Fig. 3 is embodiment 3 and self-supporting soft graphite alkene/carbon nanotube Composite Paper.Wherein, X-coordinate means that the every gram of specific storage/MAH, ordinate zou mean voltage/volt.
The drilling mould schematic perspective view that Fig. 4 a is embodiment 4.
The cross-sectional schematic of the drilling mould that Fig. 4 b is embodiment 4.
The flexible graphene oxide of the self-supporting that Fig. 5 a is embodiment 4/silicon composite membrane;
Graphene/silicon laminated film after the flexible graphene oxide of the self-supporting that Fig. 5 b is Fig. 5 a/silicon laminated film reduction, 9mm * 9mm, optical photograph;
Fig. 5 c is the self-supporting soft graphite alkene that obtains of embodiment 4/silicon composite gridding, 9mm * 9mm, optical photograph.
The self-supporting soft graphite alkene that Fig. 6 is embodiment 4/silicon composite membrane and the first charge-discharge curve of graphene/silicon composite gridding electrode in lithium ion battery.X-coordinate is the every gram of specific storage/MAH, and ordinate zou is voltage/volt.
The self-supporting soft graphite alkene that Fig. 7 is embodiment 4/silicon composite membrane and high rate performance and the cycle performance of graphene/silicon composite gridding electrode in lithium ion battery, X-coordinate is cycle index, ordinate zou is the every gram of specific storage/MAH.
Embodiment
What in the present embodiment, adopt is all the graphene oxide solution of 1mg/ml, and graphene oxide solution is the graphene oxide solution of the routine that adopts existing conventional preparation method to make, and other his concentration is equally applicable to the present invention, 0.01～0.05g/ml for example, solvent is not limit yet, the solvent that adopts this area Graphene commonly used to share all can, for example: water, ethanol, methyl alcohol, chloroform, dimethyl formamide, N-Methyl pyrrolidone, dilute ammonia solution etc.
Embodiment 1: prepare the graphene oxide grid
The present embodiment 1 prepares the graphite oxide aqueous solution of the 1mg/ml that the graphene oxide grid material adopts this area conventional chemical method for oxidation to prepare, and preparation process is prior art, repeats no more.
After this grid material utilizes vacuum apparatus of the prior art to improve, graphene solution one step is filtered and prepared the graphene mesh grid material.As shown in Figure 1 and Figure 2, the filtration unit after this improvement is to set up a set of drilling accessory become by stainless steel column array group on the basis of traditional filtering device, and coordinates double-deck filter paper of the present invention to use.The size of this device can be adjusted and produce according to the size of required graphene-based grid material has corresponding length and wide vacuum apparatus.
Vacuum apparatus funnel of the prior art is divided into upper and lower two portions, funnel lower part 10 has a filtrate chamber 11 that holds filtrate, for allow solvent can be freely by and enter the filtrate chamber, Gu be porous core or the porous aluminium sheet with filter pore 111 at filtrate chamber upper surface, select the porous aluminium sheet when size is larger,, filtrate chamber sidewall is communicated in vaccum-pumping equipment by a bleeding point 12; The tubular that funnel upper part 20 is upper lower open mouth or frame shape, with funnel lower part 10 adaptations, it is corresponding adaptive one by one with the guide pillar 13 on described funnel lower part 10 that its lower edge is provided with a plurality of guide holes, and vacuum filtration device upper and lower half is divided by clamp structure pressure seal of the prior art, can prevent that filtrate from spilling between lower part from funnel.In the present invention, on the open topped of funnel upper part 20, also be provided with a drilling accessory 30, described drilling accessory is a block plate 31, be connected with a plurality of stainless steel columns at its lower surface and arrange the stainless steel column array 32 formed, this stainless steel column array can be arranged, can be also other array, the steel column spacing of described stainless steel column array: 1mm(steel column spacing 1-5mm all can), steel column shape: circular (be trilateral or other Polygons also can); Steel column cross-sectional diameter or size dimension: 1mm(0.1mm to 1mm all can, for example 0.5mm, 0.3mm); Described steel plate 31 is buckled on the open topped of described funnel upper part 20 hermetically, and described stainless steel column array stretches into wherein.
