CN105870426A - V2O5 nanowire paper for energy storage device electrodes and preparation method - Google Patents
V2O5 nanowire paper for energy storage device electrodes and preparation method Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses V2O5 nanowire paper for energy storage device electrodes and a preparation method. The preparation method is a pure V2O5 nanowire paper preparation method or a composite V2O5 nanowire paper preparation method, ultra-long vanadium oxide nanowires are prepared by adopting a one-step hydrothermal method, are dispersed and then are made into a film through suction filtration or thermal evaporation, and the ultra-long one-dimensional nanowires can be well self-assembled into a macroscopic two-dimensional paper structure. The pure V2O5 nanowire paper can be directly cut into small round pieces to serve as an electrode material for button cells without adhesive current collectors. According to another method, graphene oxide is subjected to in-situ reduction on the structure using the vanadium oxide nanowires as a framework by adopting a two-step reduction method to form the composite V2O5 nanowire paper, and the V2O5 nanowire paper can be directly cut into small round pieces to serve as the electrode material for button cells without adhesive current collectors. The capacity of the composite V2O5 nanowire paper exceeds the theoretical capacity, cycle performance is very good, and V2O5 is compounded into graphene, so that the electric conductivity of the V2O5 is greatly improved, and meanwhile the structural stability of the V2O5 is also greatly improved.
Description
Technical field
The present invention relates to a kind of V for energy storage device electrode2O5Nano wire paper and preparation method, be specifically related to a kind of storage
The preparation side of energy device (lithium ion battery, sodium-ion battery, all-solid lithium-ion battery, ultracapacitor etc.) electrode material
Method, belongs to solid state battery electrode material and preparing technical field thereof.
Background technology
Lithium ion battery is because its high-energy-density and long circulation life are widely used to new-energy automobile, mixing is moved
In power automobile, various portable electrical equipment.And the less expensive sodium-ion battery of cost, aluminium ion battery also begin to fine appearing
Angle；Ultracapacitor is a kind of novel energy-storing device between electrolysis condenser and battery, and it has and is better than conventional batteries
High power density and more preferable cycle life；The poor safety performance depending on liquid electrolyte compared to conventional batteries and cause
Etc. problem, all-solid lithium-ion battery has higher security performance, bigger energy density and wider array of operation interval temperature
Degree.Therefore the application of all-solid-state battery is more and more extensive.But, the electrode material of the energy storage device such as existing lithium ion battery
Being mostly powder, being prepared into electrode material needs to add the additives such as conductive agent, bonding agent, collector, and these add
Agent hinders the overall electrochemical energy storage performance of electrode material to a certain extent, is that it limits electrode material energy especially close
Degree, the lifting of cycle life.Therefore, design a kind of adhesive-free or have the novel storage possessing self-supporting performance of a small amount of bonding agent
Energy electrode, is one and improves energy density and the fine scheme of cycle life.The nano material self supporting structure of existing document report,
Such as patent of invention " ultralong monocrystal V2O5 nano wire/graphene anode material and preparation method " (201110107696.4), institute is public
Open technical scheme etc., be all based on the graphene film of two dimension large scale as skeleton, more compound upper other active substance systems
Become, the V that wherein electrode interior is comprised2O5Active ingredient≤50%, although Graphene is only conducive to improving electricity in composite
The electronic conductance of pole material, particularly the highest as the theoretical capacity of their ion storage of transition metal oxide, but electronics is electric
Leading poor with structural, though compound upper Graphene improves respective performances, but the self-supporting material with Graphene as substrate does not has
The highest volume and capacity ratio.Research shows, V2O5Ion can be embedded and deviate from by material well, has bigger table
Area and short the evolving path, it is provided that more electro-chemical activity site and the concentration polarization weakening electrode material, theoretical
Capacity is big, Stability Analysis of Structures, easily preparation, inexpensive.The V of nanoscale2O5Can improve the diffusion coefficient of lithium ion, but V2O5
As transition metal oxide, have its inborn deficiency: i.e. electronic conductance is poor, high rate performance and cycle performance bad, it improves
Method is: (1) uses nanoscale vanadium, such as nano wire, nanometer rods, nanometer sheet, micron ball etc.；(2) by nanoscale
Vanadium and the Material cladding such as the good CNT of electric conductivity or Graphene.Same, the material that these two kinds of methods prepare does electrode
Sheet, is also to be in setting ratio: active substance: conductive agent: bonding ≈ 8:1:1 ratio makes.On the other hand, even if by powder
Shape V2O5It is combined with a small amount of Graphene, also cannot be fabricated to the membrane structure electrode material of macroscopic view.In contrast, according to
V2O5Active substance nano wire is skeleton, or directly prepares the V of overlength2O5Nano wire, and this nano wire is self-assembled into grand
The two-dimentional paper structure seen, then this kind of two-dimentional paper structure is directly cut into sequin, serve as the electrode material of button cell, no
Use bonding agent collector, a kind of extraordinary electrode material.
