CN108258198A - Graphene/carbon nanobelt three-dimensional structure electrode and preparation method thereof and the application in energy-storage battery electrodes conduct network - Google Patents
Graphene/carbon nanobelt three-dimensional structure electrode and preparation method thereof and the application in energy-storage battery electrodes conduct network Download PDFInfo
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Abstract
Application the invention discloses a kind of graphene/carbon nanobelt three-dimensional structure electrode and preparation method thereof and in energy-storage battery electrodes conduct network, belongs to technical field of lithium ion.The present invention, by controlling the ratio and content of the graphene oxide (GO) initially added and oxidation carbon nanobelts (GONR), can obtain the electrode material of different multiplying performance using the method for sprayed deposit and vacuum filtration.Graphene is arranged in parallel in the nanobelt three-dimensional structure electrode containing graphene/carbon, and lithium iron phosphate particles prevent the reunion of graphene in interlayer, and simultaneous oxidation carbon nanobelts are wrapped in around lithium iron phosphate particles；The mass fraction of graphene and carbon nanobelts is 2 5% in electrode after Overheating Treatment；The self-supporting material prepared can be directly as electrode, and after tablet press machine is suppressed, electrode can be closer.
Description
Technical field
The invention belongs to technical field of lithium ion, be related to a kind of graphene/carbon nanobelt three-dimensional structure electrode and its
Preparation method and application.
Background technology
One of the positive electrode of LiFePO4 as most promising lithium ion battery, has greatly attracted people's
Interest, this is because it has many advantages, such as that at low cost, pollution is small, cycle performance is excellent, thermal stability is good and security performance is high.
However LiFePO 4 material Conductivity Ratio relatively low (10 itself-10S·m-1The order of magnitude) the shortcomings that limit its large-scale commercial especially
It is the application in high-power field.In order to solve the problems, such as that this is main, people have done many effort, are mixed including metal ion
Miscellaneous, carbon coating, particle nanosizing etc..Wherein, by lithium iron phosphate particles nanosizing seemingly most efficient method, because this causes
The transmission path of lithium ion greatly reduces, while the surface area of active material greatly increases.
Unfortunately, although lithium iron phosphate particles nanosizing can be improved to the performance of battery, the vibration density of material
Degree also can greatly increase, and then lead to the reduction of volume energy density.And the LiFePO4 of commercialization be usually micron order or
Person is the powder of submicron order, and tap density will be far longer than nano-grade size prepared by the methods of laboratory passes through hydro-thermal
LiFePO4.In addition, in the electrode production process of traditional lithium ion battery, generally require the conductions such as addition conductive black and add
Add agent to increase the electric conductivity of system, and need binding agent and collector.These undoubtedly increase the quality of entire electrode with
And volume.
Carbon nanobelts (GNR) are a kind of quasi one-dimensional materials, generally by the method for chemical oxidation that carbon nanotube edge is long
It opens and is made in degree direction.Compared with carbon nanotube is as conductive material, the flexibility of carbon nanobelts is high, available surface area compared with
Greatly.
Graphene (G) is used as a kind of two-dimensional structure material, since it is with surface area is big, good conductivity, chemical stability
The advantages that good, is often used as conductive additive and backing material in energetic domains.LiFePO4 and graphene are passed through into physics
Method, which mixes or graphene is added in LiFePO4 building-up process, can realize the mixing of the two.But it realizes high
Effective combine of density and high-energy is relatively difficult.It is in addition, equal by chemical vapor deposition (CVD) or hydro-thermal etc.
The electrode material of graphene-based self-supporting can be prepared, but the material finally obtained causes volume energy close due to its porosity
Degree is in a disadvantageous position.
The self-supporting electrode of graphene and active material can also be prepared by way of vacuum filtration, but for commodity
The iron phosphate powder of change is relatively difficult.This is because realize homodisperse formula of the graphene oxide in polar solvent
It is easier, but is highly difficult for the bigger commercialization lithium iron phosphate particles of size and density.
