CN106952747B - A kind of preparation method of high power capacity self-supporting manganese dioxide/carbon combination electrode - Google Patents
A kind of preparation method of high power capacity self-supporting manganese dioxide/carbon combination electrode Download PDFInfo
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Abstract
The invention belongs to electrochemical technology fields, and in particular to a kind of preparation method of high power capacity self-supporting manganese dioxide/carbon combination electrode.The preparation method is that：Manganese sulfate and water-soluble structure stabilizer are dissolved in aqueous sulfuric acid first and form mixed solution, the radius of the metal cation of the water-soluble structure stabilizer is 1~1.52 × 10‑10m；Then the carbonaceous material for selecting surface cleaning clean is as anode, using mixed solution is as electrolyte obtained by step 1, at 15 DEG C or less, oxidizing and electrochemical, which is carried out, in anode deposits manganese dioxide, semi-finished product are obtained, when carrying out anodic oxidation electrochemical deposition, control anode potential is greater than or equal to 0.14V；Then semi-finished product are placed in the solution containing water-soluble structure stabilizer, carry out hydro-thermal reaction in 120 200 DEG C, obtains the high power capacity self-supporting manganese dioxide/carbon combination electrode.Preparation process of the present invention is simple, products obtained therefrom function admirable, is convenient for industrialization production.
Description
Technical field
The invention belongs to electrochemical technology fields, and in particular to a kind of high power capacity self-supporting manganese dioxide/carbon combination electrode
Preparation method.
Technical background
Ultracapacitor is a kind of new concept energy storage device between battery and conventional electrostatic container, with aluminium electricity
The conventional electrostatics capacitor such as electrolysis condenser is compared, and it is to pass that ultracapacitor, which has higher specific capacitance, storable energy density,
10 times or more of system electrostatic condenser；And compared with battery, ultracapacitor has the power density of bigger, and has charge and discharge
It is efficient, the characteristics such as have extended cycle life.Since with above many superiority, the exploitation of supercapacitor technologies is constantly subjected to
Academia, industrial circle and military service most attention, and gradually in electronic instrument backup power supply and rocket, guided missile, artificial
It is applied in terms of the point starting ignition power supply of satellite, spaceship space station etc., the super high power electricity of wherein starting ignition
Container can provide MW grades of especially big startup power.
Compared with battery, the main problem that ultracapacitor is faced is that energy density is relatively low.In order to improve super electricity
The performance of container keeps the advantages such as its big specific power rate while carrying high-energy-density, around with electric double layer capacitance and farad
The research of the transition metal oxide electrode of fake capacitance behavior is concerned.RuO2It is Z as electrode material for super capacitor
It can not only realize high-power charge and discharge, while specific energy is also relatively high, but its is of high cost and be difficult to obtain in civilian industry
Obtain business promotion.In order to seek cheap electrode material for super capacitor, NiO, Co are surrounded3O4、V2O5、MnO2Equal oxo transition metals
The preparation of compound material and Electrochemical Properties are unfolded in succession.Wherein MnO2It is resourceful due to having theoretical specific capacitance height
The advantages that paid attention to.But due to electron conduction difference of material etc., the MnO that actually synthesizes2Specific capacitance is not high.For
This, people are mainly compound by the material and suitable carbon material progress, and the electronics inside electrode material is provided by carbon skeleton
Channel, so as to improve the electronic conductance performance of entire electrode.But most research be all be prepared into first the carbon of powder morphology/
Manganese dioxide composite material, then apply to invest after these powder body materials are mixed with binder and prepare electrode on collector, this just holds
It easily causes poor contact between electrode active material and collector and influences the charge-discharge performance of electrode.In addition, by being electrolysed sulphur
Sour manganese solution prepares manganese dioxide on different carbon skeleton surfaces, to prepare the manganese dioxide/carbon without binder, self-supporting
Combination electrode is current research hotspot, but from the report the case where from the point of view of, the emphasis of these research work be all concentrated mainly on as
What is prepared on different carbon skeletons, is not controlled carbon skeleton superficial silicon dioxide manganese own institutions, mainly using normal
The process of preparing of rule electrolytic manganese dioxide prepares manganese dioxide on carbon skeleton, i.e., mainly by being electrolysed two at normal temperatures
Manganese oxide aqueous solution γ type manganese dioxide.Clearly as the internal tunnel structure of γ type manganese dioxide is 1 × 2 or 1 × 1 type tunnel
Road, this is unfavorable for the transmission of electrode material charged ion balance in charge and discharge process, influences the capacitive property of material.
