CN110518260A - A kind of production method of modified vanadium cell porous electrode graphite felt - Google Patents
A kind of production method of modified vanadium cell porous electrode graphite felt 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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
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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
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- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
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Abstract
The present invention relates to a kind of production method of modified vanadium cell porous electrode graphite felt, method particularly includes: pre- oxygen felt sequentially enters the low-temperature carbonization area of continuous fritting furnace and high temperature graphitization area and is sintered, enters back into continuous activating oven activation processing；Before graphite felt is activated, it is uniformly sprinkled into catalyst bismuth nitrate powder on graphite felt surface, is realized " a kind of catalyst, two step modified effects "；The bismuth nitrate being added can not only aoxidize felt body surface face, form it into nano micropore structure, increase specific surface area, while bismuth nitrate can decompose in activation process, the product deposition after decomposition further modifies Carbon felt surface in Carbon felt surface.Advantages of the present invention: electrochemical reaction activity not only can be improved, the side reaction of electrode can also be inhibited, improve battery.Save the cost in industrial production, method is simply easily operated, and the feature of environmental protection is strong.
Description
Technical field
The invention belongs to the technical field of electrode material production method, specifically a kind of modified vanadium cell porous electrode
The production method of graphite felt.
Background technique
With the development of industrialization, mankind's early-stage development is largely displayed using the drawbacks of fossil fuels such as coal, petroleum,
Bring environmental pollution and therefore caused climate change, threaten in the reduction and use process of these non-renewable resources
The mankind normally produce, live, and are the common challenges of facing mankind.The new energy such as water energy, wind energy, biological energy source, solar energy, geothermal energy
Source electricity generation system has many advantages, such as that resourceful, renewable, effect on environment is small, distribution is wide, but due to its energy density is low,
The disadvantages of having a rest property and big fluctuation, can not achieve continuous energy supply.The exploitation of energy storage technology can turn those unstable energy
Chemical conversion electric energy stores, and controls the consumption of energy, to the integration of renewable energy, utilizes important role.Now, people
Explored, had developed the energy storage means of diversified forms, these energy storage modes can be divided mainly into physics energy storage, chemistry storage
Energy, Power Flow and phase-change accumulation energy etc..And in numerous energy storage modes, redox flow batteries are due to its power, capacity
Greatly, high-efficient, the features such as service life is long, it can be used for building extensive, powerful peak regulation energy-accumulating power station, improve the stabilization of power grid
Property；It can also be combined with renewable energy power generations such as solar energy, wind energy, water energys, establish energy storage, power generation system in outlying district
System, these unstable energy conversions are stored at electric energy, are exported when needed.At present both at home and abroad to flow battery
Research be concentrated mainly on vanadium redox battery, iron/chrome liquor galvanic battery, sodium polysulfide/bromine redox flow cell, zinc/
Bromine flow battery etc..
Wherein, compared with other energy-storage batteries, all-vanadium flow battery has following characteristics:
1. the output power of battery depends on the size and number of pile, stored energy capacitance depends on electrolyte volume and concentration, because
This its design is very flexible, Yao Zengjia output power, as long as increasing the area of pile and the quantity of pile, Yao Zengjia energy storage is held
Amount, as long as increasing the volume of electrolyte；
2. the active material of all-vanadium flow battery is the vanadium ion for being dissolved in the different valence state of aqueous solution, in all-vanadium flow battery
During charge and discharge, only ionic valence condition changes, and undergoing phase transition is not reacted, and charge and discharge answer speed is fast；
3. electrolyte metal ion only has vanadium ion a kind of, positive and negative electrolyte active material will not occur and intersect pollution
Problem, battery is long, and electrolyte solution regenerating easily is recycled；
4. charging-discharging performances are good, can deep discharge without damaging battery, self discharge is low.When system is in close pattern, storage tank
In electrolyte without self-discharge phenomenon；
5. flow battery addressing freedom degree is big, system can Full automatic sealing operation, pollution-free, maintenance is simple, and operating cost is low；
6. electrolyte solution is aqueous solution, battery system is highly-safe without potential explosion or fire hazard；
7. battery component is mostly cheap Carbon Materials, engineering plastics, material source is abundant, and dirt will not be generated in removal process
Dye, it is environmental-friendly；
8. energy efficiency is high, up to 70%, cost performance is good；
9. it is fast to start speed, if can start in 2 min in pile full of electrolyte, charging and discharging state is cut in the process of running
It changes and only needs 0.02 s；
10. battery system state-of-charge (SOC) in real time, can be monitored accurately, is conducive to power grid and is managed, dispatches.