Summary of the invention
The problem that it is an object of the invention to propose for background technology, designs a kind of V for energy storage device electrode2O5Receive
Rice noodle paper and preparation method, be the vanadium oxide nanowires having been prepared overlength by one step hydro thermal method, then sucking filtration after dispersion
Or thermal evaporation film forming, the one-dimensional nano line of described overlength yardstick can be self-assembled into the two-dimentional paper structure of macroscopic view well.This
Kind nanometer paper can directly be cut into sequin and serve as the electrode material of button cell, it is not necessary to use bonding agent collector, Jing Guochu
The lithium electricity electro-chemical test of step, the capacity of this pure zirconia vanadium nano wire and cycle life are than the electricity in the document partly reported
Chemical property is not bad；Or use two step reduction method to make graphene oxide reduce in situ with vanadium oxide nanowires as skeleton
Structure on, formed nano wire graphene layer Rotating fields, this composite without add bonding agent, collector can be direct
Being cut into the sequin electrode material for button cell, through preliminary electro-chemical test, the capacity of this composite is super
Crossing theoretical capacity and cycle performance is the best, Graphene is combined into vanadium oxide, not only substantially improves the electronic conductance of vanadium oxide,
Structural stability to vanadium oxide also has the biggest consolidation effect simultaneously.
In order to achieve the above object, the present invention is by the following technical solutions:
A kind of V for energy storage device electrode2O5Nano wire paper, it is characterised in that: described V2O5Nano wire paper is pure V2O5Nanometer
Line paper, including: pure V2O5The pure V of the macroscopic view two dimension paper structure that one-dimensional super long nano wire is self-assembled into2O5Nano wire paper；Described
Pure V2O5Nano wire thickness of paper degree is 8～30 μm, pure V2O5Pure V in nano wire paper2O5Nanowire length is: 0.001~10 mm
Between；Described V2O5Nano wire paper is cut into the sequin being sized and is i.e. directly used in the electrode material of button cell.
A kind of V for energy storage device electrode2O5Nano wire paper, it is characterised in that: described V2O5Nano wire paper
Or redox graphene and V2O5The compound V of preparation after nano wire is compound2O5Nano wire paper, including: pure V2O5One-dimensional super
Long nano wire be self-assembled into macroscopic view two dimension paper structure and, reduce in situ at described pure V2O5Oxygen on nano wire skeleton
Functionalized graphene；The quality of described graphene oxide is not more than described compound V2O5The 15% of nano wire paper gross mass.
A kind of V for energy storage device electrode2O5The preparation method of nano wire paper, including: pure V2O5Nano wire
Preparation Method made of paper and compound V2O5Nano wire Preparation Method made of paper；It is characterized in that: the processing step of each preparation method is respectively as follows:
One, pure V2O5Nano wire Preparation Method made of paper
Step 1: preparation overlength V2O5Nano wire
1.1 weigh 0.008mol(1.456g) V2O5Powder, ultrasonic disperse is in the deionized water of 120ml；
1.2 are slowly added to 20ml hydrogen peroxide (H in the solution of step 1.1 preparation2O2) (30wt.%), mixed solution becomes palm fibre
Red and with a large amount of bubbles；
After 1.3 mixed solution magnetic agitation 30min that just prepared by step 1.2, it is transferred in the polytetrafluoro reactor of 200ml
In gallbladder；
230 DEG C of insulation 12h in constant temperature oven placed by reactor by 1.4；
1.5 step 1.4 is processed after hydrothermal product clean three times with high purity water and ethanol are the most each respectively, then place 100 DEG C
Vacuum drying 4h；
1.6 step 1.5 is processed after sample roasting 3h at 400 DEG C in atmosphere, i.e. make overlength V2O5Nano wire；
Step 2: prepare pure V2O5Nano wire paper
2.1 weigh overlength V by step 1 preparation2O5Nano wire 300mg, is placed in the there-necked flask of 250ml；
2.2 high purity waters adding 250ml in described there-necked flask, place into the big magneton of a long 5cm；