Invention content
The invention aims to provide a kind of preparation method of high power capacity self-supporting manganese dioxide/carbon combination electrode.
A kind of method preparing high power capacity self-supporting manganese dioxide/carbon combination electrode of the present invention, includes the following steps：
Step 1
Manganese sulfate and water-soluble structure stabilizer are dissolved in aqueous sulfuric acid and form mixed solution；The water-soluble structure
Stabilizer is the sulfate with metal cation；The radius of the metal cation is 1~1.52 × 10-10m；
Step 2
The carbonaceous material for selecting surface cleaning clean is as anode, using mixed solution obtained by step 1 as electrolyte；
15 DEG C deposit manganese dioxide hereinafter, carrying out oxidizing and electrochemical in anode, obtain semi-finished product；Carry out anodic oxidation electrochemical deposition
When, control anode potential is greater than or equal to 0.14V, and the anode potential is the potential relative to Mercurous sulfate electrode；
Step 3
Semi-finished product obtained by step 2 are placed in the solution containing water-soluble structure stabilizer, water is carried out in 120-200 DEG C
Thermal response；Obtain the high power capacity self-supporting manganese dioxide/carbon combination electrode.
Preferably, a kind of method preparing high power capacity self-supporting manganese dioxide/carbon combination electrode of the present invention, step
One, the institute of water-soluble structure stabilizer described in step 3 band metal cation is selected from Ce3+、La3+、K+、Rb+It is at least one.
Preferably, a kind of method preparing high power capacity self-supporting manganese dioxide/carbon combination electrode of the present invention, step
In one, a concentration of 0.5~3mol/L of sulfuric acid in the mixed solution, the water-soluble structure stabilizer a concentration of 0.01~
0.1mol/L, a concentration of 0.1~1mol/L of manganese sulfate.
A kind of method preparing high power capacity self-supporting manganese dioxide/carbon combination electrode of the present invention, by surface cleaning processing,
Obtain the clean carbonaceous material of surface cleaning.
Preferably, a kind of method preparing high power capacity self-supporting manganese dioxide/carbon combination electrode of the present invention, step
In two, when anode carries out oxidizing and electrochemical deposition manganese dioxide, the temperature for controlling electrolyte is 5~15 DEG C.
A kind of method preparing high power capacity self-supporting manganese dioxide/carbon combination electrode of the present invention carries out anodic oxidation electrification
When learning deposition, a variety of electrochemical deposition methods can be used and carry out；Preferably pulse, constant pressure or constant current co-electrodeposition method.
Preferably, a kind of method preparing high power capacity self-supporting manganese dioxide/carbon combination electrode of the present invention, step
In three, the time of hydro-thermal reaction is preferably 8-24 hours.
Preferably, a kind of method preparing high power capacity self-supporting manganese dioxide/carbon combination electrode of the present invention, step
In three, the solution containing water-soluble structure stabilizer is the solution that solute is water-soluble structure stabilizer；The solute is water-soluble
In the solution of property structural stabilizing agent, a concentration of 0.02~0.2mol/L of water-soluble structure stabilizer.
Preferably, a kind of method preparing high power capacity self-supporting manganese dioxide/carbon combination electrode of the present invention, step
Mn in gained high power capacity self-supporting manganese dioxide/carbon combination electrode in three4+/Mn3+Ratio be 1-5:1, further preferably
2.5~5:1.
Preferably, a kind of method preparing high power capacity self-supporting manganese dioxide/carbon combination electrode of the present invention, gained
In high power capacity self-supporting manganese dioxide/carbon combination electrode, manganese dioxide is the α type manganese dioxide with 2 × 2 tunnel structures.
Principle and advantage
The present invention in the direct electro-deposition manganese dioxide in carbon skeleton surface by preparing self-supporting manganese dioxide/carbon compound electric
Pole, by the way that manganese dioxide structure stabiliser salt is added into electrodeposit liquid and carries out anodic oxidation electro-deposition at low temperature to control
The structure of manganese dioxide obtains the α type manganese dioxide with 2 × 2 tunnel structures, improves charged ion balance in manganese dioxide material
Diffusion in material.The stability for improving material crystal structure is handled by follow-up hydrothermal simultaneously, and Mn in material can be adjusted4 +/Mn3+Ratio, and then optimize charge and discharge process in electrode reaction resistance, to improve its capacitive property.