At present both at home and abroad all-vanadium flow battery main manufacturing enterprise have Dalian Raycom energy storage company (Rongke Power),
SUMITOMO CHEMICAL Electric Industrial Co., Ltd (Sumitomo Electric Industries) and Beijing Pu Neng company.
The electrode material of all-vanadium flow battery requires the anti-Strong oxdiative of the burn into of resistance to strong acid, has excellent electro-chemical activity, leads
Electrical property, reproducibility, stability and mechanical strength.Graphite felt, especially PAN based graphite felt electrode and viscose-based graphite felt
Electrode, due to that can provide sufficient redox reaction active sites and good electronics is passed with biggish specific surface area
The property led, mechanical stability and be widely used in all-vanadium flow battery.Although the comprehensive performance of graphite felt is superior, as electricity
Extremely electro-chemical activity is not still able to satisfy the increasingly developed requirement of vanadium cell, needs to be modified graphite felt processing to mention
Its high chemical property.And since carbon material overpotential of hydrogen evolution is lower, with the continuous raising of charging voltage, V2+ /V3+Instead
It should be replaced by liberation of hydrogen side reaction.On the one hand liberation of hydrogen side reaction is easy to cause material surface to be etched, another aspect material surface
Oxygen-containing functional group be consumed so that active site reduce, reduce negative reaction rate, battery coulombic efficiency and energy efficiency
It is greatly reduced, the decaying for accelerating battery capacity even results in battery life and terminates in advance.Therefore, modified to electrode graphite felt
It is an important development direction of vanadium redox flow battery electrode.
Summary of the invention
The purpose of the invention is to modified electrode graphite felt, extend the use of battery while improving its electro-chemical activity
Service life provides a kind of preparation method of high-performance electrode graphite felt that can be used under high current densities.
The present invention provides a kind of preparation method of high-performance electrode graphite felt that can be used under high current densities,
Concrete operations are as follows:
A kind of production method of modified vanadium cell porous electrode graphite felt, it is characterised in that: pre- oxygen felt sequentially enters continuous sintering
The low-temperature carbonization area and high temperature graphitization area of furnace are sintered, enter back into continuous activating oven activation processing；It is sintered in sintering furnace
Inert protective gas is passed through in journey, the sintering time of sintering furnace is 30-1500 minutes, and sintering furnace is 750-1350 DEG C in furnace temperature and is
Carbonizing zone, it is high temperature graphitization area that furnace temperature, which is 1800-2400 DEG C, becomes graphite felt after high temperature graphitization area is sintered；To
When graphite felt is cooled to 100-150 DEG C, it is uniformly first sprinkled into catalyst bismuth nitrate powder on graphite felt surface, subsequently into continuous living
Change furnace to be activated, activation furnace activation temperature is 400-1000 DEG C, and activation time is 10-350 minutes, in activation process
It is passed through oxidizing gas；Room temperature is down to after activation again and contains nanometer level microporous vanadium battery electrode graphite up to what bismuth was modified
Felt finished product.
Before graphite felt enters continuous activating oven activation processing, catalyst nitric acid bismuth meal is uniformly sprinkled on graphite felt surface
End, bismuth nitrate decomposites nitrate anion at high temperature, nitrate ion can be made with oxide etch carbon fiber surface crystallite lattice by
It destroys, reduces its crystallite dimension, formed in carbon fiber surface nanometer level microporous.The electrode aperture of usual carbon fiber is tens micro-
Rice, mainly as macroscopical access of electrolyte of vanadium redox battery flowing.And nanometer level microporous sufficient work is provided for electrochemical reaction
Property site, increase its surface by a large amount of oxygen-containing functional group, and then play the role of the redox reaction for being catalyzed vanadium ion；It is this
Porous structure increases electrode specific surface area does not influence the permeability of electrode simultaneously.