Invention content
In order to solve the problems in the existing technology, the present invention, which combines sprayed deposit and vacuum filtration, prepares stone
Black alkene/carbon nanobelts three-dimensional structure electrode, provide a kind of preparation method comprising graphene/carbon nanobelt three-dimensional structure electrode and
Its application in energy-storage battery electrodes conduct network.The present invention is using sprayed deposit and the method being filtered by vacuum, by controlling just
Begin the graphene oxide (GO) of addition and the ratio and content of oxidation carbon nanobelts (GONR), can obtain different multiplying performance
Electrode material.It is described to be characterized in that graphene is arranged in parallel containing graphene/carbon nanobelt three-dimensional structure electrode, LiFePO4
Particle prevents the reunion of graphene in interlayer, and simultaneous oxidation carbon nanobelts are wrapped in around lithium iron phosphate particles；Through Overheating Treatment
The mass fraction of graphene and carbon nanobelts is in 2-5% in electrode afterwards；The self-supporting material prepared can be directly as electricity
Pole, after tablet press machine is suppressed, electrode can be closer.
Present invention firstly provides a kind of preparation methods of graphene/carbon nanobelt three-dimensional structure electrode, are as follows：
The first step is long by carbon nanotube edge using potassium permanganate as oxidant using the concentrated sulfuric acid and concentrated phosphoric acid mixture as solvent
It spends direction to open, forms oxidation carbon nanobelts (GONR).Unreacted potassium permanganate is reacted away by hydrogen peroxide, is then passed through
Obtained product is separated in centrifugation, is washed with deionized several times.
The volume ratio of the concentrated sulfuric acid and concentrated phosphoric acid is 9:1.
Oxidation carbon nanobelts (GONR), graphene oxide (GO) and LiFePO4 (LFP) are respectively placed in pole by second step
Property solvent in, then mixing and ultrasound make it homodisperse, obtain mixed solution.Then mixed solution is added to inhaler
Feed bin in, under pressure, with certain rate, above mixed solution gas blowout to the filter membrane being filtered by vacuum.
Described polar solvent selection N,N-dimethylformamide (DMF), DMAC N,N' dimethyl acetamide (DMA), N- methyl-
2-Pyrrolidone (NMP) etc..
The filter membrane is organic filter membrane, such as nylon leaching film.
The conditional parameter of the gas blowout is：Pressure is 5-20MPa, speed 2-5mL/min.
The mass ratio of the graphene oxide and oxidation carbon nanobelts is 1:4-4:1.
Third walks, and after spraying, will be covered with the filter membrane drying of product, then detaches product and filter membrane.By product
It is restored in argon nitrogen atmosphere high temperature, then after the compacting of tablet press machine, the graphene/carbon nanobelt three-dimensional for obtaining the present invention is answered
Composite electrode can be used directly as the anode of energy-storage battery.
The condition of the high temperature reduction is：Argon gas/hydrogen (V/V, 90/10) atmosphere, 700 DEG C of high-temperature process 5h.
The tablet press machine pressing pressure is 30-50MPa.
The graphene/carbon nanobelt three-dimensional structure electrode is directly used in energy-storage battery electrodes conduct network, half electricity
Pond specific discharge capacity under 1C is 128~130mAhg-1, the specific capacity of 20C is 53~90mAhg-1.
The advantage of the invention is that：
1st, carbon nanotube is opened for by carbon nanobelts using chemical method along its length, increases the flexibility of material, together
When increase the contact area of carbon nanobelts and LiFePO4.
2nd, by the way of spraying, it can realize that LiFePO4, graphene oxide, oxidation carbon nanobelts are other in the micron-scale
It is homodisperse.The effect of vacuum filtration can ensure that liquid in spray droplet is quickly removed once touching filter cake, simultaneously to the greatest extent
It is possible to ensure the ductility of graphene oxide, and the compactness of electrode can be increased.
3rd, the advantages of mode that graphene oxide and oxidation carbon nanobelts combine, is that it is whole that graphene oxide is to maintain electrode
The main component of body and mechanical property, and oxidation nanometer band can be that graphene contacts not due to its flexible and quasi- one-dimensional
The lithium iron phosphate particles arrived provide conductive network.
4th, product still needs the compacting by tablet press machine after thermal reduction, to further increase the densification of material
Property.
