CN102376452B - Super capacitor assembled by manganese series oxide electrodes with meshed nano-structures - Google Patents

Super capacitor assembled by manganese series oxide electrodes with meshed nano-structures Download PDF

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CN102376452B
CN102376452B CN 201110402732 CN201110402732A CN102376452B CN 102376452 B CN102376452 B CN 102376452B CN 201110402732 CN201110402732 CN 201110402732 CN 201110402732 A CN201110402732 A CN 201110402732A CN 102376452 B CN102376452 B CN 102376452B
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electrode
manganese series
ultracapacitor
electrolyte
capacitor
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CN102376452A (en
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孟惠民
王书真
史艳华
俞宏英
孙冬柏
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University of Science and Technology Beijing USTB
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Abstract

The invention relates to a super capacitor assembled by manganese series oxide electrodes with meshed nano-structures, which is large in specific capacity and low in cost. The super capacitor assembled by the manganese series oxide electrodes with the meshed nano-structures is characterized by comprising at least one manganese series oxide electrode with a unique meshed nano-structure, a membrane soaking in an electrolyte solution is clamped between the manganese series oxide electrode with the unique meshed nano-structure and a congeneric electrode or other electrodes such as an active carbon electrode and the like, a shell is coated outside and a negative wire and a positive wire are led out, thus the super capacitor is assembled. The super capacitor assembled by the manganese series oxide electrodes with the meshed nano-structures adopts composite oxides of transition metal manganese, which are abundant in material, as electrode material instead of precious metal, so that the super capacitor is low in cost.