The present invention is electrolysed the manganese sulfate solution containing high sulfuric acid concentration at low temperature, and cooperation stabilizer, hydro-thermal process obtain
Unexpected effect.It is in particular in：Using carbon paper as carbon source, under the synergistic effect of other conditions gained manganese dioxide/
Carbon composite electrode its capacity retention ratio when sweep speed is increased to 200mV is also greater than 60%.
Compared with existing preparation process, technical thought of the invention and technological principle have outstanding feature and technology excellent
Gesture：
(1) present invention proposes heavy by anodic oxidation electricity from sulfur acid manganese, sulfuric acid and structural stability mixed salt solution
Product α type manganese dioxide；
(2) by carrying out hydro-thermal process in the aqueous solution of the salt containing structural stability, the knot in material tunnel is on the one hand improved
Structure stability, while the composition of different valence state manganese is adjusted, optimize the electrode reaction resistance of material；
(3) it is combined with hydro-thermal method by anodic electrodeposition, the self-supporting manganese dioxide/carbon combination electrode of preparation is with suitable
In 2 × 2 tunnel structures and manganese composition of the diffusion of charged ion balance, there is high specific capacitance feature.
(4) manganese dioxide/carbon combination electrode of the present invention using carbon paper as carbon source when sweep speed is increased to 200mV its
Capacity retention ratio is also greater than 60%；(manganese dioxide/carbon using carbon paper as carbon source is compound far beyond similar product for its performance
Electrode).After carbon source is replaced, performance is also superior to similar product.
Description of the drawings
Attached drawing 1 is that the cycle using the manganese dioxide/carbon combination electrode prepared by the embodiment of the present invention 1 at 2mV/s lies prostrate
Pacify curve graph；
Attached drawing 2 is using cycle of the manganese dioxide/carbon combination electrode at 200mV/s prepared by the embodiment of the present invention 1
Volt-ampere curve figure；
1 curve can calculate specific capacitance and high rate performance of the electrode material at 2mV/s with reference to the accompanying drawings.
2 curve can calculate specific capacitance and high rate performance of the electrode material at 200mV/s with reference to the accompanying drawings.In conjunction with Fig. 1's
Capacity retention ratio can be obtained by calculating data.
Specific embodiment
Unless otherwise defined, all technical terms used hereinafter and the normally understood meaning of those skilled in the art
It is identical.Technical term used herein is intended merely to the purpose of description specific embodiment, is not intended to the limitation present invention
Protection domain.
Except there is a special instruction, the various reagents used in the present invention, raw material be can be commercially commodity or
Person can pass through product made from well known method.
The specific implementation mode of the present invention is as follows：
Embodiment 1
It prepares and contains MnSO4And CeSO4With the mixed aqueous solution of sulfuric acid, a concentration of 0.5mol/L of manganese sulfate in mixed solution,
Cerous sulfate a concentration of 0.01mol/L, sulfuric acid concentration 0.5mol/L.It is 4 × 1cm that carbon paper, which is cut into area,2Carbon paper band conduct
Collector, carries out ultrasonic washing with 10% aqueous sulfuric acid and acetone to the collector successively, and final rinse water is simultaneously dried.
It is 4 × 4cm with area2Titanium net electrode be to electrode, above-mentioned mixed solution is electrodeposit liquid, the collector after surface clean
For anode, (work area is 1 × 1cm2), constant current anode oxidation electro-deposition is carried out, electrodeposit liquid temperature is 5 DEG C, current density
4mA/cm2, electrodeposition time is 2 minutes.Gained manganese dioxide/carbon combination electrode is cleaned after the completion of electro-deposition, is put into
Equipped with 0.02mol/L CeSO48 hours are kept the temperature in the autoclave of aqueous solution and at 200 DEG C, is taken out after autoclave drops to room temperature
Combination electrode most obtains required combination electrode after water flushing and drying afterwards.Mn in combination electrode4+/Mn3+Ratio be 4.9:
1；
It is electrolyte with the aqueous sodium persulfate solution of 0.5mol/L, the manganese oxide composite electrodes of above-mentioned preparation are working electrode,
Area is 4 × 4cm2Platinum electrode be auxiliary electrode assembling three-electrode system, carry out cyclic voltammetry, test potential range
For -0.4~0.4V (relative to Mercurous sulfate electrode), sweep speed is 2mV/s and 200mV/s.According to cyclic voltammetry curve meter
It is 359.5F/g to calculate specific capacitance of the electrode active material at 2mV/s, and cyclic voltammetry curve is still when sweep speed is increased to 200mV
So keep approximate rectangular, capacity retention ratio 60.8%.