Also be provided with double-deck filter paper between the upper and lower two portions of the funnel of vacuum apparatus of the present invention, the thick porous carbon film 42 of 100 μ m – 1000 μ m that described double-deck filter paper is Mierocrystalline cellulose qualitative filter paper 41 and surface deposition thereof.The preparation method of porous carbon film is as follows: at first, the commercially available multi-walled carbon nano-tubes of about 50 nanometers of the commercially available diameter of 6 gram (also can replace carbon nanotube with carbon nanofiber) is joined to 1000 ml volumes than in the mixed acid solution for the sulfuric acid of 1:1 and nitric acid, 70 ℃ of lower back flow reaction 10 hours, with after 400 ml deionized water dilutions, after cleaning respectively three times with deionized water and dehydrated alcohol, add 4000 milliliters of dehydrated alcohols, ultrasonic dispersion obtains approximately 4000 milliliters of carbon nano tube suspension after 60 minutes.Then by 240 millimeters of the length of sides, (can be other size, get final product corresponding with the funnel size) square Mierocrystalline cellulose qualitative filter paper is installed to (being that sealed clamping is between the upper and lower two portions of funnel) in the corresponding square Büchner funnel of the present embodiment, carbon nano tube suspension is joined in this funnel subsequently, after vacuum filtration completes, just obtain the double-deck filter paper of corresponding Mierocrystalline cellulose filter paper/porous carbon nanotube films between the upper and lower two portions of funnel, through measuring, the porous-film thickness obtained is 100 μ m.
Then, the graphene oxide solution of ready 1800ml1mg/ml is poured into containing in the funnel of above-mentioned double-deck filter paper, subsequently drilling accessory 30 is buckled and sealed from the funnel top, the end of steel column is conflicted on described double-deck filter paper, start vacuum pump after installing and carry out suction filtration, obtain thickness and be 40 microns, length and width and be respectively the graphene oxide grid of 220 millimeters.After this graphene oxide grid is dried to two hours under 60 ℃, the graphene oxide grid is peeled off from double-deck filter paper, in dehydrated alcohol after 10 seconds, Rapid Cleaning was removed the carbon nanotube of surface adsorption, the graphene oxide grid is dried to the graphene oxide grid that obtains 40 microns of the clean and tidy thickness of surface clean.This graphene oxide grid is the same with Graphene paper possesses excellent mechanical property.
Can also, by the size (being the size of Mierocrystalline cellulose qualitative filter paper and funnel) of adjusting suction filtration device funnel, the graphene oxide solution that adopts different amounts, make thickness: 40 μ m, length: 2cm – 20m, width: 2cm – 20m in the present invention; Can also make length: 2cm – 20m, width: 2cm – 20m graphene oxide paper, thickness has 200 nanometers, 500 nanometers, and 3.9 microns, 4 microns, 4.5 microns, 20 microns, 40 microns, 50 microns, 100 microns, 200 microns are waited sizes, repeat no more.Under modern mechanical and automatic technology auxiliary, operation and the application of large size suction filtration device can realize.
Embodiment 2: the Graphene grid of preparation reduction
The graphene mesh grid material is that to take the made graphene oxide grid according to embodiment 1 be precursor; at first under 250 ℃ of argon shield atmosphere, anneal 2 hours; high temperature reduction 5 hours under 800 ℃ of argon shields more subsequently, final Graphene grid highly reduced that obtains.The Graphene grid of this reduction has excellent mechanical property and electrical and thermal conductivity performance, compare Graphene paper, this graphene mesh grid material has higher conduction and heat conductivility, and the Graphene grid still keeps snappiness preferably, Graphene paper because of a large amount of bubbles in reduction process between graphene layer havoc mechanical property and the snappiness of Graphene paper.Anode material using this graphene mesh grid material as lithium ion battery, can exempt the use of collector, binding agent and conductive agent, the graphene mesh grid material has very high volume energy density simultaneously, due to its excellent conductivity and reduction more uniformly and effectively, this graphene mesh grid material possesses better cycle performance and high rate performance simultaneously.As shown in Figure 2, the charge ratio capacity of this graphene mesh grid material (9mm * 9mm) is respectively up to 334mAh/g for the constant current charge-discharge test result, and capacity is much larger than the 275mAh/g of the self-supporting soft graphite alkene paper (without grid) with its stack pile size.Annotate: " self-supporting " meaning is can be independently as a kind of material, without other matrix as upholder.
What prepare that graphene/carbon nanotube composite gridding material adopts is the mono-layer graphite oxide alkene solution of embodiment 1 described 1mg/ml.And adopt commercial multi-walled carbon nano-tubes, diameter 10-15 nanometer.The 0.34g carbon nanotube is added in 340 milliliters of dehydrated alcohols to ultrasonic dispersion 1 hour, add immediately in 3060 milliliters of graphene oxide solution, continue ultrasonic dispersion in ultrasonic cleaning tank and make stable graphene oxide/carbon nanotube composite solution after 1 hour.
Prepare the double-deck filter paper that vacuum apparatus (funnel size difference) that graphene/carbon nanotube composite gridding material still uses embodiment 1 described structure and same method make graphene oxide and composite solution one step thereof are filtered to preparation.Steel column spacing: 0.8mm on the drilling accessory in the present embodiment, steel column shape: cylinder; Steel column size: 0.5mm.
