CN103482620B - Oxidation or reduced graphene base net grid material and preparation method thereof - Google Patents
Oxidation or reduced graphene base net grid material and preparation method thereof Download PDFInfo
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Abstract
Oxidation or reduced graphene base net grid material, is characterized in that: in oxidation or reduced graphene base macroscopic material, be distributed with multiple grid; Described oxidation or reduced graphene base macroscopic material are of a size of: thickness: 200nm – 200 μm, length: 2cm – 20m, width: 2cm – 20m; Described size of mesh opening: 0.1mm-1mm; Mesh spacing: 1mm-5mm.This material preparation method oxidation or reduced graphene base composite solution is poured in the Suction filtration device with double-layer filter paper to carry out suction filtration, the formation of grid can be in traditional Suction filtration device, increase drilling accessory one step suction filtration complete, also can be that first suction filtration forms oxidation or reduced graphene paper, then use special drilling mould molding grid.It is little that the present invention well solves the effective electrochemically active specific surface area of the 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 Graphene and matrix material scale operation thereof and cleared away obstacle in the practical application in each field.
Description
Technical field
The present invention relates to new carbon and preparation method thereof, particularly the graphene-based grid material of one and industrialized process for preparing thereof.
Background technology
Graphene (Graphene) a kind ofly forms with sp2 hybridized orbital the flat film that hexangle type is honeycomb lattice by carbon atom, only has the two-dimensional material of a carbon atom thickness.Graphene is not only the nano material that the thinnest intensity is 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 is more than 15000cm
2/ Vs, electrical and thermal conductivity is all higher than carbon nanotube and diamond, and resistivity only about 10
-6Ω cm, than copper or silver lower, be the material that at present resistivity is minimum in the world.
Oxidation or reduced graphene paper [Graphene (oxide) paper] are by individual layer or the two dimension macroscopic view graphene new material that multilayer is oxidized or reduced graphene is successively piled up self-assembly and prepared.Oxidation or the Thickness Ratio paper of reduced graphene paper thin, the light intensity of quality is high, and has outstanding snappiness, and environmental protection and renewable.In view of the characteristic that graphene paper light weight intensity is large, this material can be used for replacing traditional steel and aluminium, is expected to first obtain application in automobile making and aviation industry.Compare traditional aircraft and automobile, the automobile made with this novel material and the light intensity of aircraft weight high, thus directly energy-saving and emission-reduction can be realized, and intensity is higher, safer, also greatly reduces Future New Energy Source design that is electronic or hybrid vehicle 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 be all the time one of emphasis of field of graphene research in the application of energy storage and conversion art with the Composite Paper of excessive metallic compound.The graphene paper of the flash of light process through laser or camera flashlamp is made the anode material of lithium ion battery by the researchist of such as Rensselaer Polytech Inst of the U.S., because the pore space structure of its uniqueness provides high-speed channel to electrolyte wets and lithium ion mobility, thus its chemical property compares fast 10 times of the graphite anode charge or discharge speed generally used, and future can drive power truck.In addition, Graphene and Sn or SnO
x, the composite graphite alkene paper of the composition such as Si, Ge has higher lithium ion storage capacity, and compared to 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.Graphene Composite Paper is also by so extensive that should to be used in electric chemical super capacitor field.
Because oxidation or reduced graphene paper have the layered nano-structure of special high-density and high strength and derivative thus special mechanics, physical and chemical performance, thus oxidation or reduced graphene paper have broad application prospects, but ultralow effective electrochemically active specific surface area of causing of its high-density layered nano-structure and impenetrability be equally also restriction its to store and as one of two-dimentional wild phase crucial barrier preparing the large-scale practical application in the fields such as high performance composite at rechargeable battery and ultracapacitor equal energy source.Existing patent documentation is also mainly for oxidation or the preparation of reduced graphene and film thereof and the novel process of modification, prepare various functional matrix material using Graphene as conductive additive, be difficult to solve in 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 one, and effectively electrochemically active specific surface area is large, utilization ratio is high and permeable oxidation or reduced graphene base net grid material, also provides its industrialized Low-cost production method 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, graphene-based macroscopic material is distributed with multiple grid; Described graphene-based macroscopic material is of a size of: thickness: 200nm – 200 μm, length: 2cm – 20m, width: 2cm – 20m; Described size of mesh opening: 0.1mm-1mm; Mesh spacing: 1mm-5mm.
In described graphene-based grid material, it is carbon nanomaterial mutually that compound is added, 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%, is the pure phase grid material of oxidation or reduced graphene composition when content is 0.