2.3 under magnetic stirring apparatus effect, with 1500～2500rpm speed, stirs 24～48h, it is ensured that V2O5Nano wire is abundant
Dispersion is in the solution；
2.4 by V described in step 2.32O5Nanowire dispersion passes through vacuum filtration film forming, or pours polytetrafluoro evaporating dish into
Thermal evaporation film forming；I.e. make macroscopical pure V2O5Nano wire paper；The pure V of described macroscopic view2O5Nano wire paper a diameter of 4～10cm；
2.5 by pure V macroscopical described in step 2.42O5Nano wire paper is cut into the sequin of 8～16mm by sheet-punching machine, becomes button
The electrode material of formula battery；
Two, compound V2O5Nano wire Preparation Method made of paper
Step 1: prepare graphene oxide
1.1 weigh 1g crystalline flake graphite and 6g potassium permanganate；
1.2 concentrated sulphuric acids measuring 27ml and the strong phosphoric acid of 3ml, be placed in the polytetrafluoro reactor inner bag of 100ml；
1.3 get out ice-water bath condition, are placed in one by reactor inner bag described in step 1.2, magnetic agitation 10min；
1.4 add crystalline flake graphite stirring 0.5h in reactor inner bag, be slowly added to potassium permanganate, be stirred within 1h
0.5h
1.5 seal reactor described in step 1.4, are placed on 24h in 70 DEG C of constant temperature ovens, complete the oxidation of Graphene；
1.6, in the ratio of (high purity water: hydrogen peroxide)=10:1, measure high purity water and the mixing of 10ml hydrogen peroxide of 100ml, and will be mixed
Close liquid and be frozen into ice cube shape；
1.7 step 1.5 is aoxidized after Graphene take out be upside down on the mixed liquor ice cube that step 1.6 is made, simple agitation makes
It fully dissolves；
1.8 measure the hydrochloric acid that 40ml concentration is 10% adds in the mixture in step 1.7, terminates reaction；
The mixture that step 1.8 prepares is poured in centrifuge tube by 1.9, and to step up, the method for rotating speed is centrifugal to be at least centrifuged
Filter three times, then outwell the supernatant being centrifuged out；
1.10 detections are by the pH value of the centrifugal rear mixture of step 1.9, it is ensured that PH is about 7, and detects mixing with barium chloride solution
Thing, it is ensured that sulfate radical-free ion in mixture, last qualified mixture is placed in polytetrafluoro evaporating dish 40 DEG C and is dried to solid；I.e.
Complete the preparation of graphene oxide；
Step 2: redox graphene and V2O5After nano wire is compound, the compound V of preparation2O5Nano wire paper
2.1 graphene oxide (GO) 100mg weighing step 1 gained, are placed in beaker the high purity water adding 100ml, ultrasonic stir
Mix and be uniformly dispersed, obtain the GO solution of 1mg/ml；
2.2 L-AAs adding 100mg in described GO solution, then ultrasonic disperse 2h, then stand 24h, and solution is gradually
Blackening, obtains graphene oxide (VrGO) solution of Vitamin C fraction reduction；
2.3 weigh overlength V2O5Nano wire 255mg, is placed in the there-necked flask of 250ml, adds the high purity water of 205ml；
2.4 under magnetic stirring apparatus with 1500～2500rpm speed, the mixed liquor in there-necked flask described in step 2.3 is stirred
24～48h, it is ensured that V2O5Nano wire is fully dispersed in aqueous；
2.5 graphene oxide (VrGO) solution measuring 45ml, add in there-necked flask described in step 2.3, continue stirring 1h and make
V2O5Nano wire is sufficiently mixed with partial reduction graphene oxide；
The 2.6 mixed liquor 250ml measuring step 2.5 preparation, are placed in reactor inner bag with the packing ratio of 70%；
Reactor is placed in 4h in the constant temperature oven of 160 DEG C by 2.7, completes the further reduction of partial reduction graphene oxide, and
V can be preserved2O5The long yardstick of nano wire, carries out reduction in situ；
Mixed liquor in reactor described in step 2.7 is passed through vacuum filtration film forming by 2.8, or pours polytetrafluoro evaporating dish into
In, 36h film forming in 60 DEG C of environment, i.e. make compound V2O5Nano wire paper, described compound V2O5Nano wire paper a diameter of 4～
10cm, thickness 8～30 μm；
2.9 by the compound V of step 2.8 gained2O5Nano wire paper is cut into the sequin of 8～16mm by sheet-punching machine, becomes button
The electrode material of formula battery.