After collecting filtrate, with the graphene oxide/carbon nanotube composite solution that is about to ready 3400 milliliters, pour in above-mentioned square-shaped hopper, after vacuum filtration completes, under 60 ℃, dry after two hours, graphene oxide/carbon nanotube composite gridding material is peeled off from double-deck filter paper, in dehydrated alcohol after 10 seconds, Rapid Cleaning was removed the carbon nanotube of surface adsorption, graphene oxide/carbon nanotube composite gridding material is dried and obtains about 20 microns of the clean and tidy thickness of surface clean, the length of side is about the graphene oxide/carbon nanotube composite gridding material of 60 centimetres.At first prepared graphene oxide/carbon nanotube composite gridding material is annealed 2 hours under 250 ℃ of argon shield atmosphere; high temperature reduction 5 hours under 800 ℃ of argon shields more subsequently, the final good graphene/carbon nanotube composite gridding material of conductivity highly reduced that obtains.Due to its excellent electrical and thermal conductivity performance, the structure of densification and superpower mechanical property, this flexible multi-functional graphene/carbon nanotube can be used as electromagnetic shielding and electrostatic protective material, is also good electrode materials simultaneously.For example using the electrode materials of this graphene/carbon nanotube composite gridding (9mm * 9mm) as lithium ion battery, the lithium sheet is as to electrode and reference electrode, the Cellgard2400 porous-film is barrier film, and the lithium perchlorate of 1 mole every liter is that electrolytic solution is assembled into the simulation lithium ion battery.The constant current charge-discharge test result as shown in Figure 3, the charge ratio capacity of this graphene/carbon nanotube composite gridding material electrode is respectively up to 243mAh/g, circulate after 20 times, the charge ratio capacity still remains on 240mAh/g, and capacity is much larger than the graphene/carbon nanotube Composite Paper (without grid) of same size.
Embodiment 4 graphene/silicon composite gridding materials
First with suction method, make graphene oxide paper in the present embodiment, and then utilize punching die to carry out the porous processing on graphene oxide paper.
Wherein, prepare graphene oxide paper and can adopt that method of embodiment 1 to prepare double-deck filter paper, then adopt the method suction filtration of prior art, also can adopt filter paper of the prior art and method of the prior art to carry out suction filtration.
As shown in Fig. 4 a, 4b, described punching die 90 consists of the die 91 cooperatively interacted and punch 92, and described die 91 is for having the stainless steel plate of porous array 911, there is the flange of protrusion both sides, make rectangular recess 94 of intermediate formation, porous array 911 just is located in groove, can be arranged, also can arrange for other, pitch of holes: adopting spacing 5mm in 1-5mm(the present embodiment, can be also 1mm, 3mm etc.), hole shape: trilateral or circle, or Polygons; Hole cross-sectional diameter or size dimension: adopting hole dimension 1mm in 0.1mm-1mm(the present embodiment, can be also 0.1mm, the draw point of 0.5mm equidimension); Described punch is provided with can be with the corresponding insertion one by one of above-mentioned porous array 911, and can produce the stainless steel column array 921 of punching effect.
What prepare that graphene/silicon composite gridding material adopts is the mono-layer graphite oxide alkene solution of embodiment 1 described 1mg/ml.And adopt commercial nano silica fume, diameter 10-50 nanometer.The 1.7g nano silica fume is added in 1700 milliliters of graphene oxide solution, and in ultrasonic cleaning tank, ultrasonic dispersion makes the nano combined solution of stable graphene oxide/silicon after 1 hour.
Place anodic alumina films of the prior art or polytetrafluoroethylporous porous membrane in suction filtration device commonly used as filter paper, the graphene oxide of 1700 milliliters that then will prepare/silicon composite solution is poured in suction filtration device commonly used, after vacuum filtration completes, dry after two hours the graphene oxide that obtains about 15 microns of the clean and tidy thickness of surface clean, the length of side and be about 60 centimetres/silicon laminated film under 60 ℃, please refer to shown in the digital optical photograph of section of Fig. 5 a.
Graphene oxide/silicon laminated film is placed in to described die 91 upper surfaces, then uses punching apparatus of the prior art, with aforementioned corresponding punch 92, carry out punching, thereby obtain graphene oxide/silicon composite gridding material.Graphene oxide after subsequently porous being processed/silicon composite gridding was placed in the retort furnace of 250 ℃ pre-treatment after 1 hour; finally under 750 ℃ of lower nitrogen protection atmospheres, thermal treatment just makes 60 centimetres of the length of sides in 2 hours; the graphene/silicon composite gridding material that thickness is 15 microns, please refer to shown in the digital optical photograph of section of Fig. 5 c.