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, it has filter funnel, and funnel size range is: 2cm × 2cm ~ 20m × 20m, or for diameter be 2cm or be ~ 20m; Be provided with double-layer filter paper in described filter funnel, above described double-layer filter paper, be provided with 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 steel column shape of cross section is trilateral or circular or Polygons; Steel column cross-sectional diameter or size dimension scope: 0.1mm-1mm; Described double-layer filter paper is the porous carbon film that the 100 μ m – 1000 μm of Mierocrystalline cellulose qualitative filter paper and surface deposition thereof is thick;
Oxidation or reduced graphene base composite solution being poured into has in the Suction filtration device of double-layer filter paper, and put into drilling accessory, described steel column end is conflicted in described double-layer filter paper, then suction filtration is carried out, graphene-based grid paper is defined on double-layer filter paper surface after suction filtration completes, dried, peel off, namely obtain the graphene mesh ruled paper that thickness is 200nm – 200 μm, its size of mesh opening is 0.1mm-1mm, mesh spacing is 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-layer filter paper and carry out suction filtration, the filter funnel size range of Suction filtration device is: 2cm × 2cm ~ 20m × 20m, or is 2cm for diameter or is ~ 20m; Described double-layer filter paper is the porous carbon film that the 100 μ m – 1000 μm of Mierocrystalline cellulose qualitative filter paper and surface deposition thereof is thick; Oxidation or reduced graphene base paper is defined at individual layer filter paper or double-layer filter paper surface after suction filtration completes;
Oxidation or the paper conversion of reduced graphene base are gone out multiple through hole, is formed and there is the oxidation or reduced graphene base net grid material that size of mesh opening is 0.1mm-1mm, mesh spacing is 1mm-5mm.
In the preparation method of described oxidation or reduced graphene base net grid material:
Described to oxidation or the paper conversion of reduced graphene base go out multiple through hole, the method adopted is: adopt punching die to carry out porous process, described punching die is made up of the die cooperatively interacted and punch, described die is the stainless steel plate with porous array, pitch of holes: 1-5mm, 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 and inserts with above-mentioned porous array one_to_one corresponding and can produce the stainless steel column array of punching effect; Oxidation or reduced graphene base paper are placed in the die upper surface with porous array, carry out punching with the corresponding die of the punch with stainless steel post array.
In the preparation method of described oxidation or reduced graphene base net grid material:
Described method A is or/and the preparation method of double-layer filter paper in method B is:
Adopt the double-layer filter paper that following steps are obtained: by one dimension carbon nanotube or/and carbon nanofiber ultrasonic disperse is in organic solvent; Then be deposited on Mierocrystalline cellulose qualitative filter paper surface by vacuum filtration method, form the porous carbon film that 100 μ m – 1000 μm is thick, thus obtained Mierocrystalline cellulose qualitative filter paper/porous nano carbon film double-layer filter paper.
In the preparation method of described oxidation or reduced graphene base net grid material:
The preparation concrete steps of described double-layer filter paper are:
Join the carbon nanotube of about for diameter 5-100nm or carbon nanofiber by the sulfuric acid of 1 ~ 3:1 volume ratio and the mixing solutions of nitric acid, carbon nanotube or the carbon nanofiber concentration in mixed acid solution is 0.01 ~ 0.05g/ml;
Back flow reaction 2-10 hour at 50-100 DEG C, after deionized water dilution, three times are cleaned respectively again with deionized water and dehydrated alcohol, then add corresponding dehydrated alcohol in the ratio adding 0.7-1.3 liter than 1g carbon nanotube or carbon nanofiber, carbon nanotube ultrasonic disperse obtains the suspension of carbon nanotube or carbon nanofiber after 5-60 minute;
The Mierocrystalline cellulose qualitative filter paper corresponding to funnel size is installed in funnel, subsequently carbon nanotube or nanofiber suspension are joined in funnel, after vacuum filtration completes, just obtain the double-layer filter paper of described cellulosic filter paper/porous carbon nanotube or carbon nanofiber membrane.
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 its lower portion is divided into, top, filtrate chamber shrouding 11 has filter pore 111, and filtrate chamber sidewall is then communicated in vaccum-pumping equipment by a bleeding point 12; Funnel upper part 20 is tubular or the frame-shaped of upper lower open mouth, and its underpart is connected with funnel lower part 10 pressure seal, and top is then removably provided with described drilling accessory; And described double-layer filter paper is between funnel upper and lower half is divided.