Start to activate when activation in-furnace temperature rises to 800 DEG C, activation time is 20-400 minutes, bismuth nitrate in activation process
Bismuth oxide can be resolved at 400-500 DEG C, the C that part bismuth oxide generates during being activated is reduced into Bi, three oxygen
Change two bismuths and bismuth is deposited on the surface of carbon felt simultaneously, also inhibits liberation of hydrogen side reaction while catalytic oxidation-reduction reacts, improve vanadium
The recyclability of battery.Room temperature is down to after activation again and contains nanometer level microporous vanadium battery electrode graphite up to what bismuth was modified
Felt.
Continuous sintering furnace superintendent 75m of the present invention, and set according to following temperature: 0-2m, room temperature；2-5m,300℃；5-
10m,750℃；10-15m, 1000 DEG C；15-20m, 1300 DEG C；20-25m, 1600 DEG C；25-30m,1900℃；30-35m,2100
℃；35-40m,2400℃；40-45m,2200℃；45-50m,1900℃；50-55m,1500℃；55-60m,1000℃；60-
65m,500℃；65-75m,100℃；Heating curve is adjusted at any time by the live felt condition of production.
The long 25m of continuous activating oven of the present invention, and set according to following temperature: 0-3m, 300 DEG C；3-6m, 500 DEG C,
6-10m,700℃；10-18m,1000℃；18-22m, 500 DEG C；22-25m, room temperature.The heating curve of activation by felt thickness
The parameters such as degree, performance, density, fiber dimensious are adjusted at any time；
Pre- oxygen felt of the present invention in continuous oven with 0.075-2.5m/min at the uniform velocity or speed change transmission；
The granular size of bismuth nitrate powder of the present invention is 50-200 mesh.
1, the continuous fritting furnace selected by the present invention and continuous activating oven series connection, sintering furnace low-temperature space are first warming up to 750-
It 1350 DEG C, enters back into high-temperature region and is warming up to 1800-2600 DEG C, being passed through inert gas shielding during this period makes to produce steady progress；
Activating furnace temperature is 600-1000 DEG C, is down to room temperature after activation again, is passed through oxidizing gas during this period, being passed through rate is
50-300m3/h；
2, the pre- oxygen felt that the present invention selects is the pre- oxygen felt of polyacrylonitrile-radical or the pre- oxygen felt of viscose glue base.
3, the pre- oxygen felt thickness selected by the present invention is within the scope of 1.5-20mm, density 0.05-0.20g/cm3。
4, catalyst bismuth nitrate selected in experiment is decomposed into Bi when activation temperature is 400-500 DEG C2O3, part
Bi2O3The C generated during being activated is reduced into Bi, Bi2O3It is deposited on Carbon felt surface simultaneously with Bi.
5, the inert gas used in the present invention is the one of which of argon gas, helium or nitrogen；Ventilation Rate is 100m3/h-
500m3/h；Oxidizing gas is the one of which of vapor, air, oxygen, carbon monoxide or carbon dioxide；Being passed through rate is
50-300m3/h。
6, activation time of the pre- oxygen felt of the present invention in activation furnace is 20-400 minutes；Activation time after optimization is 30-
350 minutes；
7, the dosage of catalyst of the present invention does adjusting appropriate, catalyst bismuth nitrate according to type and thickness, the density of raw material felt
Dosage be pre- oxygen felt weight 2%-8%；
8, the electro-chemical activity for the graphite felt for selecting the method for the present invention to obtain can significantly improve, in high electric density 300mA/cm2, voltage
Efficiency increase rate is about 10%-13%；
The advantages of this method is:
(1) modified electrode graphite felt is primarily due to oxidation and forms it into nano micropore structure, increases the specific surface of electrode
Product, makes to increase more oxygen-containing functional groups in activation process, improves the wetability and electro-chemical activity of graphite felt.And metal Bi is repaired
Electrode graphite felt after decorations not only improves the electric conductivity of electrode, also reduces VO2+/VO2 +The redox overpotential of electricity pair,
Inhibit liberation of hydrogen side reaction, improve cyclical stability, extends battery.