Fig. 5 a, 5b, 5c have showed the digital optical photograph of graphene oxide/silicon laminated film, graphene/silicon laminated film and graphene/silicon composite gridding section (9mm * 9mm), wherein, can see background after Fig. 5 c, show better the light transmission of grid hole.Electrode materials using the graphene/silicon laminated film as lithium ion battery, the lithium sheet is as to electrode and reference electrode, and the Cellgard2400 porous-film is barrier film, and the lithium perchlorate of 1 mole every liter is that electrolytic solution is assembled into the simulation lithium ion battery.As shown in Figure 6, the electric discharge of this graphene/silicon composite gridding and charge ratio capacity are respectively up to 2220 and 1817mAh/g, a little less than 2300 and 1887mAh/g of graphene/silicon laminated film for the constant current charge-discharge test result.But as shown in Figure 7, the same test battery, under same current density, after the charge and discharge cycles under 63 different current densities, the electric discharge of graphene/silicon Compound Fabric grid and charge ratio capacity still remain on 861 and 816mAh/g, far above 480 and 466mAh/g of graphene/silicon laminated film.
In the present embodiment, be that first suction filtration makes graphene oxide paper, punching afterwards, then reduction, can be also that first suction filtration makes graphene oxide paper, afterwards reduction, then punching, but reduction technique better effects if after first punching, because drilling itself just contributes to reduction.
In the present invention, for the preparation of double-deck filter paper, as long as by the one dimension carbon nanotube or/and carbon nanofiber is ultrasonic is scattered in organic solvent; Then be deposited on Mierocrystalline cellulose qualitative filter paper surface by the vacuum filtration method, form the thick porous carbon film of 100 μ m – 1000 μ m, just make the double-deck filter paper of Mierocrystalline cellulose qualitative filter paper/porous nano carbon film, the preparation method of its porous carbon film is a kind of in embodiment 1 not only.Preferably: the carbon nanotube of the about 5-100nm of diameter or carbon nanofiber are joined in the mixing solutions by the sulfuric acid of 1～3:1 volume ratio and nitric acid, and carbon nanotube or the carbon nanofiber concentration in mixed acid solution is 0.01～0.05g/ml; At 50-100 ℃ of lower back flow reaction 2-10 hour, with after the deionized water dilution, with deionized water and dehydrated alcohol, clean respectively three times again, then add corresponding dehydrated alcohol, the ultrasonic suspension that disperses to obtain after 5-60 minute carbon nanotube or carbon nanofiber of carbon nanotube in add the ratio that 0.7-1.3 rises than 1g carbon nanotube or carbon nanofiber; To be installed in funnel with the corresponding Mierocrystalline cellulose qualitative filter paper of funnel size, subsequently carbon nanotube or nanofiber suspension are joined in funnel, just obtain the double-deck filter paper of described Mierocrystalline cellulose filter paper/porous carbon nanotube or carbon nanofiber membrane after vacuum filtration completes.Illustrate as follows:
1. according to above-mentioned approximate method, preparing double-deck filter paper, difference is that the mixing of the sulfuric acid that adopts the commercially available multi-walled carbon nano-tubes of about 10 nanometers of 3 gram diameter to join to collect after 200 milliliters of graphite intercalations and nitric acid is reclaimed in the mixed acid solution of sulfuric acid that solution or volume ratio are 2:1 and nitric acid, 100 ℃ of lower back flow reaction 2 hours, with after 1500 ml deionized water dilutions, after cleaning respectively three times with deionized water and dehydrated alcohol, add 4000 milliliters of dehydrated alcohols, ultrasonic dispersion obtains approximately 4000 milliliters of carbon nano tube suspension after 30 minutes.The Mierocrystalline cellulose qualitative filter paper that is 150 millimeters by diameter is installed to corresponding Büchner funnel, carbon nano tube suspension is joined by funnel subsequently, after completing, suction filtration just obtains the double-deck filter paper of corresponding Mierocrystalline cellulose filter paper/porous carbon nanotube films, through measuring the porous carbon film that 900 μ m are thick.
2. the mixing that the commercially available carbon nano fiber of 5 gram (about 75 nanometers of diameter) is joined to 500 milliliters of sulfuric acid and nitric acid (volume ratio 3:1) is reclaimed in solution, with after 1500 ml deionized water dilutions, 50 ℃ of lower back flow reaction after 5 hours, after cleaning respectively three times with deionized water and dehydrated alcohol, add 5000 milliliters of dehydrated alcohols, ultrasonic dispersion obtains 5000 milliliters of carbon nano tube suspension after 15 minutes.The square Mierocrystalline cellulose qualitative filter paper of 60 centimetres of the length of sides is installed to corresponding square Büchner funnel, subsequently suspension is joined in funnel, after completing, suction filtration just obtains the double-deck filter paper of corresponding Mierocrystalline cellulose filter paper/porous carbon nanotube films, through measuring the porous carbon film that 350 μ m are thick.