In the preparation method of described oxidation or reduced graphene base net grid material:
Described oxidation or reduced graphene base composite solution are oxidation or the reduced graphene solution of 0.1 ~ 15mg/ml or compound interpolation are distributed to the described oxidation or reduced graphene base composite solution that obtain in this oxidation or reduced graphene solution mutually; It is carbon nanomaterial mutually that compound is added, 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:
When employing is graphite oxide thiazolinyl composite solution, obtained described graphene oxide base net grid material; then be handled as follows: anneal 2 hours under 250 DEG C of argon atmosphere; high temperature reduction 5 hours under 400 ~ 800 DEG C of argon shields more subsequently, finally obtains reduced graphene grid material highly reduced.
Compared with prior art, it is little that oxidation of the present invention or reduced graphene base composite gridding material and efficient preparation technology well solve the effective electrochemically active specific surface area of the 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.
First, this oxidation or reduced graphene or its composite gridding material are except the performance such as excellent mechanical, conductive and heat-conductive with conventional oxidation or reduced graphene and laminated film thereof, compare and also possess chemical property superior especially, can be used as high-performance lithium/Magnesium ion battery, lithium-air battery and electrode of super capacitor.Porous process is carried out to oxidation or reduced graphene or its compound two-dimensional film, substantially increase effective electrochemical surface area of oxidation or reduced graphene macroscopic material, increase the effective rate of utilization of effective Graphene and matrix material thereof, also can be used as two-dimentional wild phase, in order to alternative carbon fibre material, strengthen organic or inorganic matrix material for the preparation of high-performance oxidation or reduced graphene grid.The macroscopic view 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, fill up the blank of grapheme material technology in this field, by promotion 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, will be oxidized or prepared by reduced graphene and the filtration of composite solution one step thereof; Also can utilize conventional Suction filtration device, first will be oxidized or reduced graphene and the preparation of composite solution suction filtration thereof from oxidation or reduced graphene or its laminated film, then carry out porous process to prepare by specially designed grinding tool.This grid material shape of a mesh and size are by designing corresponding Suction filtration device and punching grinding tool realizes.Present invention process is simple, is easy to industrialization.
Accompanying drawing explanation
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail:
Fig. 1 a is the Suction filtration device of embodiment 1 and the schematic perspective view of drilling accessory.
Fig. 1 b is the Suction filtration device of embodiment 1 and the structure cross-sectional schematic of drilling accessory.
Fig. 2 is the first charge-discharge graphic representation of electrode in lithium ion battery of the graphene mesh grid material that obtains of embodiment 2 and self-supporting Flexible graphene paper.Wherein, X-coordinate represents specific storage/MAH every gram, ordinate zou represents voltage/volt.
Fig. 3 is the graphene/carbon nano-tube composite gridding of embodiment 3 and the charging and discharging curve of electrode in lithium ion battery of self-supporting Flexible graphene/carbon nanotube Composite Paper.Wherein, X-coordinate represents specific storage/MAH every gram, ordinate zou represents voltage/volt.
Fig. 4 a is the drilling mould schematic perspective view of embodiment 4.
Fig. 4 b is the cross-sectional schematic of the drilling mould of embodiment 4.
Fig. 5 a is the flexible graphene oxide/silicon composite membrane of self-supporting of embodiment 4;
Fig. 5 b is the graphene/silicon laminated film after the flexible graphene oxide of the self-supporting/silicon laminated film reduction of Fig. 5 a, 9mm × 9mm, optical photograph;
Fig. 5 c is self-supporting Flexible graphene/silicon composite gridding that embodiment 4 obtains, 9mm × 9mm, optical photograph.
Fig. 6 is self-supporting Flexible graphene/silicon composite membrane and the first charge-discharge curve of graphene/silicon composite gridding electrode in lithium ion battery of embodiment 4.X-coordinate is specific storage/MAH every gram, and ordinate zou is voltage/volt.
Fig. 7 is high rate performance in lithium ion battery of the self-supporting Flexible graphene/silicon composite membrane of embodiment 4 and graphene/silicon composite gridding electrode and cycle performance, and X-coordinate is cycle index, and ordinate zou is specific storage/MAH every gram.
Embodiment
What adopt in the present embodiment is all the graphene oxide solution of 1mg/ml, and graphene oxide solution is the graphene oxide solution of the routine adopting existing customary preparation methods to obtain, and other his concentration is equally applicable to the present invention, such as 0.01 ~ 0.05g/ml, solvent is not also limit, the solvent that the Graphene adopting this area to commonly use share, such as: water, ethanol, methyl alcohol, chloroform, dimethyl formamide, N-Methyl pyrrolidone, dilute ammonia solution etc.