Description

A kind of ultracapacitor with the assembling of mesh nano-structure manganese series oxides electrode
Technical field
The present invention relates to a kind of ultracapacitor that specific capacity is big, cost is low that adopts the assembling of mesh nano-structure manganese series oxides electrode.
Background technology
Ultracapacitor is the novel energy-storing device between chemical cell and common electrostatic condenser, its energy storage energy density is far above electrostatic condenser, and discharge energy density is far above chemical cell, all have good application prospects in fields such as electric motor car, satellite and the pulse powers, can assist even the battery system that begun to substitute current use uses when requiring occasion such as high power discharge.The capacity of original ordinary capacitor can only reach the microfarad order of magnitude, and the energy that can store is minimum, as the filtering in the electronic circuit, AC coupled device, oscillation circuit element etc.And the energy force rate ordinary capacitor of ultracapacitor store charge exceeds several magnitude, and this also is that it is called as the reason of " super ".But the title of present ultracapacitor is disunity still, ultracapacitor (Supercapacitor), ultra-capacitor (Ultracapacitor), electrochemical capacitor (Electrochemical Capacitor), double charge layer capacitor (Electrical Double Layer Capacitor are arranged, EDLC) or double electric layer capacitor (Double Layer Capacitor, DLC) etc.Reason for this class capacitor electrode material, electrolyte etc. not simultaneously, its charge storage and discharge mechanism are not quite similar, and generally are divided into electric double layer capacitance and pseudo capacitance two class Charge Storage discharge mechanisms.Its capacitive property depends on the electrode electric double layer on the one hand, so big more its capacitance of electrode specific surface area is big more, and the activated carbon electrodes ultracapacitor that current production rate is maximum is mainly the double electric layer capacitor of this type of mechanism; On the other hand, in the feature potential range, electrode surface takes place fast, reversible, faraday's reaction of no phase transformation, and be accompanied by owing electromotive force deposition or realizing that intracell " embedding is taken off " electric charge is storing of energy of proton or ion, then its capacitance is not only relevant with electric double layer, also react relevant with electrode surface faraday, so capacitance value is generally 10～100 times of double electric layer capacitor, the metal oxide electrode ultracapacitor generally belongs to the electrochemical capacitor of this type of mechanism, electrochemical capacitor can be much larger than the electric double layer capacitance of material with carbon element, so metal oxide electrode material has been subjected to paying close attention to widely in recent years.
Metal oxide electrode material mainly contains ruthenium-oxide, nickel oxide, cobalt oxide, manganese oxide, iron oxide and aluminium oxide etc.That the metal oxide based super capacitor is at present successful is ruthenium-oxide electrode/H 2SO 4Water solution system is by Canadian Conway [1]Find at first, it is characterized in that cyclic voltammetry curve almost is the rectangle of symmetry, does not have sharp-pointed redox peak.Park [2]Deng having made RuO with the cathode electrodeposition method 2Membrane electrode, its unipolar specific capacity is up to 788Fg -1But RuO 2High price and its toxicity have limited its large-scale commercial, and it is imperative to seek cheap electrode material.Kyung W N [3]Deng employing electrochemical deposition Ni (OH) 2Heat treatment makes porous NiO again xFilm, unipolar specific capacity are 277 Fg -1Anderson [4]Deng preparing MnO with sol-gal process and electrochemical deposition method respectively 2, find with the MnO of sol-gal process than the electrodeposition process preparation 2Specific capacity exceed 1/3rd.But still do not find so far a kind ofly can replace RuO fully at aspect of performance 2New metal oxide materials.And deliver at present be single electrode than capacitance values, rather than be assembled into into the electric capacity of capacitor.
Chinese patent patent No. ZL200710176693.X patent [5], a kind of preparation method of nanometer mesh-like structure manganese series oxides electrode has been proposed, electrode preparation is with low cost, and is environmentally friendly green material.The invention provides a kind of is the capacitor of electrode assembling with this type of nanometer mesh-like structure manganese series oxides, and this capacitor not only quality is bigger than electric capacity, and comparatively speaking cost is low.
Reference:
[1]Conway?B?E.?Transition?from?super?capacitor?to?battery?behavior?in?electrochemical?energy?storage[J].?Electrochem?Soc，1991，138(6):1539-1548.
[2]?Park?B?O,?Lokhande?D?C,?Park?H?S,?Jung?K?D,?Joo?O?S.?Performance?of?supercapacitor?with?electrodeposited?ruthenium?oxide?film?electroded-effect?of?film?thickness[J].?Power?Source,?2004,134(1):148-152.
[3]?Kyung?Wan?Nam,?Kwang?Bum?Kim.?A?study?of?the?NiO x?electrode?via?electrochemicalroute?for?supercapacitor?applications?and?their?charge?storge?mechanism[J].?Electrochem?Soc,2002,149(3):346-354.
[4]?Anderson?M?A,?Pang?S?C,?Chapman?T?W.?Novel?electrode?material?for?thin?film?ultracapacitors:?comparison?of?electrochemical?properties?of?sol-gel?derived?and?electrode?deposided?manganese?dioxide[J].?Electrochem?Soc,2000,147(2):444-450.
[5] Meng Huimin, Shi Yanhua, Sun Dongbai, Yu Hongying, Fan Zishuan, Wang Xudong. a kind of mesh nano-structure manganese series oxides coating and preparation method thereof [P]. the patent No.: ZL200710176693.X.
Summary of the invention
The objective of the invention is to use mesh nano-structure manganese series oxides electrode, with same electrode or with other electrode therebetween such as activated carbon electrodes to be soaked with the barrier film of electrolyte solution, bag is with shell and draw negative pole pole and Positive Poles, is assembled into the ultracapacitor that specific capacity is big, cost is low.
