CN107039659A - A kind of preparation method of vanadium redox flow battery electrode material - Google Patents
A kind of preparation method of vanadium redox flow battery electrode material Download PDFInfo
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- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
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- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
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- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0069—Electro-spinning characterised by the electro-spinning apparatus characterised by the spinning section, e.g. capillary tube, protrusion or pin
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- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0092—Electro-spinning characterised by the electro-spinning apparatus characterised by the electrical field, e.g. combined with a magnetic fields, using biased or alternating fields
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Abstract
The present invention relates to battery manufacture and energy storage field, specially a kind of preparation method of vanadium redox flow battery electrode material.First using alkaline lignin as examination material, utilize phenolic hydroxyl group active function groups in alkaline lignin structure, the alkaline lignin portion of methylolation is substituted into resorcinol and synthesizes organogel with formaldehyde under catalyst action, using the gel as precursor, the spinning liquid as precursor needed for preparation experiment passes through the method for electrostatic spinning, prepare fiber precursor electrode material, electrode material presoma is pre-oxidized using vacuum/atmosphere furnace, is carbonized in an inert atmosphere, carbon fiber electrode material is obtained.The vanadium cell carbon fiber electrode material prepared using the inventive method, fibre diameter is in Nano grade, specific surface area is greatly increased compared to traditional carbon felt class electrode material, due to the pre-oxidation treatment in later stage, the oxygen content of fiber surface also improves a lot, the preparation available for vanadium cell carbon fiber electrode material.
Description
Technical field
The present invention relates to battery manufacture and energy storage field, specially a kind of preparation of vanadium redox flow battery electrode material
Method.
Background technology
Vanadium redox battery (vanadium cell) is as a kind of new electrochemical energy storage system, with efficient, peace
The advantages of complete and environmental protection, applied as regenerative resource scale electrification energy storage, peak load regulation network etc., be always in recent years battery grind
The focus studied carefully.Electrode is to influence one of critical material of vanadium cell performance, the method for selection and the modified optimization of its active material
It is also the principal element for restricting the further industrialized development of vanadium cell and application also in further research.
Carbon material specific surface area by representative of graphite felt is big, pliability is good, is easy to process and assembles, and is suitable as vanadium electricity
Pond electrode material.But, graphite felt is poor to the electrochemical catalysis activity of different valence state vanadium ion, the commercial graphite of different batches
Felt performance has differences, even if can not also ensure that overall performance is homogeneous, constrains whole energy-storage system with a batch of graphite felt
Output power density and energy efficiency.Although by adjust graphite felt surface physics structure (surface topography, specific surface area,
Composite catalyst) and chemical constitution (surface functional group) its chemical property can be improved to a certain extent.But existing modification
Method does not investigate influence of the carbon material bulk properties (such as degree of graphitization, microstructure) to electro-chemical activity, and modification experiment bar
Part is more complicated, and existing load method of modifying can not ensure stability of the effective catalyst on carbon fiber, i.e. catalyst has very much
It may be washed away in battery charge and discharge process by liquid stream.It is difficult to meet the long-term electrochemical stability of vanadium battery electrode and high activity
Technical requirements.
Electrostatic spinning technique provides new taste for the research carbon nano-fiber electrode that specific surface area is big, electro-chemical activity is high
Examination.But, electrostatic spinning PAN base carbon fibre precursor polyacrylonitrile faces that consumption is big, carbonization rate is low, expensive and not
Reproducible problem.Therefore, new green, the carbon precursor of environmental protection are explored, high-specific surface area, high conductivity, high electrification is prepared
Learn activity, the carbon nano-fiber electrode of structure-controllable turns into the important directions that vanadium cell develops, be also that vanadium cell development is urgently solved
One of key issue certainly.
Lignin is the natural polymer that cellulose is only second in quantity, and carbon content is high, using phenyl-propane as construction unit.
But, because aromatic monocyclic constitutes complicated stereochemical structure in lignin molecule structure, crosslinking bonding is strong, the carbon for causing it to prepare
Fiber is axially oriented poor, and fibre strength is low, even if high-temperature process, and carbon fiber surface crystal growth is difficult, carbonized fiber
Degree of graphitization is low, poorly conductive, its hardly possible is turned into the electrode material of excellent performance.
The content of the invention
It is an object of the invention to provide a kind of method for preparing vanadium redox flow battery electrode material, using present invention preparation
Vanadium cell electrode material, carbon fiber diameter is in Nano grade, and specific surface area is compared to traditional used electrode material significantly
Increase, due to using lignin-base organogel be carbon precursor, the inventive method prepare vanadium cell electrode material have than
Surface area height, good conductivity, electro-chemical activity are good, environmental protection advantage.
The technical scheme is that：
A kind of preparation method of vanadium redox flow battery electrode material, the preparation of preparation, spinning solution comprising precursor, electrostatic
Spinning, pre-oxidation and carbonization, five steps of cleaning-drying, precursor is using alkaline lignin as base material, by lignin dissolution to alkali
In solution, addition formaldehyde, resorcinol, stirring extremely forms organogel in the presence of metal salt catalyst, be aged through closing,
Crush, obtain the organic xerogel of precursor；
Wherein, the mean molecule quantity of alkaline lignin is 1000~20000, and aqueous slkali is sodium hydroxide solution, hydroxide
Potassium solution or ammoniacal liquor, metal salt catalyst are cobalt salt, nickel salt or molysite.
The preparation method of described vanadium redox flow battery electrode material, it is in the preparation process of precursor, lignin is molten
Solution is into aqueous slkali, and the mass ratio of lignin and aqueous slkali is 5：1~50：1, stirred after adding formaldehyde, adjust pH value
For 8~14.
The preparation method of described vanadium redox flow battery electrode material, in the preparation process of precursor, alkaline lignin
Mol ratio with resorcinol is 2：1~1：20, the mol ratio of alkaline lignin+resorcinol and formaldehyde is 1：2~1：50, alkali
Property lignin+resorcinol and metal salt catalyst mol ratio be 20：1~100：1.
The preparation method of described vanadium redox flow battery electrode material, in the preparation process of precursor, stirring to formation
The mixing time of organogel is 0.5~24h.
The preparation method of described vanadium redox flow battery electrode material, in the preparation process of spinning solution, after crushing
The organic xerogel of precursor is added in nitrogen, nitrogen dimethylformamide organic solution with polyacrylonitrile, stirs equal under water bath condition
It is even；Wherein, the mean molecule quantity of polyacrylonitrile is 80000~200000, and the mass ratio of organic xerogel and polyacrylonitrile is
5：95~90：10, organic xerogel+polyacrylonitrile and nitrogen, the mass ratio of nitrogen dimethylformamide are 5：95~20：80, water
Bath temperature is 20~80 DEG C.
The preparation method of described vanadium redox flow battery electrode material, during electrostatic spinning, by the preceding body 2) obtained
Electrode material precursor fibre precursor is made through electrostatic spinning technique in body spinning solution；The technological parameter of electrostatic spinning is：Syringe needle
Pinhole diameter is 0.3~2mm, and the capacity of syringe is 20~500mL, and the injection flow that syringe is controlled is 0.2~5mL/h.
The preparation method of described vanadium redox flow battery electrode material, the voltage between syringe needle and transfer roller is 10~40kV,
The distance between syringe needle and transfer roller are 10~30cm, and the rotating speed of transfer roller is 0~3000r/min, and spinning temperature is 15~30 DEG C, is spun
Silk humidity is 20~50%RH.
The preparation method of described vanadium redox flow battery electrode material, in pre-oxidation and carbonisation, Pre oxidation
For 200~500 DEG C, the time is 1~3h, and the programming rate of pre-oxidation treatment is 2~20 DEG C/min；Carburizing temperature be 800~
1500 DEG C, the time is 1~10h, and the programming rate of carbonization treatment is 2~20 DEG C/min；Pre-oxidation and carbonization protect gas in inertia
Carried out in atmosphere, the flow of gas is 20~150mL/min in inert protective atmosphere.
The preparation method of described vanadium redox flow battery electrode material, during cleaning-drying, by the electricity after cleaning
Pole material, is dried in vacuum drying chamber or air dry oven, and drying temperature is 60~100 DEG C, and processing time is 24~48h,
Electrode material thickness after drying is in 0.1~5mm.
The preparation method of described vanadium redox flow battery electrode material, the electrode material finally given is by carbon nano-fiber
The controllable block materials of the thickness that is entwined.
The present invention design philosophy be：
The method comprises the steps of firstly, preparing lignin-base gel precursor, then the precursor spinning solution needed for preparation experiment, passes through
The method of electrostatic spinning, is prepared required fiber precursor, fiber precursor is pre-oxidized using vacuum/atmosphere furnace afterwards
(temperature control is at 200~500 DEG C), are carbonized (temperature control is at 800~1500 DEG C) in an inert atmosphere, obtain required electricity
Pole material.After resulting electrode material is cleaned, dried, you can carry out the charge-discharge test of battery.Using the present invention
Method prepare vanadium cell electrode material, carbon fiber diameter is in Nano grade, and specific surface area is compared to traditional used electricity
Pole material is greatly increased, due to the pre-oxidation treatment in later stage so that the also very big raising, functional group pair of the oxygen content of fiber surface
Electrode reaction also has preferable catalytic action, is expected to greatly improve the energy efficiency of battery, and by controlling precursor system
Standby parameter, electrostatic spinning process parameter and pre-oxidation, carbocyclic ring condition etc., can effectively control microscopic appearance, composition of material etc.,
Efficient, practical technique that the preparation method is prepared for a kind of electrode used for all-vanadium redox flow battery.
The present invention has the advantage that and technique effect：
1. the lignin of nature rich reserves is applied to the preparation of vanadium cell electrode material by the present invention, with green,
Environmental protection, the advantage that cost is low, carbonization rate is high.
2. the present invention is reacted by precursor, the lignin-base carbon nano-fiber with graphite flake layer stacking provisions is prepared,
Electrode conductivuty is good, and catalytic activity is high.
3. the method proposed by the present invention for preparing vanadium cell electrode material can prepare what carbon nano-fiber was worked out
Electrode material so that the specific surface area of electrode is greatly improved, so as to increase electrode reaction area, in preoxidation process, passes through
Control preoxidation time and temperature can control the oxygen content of fiber surface, and the hydrophily of electrode is improved, and oxygen-containing official
Can group's reacting with certain catalytic action, so as to improve the energy efficiency of battery to electrode.
4. the electrospinning device of the invention to be used is simple, experiment condition is content with very little, and by controlling to test
Parameter etc. can be very good to control the microscopic appearance of fiber.
5. the inventive method is cheap, easily operated, the vanadium cell electricity consumption with high electrochemical activity can be prepared
Pole material.
6. the present invention can solve to have vanadium battery electrode reaction in the prior art in the active relative of electrode material surface
The problems such as relatively low, electrode material catalytic performance is unstable.
Brief description of the drawings
Fig. 1 is electrostatic spinning apparatus schematic diagram.In figure, 1 promotes pump；2 shower nozzles；3 receivers；4 high voltage power supplies.
Embodiment
In specific implementation process, the present invention using alkaline lignin as examination material, utilizes phenol in alkaline lignin structure first
Hydroxyl activity functional group, substitutes resorcinol by the alkaline lignin portion of methylolation and has been synthesized under catalyst action with formaldehyde
Machine gel, using the gel as precursor, the spinning liquid as precursor needed for preparation experiment, by the method for electrostatic spinning, is prepared
Fiber precursor electrode material, (200~500 DEG C of temperature) is pre-oxidized to electrode material presoma using vacuum/atmosphere furnace,
It is carbonized (800~1500 DEG C of temperature) in inert atmosphere, obtains carbon fiber electrode material.Gained carbon fiber electrode material is carried out clear
After washing, drying, you can carry out the charge-discharge test of battery.The vanadium cell carbon fiber electrode material prepared using the inventive method,
Fibre diameter is in Nano grade, and specific surface area is greatly increased compared to traditional carbon felt class electrode material, due to the pre-oxidation in later stage
Processing, the oxygen content of fiber surface also improves a lot, the preparation available for vanadium cell carbon fiber electrode material.
As shown in figure 1, electrostatic spinning apparatus of the present invention mainly includes：Promote pump 1, shower nozzle 2, high voltage power supply 4 and receiver
3, promote pump 1 to be connected with the shower nozzle 2 of electrostatic spinning apparatus, the shower nozzle 2 of electrostatic spinning apparatus connects the positive pole of high voltage power supply 4, receive
Device 3 is grounded or negative pole, forms high voltage electric field therebetween.In spinning process, pump 1 is promoted to extrude spinning solution, drop is in height
Surface tension formation jet is overcome in piezoelectric field due to electrostatic repulsion, and is solidified into nanometer or micron order fiber, the fibre being spun into
Dimension is collected (being usually flat board or transfer roller) by receiver 3.
Below, the present invention is further elaborated on by embodiment.
Embodiment 1
In the present embodiment, the preparation method of vanadium redox flow battery electrode material is as follows：
1) in the NaOH aqueous solution for being 0.5mol/L by alkaline lignin dissolution to concentration, addition formaldehyde, alkaline lignin+
The mol ratio of resorcinol and formaldehyde is 1：2, stir, mixing time is 1h, carry out hydroxymethylation, it is water-soluble with NaOH
Liquid regulation pH value is 9.Resorcinol is added into above-mentioned solution, the mol ratio of alkaline lignin and resorcinol is 2：1.Then
Acetylacetone,2,4-pentanedione ferrous solution is slowly added to, the mol ratio for adjusting alkaline lignin+resorcinol and metal salt catalyst is 20：1, hold
Continuous stirring is completely dissolved to it, is stirred vigorously to reaction and is formed gel, mixing time is 1h.Gel is transferred to vacuum drying chamber
Room temperature is cooled in taking out sample after 80 DEG C of dryings, closing ageing, organic xerogel is made, is preserved after the gel is crushed.
2) by organic xerogel after crushing and polyacrylonitrile with 1：10 mass ratio is added to nitrogen, nitrogen dimethyl formyl
In amine (DMF) organic solution, stirred under water bath condition, mixing time is 2h.Organic xerogel+polyacrylonitrile and nitrogen, nitrogen
The mass ratio of dimethylformamide is 1：10, bath temperature is 50 DEG C.
3) electrode material precursor fibre precursor is made through electrostatic spinning technique in the precursor spinning solution 2) obtained.Electrostatic
The parameter of spinning technique is：The pinhole diameter of syringe needle is 0.36mm, and the capacity of syringe is 20mL, the injected current of syringe control
Measure as 0.2mL/h, the voltage between syringe needle and transfer roller is 15kV, the distance between syringe needle and transfer roller are 10cm, the rotating speed of transfer roller
For 50r/min, spinning temperature is 20 DEG C, and spinning humidity is 40%RH.
4) the precursor fibre precursor obtained by 3) is pre-oxidized and is carbonized by atmosphere furnace；Wherein, temperature is pre-oxidized
Spend for 200 DEG C, programming rate is 5 DEG C/min, and the time is 1h；Carburizing temperature is 800 DEG C, and programming rate is 5 DEG C/min, and the time is
2h, protective gas is nitrogen, and the flow of protective gas is 100mL/min.
5) carbon fiber electrode material obtained by 4) is cleaned or is cleaned by ultrasonic with deionized water, ultrasonic time is 10min.
Dried in vacuum drying chamber or in air dry oven, drying temperature is 60 DEG C, and processing time is 24h, carbon fiber is obtained after drying
Electrode, electrode material thickness is in 0.5mm.
In the present embodiment, reacted using precursor, electrostatic spinning process parameter and pre-oxidation, the control of Carbonization Conditions, system
For all-vanadium flow battery carbon fiber electrode material is gone out, the fibrous material of Nano grade can be obtained, this makes its specific surface area than existing
There is electrode material to have the increase of the order of magnitude, so as to greatly increase the effective area of the electrode reaction of vanadium ion.
Embodiment 2
It is with the difference of embodiment 1, the preparation method of the present embodiment vanadium redox flow battery electrode material is as follows：
1) in the NaOH aqueous solution for being 0.4mol/L by alkaline lignin dissolution to concentration, addition formaldehyde, alkaline lignin+
The mol ratio of resorcinol and formaldehyde is 1：3, stir, mixing time is 2h, carry out hydroxymethylation, it is water-soluble with NaOH
Liquid regulation pH value is 9.Resorcinol is added into above-mentioned solution, the mol ratio of alkaline lignin and resorcinol is 1：5.Then
Cobalt nitrate solution is slowly added to, the mol ratio for adjusting alkaline lignin+resorcinol and metal salt catalyst is 30：1, persistently stir
Mix to it and be completely dissolved, be stirred vigorously to reaction and form gel, mixing time is 3h.Gel is transferred to vacuum drying chamber in 85
DEG C drying, takes out sample after closing ageing and is cooled to room temperature, organic xerogel is made, will the gel crush after preserve.
2) by organic xerogel after crushing and polyacrylonitrile with 1：10 mass ratio is added to nitrogen, nitrogen dimethyl formyl
In amine organic solution, stirred under water bath condition, mixing time is 2h.Organic xerogel+polyacrylonitrile and nitrogen, nitrogen dimethyl
The mass ratio of formamide is 1：15, bath temperature is 20 DEG C.
3) electrode material precursor fibre precursor is made through electrostatic spinning technique in the precursor spinning solution 2) obtained.Electrostatic
The parameter of spinning technique is：The pinhole diameter of syringe needle is 0.36mm, and the capacity of syringe is 20mL, the injected current of syringe control
Measure as 0.2mL/h, the voltage between syringe needle and transfer roller is 15kV, the distance between syringe needle and transfer roller are 10cm, the rotating speed of transfer roller
For 50r/min, spinning temperature is 20 DEG C, and spinning humidity is 40%RH.
4) the precursor fibre precursor obtained by 3) is pre-oxidized and is carbonized by atmosphere furnace；Wherein, temperature is pre-oxidized
Spend for 200 DEG C, programming rate is 5 DEG C/min, and the time is 1h；Carburizing temperature is 800 DEG C, and programming rate is 5 DEG C/min, and the time is
2h, protective gas is nitrogen, and the flow of protective gas is 100mL/min.
5) carbon fiber electrode material obtained by 4) is cleaned or is cleaned by ultrasonic with deionized water, ultrasonic time is 10min.
Dried in vacuum drying chamber or in air dry oven, drying temperature is 70 DEG C, and processing time is 24h, carbon fiber is obtained after drying
Electrode, electrode material thickness is in 0.3mm.
In the present embodiment, reacted using precursor, electrostatic spinning process parameter and pre-oxidation, the control of Carbonization Conditions, system
For all-vanadium flow battery carbon fiber electrode is gone out, the fibrous material of Nano grade is obtained, this makes its specific surface area than existing electrode material
Material has the increase of the order of magnitude, so as to greatly increase the effective area of the electrode reaction of vanadium ion.
Embodiment 3
It is with the difference of embodiment 1, the preparation method of the present embodiment vanadium redox flow battery electrode material is as follows：
1) in the ammonia spirit for being 0.4mol/L by alkaline lignin dissolution to concentration, addition formaldehyde, alkaline lignin+
The mol ratio of benzenediol and formaldehyde is 1：4, stir, mixing time is 3h, carry out hydroxymethylation, adjusted with ammonia spirit
It is 9 to save pH value.Resorcinol is added into above-mentioned solution, the mol ratio of alkaline lignin and resorcinol is 1：4.Then it is slow
Cobalt nitrate solution is added, the mol ratio for adjusting alkaline lignin+resorcinol and metal salt catalyst is 40：1, continue stirring until
It is completely dissolved, and is stirred vigorously to reaction and forms gel, and mixing time is 4h.Gel is transferred to vacuum drying chamber dry in 85 DEG C
It is dry, take out sample after closing ageing and be cooled to room temperature, organic xerogel is made, preserved after the gel is crushed.
2) by organic xerogel after crushing and polyacrylonitrile with 2：10 mass ratio is added to nitrogen, nitrogen dimethyl formyl
In amine organic solution, stirred under water bath condition, mixing time is 2h.Organic xerogel+polyacrylonitrile and nitrogen, nitrogen dimethyl
The mass ratio of formamide is 1：5, bath temperature is 30 DEG C.
3) electrode material precursor fibre precursor is made through electrostatic spinning technique in the precursor spinning solution 2) obtained.Electrostatic
The parameter of spinning technique is：The pinhole diameter of syringe needle is 0.45mm, and the capacity of syringe is 20mL, the injected current of syringe control
Measure as 0.2mL/h, the voltage between syringe needle and transfer roller is 20kV, the distance between syringe needle and transfer roller are 15cm, the rotating speed of transfer roller
For 100r/min, spinning temperature is 25 DEG C, and spinning humidity is 40%RH.
4) the precursor fibre precursor obtained by 3) is pre-oxidized and is carbonized by atmosphere furnace；Wherein, temperature is pre-oxidized
Spend for 200 DEG C, programming rate is 5 DEG C/min, and the time is 1h；Carburizing temperature is 800 DEG C, and programming rate is 5 DEG C/min, and the time is
2h, protective gas is nitrogen, and the flow of protective gas is 80mL/min.
5) carbon fiber electrode material obtained by 4) is cleaned or is cleaned by ultrasonic with deionized water, ultrasonic time is 10min.
Dried in vacuum drying chamber or in air dry oven, drying temperature is 70 DEG C, and processing time is 24h, carbon fiber is obtained after drying
Electrode, electrode material thickness is in 1.5mm.
In the present embodiment, reacted using precursor, electrostatic spinning process parameter and pre-oxidation, the control of Carbonization Conditions, system
For all-vanadium flow battery carbon fiber electrode is gone out, the fibrous material of Nano grade is obtained, this makes its specific surface area than existing electrode material
Material has the increase of the order of magnitude, so as to greatly increase the effective area of the electrode reaction of vanadium ion.
Embodiment 4
It is with the difference of embodiment 1, the preparation method of the present embodiment vanadium redox flow battery electrode material is as follows：
1) in the ammonia spirit for being 1mol/L by alkaline lignin dissolution to concentration, formaldehyde, alkaline lignin+isophthalic are added
The mol ratio of diphenol and formaldehyde is 1：5, stir, mixing time is 3h, carry out hydroxymethylation, adjusted with ammonia spirit
PH value is 10.Resorcinol is added into above-mentioned solution, the mol ratio of alkaline lignin and resorcinol is 1：5.Then it is slow
Nickel nitrate solution is added, the mol ratio for adjusting alkaline lignin+resorcinol and metal salt catalyst is 50：1, continue stirring until
It is completely dissolved, and is stirred vigorously to reaction and forms gel, and mixing time is 4h.Gel is transferred to vacuum drying chamber dry in 85 DEG C
It is dry, take out sample after closing ageing and be cooled to room temperature, organic xerogel is made, preserved after the gel is crushed.
2) by organic xerogel after crushing and polyacrylonitrile with 1：10 mass ratio is added to nitrogen, nitrogen dimethyl formyl
In amine organic solution, stirred under water bath condition, mixing time is 3h.Organic xerogel+polyacrylonitrile and nitrogen, nitrogen dimethyl
The mass ratio of formamide is 2：8, bath temperature is 40 DEG C.
3) electrode material precursor fibre precursor is made through electrostatic spinning technique in the precursor spinning solution 2) obtained.Electrostatic
The parameter of spinning technique is：The pinhole diameter of syringe needle is 0.59mm, and the capacity of syringe is 20mL, the injected current of syringe control
Measure as 0.3mL/h, the voltage between syringe needle and transfer roller is 25kV, the distance between syringe needle and transfer roller are 20cm, the rotating speed of transfer roller
For 500r/min, spinning temperature is 25 DEG C, and spinning humidity is 40%RH.
4) the precursor fibre precursor obtained by 3) is pre-oxidized and is carbonized by atmosphere furnace；Wherein, temperature is pre-oxidized
Spend for 300 DEG C, programming rate is 5 DEG C/min, and the time is 1h；Carburizing temperature is 900 DEG C, and programming rate is 5 DEG C/min, and the time is
2h, protective gas is nitrogen, and the flow of protective gas is 100mL/min.
5) carbon fiber electrode material obtained by 4) is cleaned or is cleaned by ultrasonic with deionized water, ultrasonic time is 10min.
Dried in vacuum drying chamber or in air dry oven, drying temperature is 80 DEG C, and processing time is 24h, carbon fiber is obtained after drying
Electrode, electrode material thickness is in 1.5mm.
In the present embodiment, reacted using precursor, electrostatic spinning process parameter and pre-oxidation, the control of Carbonization Conditions, system
For all-vanadium flow battery carbon fiber electrode material is gone out, nano-scale fiber can be obtained, this makes its specific surface area than existing electrode material
Material has the increase of the order of magnitude, so as to greatly increase the effective area of vanadium ion electrode reaction.
Embodiment 5
It is with the difference of embodiment 1, the preparation method of the present embodiment vanadium redox flow battery electrode material is as follows：
1) in the ammonia spirit for being 1mol/L by alkaline lignin dissolution to concentration, formaldehyde, alkaline lignin+isophthalic are added
The mol ratio of diphenol and formaldehyde is 1：3, stir, mixing time is 4h, carry out hydroxymethylation, adjusted with ammonia spirit
PH value is 10.Resorcinol is added into above-mentioned solution, the mol ratio of alkaline lignin and resorcinol is 1：4.Then it is slow
Nickel nitrate solution is added, the mol ratio for adjusting alkaline lignin+resorcinol and metal salt catalyst is 60：1, continue stirring until
It is completely dissolved, and is stirred vigorously to reaction and forms gel, and mixing time is 4h.Gel is transferred to vacuum drying chamber dry in 80 DEG C
It is dry, take out sample after closing ageing and be cooled to room temperature, organic xerogel is made, preserved after the gel is crushed.
2) by organic xerogel after crushing and polyacrylonitrile with 2：10 mass ratio is added to nitrogen, nitrogen dimethyl formyl
In amine organic solution, stirred under water bath condition, mixing time is 3h.Organic xerogel+polyacrylonitrile and nitrogen, nitrogen dimethyl
The mass ratio of formamide is 1：15, bath temperature is 60 DEG C.
3) electrode material precursor fibre precursor is made through electrostatic spinning technique in the precursor spinning solution 2) obtained.Electrostatic
The parameter of spinning technique is：The pinhole diameter of syringe needle is 0.75mm, and the capacity of syringe is 20mL, the injected current of syringe control
Measure as 0.4mL/h, the voltage between syringe needle and transfer roller is 30kV, the distance between syringe needle and transfer roller are 15cm, the rotating speed of transfer roller
For 600r/min, spinning temperature is 25 DEG C, and spinning humidity is 40%RH.
4) the precursor fibre precursor obtained by 3) is pre-oxidized and is carbonized by atmosphere furnace；Wherein, temperature is pre-oxidized
Spend for 300 DEG C, programming rate is 5 DEG C/min, and the time is 1h；Carburizing temperature is 1000 DEG C, and programming rate is 5 DEG C/min, time
For 2h, protective gas is nitrogen, and the flow of protective gas is 100mL/min.
5) carbon fiber electrode material obtained by 4) is cleaned or is cleaned by ultrasonic with deionized water, ultrasonic time is 10min.
Dried in vacuum drying chamber or in air dry oven, drying temperature is 70 DEG C, and processing time is 24h, carbon fiber is obtained after drying
Electrode, electrode material thickness is in 0.5mm.
In the present embodiment, reacted using precursor, electrostatic spinning process parameter and pre-oxidation, the control of Carbonization Conditions, system
For all-vanadium flow battery carbon fiber electrode material is gone out, nano-scale fiber can be obtained, this makes its specific surface area than existing electrode material
Material has the increase of the order of magnitude, so as to greatly increase the effective area of vanadium ion electrode reaction.
Embodiment 6
It is with the difference of embodiment 1, the preparation method of the present embodiment vanadium redox flow battery electrode material is as follows：
1) in the KOH aqueous solution for being 1mol/L by alkaline lignin dissolution to concentration, addition formaldehyde, alkaline lignin+
The mol ratio of benzenediol and formaldehyde is 1：2, stir, mixing time is 2h, carry out hydroxymethylation, use the KOH aqueous solution
It is 10 to adjust pH value.Resorcinol is added into above-mentioned solution, the mol ratio of alkaline lignin and resorcinol is 1：4.Then
Nickel nitrate solution is slowly added to, the mol ratio for adjusting alkaline lignin+resorcinol and metal salt catalyst is 40：1, persistently stir
Mix to it and be completely dissolved, be stirred vigorously to reaction and form gel, mixing time is 3h.Gel is transferred to vacuum drying chamber in 85
DEG C drying, takes out sample after closing ageing and is cooled to room temperature, organic xerogel is made, will the gel crush after preserve.
2) by organic xerogel after crushing and polyacrylonitrile with 3：10 mass ratio is added to nitrogen, nitrogen dimethyl formyl
In amine organic solution, stirred under water bath condition, mixing time is 3h.Organic xerogel+polyacrylonitrile and nitrogen, nitrogen dimethyl
The mass ratio of formamide is 1：10, bath temperature is 70 DEG C.
3) electrode material precursor fibre precursor is made through electrostatic spinning technique in the precursor spinning solution 2) obtained.Electrostatic
The parameter of spinning technique is：The pinhole diameter of syringe needle is 0.75mm, and the capacity of syringe is 20mL, the injected current of syringe control
Measure as 0.4mL/h, the voltage between syringe needle and transfer roller is 20kV, the distance between syringe needle and transfer roller are 20cm, the rotating speed of transfer roller
For 800r/min, spinning temperature is 25 DEG C, and spinning humidity is 40%RH.
4) the precursor fibre precursor obtained by 3) is pre-oxidized and is carbonized by atmosphere furnace；Wherein, temperature is pre-oxidized
Spend for 300 DEG C, programming rate is 5 DEG C/min, and the time is 1h；Carburizing temperature is 1100 DEG C, and programming rate is 5 DEG C/min, time
For 2h, protective gas is nitrogen, and the flow of protective gas is 100mL/min.
5) carbon fiber electrode material obtained by 4) is cleaned or is cleaned by ultrasonic with deionized water, ultrasonic time is 20min.
Dried in vacuum drying chamber or in air dry oven, drying temperature is 80 DEG C, and processing time is 24h, carbon fiber is obtained after drying
Electrode, electrode material thickness is in 0.3mm.
In the present embodiment, reacted using precursor, electrostatic spinning process parameter and pre-oxidation, the control of Carbonization Conditions, system
For all-vanadium flow battery carbon fiber electrode material is gone out, nano-scale fiber can be obtained, this makes its specific surface area than existing electrode material
Material has the increase of the order of magnitude, so as to greatly increase the effective area of vanadium ion electrode reaction.
Embodiment 7
In the present embodiment, the preparation method of vanadium redox flow battery electrode material is as follows：
1) it is alkaline wooden by alkaline lignin dissolution to concentration in the 1.5mol/L KOH aqueous solution, to add formaldehyde
The mol ratio of element+resorcinol and formaldehyde is 1：3, stir, mixing time is 2h, carry out hydroxymethylation, use KOH water
Solution regulation pH value is 9.Resorcinol is added into above-mentioned solution, the mol ratio of alkaline lignin and resorcinol is 1：5.So
After be slowly added to nickel nitrate solution, the mol ratio of the alkaline lignin+resorcinol of regulation and metal salt catalyst is 30：1, continue
Stirring is completely dissolved to it, is stirred vigorously to reaction and is formed gel, mixing time is 4h.By gel be transferred to vacuum drying chamber in
85 DEG C of dryings, take out sample after closing ageing and are cooled to room temperature, organic xerogel is made, preserved after the gel is crushed.
2) by organic xerogel after crushing and polyacrylonitrile with 4：10 mass ratio is added to nitrogen, nitrogen dimethyl formyl
In amine organic solution, stirred under water bath condition, mixing time is 3h.Organic xerogel+polyacrylonitrile and nitrogen, nitrogen dimethyl
The mass ratio of formamide is 1：10, bath temperature is 80 DEG C.
3) electrode material precursor fibre precursor is made through electrostatic spinning technique in the precursor spinning solution 2) obtained.Electrostatic
The parameter of spinning technique is：The pinhole diameter of syringe needle is 0.80mm, and the capacity of syringe is 20mL, the injected current of syringe control
Measure as 0.3mL/h, the voltage between syringe needle and transfer roller is 25kV, the distance between syringe needle and transfer roller are 15cm, the rotating speed of transfer roller
For 900r/min, spinning temperature is 25 DEG C, and spinning humidity is 40%RH.
4) the precursor fibre precursor obtained by 3) is pre-oxidized and is carbonized by atmosphere furnace；Wherein, temperature is pre-oxidized
Spend for 300 DEG C, programming rate is 5 DEG C/min, and the time is 1h；Carburizing temperature is 1200 DEG C, and programming rate is 5 DEG C/min, time
For 2h, protective gas is nitrogen, and the flow of protective gas is 100mL/min.
5) carbon fiber electrode material obtained by 4) is cleaned or is cleaned by ultrasonic with deionized water, ultrasonic time is 20min.
Dried in vacuum drying chamber or in air dry oven, drying temperature is 60 DEG C, and processing time is 24h, carbon fiber is obtained after drying
Electrode, electrode material thickness is in 0.8mm.
In the present embodiment, reacted using precursor, electrostatic spinning process parameter and pre-oxidation, the control of Carbonization Conditions, system
For all-vanadium flow battery carbon fiber electrode material is gone out, nanometer stage material can be obtained, this makes its specific surface area than existing electricity
Pole material has the increase of the order of magnitude, greatly increases the effective area of vanadium ion electrode reaction.
Embodiment result shows that the present invention, which reacts the complicated unordered 3-D solid structure of lignin by precursor, to be changed
For the ordered structure with aromatic series plane, after spinning, carbonization, carbon nano-fiber axial orientation degree, reinforcing fiber power are improved
Learn performance；Two-dimension graphite sheet layer stacking provisions are set up, increases graphitic layers amount of edge, improves leading for the carbon nano-fiber electrode
Electrical and electro-chemical activity.The present invention is a kind of new idea of vanadium cell lignin-base carbon nano-fiber electrode, to preparing high ratio
The carbon nano-fiber electrode of surface area, electric conductivity and high electrochemical activity, promotes the application of lignin-base carbon nano-fiber electrode
And the practical of vanadium cell has positive meaning.
Claims (10)
1. a kind of preparation method of vanadium redox flow battery electrode material, it is characterised in that：Preparation, spinning solution comprising precursor
Preparation, electrostatic spinning, pre-oxidation and carbonization, five steps of cleaning-drying, precursor is using alkaline lignin as base material, by lignin
It is dissolved into aqueous slkali, adds formaldehyde, resorcinol, stirring is passed through to organogel is formed in the presence of metal salt catalyst
Closing ageing, crushing, obtain the organic xerogel of precursor；
Wherein, the mean molecule quantity of alkaline lignin is 1000~20000, and aqueous slkali is sodium hydroxide solution, potassium hydroxide is molten
Liquid or ammoniacal liquor, metal salt catalyst are cobalt salt, nickel salt or molysite.
2. the preparation method of vanadium redox flow battery electrode material according to claim 1, it is characterised in that in precursor
In preparation process, by lignin dissolution into aqueous slkali, the mass ratio of lignin and aqueous slkali is 5：1~50：1, add first
Stirred after aldehyde, regulation pH value is 8~14.
3. the preparation method of vanadium redox flow battery electrode material according to claim 1, it is characterised in that in precursor
In preparation process, the mol ratio of alkaline lignin and resorcinol is 2：1~1：20, alkaline lignin+resorcinol and formaldehyde
Mol ratio be 1：2~1：50, the mol ratio of alkaline lignin+resorcinol and metal salt catalyst is 20：1~100：1.
4. the preparation method of vanadium redox flow battery electrode material according to claim 1, it is characterised in that in precursor
In preparation process, stirring to the mixing time of formation organogel is 0.5~24h.
5. the preparation method of vanadium redox flow battery electrode material according to claim 1, it is characterised in that in spinning solution
In preparation process, the organic xerogel of precursor after crushing and polyacrylonitrile are added to nitrogen, nitrogen dimethylformamide organic molten
In liquid, stirred under water bath condition；Wherein, the mean molecule quantity of polyacrylonitrile be 80000~200000, organic xerogel with
The mass ratio of polyacrylonitrile is 5：95~90：10, organic xerogel+polyacrylonitrile and nitrogen, the quality of nitrogen dimethylformamide
Ratio is 5：95~20：80, bath temperature is 20~80 DEG C.
6. the preparation method of vanadium redox flow battery electrode material according to claim 1, it is characterised in that in electrostatic spinning
During, electrode material precursor fibre precursor is made through electrostatic spinning technique in the precursor spinning solution 2) obtained；Static Spinning
Silk technological parameter be：The pinhole diameter of syringe needle is 0.3~2mm, and the capacity of syringe is 20~500mL, syringe control
Injection flow is 0.2~5mL/h.
7. the preparation method of vanadium redox flow battery electrode material according to claim 6, it is characterised in that syringe needle and transfer roller
Between voltage be 10~40kV, the distance between syringe needle and transfer roller is 10~30cm, and the rotating speed of transfer roller is 0~3000r/min,
Spinning temperature is 15~30 DEG C, and spinning humidity is 20~50%RH.
8. the preparation method of vanadium redox flow battery electrode material according to claim 1, it is characterised in that in pre-oxidation and
In carbonisation, Pre oxidation is 200~500 DEG C, and the time is 1~3h, the programming rate of pre-oxidation treatment for 2~20 DEG C/
min；Carburizing temperature is 800~1500 DEG C, and the time is 1~10h, and the programming rate of carbonization treatment is 2~20 DEG C/min；Pre-oxidation
And the flow of gas in progress, inert protective atmosphere that is carbonized in inert protective atmosphere is 20~150mL/min.
9. the preparation method of vanadium redox flow battery electrode material according to claim 1, it is characterised in that be cleaned and dried
During, the electrode material after cleaning is dried in vacuum drying chamber or air dry oven, drying temperature is 60~100
DEG C, processing time is 24~48h, and the electrode material thickness after drying is in 0.1~5mm.
10. the preparation method of the vanadium redox flow battery electrode material according to one of claim 1~9, it is characterised in that most
The electrode material obtained eventually is the controllable block materials of the thickness being entwined by carbon nano-fiber.
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| CN113113620A (en) * | 2021-04-16 | 2021-07-13 | 龙泉市强宏环保科技有限公司 | Preparation method of alkaline zinc-iron flow battery |
| CN115350571A (en) * | 2022-07-18 | 2022-11-18 | 哈尔滨工业大学（深圳） | Preparation method of integrated gas diffusion electrode |
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