Embodiment 1: prepare graphene oxide grid
The present embodiment 1 prepares the graphene oxide water solution of the 1mg/ml that 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 prepares graphene mesh grid material.As shown in Figure 1 and Figure 2, the filtration unit after this improvement is on the basis of traditional filtering device, set up a set of drilling accessory become by stainless steel column array group, and coordinates double-layer filter paper of the present invention to use.The size of this device can adjust according to the size of required graphene-based grid material and produce 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 the filtrate chamber 11 that is held filtrate, freely can pass through to allow solvent and enter filtrate chamber, Gu be porous core or the porous aluminium sheet with filter pore 111 at filtrate chamber upper surface, porous aluminium sheet is selected when size is larger,, filtrate chamber sidewall is then communicated in vaccum-pumping equipment by a bleeding point 12; Funnel upper part 20 is tubular or the frame-shaped of upper lower open mouth, adaptive with funnel lower part 10, guide pillar 13 one_to_one corresponding that its lower edge is provided with in multiple guide hole and described funnel lower part 10 is adaptive, and Vacuum filtration device upper and lower half is divided by clamp structure pressure seal of the prior art, can prevent filtrate from spilling between funnel inferior and superior halves is divided.In the present invention, in 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 the stainless steel column array 32 of multiple stainless steel column arrangement at its lower surface, this stainless steel column array can be arranged, also can be other array, the steel column spacing of described stainless steel column array: 1mm(steel column spacing is at 1-5mm), steel column shape: circular (for trilateral or other Polygons also can); Steel column cross-sectional diameter or size dimension: 1mm(at 0.1mm to 1mm, such as 0.5mm, 0.3mm); Described steel plate 31 is buckled in the open topped of described funnel upper part 20 hermetically, and described stainless steel column array stretches into wherein.
Between the upper and lower two portions of the funnel of vacuum apparatus of the present invention, be also provided with double-layer filter paper, described double-layer filter paper is the porous carbon film 42 that the 100 μ m – 1000 μm of Mierocrystalline cellulose qualitative filter paper 41 and surface deposition thereof is thick.The preparation method of porous carbon film is as follows: first, the commercially available multi-walled carbon nano-tubes (also can replace carbon nanotube with carbon nanofiber) of 6 grams of about 50 nanometers of commercially available diameter is joined 1000 ml volumes ratios in the sulfuric acid of 1:1 and the mixed acid solution of nitric acid, back flow reaction 10 hours at 70 DEG C, after 400 ml deionized water dilutions, after cleaning three times respectively with deionized water and dehydrated alcohol, add 4000 milliliters of dehydrated alcohols, ultrasonic disperse obtains about 4000 milliliters of carbon nano tube suspension after 60 minutes.Then (can be other size by the length of side 240 millimeters, corresponding to funnel size) square Mierocrystalline cellulose qualitative filter paper be installed to (namely sealed clamping is between the upper and lower two portions of funnel) in the corresponding square Büchner funnel of the present embodiment, subsequently carbon nano tube suspension is joined in this funnel, after vacuum filtration completes, just between the upper and lower two portions of funnel, obtain the double-layer filter paper of corresponding cellulosic filter paper/porous carbon nanotube films, through measuring, the porous-film thickness obtained is 100 μm.
Then, the graphene oxide solution of ready 1800ml1mg/ml is poured in the funnel containing above-mentioned double-layer filter paper, subsequently drilling accessory 30 buckled from funnel and seal, the end of steel column is conflicted in described double-layer filter paper, start vacuum pump after installing and carry out suction filtration, obtain the graphene oxide grid that thickness is 40 microns, length and width is respectively 220 millimeters.After this graphene oxide grid is dried two hours at 60 DEG C, graphene oxide grid is peeled off from double-layer filter paper, in dehydrated alcohol after the carbon nanotube of Rapid Cleaning removing in 10 seconds surface adsorption, graphene oxide grid is dried the graphene oxide grid namely obtaining the clean and tidy thickness of surface clean 40 microns.This graphene oxide grid is the same with graphene paper possesses excellent mechanical property.
Can also by the size (i.e. the size of Mierocrystalline cellulose qualitative filter paper and funnel) of adjustment Suction filtration device funnel, the graphene oxide solution adopting different amount in the present invention, obtained thickness: 40 μm, length: 2cm – 20m, width: 2cm – 20m; Can also obtain length: 2cm – 20m, width: 2cm – 20m graphene oxide paper, thickness then has 200 nanometers, 500 nanometers, 3.9 microns, 4 microns, 4.5 microns, 20 microns, 40 microns, 50 microns, 100 microns, and 200 microns are waited sizes, repeat no more.Modern mechanical and automatic technology auxiliary under, the operation of large size Suction filtration device and application can realize.