The key problem that the present invention will solve is, low cost prepares the graphene mesh grid material, as for the compound phase wherein added, adding kind and addition is to determine according to the performance requriements of application scenario, and compound phase be added to method general in prior art, the content of compound interpolation in oxidation or reduced graphene grid is 0 to 70wt%, when content is 0 without adding phase.Described compound interpolation is nano-silicon or silicon compound mutually; Or, nanometer tin or tin compound, or, nanometer cobalt compound or nanostructured manganese compound or nano nickel compound or Nanoscale Iron compound or nano V compound; Or be one or more in carbon nanomaterial.No matter be simple oxidation or reduced graphene grid, still added compound phase and oxidation or the reduced graphene grid made, can be first with method preparation of the present invention.
The present invention is for making the reduced graphene grid material, the graphene oxide grid material is reduced in adopting above-described embodiment, can also when suction filtration, directly adopt the reduced graphene composite solution to carry out suction filtration, the reduced graphene composite solution is prepared to get final product according to the method for prior art, perhaps adopt following method to make: the graphene oxide solution of 0.1～15mg/ml or graphite oxide thiazolinyl composite solution first are reduced into to reduced graphene solution or graphene-based composite solution, illustrate as follows: the 0.01mol tindichloride is dissolved in 1500ml graphene oxide solution, speed with 300rpm under 90 ℃ at the uniform velocity stirs, add subsequently the 3ml hydrazine hydrate solution, for the aqueous solution, N wherein
2h
4content is 50-60%, uses ammoniacal liquor regulator solution pH value to 10 left and right simultaneously, after reaction 1h.Obtained approximately 1500 milliliters of reduced graphene/SnOx mixing solutionss are carried out to 30 minutes supersound process, make the nano combined solution of stable reduced graphene/SnOx.Also can so prepare by the reduced graphene solution of other compound phase or pure phase.Only as an example, not as restriction.
Claims (10)
1. an oxidation or reduced graphene base net grid material, is characterized in that: be distributed with a plurality of grids on graphene-based macroscopic material; Described graphene-based macroscopic material is of a size of: thickness: 200nm – 200 μ m, length: 2cm – 20m, width: 2cm – 20m; Described size of mesh opening: 0.1mm-1mm; Mesh spacing: 1mm-5mm.
2. a kind of oxidation according to claim 1 or reduced graphene base net grid material, it is characterized in that, in described graphene-based grid material, compound interpolation is carbon nanomaterial mutually, or be transition metal or transistion metal compound, or be one or more in nano-silicon, or be high molecule nano material; The content of compound interpolation in oxidation or reduced graphene base paper is 0 to 70wt%, when content is 0, is the pure phase grid material that oxidation or reduced graphene form.
3. a kind of oxidation according to claim 1 or reduced graphene base net grid material, is characterized in that, described mesh shape is circular, or oval, or trilateral, or Polygons.
4. the preparation method of an oxidation claimed in claim 1 or reduced graphene base net grid material, is characterized in that, is preparation method A or B;
Described method A is:
Adopt vacuum apparatus, filter funnel is arranged on it, the funnel size range is: 2cm * 2cm～20m * 20m, or be 2cm or be～20m for diameter; Be provided with double-deck filter paper in described filter funnel, above described double-deck filter paper, be provided with the drilling accessory; Described drilling accessory is provided with stainless steel column array, the steel column spacing of described stainless steel column array: 1-5mm, and the steel column shape of cross section is trilateral or circle or Polygons; Steel column cross-sectional diameter or size dimension scope: 0.1mm-1mm; The thick porous carbon film of 100 μ m – 1000 μ m that described double-deck filter paper is Mierocrystalline cellulose qualitative filter paper and surface deposition thereof;
Oxidation or reduced graphene base composite solution are poured in the suction filtration device with double-deck filter paper, and put into the drilling accessory, described steel column end is conflicted on described double-deck filter paper, then carry out suction filtration, after completing, suction filtration formed graphene-based grid paper on double-deck filter paper surface, by its oven dry, peel off, obtaining thickness is the graphene mesh ruled paper of 200nm – 200 μ m, its size of mesh opening is that 0.1mm-1mm, mesh spacing are 1mm-5mm;
Described method B is:
Oxidation or reduced graphene base composite solution are poured in the suction filtration device with individual layer filter paper or double-deck filter paper and carried out suction filtration, and the filter funnel size range of suction filtration device is: 2cm * 2cm～20m * 20m, or be 2cm or be～20m for diameter; The thick porous carbon film of 100 μ m – 1000 μ m that described double-deck filter paper is Mierocrystalline cellulose qualitative filter paper and surface deposition thereof; After completing, suction filtration formed oxidation or reduced graphene base paper at individual layer filter paper or double-deck filter paper surface;
Oxidation or the paper conversion of reduced graphene base are gone out to a plurality of through holes, and it is oxidation or the reduced graphene base net grid material that 0.1mm-1mm, mesh spacing are 1mm-5mm that formation has size of mesh opening.