Description of the drawings
Fig. 1 is the schematic diagram of the graphene/carbon nanobelt three-dimensional structure prepared by the present invention.
Fig. 2 is the images of transmissive electron microscope of the carbon nanotube and prepared oxidation carbon nanobelts used in the present invention.
Fig. 3 is the scanning in the section of the combination electrode with graphene/carbon nanobelt three-dimensional structure prepared by embodiment 1
Sem image.
Fig. 4 a~4d are the high rate performance of three-dimensional structure electrode prepared by Examples 1 to 3 and scrape slurry mode by tradition
The high rate performance of the electrode of preparation.
Specific embodiment
Below in conjunction with the drawings and specific embodiments, the invention will be further described.
Embodiment 1：
Prepare graphene/carbon nanobelt three-dimensional combination electrode (mass ratio mGO:mGONR=2.5:2.5)：
(1) concentrated sulfuric acid 36mL, concentrated phosphoric acid 4mL are added in three-necked flask, addition 200mg carbon nanotubes, ultrasonic 0.5h,
Mechanical agitation 2h again.The potassium permanganate of 1g is slowly added to, 1h is stirred at room temperature.Then temperature is improved to 75 DEG C, reacts 2h.Reaction knot
Shu Hou is purified.The purifying is specially：
First, heat source is removed, is cooled to room temperature, then add in the H containing 10mL mass fractions 35%2O2Ice water mix
Object is closed, unreacted potassium permanganate is reacted away.Separation (10000rpm, 30min) is then centrifuged for, obtains GONR solids.Gained
To GONR solids be washed with deionized 3 times.
As shown in Fig. 2, carbon nanotube used is opened along its length, oxidation carbon nanobelts are obtained.
(2) configuration concentration is 1mg mL-1Graphene oxide-N,N-dimethylformamide (DMF) solution and a concentration of 1mg
mL-1Oxidation carbon nanobelts-N,N-dimethylformamide (DMF) solution.98mg commercialization iron phosphate powders are added to
In 40mL n,N-Dimethylformamide (DMF) solution, magnetic agitation.Then 2.5mL graphene oxides are slowly added dropwise-DMF solution
And 2.5mL oxidation carbon nanobelts-DMF solution, ultrasonic 10min, obtains mixed solution.Then mixed solution is added to spraying
In the feed bin of device, above gas blowout to the nylon leaching film of vacuum filtration.Gas blowout feeding speed is 2mL/min, and gas blowout pressure is
5MPa。
(3) after spraying, the 40 DEG C of drying in an oven of the filter membrane of product be will be covered with, by product it is large stretch of tear, tear
Sample after lower is restored in tube furnace high temperature.High temperature reducing conditions are：Argon gas/hydrogen (V/V, 90/10) atmosphere, 700 DEG C of height
Temperature processing 5h.Resulting materials obtain graphene/carbon nanobelt three-dimensional combination electrode after tablet press machine 30MPa pressure densification realities, can
To be used directly as the anode of battery.As shown in Figure 1, graphene is unfolded arranged in parallel, nanobelt is coated on graphene particles
Above, conductive bridge is erected between graphene and LiFePO4 particle.
Embodiment 2：
Prepare graphene/carbon nanobelt three-dimensional combination electrode (mass ratio mGO：mGONR=4:1)：
(1) concentrated sulfuric acid 36mL, concentrated phosphoric acid 4mL are added in three-necked flask, add in 200mg carbon nanotubes, ultrasonic 0.5h.
Mechanical agitation 2h.The potassium permanganate of 1g is slowly added to, 1h is stirred at room temperature.Then temperature is improved to 75 DEG C, reacts 2h.Reaction terminates
Afterwards, it is purified.The purifying is specially：
First, heat source is removed, is cooled to room temperature, then add in the H containing 10mL mass fractions 35%2O2Ice water mix
Close object.Separation (10000rpm, 30min) is then centrifuged for, obtains GONR solids.Obtained solid is washed with deionized 3 times.