A kind of V for energy storage device electrode2O5The preparation method of nano wire paper, it is characterised in that: described pure
V2O5In nano wire Preparation Method made of paper, pure V2O5Nano wire paper method for controlling thickness is: for the V setting concentration2O5Nano wire water
Dispersion liquid, by controlling the volume of described aqueous dispersions, final pure V after reaching film forming2O5Nano wire paper thickness requirement.
A kind of V for energy storage device electrode2O5The preparation method of nano wire paper, it is characterised in that: described multiple
Close V2O5In nano wire Preparation Method made of paper, compound V2O5The ml of the thickness of nano wire paper mixed liquor measured with before film forming just measures into
Ratio.
The invention has the beneficial effects as follows: energy storage device electrode material (lithium electricity, the sodium utilizing method provided by the present invention to obtain
Electricity, all-solid-state battery, ultracapacitor), compared to traditional electrode material, have that preparation technology is simple, safety is high, can be big
Batch production, the energy storage device that the electrode material utilizing the present invention to prepare manufactures, there is higher specific capacity and longer following
The ring life-span.
Accompanying drawing explanation
Fig. 1 is the pure V of the embodiment of the present invention one preparation2O5Nano wire paper optical photograph figure.
Fig. 2 is pure V in Fig. 12O5Nano wire paper scanning electron microscope (SEM) photograph.
Fig. 3 is the compound V of embodiment two preparation2O5Nano wire paper optical photograph figure.
Fig. 4 is composite nano-line paper scanning electron microscope (SEM) photograph in Fig. 3.
Fig. 5 is respectively with pure V2O5Nano wire paper or compound V2O5Nano wire paper is the lithium ion battery specific volume of electrode material
Amount comparison diagram.
Fig. 6 is respectively with pure V2O5Nano wire paper or compound V2O5Nano wire paper is the lithium ion battery circulation of electrode material
Life span comparison schemes.
Detailed description of the invention
Below in conjunction with accompanying drawing, embodiments of the present invention is further illustrated, for making the purpose of the present invention, technical scheme and excellent
Point is clearer, below technical scheme in the present invention be clearly and completely described, it is clear that described embodiment is this
Invent a part of embodiment rather than whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art exist
Do not make the every other embodiment obtained under creative work premise, broadly fall into the scope of protection of the invention.
Accompanying drawing 1, Fig. 2 are pure V respectively2O5Nano wire paper optics gray scale pictures (actual in golden yellow) and scanning electron microscope (SEM) photograph；It is
Pure V2O5The pure V of the macroscopic view two dimension paper structure that one-dimensional super long nano wire is self-assembled into2O5Nano wire paper；In Fig. 2, nanometer line length
Spend:0.001~10Between mm, in Fig. 1, pure V2O5The thickness of nano wire paper is 8～30 μm；By V pure in Fig. 12O5Nano wire paper
It is cut into the sequin of diameter 8～16mm, i.e. can be directly used for the electrode material of button cell.
Accompanying drawing 3, Fig. 4 are compound V respectively2O5Nano wire paper optics gray scale pictures (actual in black) and scanning electron microscope (SEM) photograph；It is
Redox graphene and V2O5After nano wire is compound, the compound V of preparation2O5Nano wire paper；In Fig. 4, nanowire length exists:0.001~10Between mm, compound V in Fig. 32O5The thickness of nano wire paper is 8～30 μm；By V pure in Fig. 32O5Nano wire paper is cut into
The sequin of diameter 8～16mm, i.e. can be directly used for the electrode material of button cell.The content of graphene oxide in Fig. 3 or Fig. 4
≤15%。
For the pure V of energy storage device electrode shown in Fig. 1 or Fig. 22O5Nano wire Preparation Method made of paper is as follows:
Step 1: preparation overlength V2O5Nano wire
1.1 weigh 0.008mol(1.456g) V2O5Powder, ultrasonic disperse is in the deionized water of 120ml；
1.2 are slowly added to 20ml hydrogen peroxide (H in the solution of step 1.1 preparation2O2) (30wt.%), mixed solution becomes palm fibre
Red and with a large amount of bubbles；
After 1.3 mixed solution magnetic agitation 30min that just prepared by step 1.2, it is transferred in the polytetrafluoro reactor of 200ml
In gallbladder；
230 DEG C of insulation 12h in constant temperature oven placed by reactor by 1.4；
1.5 step 1.4 is processed after hydrothermal product clean three times with high purity water and ethanol are the most each respectively, then place 100 DEG C