Embodiment 2: the Graphene grid of preparation reduction
Graphene mesh grid material be with according to the made graphene oxide grid of embodiment 1 for precursor; first anneal 2 hours under 250 DEG C of argon atmosphere; high temperature reduction 5 hours under 800 DEG C of argon shields more subsequently, finally obtains Graphene grid highly reduced.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 Graphene grid still keeps good snappiness, graphene paper is then because of mechanical property and the snappiness of a large amount of in reduction process bubble havoc graphene paper between graphene layer.Using the anode material of this graphene mesh grid material as lithium ion battery, the use of collector, binding agent and conductive agent can be exempted, graphene mesh grid material has very high volume energy density simultaneously, simultaneously due to its excellence conductivity and reduce more uniformly and effectively, this graphene mesh grid material possesses better cycle performance and high rate performance.As shown in Figure 2, the charge specific capacity of this graphene mesh grid material (9mm × 9mm) is respectively up to 334mAh/g, and capacity is much larger than the 275mAh/g of the self-supporting Flexible graphene paper (mesh free) with its stack pile size for constant current charge-discharge test result.Note: " self-supporting " is meant to can independently as a kind of material, without the need to other matrix as upholder.
Embodiment 3 prepares graphene/carbon nano-tube composite gridding material
The single-layer graphene oxide solution of what preparation graphene/carbon nano-tube composite gridding material adopted is 1mg/ml described in embodiment 1.And adopt commercial multi-walled carbon nano-tubes, diameter 10-15 nanometer.0.34g carbon nanotube to be added in 340 milliliters of dehydrated alcohols ultrasonic disperse 1 hour, add immediately in 3060 milliliters of graphene oxide solution, continue graphene oxide/carbon nanotube composite solution that ultrasonic disperse is obtained stable after 1 hour in ultrasonic cleaning tank.
Graphene oxide and composite solution one step thereof are filtered preparation by the double-layer filter paper that preparation graphene/carbon nano-tube composite gridding material still uses the vacuum apparatus of structure described in embodiment 1 (funnel size is different) and same method to obtain.Steel column spacing: 0.8mm on drilling accessory in the present embodiment, steel column shape: cylinder; Steel column size: 0.5mm.
After collecting filtrate, pour in above-mentioned square-shaped hopper with the graphene oxide/carbon nanotube composite solution by ready 3400 milliliters, after vacuum filtration completes, dry at 60 DEG C after two hours, graphene oxide/carbon nanotube composite gridding material is peeled off from double-layer filter paper, in dehydrated alcohol after the carbon nanotube of Rapid Cleaning removing in 10 seconds surface adsorption, graphene oxide/carbon nanotube composite gridding material is dried and namely 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.First obtained graphene oxide/carbon nanotube composite gridding material is annealed 2 hours under 250 DEG C of argon atmosphere; high temperature reduction 5 hours under 800 DEG C of argon shields more subsequently, finally obtains the good graphene/carbon nano-tube composite gridding material of the conductivity that highly reduces.Due to the electrical and thermal conductivity performance of its excellence, fine and close structure and superpower mechanical property, this flexible multi-functional graphene/carbon nano-tube can be used as electromagnetic shielding and electrostatic protective material, is also excellent electrode materials simultaneously.Such as using this graphene/carbon nano-tube composite gridding (9mm × 9mm) as the electrode materials of lithium ion battery, lithium sheet is as to electrode and reference electrode, Cellgard2400 porous-film is barrier film, and the lithium perchlorate of 1 mole often liter is that electrolytic solution is assembled into simulation lithium ion battery.Constant current charge-discharge test result as shown in Figure 3, the charge specific capacity of this graphene/carbon nano-tube composite gridding material electrodes is respectively up to 243mAh/g, circulate after 20 times, charge specific capacity still remains on 240mAh/g, and capacity is much larger than the graphene/carbon nano-tube Composite Paper (mesh free) of same size.
Embodiment 4 graphene/silicon composite gridding material
First obtain graphene oxide paper with suction method in the present embodiment, and then graphene oxide paper utilized punching die to carry out porous process.
Wherein, preparation graphene oxide paper can adopt that method of embodiment 1 to prepare double-layer filter paper, then adopts the method suction filtration of prior art, filter paper of the prior art and method of the prior art also can be adopted to carry out suction filtration.
As shown in Fig. 4 a, 4b, described punching die 90 is made up 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 intermediate formation rectangular recess 94, porous array 911 is just established in a groove, can be arranged, also can be other arrangement, pitch of holes: adopt spacing 5mm in 1-5mm(the present embodiment also can be 1mm, 3mm etc.), hole shape: trilateral or circle, or Polygons; Hole cross-sectional diameter or size dimension: adopt hole dimension 1mm in 0.1mm-1mm(the present embodiment also can be the draw points of 0.1mm, 0.5mm equidimension); Described punch is provided with and can inserts with above-mentioned porous array 911 one_to_one corresponding and can produce the stainless steel column array 921 of punching effect.