(2) configuration concentration is 1mg mL-1Graphene oxide-N,N-dimethylformamide (DMF) solution and a concentration of 1mg
mL-1Oxidation carbon nanobelts-N,N-dimethylformamide (DMF) solution.98mg commercialization iron phosphate powders are added to
40mLN, in dinethylformamide (DMF) solution, magnetic agitation.Then be slowly added dropwise 4mL graphene oxides DMF solution and
1mL aoxidizes carbon nanobelts DMF solution, ultrasonic 10min.It is then added in the feed bin of spraying device, gas blowout to vacuum filtration
Above nylon leaching film.Gas blowout feeding speed is about 5mL/min, and gas blowout pressure is 20MPa.
(3) after spraying, the 40 DEG C of drying in an oven of the filter membrane of product be will be covered with, by product it is large stretch of tear, general
Product after tearing is restored in tube furnace high temperature.High temperature reducing conditions are：Argon gas/hydrogen (V/V, 90/10) atmosphere, 700 DEG C
High-temperature process 5h.To get to the graphene/carbon nanobelt three after tablet press machine 30MPa pressure densification realities after high temperature reduction
Combination electrode is tieed up, can be used directly as the anode of battery.
Embodiment 3
Prepare graphene/carbon nanobelt three-dimensional combination electrode (mGO：mGONR=1:4)：
(1) concentrated sulfuric acid 36mL, concentrated phosphoric acid 4mL are added in three-necked flask, add in 200mg carbon nanotubes, ultrasonic 0.5h.
Mechanical agitation 2h.The potassium permanganate of 1g is slowly added to, 1h is stirred at room temperature.Then temperature is improved to 75 DEG C, reacts 2h.Reaction terminates
Afterwards, it is purified.The purifying is specially：
First, heat source is removed, is cooled to room temperature, then add in the H containing 10mL mass fractions 35%2O2Ice water mix
Close object.Separation (10000rpm, 30min) is then centrifuged for, obtains GONR solids.Obtained solid is washed with deionized 3 times.
(2) configuration concentration is 1mg mL-1Graphene oxide-N,N-dimethylformamide (DMF) solution and a concentration of 1mg
mL-1Oxidation carbon nanobelts DMF solution.98mg commercialization iron phosphate powders are added to 40mL N,N-dimethylformamides
(DMF) in solution, magnetic agitation.Then 1mL graphene oxides DMF solution is slowly added dropwise and 4mL oxidation carbon nanobelts DMF is molten
Liquid, ultrasonic 10min.It is then added in the feed bin of spraying device, then above gas blowout to the nylon leaching film of vacuum filtration.Feed
Speed is about 2mL/min, and gas blowout pressure is 5MPa.
(3) after spraying, filter membrane 40 DEG C of drying in an oven of product are will be covered with, product can be large stretch of from filter membrane
It tears on ground.Product after tearing is restored in tube furnace high temperature.High temperature reducing conditions are：Argon gas/hydrogen (V/V, 90/10) gas
Atmosphere, 700 DEG C of high-temperature process 5h.Product after high temperature reduction is after tablet press machine 50MPa pressure densification realities to get to the stone of the present invention
Black alkene/carbon nanobelts three-dimensional combination electrode can be used directly as the anode of battery.
Electrode density in embodiment 1 after overcompaction reaches 2.50mg/cm3.As shown in figure 3, for prepared graphite
The scanning electron microscopic picture of alkene/carbon nanobelts three-dimensional structure electrode.It can be seen from the figure that graphene is arranged in parallel；And carbon nanometer
Band is coated on the surface of LiFePO4 between the lamella of graphene, between lithium iron phosphate particles and lithium iron phosphate particles
Conductive bridge is erected between graphene.Meanwhile we are it is also seen that lithium iron phosphate particles heap in the product finally obtained
Product is closely.Graphene/carbon nanobelt three-dimensional combination electrode using quality after compacting as 4mg is anode, and lithium piece is cathode, dense
Spend the LiPF for 1M6It is dissolved in volume ratio 1:1 ethylene carbonate and the mixed solvent of dimethyl carbonate are electrolyte, full of
In the glove box of argon gas, button cell (model 2032) is assembled.Shown in the performance of half-cell such as Fig. 4 (a), specific capacity is under 1C
130mAh·g-1, the specific capacity of 20C is 90mAhg-1, the quality of entire electrode (calculating of specific capacity according to).