Vacuum drying 4h；
1.6 step 1.5 is processed after sample roasting 3h at 400 DEG C in atmosphere, i.e. make overlength V2O5Nano wire；
Step 2: prepare pure V2O5Nano wire paper
2.1 weigh overlength V by step 1 preparation2O5Nano wire 300mg, is placed in the there-necked flask of 250ml；
2.2 high purity waters adding 250ml in described there-necked flask, place into the big magneton of a long 5cm；
2.3 under magnetic stirring apparatus effect, with 1500～2500rpm speed, stirs 24～48h, it is ensured that V2O5Nano wire is abundant
Dispersion is in the solution；
2.4 by V described in step 2.32O5Nanowire dispersion passes through vacuum filtration film forming, or pours polytetrafluoro evaporating dish into
Thermal evaporation film forming；I.e. make macroscopical pure V2O5Nano wire paper；The pure V of described macroscopic view2O5Nano wire paper a diameter of 4～10cm；
2.5 by pure V macroscopical described in step 2.42O5Nano wire paper is cut into the sequin of 8～16mm by sheet-punching machine, becomes button
The electrode material of formula battery；
For the compound V of energy storage device electrode shown in Fig. 3 or Fig. 42O5Nano wire Preparation Method made of paper is as follows:
Step A: prepare graphene oxide
1.1 weigh 1g crystalline flake graphite and 6g potassium permanganate；
1.2 concentrated sulphuric acids measuring 27ml and the strong phosphoric acid of 3ml, be placed in the polytetrafluoro reactor inner bag of 100ml；
1.3 get out ice-water bath condition, are placed in one by reactor inner bag described in step 1.2, magnetic agitation 10min；
1.4 add crystalline flake graphite stirring 0.5h in reactor inner bag, be slowly added to potassium permanganate, be stirred within 1h
0.5h
1.5 seal reactor described in step 1.4, are placed on 24h in 70 DEG C of constant temperature ovens, complete the oxidation of Graphene；
1.6, in the ratio of (high purity water: hydrogen peroxide)=10:1, measure high purity water and the mixing of 10ml hydrogen peroxide of 100ml, and will be mixed
Close liquid and be frozen into ice cube shape；
1.7 step 1.5 is aoxidized after Graphene take out be upside down on the mixed liquor ice cube that step 1.6 is made, simple agitation makes
It fully dissolves；
1.8 measure the hydrochloric acid that 40ml concentration is 10% adds in the mixture in step 1.7, terminates reaction；
The mixture that step 2.8 prepares is poured in centrifuge tube by 1.9, and to step up, the method for rotating speed is centrifugal to be at least centrifuged
Filter three times, then outwell the supernatant being centrifuged out；
1.10 detections are by the pH value of the centrifugal rear mixture of step 1.9, it is ensured that PH is about 7, and detects mixing with barium chloride solution
Thing, it is ensured that sulfate radical-free ion in mixture, last qualified mixture is placed in polytetrafluoro evaporating dish 40 DEG C and is dried to solid；I.e.
Complete the preparation of graphene oxide.
Step B: redox graphene and V2O5After nano wire is compound, the compound V of preparation2O5Nano wire paper
2.1 weigh the graphene oxide 100mg obtained by step A, are placed in beaker the high purity water adding 100ml, ultrasonic agitation
It is uniformly dispersed, obtains the graphene oxide solution of 1mg/ml；
2.2 L-AAs adding 100mg in described graphene oxide solution, then ultrasonic disperse 2h, then stand 24h,
Solution blackening gradually, obtains the graphene oxide (VrGO) of Vitamin C fraction reduction；
2.3 weigh overlength V by step one preparation2O5Nano wire 255mg, is placed in the there-necked flask of 250ml, adds 205ml
High purity water；
2.4 under magnetic stirring apparatus with 1500～2500rpm speed, the mixed liquor in there-necked flask described in step 2.3 is stirred
24～48h, it is ensured that V2O5Nano wire is fully dispersed in aqueous；
2.5 graphene oxide (VrGO) solution measuring 45ml, add in there-necked flask described in step 2.3, continue stirring 1h and make
V2O5Nano wire is sufficiently mixed with partial reduction graphene oxide；
The 2.6 mixed liquor 250ml measuring step 2.5 preparation, are placed in reactor inner bag with the packing ratio of 70%；
Reactor is placed in 4h in the constant temperature oven of 160 DEG C by 2.7, completes the further reduction of partial reduction graphene oxide, and
V can be preserved2O5The long yardstick of nano wire, carries out reduction in situ；
Mixed liquor in reactor described in step 2.7 is passed through vacuum filtration film forming by 2.8, or pours polytetrafluoro evaporating dish into
In, 36h film forming in 60 DEG C of environment, i.e. make compound V2O5Nano wire paper, described compound V2O5Nano wire paper a diameter of 4～
10cm, thickness 8～30 μm；Compound V2O5The thickness of nano wire paper, the ml amount of mixed liquor measured to before film forming is directly proportional.