Comparative example 1
Other conditions are consistent with embodiment 1, and only electrolyte is the mixed solution of common manganese sulfate and sodium sulphate, sulfuric acid
The concentration of manganese and sodium sulphate is 0.5mol/L, and the temperature of electrodeposit liquid is room temperature (25 DEG C), by manganese dioxide obtained by electro-deposition
Electrode directly carries out cyclic voltammetry, specific capacitance of the electrode active material at 2mV/s in gained manganese oxide composite electrodes
Only 262F/g, cyclic voltammetry curve shape is spindle, capacity retention ratio 25.8% when sweep speed is increased to 200mV..
Comparative example 2
Other conditions are consistent with embodiment 1, and only electrolyte is the mixed solution of common manganese sulfate and sodium sulphate, sulfuric acid
The concentration of manganese and sodium sulphate is 0.5mol/L, and the temperature of electrodeposit liquid is room temperature (25 DEG C), by manganese dioxide obtained by electro-deposition
Electrode carries out hydro-thermal process in 0.02mol/L metabisulfite solutions, and electrode active material exists in gained manganese oxide composite electrodes
Specific capacitance under 2mV/s is only 249F/g, and cyclic voltammetry curve shape is maintained as approximate square when sweep speed is increased to 200mV
Shape, capacity retention ratio 42.8%.
Embodiment 2
With embodiment 1, the lanthanum sulfate that only uses replaces cerous sulfate for operating process, and lanthanum sulfate is a concentration of in mixed solution
0.05mol/L, sulfuric acid concentration 1mol/L.A concentration of 0.1mol/L of lanthanum sulfate, hydro-thermal process temperature in hydro-thermal process solution
It it is 180 DEG C, hydrothermal conditions are to obtain within 12 hours combination electrode, Mn in combination electrode4+/Mn3+Ratio be 3.7:1；
Specific capacitance of the electrode obtained active material at 2mV/s is 330.2F/g, and sweep speed recycles when being increased to 200mV
Volt-ampere curve still maintains approximate rectangular, capacity retention ratio 64.1%.
, embodiment 3
With embodiment 1, the potassium sulfate that only uses replaces cerous sulfate for operating process, and potassium sulfate is a concentration of in mixed solution
0.1mol/L, sulfuric acid concentration 3mol/L.A concentration of 0.2mol/L of potassium sulfate, hydro-thermal process temperature are in hydro-thermal process solution
120 DEG C, hydrothermal conditions are 24 hours, obtain combination electrode, Mn in combination electrode4+/Mn3+Ratio be 4.8:1；
Specific capacitance of the electrode obtained active material at 2mV/s is 351.2F/g, and sweep speed recycles when being increased to 200mV
Volt-ampere curve still maintains approximate rectangular, capacity retention ratio 60.2%.
Comparative example 3
Other uniform embodiments 3 of condition are completely the same, the difference is that in hydro-thermal process solution lanthanum sulfate it is a concentration of
0.3mol/L, gained manganese oxide composite electrodes in specific capacitance of the electrode active material at 2mV/s be only 235F/g, scanning speed
Cyclic voltammetry curve still maintains approximate rectangular when rate is increased to 200mV, capacity retention ratio 62.1%.
Embodiment 4
With embodiment 1, the rubidium sulfate that only uses replaces cerous sulfate for operating process, and rubidium sulfate is a concentration of in mixed solution
0.08mol/L, sulfuric acid concentration 2mol/L.A concentration of 0.05mol/L of rubidium sulfate, hydro-thermal process temperature in hydro-thermal process solution
It it is 150 DEG C, hydrothermal conditions are to obtain within 20 hours combination electrode, Mn in combination electrode4+/Mn3+Ratio be 2.6:1；
Specific capacitance of the electrode obtained active material at 2mV/s is 305.2F/g, and sweep speed recycles when being increased to 200mV
Volt-ampere curve still maintains approximate rectangular, capacity retention ratio 65.3%.