Chemical property such as Fig. 4 (b) and 4 (c) of the electrode material of three-dimensional structure prepared by embodiment 2 and embodiment 3
It is shown.Specific capacity is 128mAhg under prepared graphene/carbon nanobelt three-dimensional combination electrode 1C in embodiment 2-1, 20C's
Specific capacity is 53mAhg-1.Specific capacity is under prepared graphene/carbon nanobelt three-dimensional combination electrode 1C in embodiment 3
129mAh·g-1, the specific capacity of 20C is 78mAhg-1.The quality of entire electrode (calculating of specific capacity according to).
Traditionally LiFePO4：Acetylene black：PVDF=8:1:1 (mass ratio) dispensing, with N- methyl -2- pyrrolidines
Ketone (NMP) is solvent, and dispensing in mortar is ground ten minutes, is then scraped slurry above aluminium foil with scraper, is dried in vacuum
It is dried 5 hours for 110 DEG C in case.Tablet press machine 30MPa is compacted, and is cut into the electrode of a diameter of 12mm, load capacity 4mg, in glove box
In be assembled into button cell.Shown in its chemical property such as Fig. 4 (d), specific capacity is 100mAhg under 1C-1, specific capacity under 20C
For 42mAhg-1The quality of entire electrode (calculating of specific capacity according to).
Traditional iron phosphate lithium electrode prepared by scraping slurry is generally used as conductive addition using acetylene black, super P etc.
Agent, in view of the characteristic that the electric conductivity of LiFePO 4 material is poor, the ratio of conductive additive used is generally in 5%-10%.Due to
The density of conventional conductive additive it is low and it is traditional scrape the problem of slurry mode hole is more, the compacting of traditional iron phosphate lithium electrode is close
Degree does not generally exceed 2.2g cm-3.(data calculated in this experiment are 1.9gcm-3).And using conduction in the present invention
As conductive additive, the ratio of conductive additive only has 2% for the excellent graphene of property and carbon nanobelts.And by filter with
And techniques, the electrode density such as subsequent tablet press machine compacting have been increased to 2.7mgcm-3.Due to phosphoric acid designed in the present invention
Iron lithium electrode has both close and conductive good advantage, and the specific discharge capacity under 20C is 90mAhg-1, volume and capacity ratio surpasses
Cross 240mAhcm-3, significantly larger than traditional approach prepare electrode (under 20C, specific discharge capacity 42mAhg-1, volume ratio
Capacity is 80mAhcm-3)。
Claims (8)
1. the preparation method of graphene/carbon nanobelt three-dimensional structure electrode, it is characterised in that：It is as follows,
The first step, using the concentrated sulfuric acid and concentrated phosphoric acid mixture as solvent, using potassium permanganate as oxidant, by carbon nanotube along length side
To opening, oxidation carbon nanobelts GONR is formed；
Oxidation carbon nanobelts, graphene oxide and LiFePO4 are respectively placed in polar solvent, then mix simultaneously by second step
Ultrasound makes it homodisperse, obtains mixed solution；Then mixed solution is added in the feed bin of inhaler, by mixed solution
Above gas blowout to the filter membrane being filtered by vacuum；
Third walks, and after spraying, will be covered with the filter membrane drying of product, then detaches product and filter membrane；By product in argon
Nitrogen atmosphere high temperature restores, and then after the compacting of tablet press machine, obtains the graphene/carbon nanobelt three-dimensional compound electric of the present invention
Pole.
2. the preparation method of graphene/carbon nanobelt three-dimensional structure electrode according to claim 1, it is characterised in that：The
The volume ratio of the concentrated sulfuric acid and concentrated phosphoric acid described in one step is 9:1.