2.9 by the compound V of step 2.8 gained2O5Nano wire paper is cut into the sequin of 8～16mm by sheet-punching machine, becomes
The electrode material of button cell.
Understand with reference to accompanying drawing 5, by the pure V being used for energy storage device electrode of preparation in the embodiment of the present invention2O5Nano wire paper or
Compound V2O5Nano wire paper is electrode material, and when lithium ion battery, this lithium ion battery specific capacity maximum is respectively
242mAh/g and 315mAh/g, is all to record under electric current density 29.4mAh/g.
Understand with reference to accompanying drawing 6, by the pure V being used for energy storage device electrode of preparation in the embodiment of the present invention2O5Nano wire paper or
Compound V2O5Nano wire paper is electrode material, when lithium ion battery, carries out the cycle life test of battery, it will be appreciated from fig. 6 that
Compound V2O5Nano wire paper test loop life-span under the high current density of 588mAh/g also has the residue of 80% to hold after 400 circles
Amount.
A kind of V for energy storage device electrode of the present invention2O5Nano wire paper is for energy storage device electrode material (lithium electricity, sodium
Electricity, all-solid-state battery, ultracapacitor), compared to traditional electrode material, have that preparation technology is simple, safety is high, can be big
Batch production, the energy storage device that the electrode material utilizing the present invention to prepare manufactures, there is higher specific capacity and longer following
The ring life-span.
Last it is noted that above example is only in order to illustrate technical scheme, it is not intended to limit；Although
With reference to previous embodiment, the present invention is described in detail, it will be understood by those within the art that: it still may be used
So that the technical scheme described in foregoing embodiments to be modified, or wherein portion of techniques feature is carried out equivalent；
And these amendment or replace, do not make appropriate technical solution essence depart from various embodiments of the present invention technical scheme spirit and
Scope.
Claims (6)
1. the V for energy storage device electrode2O5Nano wire paper, for button cell or the electrode material of other energy storage device
Processing；It is characterized in that: described V2O5Nano wire paper is pure V2O5Nano wire paper, including: pure V2O5One-dimensional super long nano wire is from group
The pure V of the macroscopic view two dimension paper structure dressed up2O5Nano wire paper；Described pure V2O5Nano wire thickness of paper degree is 8～30 μm, pure V2O5Receive
Pure V in rice noodle paper2O5Nanowire length is:0.001~10Between mm；Described V2O5Nano wire paper is cut into be sized little
Disk is i.e. directly used in the electrode material of button cell.
A kind of V for energy storage device electrode2O5Nano wire paper, it is characterised in that: described V2O5Nanometer
Line paper or redox graphene and V2O5The compound V of preparation after nano wire is compound2O5Nano wire paper, including: pure V2O5One
Dimension overlong nanowire be self-assembled into macroscopic view two dimension paper structure and, reduce in situ at described pure V2O5On nano wire skeleton
Graphene oxide；The quality of described graphene oxide is not more than described compound V2O5The 15% of nano wire paper gross mass.