What prepare that graphene/silicon composite gridding material adopts is the single-layer graphene oxide solution of 1mg/ml described in embodiment 1.And adopt commercial nano silica fume, diameter 10-50 nanometer.1.7g nano silica fume is added in 1700 milliliters of graphene oxide solution, graphene oxide/silicon nanocomposite solution that ultrasonic disperse is obtained stable after 1 hour in ultrasonic cleaning tank.
Anodic alumina films of the prior art or polytetrafluoroethylporous porous membrane is placed as filter paper in conventional Suction filtration device, then the graphene oxide of prepare 1700 milliliters/silicon composite solution is poured in conventional Suction filtration device, after vacuum filtration completes, dry after two hours at 60 DEG C namely obtain about 15 microns of the clean and tidy thickness of surface clean, the length of side is about the graphene oxide/silicon laminated film of 60 centimetres, shown in the digital optical photograph that please refer to the section of Fig. 5 a.
Graphene oxide/silicon laminated film is placed in described die 91 upper surface, then uses punching apparatus of the prior art, carry out punching with aforementioned corresponding punch 92, thus obtain graphene oxide/silicon composite gridding material.Subsequently the graphene oxide after porous process/silicon composite gridding to be placed in the retort furnace of 250 DEG C pre-treatment after 1 hour; finally at 750 DEG C, under nitrogen protection atmosphere, thermal treatment just obtains the length of side 60 centimetres in 2 hours; the graphene/silicon composite gridding material of thickness 15 microns, shown in the digital optical photograph that please refer to the section of Fig. 5 c.
Fig. 5 a, 5b, 5c illustrate the digital optical photograph of graphene oxide/silicon laminated film, graphene/silicon laminated film and graphene/silicon composite gridding section (9mm × 9mm), wherein, can background be seen after Fig. 5 c, illustrate the light transmission of grid hole better.Using the electrode materials of graphene/silicon laminated film as lithium ion battery, lithium sheet is as to electrode and reference electrode, and Cellgard2400 porous-film is barrier film, and the lithium perchlorate of 1 mole often liter is that electrolytic solution is assembled into simulation lithium ion battery.Constant current charge-discharge test result as shown in Figure 6, the electric discharge of this graphene/silicon composite gridding and charge specific capacity respectively up to 2220 and 1817mAh/g, a little less than 2300 and 1887mAh/g of graphene/silicon laminated film.But as shown in Figure 7, 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 specific 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 obtains graphene oxide paper, punching afterwards, then reduce, also can be that first suction filtration obtains graphene oxide paper, reduce afterwards, then punching, but reduction technique better effects if after first punching, because drilling inherently contributes to reduction.
In the present invention, for the preparation of double-layer filter paper, as long as by one dimension carbon nanotube or/and carbon nanofiber ultrasonic disperse is in organic solvent; Then be deposited on Mierocrystalline cellulose qualitative filter paper surface by vacuum filtration method, form the porous carbon film that 100 μ m – 1000 μm is thick, just obtained Mierocrystalline cellulose qualitative filter paper/porous nano carbon film double-layer filter paper, the preparation method of its porous carbon film one not only in embodiment 1.Preferably: join the carbon nanotube of about for diameter 5-100nm or carbon nanofiber by the sulfuric acid of 1 ~ 3:1 volume ratio and the mixing solutions of nitric acid, carbon nanotube or the carbon nanofiber concentration in mixed acid solution is 0.01 ~ 0.05g/ml; Back flow reaction 2-10 hour at 50-100 DEG C, after deionized water dilution, three times are cleaned respectively again with deionized water and dehydrated alcohol, then add corresponding dehydrated alcohol in the ratio adding 0.7-1.3 liter than 1g carbon nanotube or carbon nanofiber, carbon nanotube ultrasonic disperse obtains the suspension of carbon nanotube or carbon nanofiber after 5-60 minute; The Mierocrystalline cellulose qualitative filter paper corresponding to funnel size is installed in funnel, subsequently carbon nanotube or nanofiber suspension are joined in funnel, after vacuum filtration completes, just obtain the double-layer filter paper of described cellulosic filter paper/porous carbon nanotube or carbon nanofiber membrane.Illustrate as follows:
1. prepare double-layer filter paper according to above-mentioned approximate method, difference is that to reclaim solution or volume ratio be in the sulfuric acid of 2:1 and the mixed acid solution of nitric acid for the mixing of sulfuric acid and the nitric acid collected after the commercially available multi-walled carbon nano-tubes of about 10 nanometers of employing 3 grams of diameters joins 200 milliliters of graphite intercalation, back flow reaction 2 hours at 100 DEG C, after 1500 ml deionized water dilutions, after cleaning three times respectively with deionized water and dehydrated alcohol, add 4000 milliliters of dehydrated alcohols, ultrasonic disperse obtains about 4000 milliliters of carbon nano tube suspension after 30 minutes.Be that the Mierocrystalline cellulose qualitative filter paper of 150 millimeters is installed to corresponding Büchner funnel by diameter, carbon nano tube suspension is joined by funnel subsequently, just obtaining the double-layer filter paper of corresponding cellulosic filter paper/porous carbon nanotube films after suction filtration completes, obtaining 900 μm of thick porous carbon films through measuring.