3. the preparation method of graphene/carbon nanobelt three-dimensional structure electrode according to claim 1, it is characterised in that：The
One step specifically,
Concentrated sulfuric acid 36mL, concentrated phosphoric acid 4mL are added in three-necked flask, add in 200mg carbon nanotubes, ultrasonic 0.5h, then machinery
Stir 2h；The potassium permanganate of 1g is slowly added to, 1h is stirred at room temperature；Then temperature is improved to 75 DEG C, reacts 2h；After reaction,
It is purified；The purifying is specially：
First, heat source is removed, is cooled to room temperature, then add in the H containing 10mL mass fractions 35%2O2Mixture of ice and water,
It is then centrifuged for detaching, obtains GONR solids；Obtained GONR solids are washed with deionized 3 times.
4. the preparation method of graphene/carbon nanobelt three-dimensional structure electrode according to claim 1, it is characterised in that：The
Polar solvent selection N,N-dimethylformamide, DMAC N,N' dimethyl acetamide or n-methyl-2-pyrrolidone described in two steps；
The filter membrane is nylon leaching film.
5. the preparation method of graphene/carbon nanobelt three-dimensional structure electrode according to claim 1, it is characterised in that：The
The conditional parameter of gas blowout described in two steps is：Pressure is 5-20MPa, speed 2-5mL/min；The graphene oxide and oxidation
The mass ratio of carbon nanobelts is 1:4-4:1.
6. the preparation method of graphene/carbon nanobelt three-dimensional structure electrode according to claim 1, it is characterised in that：The
The condition of high temperature reduction described in three steps is：Argon/hydrogen atmosphere, volume ratio 90:10,700 DEG C of high-temperature process 5h；The tabletting
Machine pressing pressure is 30-50MPa.
7. a kind of graphene/carbon nanobelt three-dimensional structure electrode, it is characterised in that：Electrode density reaches 2.50mg/cm3, graphene
Unfold arranged in parallel, nanobelt is coated on above graphene particles, is erected between graphene and LiFePO4 particle conductive
Bridge.
8. a kind of application of graphene/carbon nanobelt three-dimensional structure electrode according to claim 7, it is characterised in that：It will
The graphene/carbon nanobelt three-dimensional structure electrode is directly used in energy-storage battery electrodes conduct network, half-cell matter under 1C
Amount specific capacity is 128~130mAhg-1, the specific capacity of 20C is 53~90mAhg-1。
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| CN109903998A (en) * | 2019-02-26 | 2019-06-18 | 内蒙古科技大学 | A kind of combination electrode and its preparation method and application |
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| CN104064735A (en) * | 2013-03-18 | 2014-09-24 | 海洋王照明科技股份有限公司 | Lithium titanate-graphene-carbon nanotube composite material and preparation method and application thereof |
| CN104716320A (en) * | 2015-03-10 | 2015-06-17 | 中国科学院过程工程研究所 | Composite-coated lithium iron phosphate, preparation method of composite-coated lithium iron phosphate, and lithium ion battery |
| CN106450174A (en) * | 2016-05-23 | 2017-02-22 | 重庆大学 | Preparation method for graphene nanobelt-lithium iron phosphate composite material |
| CN107394184A (en) * | 2017-08-11 | 2017-11-24 | 福州大学 | A kind of molybdenum disulfide/graphene nano belt composite with loose three-dimensional winding arrangement and its preparation method and application |
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| CN104064735A (en) * | 2013-03-18 | 2014-09-24 | 海洋王照明科技股份有限公司 | Lithium titanate-graphene-carbon nanotube composite material and preparation method and application thereof |
| CN104716320A (en) * | 2015-03-10 | 2015-06-17 | 中国科学院过程工程研究所 | Composite-coated lithium iron phosphate, preparation method of composite-coated lithium iron phosphate, and lithium ion battery |
| CN106450174A (en) * | 2016-05-23 | 2017-02-22 | 重庆大学 | Preparation method for graphene nanobelt-lithium iron phosphate composite material |
| CN107394184A (en) * | 2017-08-11 | 2017-11-24 | 福州大学 | A kind of molybdenum disulfide/graphene nano belt composite with loose three-dimensional winding arrangement and its preparation method and application |
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| CN109903998A (en) * | 2019-02-26 | 2019-06-18 | 内蒙古科技大学 | A kind of combination electrode and its preparation method and application |
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