5. the preparation method of oxidation according to claim 4 or reduced graphene base net grid material, is characterized in that,
Described oxidation or the paper conversion of reduced graphene base are gone out to a plurality of through holes, the method adopted is: adopt punching die to carry out the porous processing, described punching die consists of the die cooperatively interacted and punch, described die is the stainless steel plate with porous array, pitch of holes: 1-5mm, the hole shape of cross section is trilateral or circle, or Polygons; The hole cross section length of side or diameter dimension are 0.1mm-1mm; Described punch is provided with the corresponding insertion one by one of above-mentioned porous array, also can produces the stainless steel column array of punching effect; Oxidation or reduced graphene base paper are placed in the die upper surface with porous array, with the corresponding die of the punch with stainless steel post array, carry out punching.
6. the preparation method of oxidation according to claim 4 or reduced graphene base net grid material, is characterized in that,
Described method A or/and the preparation method of the double-deck filter paper in method B be:
The double-deck filter paper that adopts following steps to make: by the one dimension carbon nanotube or/and carbon nanofiber is ultrasonic is scattered in organic solvent; Then be deposited on Mierocrystalline cellulose qualitative filter paper surface by the vacuum filtration method, form the thick porous carbon film of 100 μ m – 1000 μ m, thereby make the double-deck filter paper of Mierocrystalline cellulose qualitative filter paper/porous nano carbon film.
7. the preparation method of oxidation according to claim 6 or reduced graphene base net grid material, is characterized in that,
The preparation concrete steps of described double-deck filter paper are:
The carbon nanotube of the about 5-100nm of diameter or carbon nanofiber are joined in the mixing solutions by the sulfuric acid of 1～3:1 volume ratio and nitric acid, and carbon nanotube or the carbon nanofiber concentration in mixed acid solution is 0.01～0.05g/ml;
At 50-100 ℃ of lower back flow reaction 2-10 hour, with after the deionized water dilution, with deionized water and dehydrated alcohol, clean respectively three times again, then add corresponding dehydrated alcohol, the ultrasonic suspension that disperses to obtain after 5-60 minute carbon nanotube or carbon nanofiber of carbon nanotube in add the ratio that 0.7-1.3 rises than 1g carbon nanotube or carbon nanofiber;
To be installed in funnel with the corresponding Mierocrystalline cellulose qualitative filter paper of funnel size, subsequently carbon nanotube or nanofiber suspension are joined in funnel, just obtain the double-deck filter paper of described Mierocrystalline cellulose filter paper/porous carbon nanotube or carbon nanofiber membrane after vacuum filtration completes.
8. the preparation method of oxidation according to claim 4 or reduced graphene base net grid material, is characterized in that,
In described method A, described funnel is divided into upper and lower two portions, be filled with the filtrate chamber of porous core or porous aluminium sheet in the funnel bottom is divided into, on top, filtrate chamber shrouding 11, have filter pore 111, filtrate chamber sidewall is communicated in vaccum-pumping equipment by a bleeding point 12; The tubular that funnel upper part 20 is upper lower open mouth or frame shape, its underpart is connected with 10 pressure seals of funnel lower part, and top removably is provided with described drilling accessory; And described double-deck filter paper is between the funnel upper and lower half is divided.
9. the preparation method of oxidation according to claim 4 or reduced graphene base net grid material, it is characterized in that the oxidation that described oxidation or reduced graphene base composite solution are 0.1～15mg/ml or reduced graphene solution or compound interpolation is distributed to mutually to described oxidation or the reduced graphene base composite solution made in this oxidation or reduced graphene solution; Compound interpolation is carbon nanomaterial mutually, or is transition metal or transistion metal compound, or is one or more in nano-silicon, or is high molecule nano material.