(2) electrode of the modified graphite felt of the present invention as all-vanadium flow battery is used, the internal resistance of cell can be reduced, make electricity
The electric current and voltage efficiency in pond significantly improve.
(3) compared with being modified frequently with coating process to carbon fiber surface, electrode graphite felt service life of the present invention is long,
There is no coatings to fall off because long-term electrolyte washes away and pollutes electrolyte phenomenon.
(4), by the way that a kind of modified effect of two steps of catalyst completion is added, cost has been saved in industrial production and method is simple
Convenient for operation.
Detailed description of the invention:
1, Fig. 1 a is that surface forms nanometer level microporous carbon fiber scanning electron microscope (SEM) photograph；
Fig. 1 b is the modified scanning electron microscope (SEM) photograph containing nanometer level microporous electrode graphite felt of bismuth；
2, it is 110mA/cm that Fig. 2, which is in current density,2Under the conditions of, unmodified graphite felt and modified graphite felt voltage efficiency compare
Figure；
3, it is 300mA/cm that Fig. 3, which is in current density,2Under the conditions of, unmodified graphite felt and modified graphite felt voltage efficiency compare
Figure.
Specific embodiment
Invention will be described in further detail by example below, but following examples is only present invention example therein
Son, does not represent rights protection scope defined by the present invention, the scope of the present invention is with claims
It is quasi-.
Embodiment 1
By the pre- oxygen felt of polyacrylonitrile-radical, (thickness is 12mm, and density is 0.12g/cm3), pass through conveyer belt (walking speed 0.083m/
Min the low-temperature carbonization area of continuous fritting furnace and high temperature graphitization area) is sequentially entered to be sintered and be activated with continuous activating oven.
Being passed through flow during the sintering process is 500m3The nitrogen protection gas of/h makes to produce stable progress.Sintering furnace is in furnace temperature
750-1350 DEG C is carbonizing zone, and it is high temperature graphitization area that furnace temperature, which is 1800-2400 DEG C,；After high temperature graphitization area is sintered at
For graphite felt；When graphite felt is cooled to 100-150 DEG C, it is uniformly first sprinkled into 6% catalyst bismuth nitrate powder on graphite felt surface,
Then graphite felt is sent into continuous activating oven, furnace body is gradually heated to 1000 DEG C, while it is 300m that steam, which is passed through rate,3/ h, warp
Activation in 300 minutes is crossed, it is finished product that room temperature is down in discharging.
The continuous sintering furnace superintendent 75m, and set according to following temperature: 0-2m, room temperature；2-5m,300℃；5-10m,750
℃；10-15m, 1000 DEG C；15-20m, 1300 DEG C；20-25m, 1600 DEG C；25-30m,1900℃；30-35m,2100℃；35-
40m,2400℃；40-45m,2200℃；45-50m,1900℃；50-55m,1500℃；55-60m,1000℃；60-65m,500
℃；65-75m,100℃.
The long 25m of the continuous activating oven, and set according to following temperature: 0-3m, 300 DEG C；3-6m, 500 DEG C, 6-
10m,700℃；10-18m,1000℃；18-22m, 500 DEG C；22-25m, room temperature.
As shown, it is 110mA/cm that Fig. 2, which is in current density,2Under the conditions of, unmodified electrode graphite felt and modified electrode
Graphite felt voltage efficiency comparison diagram., it is evident that modified electrode graphite felt voltage efficiency is than electrode before modified from figure
Graphite felt voltage efficiency attenuation amplitude reduces, while voltage efficiency improves 3% -4%.