A kind of V for energy storage device electrode2O5The preparation method of nano wire paper, including: pure V2O5Receive
Rice noodle Preparation Method made of paper；It is characterized in that: processing step is:
Step 1: preparation overlength V2O5Nano wire
1.1 weigh 0.008mol (1.456g) V2O5Powder, ultrasonic disperse is in the deionized water of 120ml；
1.2 are slowly added to 20ml hydrogen peroxide (H in the solution of step 1.1 preparation2O2) (30wt.%), mixed solution becomes reddish brown
Color with a large amount of bubbles；
After 1.3 mixed solution magnetic agitation 30min that just prepared by step 1.2, it is transferred to the polytetrafluoro reactor inner bag of 200ml
In；
230 DEG C of insulation 12h in constant temperature oven placed by reactor by 1.4；
1.5 step 1.4 is processed after hydrothermal product clean three times with high purity water and ethanol are the most each respectively, then place 100 DEG C
Vacuum drying 4h；
1.6 step 1.5 is processed after sample roasting 3h at 400 DEG C in atmosphere, i.e. make overlength V2O5Nano wire；
Step 2: prepare pure V2O5Nano wire paper
2.1 weigh overlength V by step 1 preparation2O5Nano wire 300mg, is placed in the there-necked flask of 250ml；
2.2 high purity waters adding 250ml in described there-necked flask, place into the big magneton of a long 5cm；
2.3 under magnetic stirring apparatus effect, with 1500～2500rpm speed, stirs 24～48h, it is ensured that V2O5Nano wire fully divides
Dissipate in the solution；
2.4 by V described in step 2.32O5Nanowire dispersion passes through vacuum filtration film forming, or pours polytetrafluoro evaporating dish heat into
Evaporation film forming；I.e. make macroscopical pure V2O5Nano wire paper；The pure V of described macroscopic view2O5Nano wire paper a diameter of 4～10cm；
2.5 by pure V macroscopical described in step 2.42O5Nano wire paper is cut into the sequin of 8～16mm by sheet-punching machine, becomes button
The electrode material of battery.
A kind of V for energy storage device electrode2O5The preparation method of nano wire paper, including: compound V2O5
Nano wire Preparation Method made of paper, it is characterised in that: processing step is:
Step 1: prepare graphene oxide
1.1 weigh 1g crystalline flake graphite and 6g potassium permanganate；
1.2 concentrated sulphuric acids measuring 27ml and the strong phosphoric acid of 3ml, be placed in the polytetrafluoro reactor inner bag of 100ml；
1.3 get out ice-water bath condition, are placed in one by reactor inner bag described in step 1.2, magnetic agitation 10min；
1.4 add crystalline flake graphite stirring 0.5h in reactor inner bag, be slowly added to potassium permanganate, be stirred for 0.5h within 1h
1.5 seal reactor described in step 1.4, are placed on 24h in 70 DEG C of constant temperature ovens, complete the oxidation of Graphene；
1.6, in the ratio of (high purity water: hydrogen peroxide)=10:1, measure high purity water and the mixing of 10ml hydrogen peroxide of 100ml, and will be mixed
Close liquid and be frozen into ice cube shape；
1.7 step 1.5 is aoxidized after Graphene take out be upside down on the mixed liquor ice cube that step 1.6 is made, simple agitation makes
It fully dissolves；
1.8 measure the hydrochloric acid that 40ml concentration is 10% adds in the mixture in step 1.7, terminates reaction；
The mixture that step 1.8 prepares is poured in centrifuge tube by 1.9, to step up the centrifugal at least centrifugal filtration of the method for rotating speed
Three times, then outwell the supernatant being centrifuged out；
1.10 detections are by the pH value of the centrifugal rear mixture of step 1.9, it is ensured that PH is about 7, and detects mixture with barium chloride solution,
Guarantee that sulfate radical-free ion in mixture, last qualified mixture are placed in polytetrafluoro evaporating dish 40 DEG C and are dried to solid；The completeest
Become the preparation of graphene oxide；
Step 2: redox graphene and V2O5After nano wire is compound, the compound V of preparation2O5Nano wire paper
The 2.1 graphene oxide 100mg weighing step 1 gained, are placed in beaker the high purity water adding 100ml, and ultrasonic agitation is divided
Dissipate uniformly, obtain the graphene oxide solution of 1mg/ml；
2.2 L-AAs adding 100mg in described graphene oxide solution, then ultrasonic disperse 2h, then stand 24h,
Solution blackening gradually, obtains graphene oxide (VrGO) solution of Vitamin C fraction reduction；
2.3 overlength V weighing step 1 preparation according to claim 32O5Nano wire 255mg, is placed in the there-necked flask of 250ml,
Add the high purity water of 205ml；
2.4 under magnetic stirring apparatus with 1500～2500rpm speed, the mixed liquor in there-necked flask described in step 2.3 is stirred
24～48h, it is ensured that V2O5Nano wire is fully dispersed in aqueous；
2.5 graphene oxide (VrGO) solution by step 2.2 preparation measuring 45ml, add there-necked flask described in step 2.3
In, continue stirring 1h and make V2O5Nano wire is sufficiently mixed with partial reduction graphene oxide；
The 2.6 mixed liquor 250ml measuring step 2.5 preparation, are placed in reactor inner bag with the packing ratio of 70%；
Reactor is placed in 4h in the constant temperature oven of 160 DEG C by 2.7, completes the further reduction of partial reduction graphene oxide, and
V can be preserved2O5The long yardstick of nano wire, carries out reduction in situ to VrGO；
Mixed liquor in reactor described in step 2.7 is passed through vacuum filtration film forming by 2.8, or pours polytetrafluoro evaporating dish into
In, 36h film forming in 60 DEG C of environment, i.e. make compound V2O5Nano wire paper, described compound V2O5Nano wire paper a diameter of 4～
10cm, thickness 8～30 μm；
2.9 by the compound V of step 2.8 gained2O5Nano wire paper is cut into the sequin of 8～16mm by sheet-punching machine, becomes button
The electrode material of battery.