2. the mixing 5 grams of commercially available carbon nano fibers (about 75 nanometers of diameter) being joined 500 milliliters of sulfuric acid and nitric acid (volume ratio 3:1) is reclaimed in solution, after 1500 ml deionized water dilutions, at 50 DEG C, back flow reaction is after 5 hours, after cleaning three times respectively with deionized water and dehydrated alcohol, add 5000 milliliters of dehydrated alcohols, ultrasonic disperse obtains 5000 milliliters of carbon nano tube suspension after 15 minutes.The square Mierocrystalline cellulose qualitative filter paper of the length of side 60 centimetres is installed to corresponding square Büchner funnel, subsequently suspension is joined in funnel, just obtaining the double-layer filter paper of corresponding cellulosic filter paper/porous carbon nanotube films after suction filtration completes, obtaining 350 μm of thick porous carbon films through measuring.
The key problem that the present invention will solve is, low cost prepares graphene mesh grid material, as for the compound phase wherein added, add kind and addition be performance requriements according to application scenario and determine, 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 interpolation phase.It is nano-silicon or silicon compound mutually that described compound is added; 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 with the addition of compound phase and the oxidation of making or reduced graphene grid, can first prepare by method of the present invention.
The present invention is obtained reduced graphene grid material, except adopting being reduced by graphene oxide grid material in above-described embodiment, can also reduced graphene composite solution be directly adopted to carry out suction filtration when suction filtration, reduced graphene composite solution method conventionally prepares, or adopt and obtain with the following method: the graphene oxide solution of 0.1 ~ 15mg/ml or graphite oxide thiazolinyl composite solution are first reduced into reduced graphene solution or graphene-based composite solution, illustrate as follows: 0.01mol tindichloride is dissolved in 1500ml graphene oxide solution, speed with 300rpm at 90 DEG C at the uniform velocity stirs, add 3ml hydrazine hydrate solution subsequently, for the aqueous solution, wherein N
2h
4content is 50-60%, uses ammoniacal liquor regulator solution pH value to about 10, after reaction 1h simultaneously.Obtained about 1500 milliliters of reduced graphene/SnOx mixing solutionss are carried out 30 minutes supersound process, obtained stable reduced graphene/SnOx nanocomposite solution.The reduced graphene solution of other compound phase or pure phase also can so be prepared.Only as an example, not as restriction.
Claims (10)
1. oxidation or a reduced graphene base net grid material, is characterized in that: in graphene-based macroscopic material, be distributed with multiple grid; Described graphene-based macroscopic material is of a size of: thickness: 200nm – 200 μm, length: 2cm – 20m, width: 2cm – 20m; Or be thickness: 200nm – 200 μm, diameter 2cm-20m; Described size of mesh opening: 0.1mm-1mm; Mesh spacing: 1mm-5mm.
2. one oxidation according to claim 1 or reduced graphene base net grid material, it is characterized in that, in described graphene-based grid material, it is carbon nanomaterial mutually that compound is added, 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%, is the pure phase grid material of oxidation or reduced graphene composition when content is 0.