As shown, it is 300mA/cm that Fig. 3, which is in current density,2Under the conditions of, unmodified electrode graphite felt and modified electrode
Graphite felt voltage efficiency comparison diagram.Dotted line is the voltage efficiency and cycle-index tendency chart of unmodified graphite felt, is followed at 1-10
In ring, voltage efficiency fluctuates between 71.62% -73.73%；With increasing for cycle-index, voltage efficiency attenuation amplitude compared with
Greatly.Solid line is the voltage efficiency and cycle-index tendency chart of modified graphite felt in figure, and interior voltage efficiency is recycled at 1-10 and is existed
It is fluctuated between 83.60% -84.68%；With the increase of cycle-index, voltage efficiency slightly decays, and attenuation amplitude is smaller.From whole
It is seen on body, modified voltage efficiency improves 10% or so than the voltage efficiency of unmodified graphite felt, and extends battery use
Service life.
Embodiment 2
By the pre- oxygen felt of polyacrylonitrile-radical, (thickness is 11mm, and density is 0.10g/cm3), production method with embodiment 1, take away by transmission
Speed is 0.089m/min, and the argon flow being passed through in sintering process is 400m3/ h is uniformly sprinkled into 5% nitric acid on graphite felt surface
Bismuth meal end, is then fed into continuous activating oven and is activated, while being passed through carbon dioxide rate is 200m3/ h, by work in 280 minutes
Change, it is finished product that material, which is down to room temperature,.
Embodiment 3
By the pre- oxygen felt of viscose glue base, (thickness is 8mm, and density is 0.133g/cm3), successively by conveyer belt (walking speed 0.1m/min)
It is sintered into the low-temperature carbonization area of continuous fritting furnace and high temperature graphitization area and is activated with continuous activating oven.Sintered
It is 300m that flow is passed through in journey3The nitrogen protection gas of/h makes to produce stable progress.Sintering furnace is 750-1350 DEG C in furnace temperature
For carbonizing zone, it is high temperature graphitization area that furnace temperature, which is 1800-2200 DEG C,；Become graphite felt after high temperature graphitization area is sintered；
When graphite felt is cooled to 100-150 DEG C, it is uniformly first sprinkled into 3% catalyst bismuth nitrate powder on graphite felt surface, then by graphite
Felt is sent into continuous activating oven, and furnace body is gradually heated to 900 DEG C, while it is 150m that carbon dioxide, which is passed through rate,3/ h, by 250 points
The activation of clock, it is finished product that room temperature is down in discharging.
The continuous sintering furnace superintendent 75m, and set according to following temperature: 0-2m, room temperature；2-5m,300℃；5-10m,750
℃；10-15m, 1000 DEG C；15-20m, 1300 DEG C；20-25m, 1600 DEG C；25-30m,1800℃；30-35m,2000℃；35-
40m,2200℃；40-45m,2000℃；45-50m,1800℃；50-55m,1500℃；55-60m,1000℃；60-65m,500
℃；65-75m,100℃.
The long 25m of the continuous activating oven, and set according to following temperature: 0-3m, 300 DEG C；3-6m, 500 DEG C, 6-
10m,700℃；10-18m,900℃；18-22m, 500 DEG C；22-25m, room temperature.
Embodiment 4
By the pre- oxygen felt of viscose glue base, (thickness is 4mm, and density is 0.125g/cm3), successively by conveyer belt (walking speed 0.1m/min)
It is sintered into the low-temperature carbonization area of continuous fritting furnace and high temperature graphitization area and is activated with continuous activating oven.Sintered
It is 200m that flow is passed through in journey3The nitrogen protection gas of/h makes to produce stable progress.Sintering furnace is 750-1350 DEG C in furnace temperature
For carbonizing zone, it is high temperature graphitization area that furnace temperature, which is 1800-2000 DEG C,；Become graphite felt after high temperature graphitization area is sintered；
When graphite felt is cooled to 100-150 DEG C, it is uniformly first sprinkled into 2% catalyst bismuth nitrate powder on graphite felt surface, then by graphite
Felt is sent into continuous activating oven, and furnace body is gradually heated to 800 DEG C, while it is 100m that carbon dioxide, which is passed through rate,3/ h, by 250 points
The activation of clock, it is finished product that room temperature is down in discharging.
The continuous sintering furnace superintendent 75m, and set according to following temperature: 0-2m, room temperature；2-5m,300℃；5-10m,650
℃；10-15m, 900 DEG C；15-20m, 1100 DEG C；20-25m, 1300 DEG C；25-30m,1600℃；30-35m,1800℃；35-
40m,2000℃；40-45m,1800℃；45-50m,1600℃；50-55m,1300℃；55-60m,1000℃；60-65m,500
℃；65-75m,100℃.