10. the preparation method of oxidation according to claim 9 or reduced graphene base net grid material; it is characterized in that; be graphite oxide thiazolinyl composite solution when what adopt, make described graphene oxide base net grid material; be handled as follows: under 250 ℃ of argon shield atmosphere, annealing is 2 hours; high temperature reduction 5 hours under 400～800 ℃ of argon shields more subsequently, final reduced graphene grid material highly reduced that obtains.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310412740.1A CN103482620B (en) | 2013-09-11 | 2013-09-11 | Oxidation or reduced graphene base net grid material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310412740.1A CN103482620B (en) | 2013-09-11 | 2013-09-11 | Oxidation or reduced graphene base net grid material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103482620A true CN103482620A (en) | 2014-01-01 |
| CN103482620B CN103482620B (en) | 2016-01-20 |
Family
ID=49823293
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310412740.1A Active CN103482620B (en) | 2013-09-11 | 2013-09-11 | Oxidation or reduced graphene base net grid material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103482620B (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104752703A (en) * | 2015-04-01 | 2015-07-01 | 广东烛光新能源科技有限公司 | Porous graphene-like material and preparation method thereof |
| CN104773722A (en) * | 2015-04-01 | 2015-07-15 | 广东烛光新能源科技有限公司 | Multifunctional device, porous quasi-graphene macroscopic body and preparation method thereof |
| CN104966813A (en) * | 2015-05-08 | 2015-10-07 | 中国科学院青岛生物能源与过程研究所 | Sodium ion battery negative electrode sheet and sodium ion battery |
| CN106328907A (en) * | 2016-11-10 | 2017-01-11 | 无锡市明盛强力风机有限公司 | Preparation method of graphene composite film containing Si nanoparticles |
| WO2019033360A1 (en) * | 2017-08-17 | 2019-02-21 | Sabic Global Technologies, B.V. | Carbon microtube composite film electrode |
| CN109415202A (en) * | 2016-03-21 | 2019-03-01 | E·V·奥尔洛娃 | Meta Materials and its manufacture and application |
| CN109830682A (en) * | 2019-02-01 | 2019-05-31 | 东北大学 | A kind of preparation method and application method of high capacity aluminum cell positive electrode |
| CN110137501A (en) * | 2019-03-29 | 2019-08-16 | 中国科学院青岛生物能源与过程研究所 | A kind of flexibility high-voltage lithium ion batteries and preparation method thereof |
| CN110540195A (en) * | 2019-08-08 | 2019-12-06 | 广东工业大学 | Graphene nanopore array and preparation method and application thereof |
| CN114630455A (en) * | 2021-11-18 | 2022-06-14 | 杭州量春科技有限公司 | Graphene heating film based on net structure and preparation method thereof |
| CN114849484A (en) * | 2022-04-24 | 2022-08-05 | 北京机械设备研究所 | Carbon paper preparation facilities |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3597594A1 (en) * | 2018-07-17 | 2020-01-22 | Graphenano Medical Care, S.L. | Graphene product and therapeutic uses thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102351165A (en) * | 2011-06-23 | 2012-02-15 | 中国科学院苏州纳米技术与纳米仿生研究所 | Large-area freestanding carbon nanotube paper and preparation method thereof |
| CN102436934A (en) * | 2011-09-15 | 2012-05-02 | 中国科学院苏州纳米技术与纳米仿生研究所 | Composite nanometer carbon paper and preparation method thereof |
| CN102926272A (en) * | 2012-10-09 | 2013-02-13 | 重庆大学 | Process for preparing biomedical graphene oxide paper |
| CN103022483A (en) * | 2012-12-07 | 2013-04-03 | 南京工业大学 | Preparation method for positive electrode material of power lithium ion battery |
-
2013
- 2013-09-11 CN CN201310412740.1A patent/CN103482620B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102351165A (en) * | 2011-06-23 | 2012-02-15 | 中国科学院苏州纳米技术与纳米仿生研究所 | Large-area freestanding carbon nanotube paper and preparation method thereof |
| CN102436934A (en) * | 2011-09-15 | 2012-05-02 | 中国科学院苏州纳米技术与纳米仿生研究所 | Composite nanometer carbon paper and preparation method thereof |
| CN102926272A (en) * | 2012-10-09 | 2013-02-13 | 重庆大学 | Process for preparing biomedical graphene oxide paper |
| CN103022483A (en) * | 2012-12-07 | 2013-04-03 | 南京工业大学 | Preparation method for positive electrode material of power lithium ion battery |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104752703A (en) * | 2015-04-01 | 2015-07-01 | 广东烛光新能源科技有限公司 | Porous graphene-like material and preparation method thereof |
| CN104773722A (en) * | 2015-04-01 | 2015-07-15 | 广东烛光新能源科技有限公司 | Multifunctional device, porous quasi-graphene macroscopic body and preparation method thereof |
| CN104966813A (en) * | 2015-05-08 | 2015-10-07 | 中国科学院青岛生物能源与过程研究所 | Sodium ion battery negative electrode sheet and sodium ion battery |
| CN109415202A (en) * | 2016-03-21 | 2019-03-01 | E·V·奥尔洛娃 | Meta Materials and its manufacture and application |