3. one 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. a preparation method for oxidation according to 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, it has filter funnel, and funnel size range is: 2cm × 2cm ~ 20m × 20m, or for diameter be 2cm ~ 20m; Be provided with double-layer filter paper in described filter funnel, above described double-layer filter paper, be provided with 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 steel column shape of cross section is trilateral or circular or Polygons; Steel column cross-sectional diameter or size dimension scope: 0.1mm-1mm; Described double-layer filter paper is the porous carbon film that the 100 μ m – 1000 μm of Mierocrystalline cellulose qualitative filter paper and surface deposition thereof is thick;
Oxidation or reduced graphene base composite solution being poured into has in the Suction filtration device of double-layer filter paper, and put into drilling accessory, described steel column end is conflicted in described double-layer filter paper, then suction filtration is carried out, graphene-based grid paper is defined on double-layer filter paper surface after suction filtration completes, dried, peel off, namely obtain the graphene mesh ruled paper that thickness is 200nm – 200 μm, its size of mesh opening is 0.1mm-1mm, mesh spacing is 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-layer filter paper and carry out suction filtration, the filter funnel size range of Suction filtration device is: 2cm × 2cm ~ 20m × 20m, or for diameter be 2cm ~ 20m; Described double-layer filter paper is the porous carbon film that the 100 μ m – 1000 μm of Mierocrystalline cellulose qualitative filter paper and surface deposition thereof is thick; Oxidation or reduced graphene base paper is defined at individual layer filter paper or double-layer filter paper surface after suction filtration completes;
Oxidation or the paper conversion of reduced graphene base are gone out multiple through hole, is formed and there is the oxidation or reduced graphene base net grid material that size of mesh opening is 0.1mm-1mm, mesh spacing is 1mm-5mm.
5. the preparation method of oxidation according to claim 4 or reduced graphene base net grid material, is characterized in that,
Described to oxidation or the paper conversion of reduced graphene base go out multiple through hole, the method adopted is: adopt punching die to carry out porous process, described punching die is made up of the die cooperatively interacted and punch, described die is the stainless steel plate with porous array, pitch of holes: 1-5mm, 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 and inserts with above-mentioned porous array one_to_one corresponding and can produce the stainless steel column array of punching effect; Oxidation or reduced graphene base paper are placed in the die upper surface with porous array, carry out punching with the corresponding die of the punch with stainless steel post array.
6. the preparation method of oxidation according to claim 4 or reduced graphene base net grid material, is characterized in that,
Described method A is or/and the preparation method of double-layer filter paper in method B is:
Adopt the double-layer filter paper that following steps are obtained: by one dimension carbon nanotube or/and carbon nanofiber ultrasonic disperse is in organic solvent; Then be deposited on Mierocrystalline cellulose qualitative filter paper surface by vacuum filtration method, form the porous carbon film that 100 μ m – 1000 μm is thick, thus obtained Mierocrystalline cellulose qualitative filter paper/porous nano carbon film double-layer filter paper.
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-layer filter paper are:
The carbon nanotube of diameter 5-100nm or carbon nanofiber are joined by the sulfuric acid of 1 ~ 3:1 volume ratio and the mixing solutions of nitric acid, carbon nanotube or the carbon nanofiber concentration in mixed acid solution is 0.01 ~ 0.05g/ml;
Back flow reaction 2-10 hour at 50-100 DEG C, after deionized water dilution, three times are cleaned respectively again with deionized water and dehydrated alcohol, then in 1g carbon nanotube or carbon nanofiber add 0.7-1.3 rise ratio add corresponding dehydrated alcohol, carbon nanotube ultrasonic disperse obtains the suspension of carbon nanotube or carbon nanofiber after 5-60 minute;
The Mierocrystalline cellulose qualitative filter paper corresponding to funnel size is installed in funnel, subsequently carbon nanotube or nanofiber suspension are joined in funnel, after vacuum filtration completes, just obtain the double-layer filter paper of described cellulosic filter paper/porous carbon nanotube or carbon nanofiber membrane.
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, is filled with the filtrate chamber of porous core or porous aluminium sheet in its lower portion is divided into, and top, filtrate chamber shrouding has filter pore, and filtrate chamber sidewall is then communicated in vaccum-pumping equipment by a bleeding point; Funnel upper part is tubular or the frame-shaped of upper lower open mouth, and its underpart is connected with the pressure seal of funnel lower part, and top is then removably provided with described drilling accessory; And described double-layer filter paper is between 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, described oxidation or reduced graphene base composite solution are oxidation or the reduced graphene solution of 0.1 ~ 15mg/ml or compound interpolation are distributed to the described oxidation or reduced graphene base composite solution that obtain in this oxidation or reduced graphene solution mutually; It is carbon nanomaterial mutually that compound is added, 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; when employing is graphite oxide thiazolinyl composite solution, obtained described graphene oxide base net grid material; then be handled as follows: anneal 2 hours under 250 DEG C of argon atmosphere; high temperature reduction 5 hours under 400 ~ 800 DEG C of argon shields more subsequently, finally obtains reduced graphene grid material highly reduced.
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Families Citing this family (11)
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| 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 |
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| CN114849484B (en) * | 2022-04-24 | 2023-09-05 | 北京机械设备研究所 | Carbon paper preparation facilities |
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 (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2765294C1 (en) * | 2018-07-17 | 2022-01-28 | Графенано Медикал Кеа, С.Л. | Graphene product and its therapeutic applications |
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