In addition to above-described embodiment and comparative example, the present invention has also been attempted during technical research and uses MnCl2And Mn
(NO3)2；However use MnCl2When, manganese ion chlorion in anodic oxidation equally can influence electrode material in anodic oxidation
Performance, and release chlorine simultaneously；Use Mn (NO3)2Then nitrate anion in cathodic reduction and can make to generate manganous hydroxide in solution, together
When can also discharge nitrogen oxides toxic gas.The performance of its products obtained therefrom is well below products obtained therefrom of the embodiment of the present invention.
Claims (8)
1. a kind of method preparing high power capacity self-supporting manganese dioxide/carbon combination electrode, it is characterised in that：The manganese dioxide is
α type manganese dioxide with 2 × 2 tunnel structures, and the preparation method includes the following steps：
Step 1
Manganese sulfate and water-soluble structure stabilizer are dissolved in aqueous sulfuric acid and form mixed solution；The water-soluble structure is stablized
Agent is the sulfate with metal cation；The radius of the metal cation is 1~1.52 × 10-10m；
Step 2
The carbonaceous material for selecting surface cleaning clean is as anode, using mixed solution obtained by step 1 as electrolyte；At 15 DEG C
Hereinafter, carrying out oxidizing and electrochemical in anode deposits manganese dioxide, semi-finished product are obtained；When carrying out anodic oxidation electrochemical deposition, control
Anode potential processed is greater than or equal to 0.14V, and the anode potential is the potential relative to Mercurous sulfate electrode；
Step 3
Semi-finished product obtained by step 2 are placed in the solution containing water-soluble structure stabilizer, it is anti-to carry out hydro-thermal in 120-200 DEG C
It answers；Obtain the high power capacity self-supporting manganese dioxide/carbon combination electrode.
2. a kind of method preparing high power capacity self-supporting manganese dioxide/carbon combination electrode according to claim 1；Its feature
It is：Step 1: the institute of water-soluble structure stabilizer described in step 3 band metal cation is selected from Ce3+、La3+、K+、Rb+At least
It is a kind of.
3. a kind of method preparing high power capacity self-supporting manganese dioxide/carbon combination electrode according to claim 1；Its feature
It is：In step 1, a concentration of 0.5~3mol/L of sulfuric acid in the mixed solution, the water-soluble structure stabilizer it is dense
Degree is 0.01~0.1mol/L, a concentration of 0.1~1mol/L of manganese sulfate.
4. a kind of method preparing high power capacity self-supporting manganese dioxide/carbon combination electrode according to claim 1；Its feature
It is：In step 2, when anode carries out oxidizing and electrochemical deposition manganese dioxide, the temperature for controlling electrolyte is 5~15 DEG C.
5. a kind of method preparing high power capacity self-supporting manganese dioxide/carbon combination electrode according to claim 1；Its feature
It is：In step 3, the time of hydro-thermal reaction is preferably 8-24 hours.
6. a kind of method preparing high power capacity self-supporting manganese dioxide/carbon combination electrode according to claim 1；Its feature
It is：In step 3, the solution containing water-soluble structure stabilizer is the solution that solute is water-soluble structure stabilizer；It is described molten
Matter is a concentration of 0.02~0.2mol/L of water-soluble structure stabilizer in the solution of water-soluble structure stabilizer.
7. a kind of method preparing high power capacity self-supporting manganese dioxide/carbon combination electrode according to claim 1；Its feature
It is：Mn in gained high power capacity self-supporting manganese dioxide/carbon combination electrode in step 34+/Mn3+Ratio be 1-5:1.
8. a kind of method preparing high power capacity self-supporting manganese dioxide/carbon combination electrode according to claim 1；Its feature
It is：When carbonaceous material used is carbon paper in step 2, gained high power capacity self-supporting manganese dioxide/carbon combination electrode is being swept
It retouches its capacity retention ratio when rate is 200mV and is also greater than 60%.
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| CN102938331A (en) * | 2012-10-11 | 2013-02-20 | 吉林大学 | Foam nickel-base MnO2/C composite electrode material and preparation method thereof |
| CN106098395A (en) * | 2016-06-02 | 2016-11-09 | 中南大学 | A kind of manganese dioxide fiber electrode and its preparation method and application |
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| CN102938331A (en) * | 2012-10-11 | 2013-02-20 | 吉林大学 | Foam nickel-base MnO2/C composite electrode material and preparation method thereof |
| CN106098395A (en) * | 2016-06-02 | 2016-11-09 | 中南大学 | A kind of manganese dioxide fiber electrode and its preparation method and application |
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