| CN106328907A (en) * | 2016-11-10 | 2017-01-11 | 无锡市明盛强力风机有限公司 | Preparation method of graphene composite film containing Si nanoparticles |
| WO2019033360A1 (en) * | 2017-08-17 | 2019-02-21 | Sabic Global Technologies, B.V. | Carbon microtube composite film electrode |
| CN109830682A (en) * | 2019-02-01 | 2019-05-31 | 东北大学 | A kind of preparation method and application method of high capacity aluminum cell positive electrode |
| CN109830682B (en) * | 2019-02-01 | 2021-04-27 | 东北大学 | Preparation method and application method of positive electrode material for high-capacity aluminum battery |
| CN110137501A (en) * | 2019-03-29 | 2019-08-16 | 中国科学院青岛生物能源与过程研究所 | A kind of flexibility high-voltage lithium ion batteries and preparation method thereof |
| CN110540195A (en) * | 2019-08-08 | 2019-12-06 | 广东工业大学 | Graphene nanopore array and preparation method and application thereof |
| CN114630455A (en) * | 2021-11-18 | 2022-06-14 | 杭州量春科技有限公司 | Graphene heating film based on net structure and preparation method thereof |
| CN114630455B (en) * | 2021-11-18 | 2023-05-16 | 杭州量春科技有限公司 | Graphene heating film based on reticular structure and preparation method thereof |
| CN114849484A (en) * | 2022-04-24 | 2022-08-05 | 北京机械设备研究所 | Carbon paper preparation facilities |
| CN114849484B (en) * | 2022-04-24 | 2023-09-05 | 北京机械设备研究所 | Carbon paper preparation facilities |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103482620B (en) | 2016-01-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103482620B (en) | Oxidation or reduced graphene base net grid material and preparation method thereof | |
| Wang et al. | Zn-ion hybrid supercapacitors: achievements, challenges and future perspectives | |
| Cheng et al. | Lithium Host: Advanced architecture components for lithium metal anode | |
| Zhang et al. | Hierarchical carbon-decorated Fe3O4 on hollow CuO nanotube array: Fabrication and used as negative material for ultrahigh-energy density hybrid supercapacitor | |
| Wang et al. | Rational construction of CoO/CoF2 coating on burnt-pot inspired 2D CNs as the battery-like electrode for supercapacitors | |
| Cao et al. | Hierarchical three-dimensional flower-like Co 3 O 4 architectures with a mesocrystal structure as high capacity anode materials for long-lived lithium-ion batteries | |
| Cao et al. | Synthesis of hierarchical porous NiO nanotube arrays for supercapacitor application | |
| Jia et al. | Hierarchically porous CuO nano-labyrinths as binder-free anodes for long-life and high-rate lithium ion batteries | |
| Feng et al. | Recent progress in nickel based materials for high performance pseudocapacitor electrodes | |
| Tian et al. | Ni (OH) 2 nanosheet@ Fe2O3 nanowire hybrid composite arrays for high-performance supercapacitor electrodes | |
| Zheng et al. | Flexible NiO micro-rods/nanoporous Ni/metallic glass electrode with sandwich structure for high performance supercapacitors | |
| Chen et al. | Ternary oxide nanostructured materials for supercapacitors: a review | |
| Zhi et al. | Nanostructured carbon–metal oxide composite electrodes for supercapacitors: a review | |
| Li et al. | Ni (OH) 2 nanosheets grown on porous hybrid g-C3N4/RGO network as high performance supercapacitor electrode | |
| CN108315834B (en) | Preparation method of array type magnetic reduced graphene oxide-carbon nanofiber | |
| Xu et al. | Straightforward synthesis of hierarchical Co3O4@ CoWO4/rGO core–shell arrays on Ni as hybrid electrodes for asymmetric supercapacitors | |
| Wang et al. | Status and opportunities of zinc ion hybrid capacitors: focus on carbon materials, current collectors, and separators | |
| Han et al. | Structural Reorganization–Based Nanomaterials as Anodes for Lithium‐Ion Batteries: Design, Preparation, and Performance | |
| CN102496719A (en) | Silicon/graphene composite material, and preparation method and application of the same | |
| CN102280260B (en) | Three-dimensional porous compound film of super-capacitor and preparation method thereof | |
| CN104134788A (en) | Three dimensional gradient metal hydroxide/oxide electrode material and manufacture method and application thereof | |
| Ghasemi et al. | Cu2O-Cu (OH) 2-graphene nanohybrid as new capacitive material for high performance supercapacitor | |
| Zhu et al. | Achieving a Zn-ion battery-capacitor hybrid energy storage device with a cycle life of more than 12,000 cycles | |
| Wen et al. | Ultrafine Ni (OH) 2 nanoneedles on N-doped 3D rivet graphene film for high-performance asymmetric supercapacitor | |
| Li et al. | Low-cost and robust production of multi-doped 2D carbon nanosheets for high-performance lithium-ion capacitors |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |