CN103400933B - The preparation method of carbon-based nano thin film thermoelectric chemical electrode based on electrophoresis method - Google Patents
The preparation method of carbon-based nano thin film thermoelectric chemical electrode based on electrophoresis method Download PDFInfo
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Abstract
The invention discloses the preparation method of a kind of carbon-based nano thin film thermoelectric chemical electrode based on electrophoresis method, including following operation: with carbon-based nano powder as raw material；Nano material and microelectrolysis matter (inorganic salt, alkali or surfactant etc.) are scattered in the dehydrated alcohol solvent such as (water or methanol, organic solvent), and sonicated after, i.e. obtain electrophoresis liquid；It is placed in electrophoresis liquid by conductive substrates with to electrode, and loads DC voltage, more than 10 seconds time, by the sample thin film that electrophoresis attachment last layer is fine and close in conductive substrates, constitute sample thin film electrode blank；Annealing, carbon-based nano membrane electrode blank step (3) obtained carries out the annealing of more than 200 DEG C under vacuum or inert gas environment, it is thus achieved that carbon-based nano membrane electrode.Nano material of the present invention is attached directly in conductive substrates, quickness and high efficiency, and after high annealing, the sheet resistance of electrode is lower, is more beneficial for promoting energy conversion efficiency.
Description
Technical field
The present invention relates to thermoelectrochemistry field of batteries, be specifically related to the electrode of thermoelectrochemistry battery, particularly relate to one
The preparation method of carbon-based nano thin film thermoelectric chemical electrode based on electrophoresis method.
Background technology
Thermoelectrochemistry battery (Thermo-electrochemical cell) is a kind of based on electrochemistry Seebeck effect
Heat-energy recovering apparatus, can be converted into electric energy by the thermal energy differential between positive pole and negative pole.For a long time, thermoelectrochemistry battery
Using noble metal platinum as its electrode material, this electrode stable work in work, but energy conversion efficiency is general, and cost is extremely
Expensive.Electrode involve great expense and energy conversion efficiency low be thermoelectrochemistry battery be affect thermoelectrochemistry battery applications be worth
Principal element.
C-based nanomaterial (CNT, Graphene etc.) have the microstructure of uniqueness and remarkable machinery, physics and
Chemical property, compared with traditional noble metal electrode, electrode based on c-based nanomaterial has that cost is relatively low, specific surface area is huge
The advantage such as greatly, electron transfer site is many.CNT electrode material is in the electrochemical devices such as lithium battery, ultracapacitor, fuel cell
It is widely used.2010, researcher demonstrates carbon nanotube paper first can be as the electrode of thermoelectrochemistry battery
Material, and the energy conversion efficiency of this electrode material is higher by 33% than traditional platinum electrode.But carbon nanotube paper is carbon nanotube powder
Being prepared from through complicated technique, and need when using to be pasted and fixed on collector carbon nanotube paper, bringing should
The inconvenience used, secondary taping process adds the sheet resistance of electrode simultaneously, reduces cell power conversion efficiency.
Summary of the invention
The invention aims to the shortcoming and defect overcoming prior art to exist, and a kind of processing technology letter is provided
The method that the electrophoresis method single, energy consumption is low prepares carbon-based nano membrane electrode, the method need not between nano material and collector
Secondary taping process, but nano material is attached directly on collector (substrate), the sheet resistance of electrode is lower, more has
It is beneficial to promote energy conversion efficiency.
For achieving the above object, the technical scheme is that and include that following operation includes following operation:
(1) with carbon-based nano powder as raw material, sample powder is purified process；
(2) sample powder after purification and microelectrolysis matter are scattered in solvent, and sonicated after, i.e. obtain electricity
Swimming liquid；
(3) it is placed in electrophoresis liquid by conductive substrates with to electrode, and loads DC voltage, more than 10 seconds time, conductive base
By the carbon-based nano thin film that electrophoresis attachment last layer is fine and close, membrane electrode blank is constituted at the end；
(4) annealing, carbon-based nano membrane electrode blank step (3) obtained is under vacuum or inert gas environment
Carry out the annealing of more than 200 DEG C, it is thus achieved that carbon-based nano membrane electrode.
Arrange further be the purification in described step (1) be carboxylated, its processing step is with strong by sample powder
Acid solution or strong base solution mixing, and sonicated after, repeatedly rinse to neutrality with deionized water, then sucking filtration obtains purification
Rear sample powder, will sample powder be dried after purification in drying baker.
Arranging the carbon-based nano powder being described further is CNT or graphene powder.
Arranging further is that in described step (2), electrolyte is inorganic salt, alkali or surfactant..
Arrange further be described solvent be the organic solvent such as water or dehydrated alcohol.
Arrange further be in described step (3) conductive substrates and to the spacing of electrode be > 0.1cm.
Setting is that the thickness of the thin film on described step (3) carbon-based nano membrane electrode blank is further > 1 μm.
Present invention process utilizes electrophoresis method to process carbon-based nano thin film in conductive substrates, constitutes carbon-based nano thin-film electro
Pole, the method need not the secondary taping process between electrode material and collector, and nano material is attached directly to conductive substrates
On, the sheet resistance of electrode is lower, is more beneficial for promoting energy conversion efficiency.
Under the technological parameter of the present invention, between carbon-based nano thin film and conductive substrates, bond strength is good, and sheet resistance is low, leads
Electricity is excellent, and by experimental verification, the present invention is compared with existing CNT paper electrode, and energy conversion efficiency improves about 13%
(see below experimental example data).
This method realizes metal simple-substance and is deposited on the contact position of nano material and conductive substrates, thus increases contact
Fastness also reduces contact resistance, forms good and stable contact.High-temperature annealing process nano material and the contact position of metal
Generate metal carbides, or make to be originally present in the physical absorption things such as nano material and the gas of metal contact position, steam and exist
It is desorbed under high temperature, thus improves its contact performance..
It addition, this technique requires low (conductive substrates) to base material；Shape unrestrictedly (can complete arbitrary surfaces
Prepared by the electrode of shape, be conducive to preparing various types of heat-energy recovering apparatus, such as tubular type retracting device)；Normal-temperature operation (is suitable for
In low melting point substrate, such as ito glass)；Electrode area is unrestricted (can prepare recovery geothermal energy, the large area energy of solar heat energy
Source retracting device) etc. advantage.
Below in conjunction with specification drawings and specific embodiments, the present invention is described further.
Accompanying drawing explanation
Fig. 1 present invention process electrophoretic apparatus schematic diagram；
The scanning electron microscope diagram of carbon nano-tube film electrode prepared by Fig. 2 present invention process；
The electrode performance test system schematic of carbon nano-tube film electrode prepared by Fig. 3 present invention；In Fig. 3,1 is electricity
Stream table, 2 is test electrode, and 3 is mixture of ice and water, and 4 is electrolyte, and 5 is temperature test and control unit, and 6 is thermocouple, and 7 are
Electrode draw-in groove, 8 is heater wire；
Carbon nano-tube film electrode prepared by Fig. 4 present invention and the temperature short-circuit current density curve of platinum electrode；
Electric current in the case of the external different resistance of carbon nano-tube film electrode prepared by Fig. 5 present invention and platinum electrode-
Power density curve.
Detailed description of the invention
Below by embodiment, the present invention is specifically described, is served only for the present invention being further described, no
It is understood that for limiting the scope of the present invention, the technician in this field can be according to the content of foregoing invention to the present invention
Make some nonessential improvement and adjustment.
Embodiment
The present embodiment uses experiment level CNT powder (multi-wall carbon nano-tube pipe powder) to be raw material, and other carbon-based nano powder are
The embodiment of raw material is identical with the present embodiment, and this experiment level CNT powder of the present embodiment originates from nanometer port, Shenzhen, a length of 5-15
μm, a diameter of 10--20nm, purity 97%.Before preparation, sample needs to process through purification (carboxylated): by the 200 dense nitre of mL
Acid (65%-68%) is poured slowly in the beaker filling 1 g CNT powder, after 1 hour supersound process, naturally cools to room
Temperature.It is centrifuged and pours out the supernatant, wash with a large amount of deionized waters, again take supernatant detection pH value, so repeat many
Secondary is neutral to clear liquid, and then sucking filtration obtains CNT powder.CNT powder is inserted in evaporating dish, in 70 DEG C in air dry oven
It is dried 10 hours.
After purification, 200mL dehydrated alcohol is poured slowly in the beaker filling trace CNT powder and anhydrous magnesium chloride, little through 1
Time supersound process, i.e. obtain the electrophoresis liquid of favorable dispersibility.Will be connected to the parallel side-by-side of the stainless steel-based end of electrophresis apparatus both positive and negative polarity
Be placed in electrophoresis liquid (Fig. 1).
The electrolyte of configuration electrophoresis liquid can also is that anhydrous magnesium chloride, anhydrous cupric chloride or Dehydrated nickel chloride, and described is molten
Agent is dehydrated alcohol, water, methanol or isopropanol.
The stainless steel-based end, is as working electrode, identical with to electrode area, is 0.4cm.Regulation electrophresis apparatus, makes two electricity
Loading DC voltage between pole, electrophoresis time is after 5 minutes, and the carbon of attachment of the stainless steel-based end last layer densification being connected with negative pole is received
Mitron thin film.Thickness is controlled by electrophoresis time and electrophoretic voltage, and electrophoresis signal sees Fig. 1.
After electrophoresis process, the CNT electrode annealing carrying out 500 ° of C under 100mTorr vacuum environment, CNT and stainless
Tack and the electrical conductivity of steel base are greatly improved.After annealing, it is possible to use some method removes in substrate attached
The CNT that the property is poor, such as uses adhesive plaster to be pasted by the CNT adhered to loosely or blow away with hair-dryer and adheres to loosely
CNT.It is prepared having obtained the carbon nanotube thin film electrode (seeing Fig. 2) of strong adhesion.
Test experiments example
The performance test of CNT electrode is carried out in the system as shown in fig. 3.The mixing of 0.4M potassium ferrocyanide/potassium ferricyanide
Aqueous solution has the highest Seebeck coefficient (1.4mV/K), so this solution is used as the electrolyte of thermoelectrochemistry battery.
Test electrode vertical the most just to be placed on draw-in groove, the distance between electrode is 5cm, and electrode area is 0.4cm (1.0cm*
0.4cm), the electrode back side and wire conductive silver glue are pasted.In order to avoid the electrode back side or elargol produce with electrolyte contacts
Measurement error, uses insulating cement to be coated completely at the electrode back side.Heater wire as high temperature source, mixture of ice and water as cold temperature source,
A fixed difference difference will be there is in the electrolyte near two such electrode.The electrolyte temperature near electrode (cold pole) that position is relatively low is steady
It is scheduled on 5 ° of C, and utilizes temperature control unit to be easily controlled the electrolyte temperature near the higher electrode in position (thermoae).Pass through
Under the different temperature difference of ammeter test, the temperature-short-circuit current density curve of CNT electrode and metal foil electrodes is shown in Fig. 4.Cold and hot pole
When the temperature difference is 60 ° of C, the short-circuit current density of battery reaches maximum, platinum electrode be 3.8mA/cm, CNT electrode be 5.3mA/cm.
And the short-circuit current density that carbon nanotube paper is under square one is about 4.8mA/cm.
When battery internal resistance is equal with non-essential resistance, the output of battery is peak power output Pmax.Use
The resistance of different resistances is connected with battery, and records the current value under different resistance, utilizes formula P=I * R to make the electricity of battery
The peak power output of battery it is readily available after stream-power curve.
Fig. 5 is the temperature difference of positive and negative electrode when being 50 ° of C, the current-power density curve of platinum electrode and carbon nanotube electrode.
For energy recycle device, energy conversion efficiency is the important indicator of its service behaviour.The thermoelectrochemistry energy content of battery
Transformation efficiency can be expressed as
Wherein, k represents solution thermal conductivity, and A represents electrode area.△ T represents the temperature difference between two-stage, d represent the two poles of the earth it
Between distance.Voc and Isc is open-circuit voltage and short circuit current respectively.So 0.25VocIsc represents the maximum work output of battery
Rate, Ak(△ T/d) it is heat energy input in battery (need keep △ T constant).Data above can use thermoelectrochemistry to survey
Test system records.
The mixed aqueous solution using the 0.4M potassium ferricyanide/potassium ferrocyanide in this experiment is electrolyte, and its thermal conductivity K is about
For 0.547W/mK.Through test, the temperature difference is 60 ° of C, when other are consistent, with CNT(electrophoresis), CNT(carbon nanotube paper), platinum
Metal is that the energy conversion efficiency of the thermoelectrochemistry battery of electrode material is respectively as follows:
CNT(electrophoresis) electrode 0.17%,
CNT(carbon nanotube paper) electrode 0.15%,
Platinum electrode 0.12%
With CNT(carbon nanotube paper) electrode compares, CNT(electrophoresis) energy conversion efficiency of electrode improves about 13%.
Claims (8)
1. the preparation method of a carbon-based nano thin film thermoelectric chemical electrode based on electrophoresis method, it is characterised in that include following work
Sequence:
(1) with carbon-based nano powder as raw material, sample powder is purified process；
(2) sample after purification and microelectrolysis matter are scattered in solvent, obtain electrophoresis liquid;
(3) being placed in electrophoresis liquid by conductive substrates with to electrode, and load DC voltage, more than 10 seconds time, in conductive substrates
By the sample thin film that electrophoresis attachment last layer is fine and close, constitute sample thin film electrode blank；
(4) annealing, sample thin film electrode blank step (3) obtained carries out 200 under vacuum or inert gas environment
Annealing more than DEG C, it is thus achieved that carbon-based nano membrane electrode.
The preparation method of a kind of carbon-based nano thin film thermoelectric chemical electrode based on electrophoresis method the most according to claim 1,
It is characterized in that: in described step (2), electrolyte is inorganic salt, alkali or surfactant.
The preparation method of a kind of carbon-based nano thin film thermoelectric chemical electrode based on electrophoresis method the most according to claim 1,
It is characterized in that: described solvent is water and various organic solvent.
The preparation method of a kind of carbon-based nano thin film thermoelectric chemical electrode based on electrophoresis method the most according to claim 3,
It is characterized in that: described organic solvent is dehydrated alcohol, methanol or isopropanol.
The preparation method of a kind of carbon-based nano thin film thermoelectric chemical electrode based on electrophoresis method the most according to claim 1,
It is characterized in that: the described purification in step (1) is carboxylated, its processing step is by sample powder and acid solution or alkali
Property solution mixing, and sonicated after, with a large amount of deionized water rinsings to neutrality, then sucking filtration obtains sample powder after purification
End, will be dried in sample powder drying baker after purification.
The preparation method of a kind of carbon-based nano thin film thermoelectric chemical electrode based on electrophoresis method the most according to claim 1,
It is characterized in that: described carbon-based nano powder is CNT or graphene powder.
The preparation method of a kind of carbon-based nano thin film thermoelectric chemical electrode based on electrophoresis method the most according to claim 1,
It is characterized in that: in described step (3), pair of conductive substrate and the spacing to electrode are more than 0.1cm.
The preparation method of a kind of carbon-based nano thin film thermoelectric chemical electrode based on electrophoresis method the most according to claim 1,
It is characterized in that: the thickness of the carbon-based nano thin film on described step (3) membrane electrode is more than 1 μm.
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| CN103767699B (en) * | 2014-01-23 | 2016-01-20 | 南京理工大学 | A kind of neuron probe based on carbon nano tube/conducting polymer and preparation method thereof |
| CN103979526B (en) * | 2014-05-22 | 2016-08-31 | 苏州捷迪纳米科技有限公司 | The purification process of carbon nano-tube macroscopic body |
| DE102019104062B3 (en) | 2019-02-18 | 2020-07-16 | Skenderbeg Klaiqi | Thermoelectric element and method of manufacture |
Citations (5)
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|---|---|---|---|---|
| CN1570220A (en) * | 2004-04-23 | 2005-01-26 | 清华大学 | Process for preparing carbon nano tube film through electrophoresis deposition |
| CN1750211A (en) * | 2004-09-14 | 2006-03-22 | 三星电机株式会社 | Fabrication method of field emitter electrode |
| CN1834305A (en) * | 2005-03-14 | 2006-09-20 | 东元奈米应材股份有限公司 | Method of improving electronic emitting source uniform of nanotube carbon produced by electrophoretic deposition |
| CN1936102A (en) * | 2005-08-05 | 2007-03-28 | 迈迪泰克有限公司 | Method for preparing nano structural composite electrode by electrophoretic deposition and products |
| CN101629317A (en) * | 2009-08-10 | 2010-01-20 | 福州大学 | Preparation method of carbon nanotube ionic electrophoretic solution |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1570220A (en) * | 2004-04-23 | 2005-01-26 | 清华大学 | Process for preparing carbon nano tube film through electrophoresis deposition |
| CN1750211A (en) * | 2004-09-14 | 2006-03-22 | 三星电机株式会社 | Fabrication method of field emitter electrode |
| CN1834305A (en) * | 2005-03-14 | 2006-09-20 | 东元奈米应材股份有限公司 | Method of improving electronic emitting source uniform of nanotube carbon produced by electrophoretic deposition |
| CN1936102A (en) * | 2005-08-05 | 2007-03-28 | 迈迪泰克有限公司 | Method for preparing nano structural composite electrode by electrophoretic deposition and products |
| CN101629317A (en) * | 2009-08-10 | 2010-01-20 | 福州大学 | Preparation method of carbon nanotube ionic electrophoretic solution |
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