The long 25m of the continuous activating oven, and set according to following temperature: 0-3m, 300 DEG C；3-6m, 500 DEG C, 6-
10m,650℃；10-18m,800℃；18-22m, 500 DEG C；22-25m, room temperature.
Claims (10)
1. a kind of production method of modified vanadium cell porous electrode graphite felt, it is characterised in that: pre- oxygen felt sequentially enters continuous burning
The low-temperature carbonization area and high temperature graphitization area of freezing of a furnace are sintered, enter back into continuous activating oven activation processing；It is sintered in sintering furnace
It is passed through inert protective gas in the process, the sintering time of sintering furnace is 30-1500 minutes, and sintering furnace is 750-1350 DEG C in furnace temperature
For carbonizing zone, it is high temperature graphitization area that furnace temperature, which is 1800-2400 DEG C, becomes graphite felt after high temperature graphitization area is sintered；
When graphite felt is cooled to 100-150 DEG C, it is uniformly first sprinkled into catalyst bismuth nitrate powder on graphite felt surface, subsequently into continuous
Activation furnace is activated, and activation furnace activation temperature is 400-1000 DEG C, and activation time is 10-350 minutes, in activation process
In be passed through oxidizing gas；Room temperature is down to after activation again and contains nanometer level microporous vanadium battery electrode stone up to what bismuth was modified
Black felt finished product.
2. production method according to claim 1, it is characterised in that: the continuous sintering furnace superintendent 75m, and according to following temperature
Degree setting: 0-2m, room temperature；2-5m,300℃；5-10m,750℃；10-15m, 1000 DEG C；15-20m, 1300 DEG C；20-25m,
1600℃；25-30m,1900℃；30-35m,2100℃；35-40m,2400℃；40-45m,2200℃；45-50m,1900℃；
50-55m,1500℃；55-60m,1000℃；60-65m,500℃；65-75m,100℃.
3. production method according to claim 1, it is characterised in that: the long 25m of the continuous activating oven, and according to following
Temperature setting: 0-3m, 300 DEG C；3-6m, 500 DEG C, 6-10m, 700 DEG C；10-18m,1000℃；18-22m, 500 DEG C；22-25m,
Room temperature.
4. production method according to claim 1, it is characterised in that: the pre- oxygen felt is in continuous oven with 0.075-
2.5m/min is at the uniform velocity or speed change transmits.
5. production method according to claim 1, it is characterised in that: the pre- oxygen felt be the pre- oxygen felt of polyacrylonitrile-radical or
The pre- oxygen felt of viscose glue base.
6. production method according to claim 1 or 5, it is characterised in that: the pre- oxygen felt with a thickness of 1.5-20mm, in advance
The density of oxygen felt is 0.05-0.20g/cm3.
7. production method according to claim 1, it is characterised in that: the inert gas is argon gas, helium or nitrogen
One of which, Ventilation Rate 100m3/h-500m3/h.
8. production method according to claim 1, it is characterised in that: it is described be passed through oxidizing gas be vapor, air,
The one of which of oxygen, ozone or carbon dioxide；Being passed through rate is 50-300m3/h.
9. production method according to claim 1, it is characterised in that: the granular size of the bismuth nitrate powder is 50-200
Mesh.
10. production method according to claim 1, it is characterised in that: the dosage of catalyst bismuth nitrate is pre- oxygen felt weight
2%-8%.
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| CN110860316A (en) * | 2019-11-30 | 2020-03-06 | 西北化工研究院有限公司 | Activation method for hydrocarbon oxidation VPO catalyst |
| CN112054215A (en) * | 2020-08-05 | 2020-12-08 | 深圳大学 | Composite electrode for redox flow battery based on all vanadium and preparation method thereof |
| CN113036128A (en) * | 2019-12-09 | 2021-06-25 | 中国科学院大连化学物理研究所 | Flexible carbon material layer and preparation method and application thereof |
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