A kind of V for energy storage device electrode2O5The preparation method of nano wire paper, it is characterised in that:
Described pure V2O5In nano wire Preparation Method made of paper, pure V2O5Nano wire paper method for controlling thickness is: for the V setting concentration2O5Receive
Rice noodle aqueous dispersions, by controlling the volume of described aqueous dispersions, final pure V after reaching film forming2O5Nano wire thickness of paper degree is wanted
Ask.
A kind of V for energy storage device electrode2O5The preparation method of nano wire paper, it is characterised in that:
Described compound V2O5In nano wire Preparation Method made of paper, compound V2O5The ml of measured mixed liquor before the thickness of nano wire paper and film forming
Amount is directly proportional.
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| CN106784652A (en) * | 2016-11-23 | 2017-05-31 | 武汉理工大学 | Barium oxide/carbon nano tube flexible film and its preparation method and application |
| CN106941049A (en) * | 2017-02-15 | 2017-07-11 | 上海交通大学 | A kind of preparation method and applications of vanadic anhydride/graphene oxide composite membrane |
| CN107059050A (en) * | 2017-04-20 | 2017-08-18 | 天津工业大学 | One-dimensional metal oxide loads titanium-based electro-catalysis membrane and preparation method and catalytic applications |
| CN108892169A (en) * | 2018-07-02 | 2018-11-27 | 武汉理工大学 | The preembedded Mg of stratiform magnesium ion0.3V2O5·1.1H2O nano material and its preparation method and application |
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| CN109761277A (en) * | 2019-01-17 | 2019-05-17 | 广东工业大学 | One kind five aoxidizes three vanadium negative electrode materials, preparation method and applications |
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| CN113224371A (en) * | 2021-04-08 | 2021-08-06 | 武汉理工大学 | High-performance heat-resistant gradient nanowire positive-grade and lithium-philic negative electrode composite solid-state lithium battery |
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| CN106941049A (en) * | 2017-02-15 | 2017-07-11 | 上海交通大学 | A kind of preparation method and applications of vanadic anhydride/graphene oxide composite membrane |
| CN106941049B (en) * | 2017-02-15 | 2019-01-22 | 上海交通大学 | A kind of preparation method and applications of vanadic anhydride/graphene oxide composite membrane |
| CN107059050A (en) * | 2017-04-20 | 2017-08-18 | 天津工业大学 | One-dimensional metal oxide loads titanium-based electro-catalysis membrane and preparation method and catalytic applications |
| CN107059050B (en) * | 2017-04-20 | 2019-02-15 | 天津工业大学 | One-dimensional metal oxide loads titanium-based electro-catalysis membrane and preparation method and catalytic applications |
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| CN109502578A (en) * | 2018-12-05 | 2019-03-22 | 中国科学院城市环境研究所 | A kind of preparation method of vanadium oxide-graphene intercalation composite material |
| CN109761277A (en) * | 2019-01-17 | 2019-05-17 | 广东工业大学 | One kind five aoxidizes three vanadium negative electrode materials, preparation method and applications |
| CN109761277B (en) * | 2019-01-17 | 2021-08-13 | 广东工业大学 | Vanadium pentoxide negative electrode material, preparation method and application thereof |
| CN110518202A (en) * | 2019-08-05 | 2019-11-29 | 三峡大学 | A kind of V of self-supporting2O5/ rGO nano-array sodium-ion battery material and preparation method thereof |
| CN110518202B (en) * | 2019-08-05 | 2021-09-21 | 三峡大学 | Self-supporting V2O5rGO nano array sodium ion battery material and preparation method thereof |
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