Technical solution of the present invention is as follows: a kind of ultracapacitor with the assembling of mesh nano-structure manganese series oxides electrode, and it is characterized in that: described ultracapacitor comprises that at least one has the manganese series oxides electrode of unique mesh nanostructure; The manganese series oxides electrode of described unique mesh nanostructure and other electrode therebetween such as electrode of the same race or activated carbon electrodes are to be soaked with the barrier film of electrolyte solution, and bag is with shell and draw negative pole and positive wire, is assembled into ultracapacitor.
Further: described manganese series oxides electrode with unique mesh nanostructure, this manganese series oxides comprises that Mn-O, Mn-Mo-O, Mn-Mo-Fe-O, Mn-Mo-V-O, Mn-Fe-V-O etc. are at MnO 2The manganese series oxides of middle other elements that mix.
Further: described capacitor diaphragm is other barrier films such as glass fibre membrane, polypropylene film, agar membrane.
Further: described capacitor electrolyte is a water based inorganic electrolyte, or organic electrolyte, or inorganic and organic mixed electrolytic solution, or solid electrolyte or gel electrolyte.
Further: the electrode of described capacitor and barrier film are plain film or plain film are carried out around volume.
Further: described capacitor is the monolithic capacitor of two electrodes assembling, or the multielectrode capacitance device of a plurality of electrode assembling.
The invention has the beneficial effects as follows:
1, the composite oxides of the transition metal manganese of employing abundant raw material do not use noble metal as electrode material, make the ultracapacitor cost low.
2, having adopted high performance manganese series oxides electrode with the poroid nanostructure of unique three dimensional network is at least one electrode of ultracapacitor, make the ultracapacitor capacitive character can be high, energy storage density is big.
Description of drawings
Accompanying drawing 1 is the supercapacitor structures figure of many group plain film electrodes and barrier film assembling.
The microscopic appearance of the mesh nano-structure manganese series oxides electrode surface that accompanying drawing 2 is among the present invention to be adopted.A.Mn-O electrode among the figure, b.Mn-Mo-O electrode, c.Mn-Mo-Fe-O electrode, d.Mn-Mo-V-O electrode, e. Mn-Fe-V-O electrode
Accompanying drawing 3 is graph of pore diameter distribution of mesh nano-structure manganese series oxides electrode surface used among the present invention.
Accompanying drawing 4 is cyclic voltammetry curves of mesh nanostructure Mn-Mo-Fe-O electrode.
Accompanying drawing 5 is the cyclic voltammetry curves that adopt the symmetrical structure ultracapacitor of mesh nanostructure Mn-Mo-Fe-O oxide electrode assembling.
Embodiment
Accompanying drawing 1 is the supercapacitor structures figure of many group plain film electrodes and barrier film assembling.1. housings among the figure, 2. negative pole pole, 3. Positive Poles, 4. electrode, 5. barrier film., organize negative pole and positive pole more and export to negative pole pole and Positive Poles with the conduction sheet that confluxes respectively to be soaked with the barrier film of electrolyte solution in two electrode therebetween, the outer envelope shell promptly is assembled into complete ultracapacitor.
The quality of ultracapacitor is by formula calculated than electric capacity (Cst):
Figure 201110402732X100002DEST_PATH_IMAGE004
In the formula, C St---quality compares electric capacity;
Q---volt-ampere electric charge;
φ 2-φ 1---potential region;
M---quality;
V---cyclic voltammetric test scan speed.
Accompanying drawing 2 is for adopting several manganese series oxides electrode surface microscopic appearances with unique mesh nanostructure of ZL200710176693.X patented method manufacturing.Field emission electron microscopic observation is mixed with the surface topography of the nanoscale manganese series oxides coating of Mo, Fe or V element, manganese series oxides coating after the doping has the poroid nanostructure of three dimensional network, though Mn oxide is the mixed oxide of two or three element of Mn, Mo, Fe and V element, but still keeping typical γ-MnO 2The crystal phase structure, doped chemical iron, molybdenum, vanadium are respectively with Fe 3+, Mo 6+, V 5+The form solid solution go into γ-MnO 2Mutually, and its tissue is that crystallization is nanocrystalline completely.The oxide of anodic electrodeposition all has the pore structure of different sizes, higher specific surface area, and the pore structure on Mn-O and Mn-Fe-V-O oxide anode surface is bigger, and the mesh of Mn-Mo-O, Mn-Mo-V-O, Mn-Mo-Fe-O is tiny, densification.The mesh of Mn-O oxide is that lamellar structure is interweaved, and the skeleton of mesh is more sturdy, and the skeleton of Mn-Fe-V-O oxide mesh is thinner.
Accompanying drawing 3 is the poroid nano-structure manganese series oxides electrode aperture of a several three dimensional networks distribution map.The main distribution of Mn-O oxide aperture is 3.6 ~ 9.4 nm, based on the mesopore greater than 2 nm.And Mn-Mo-O, Mn-Mo-V-O, the main distribution of Mn-Fe-V-O oxide aperture are 0.85 ~ 2.5 nm, based on micropore less than 2 nm, and main distribution 0.5 ~ 2.5 nm of Mn-Mo-Fe-O oxide aperture scope, in the majority less than the micropore of 2 nm.The ratio that the micropore pore volume of Mn-Mo-O, Mn-Mo-V-O, Mn-Mo-Fe-O, Mn-Fe-V-O oxide accounts for whole pore volume will be higher than the Mn-O oxide.In Mn oxide, mix behind Mo, Fe, the V element, refinement the nanostructure of Mn oxide, significantly refinement the size of nanostructure, greatly increased the true specific area of electrode, the surface activity number of spots significantly increases; Mn oxide after the doping has the poroid nanostructure feature of tiny three dimensional network, the mesh-structured body phase that makes electrolyte be easier to enter electrode, it is long-pending to increase the real surface that oxide coating contacts with solution, increase the probability of pseudo-capacitance reaction, can further increase Mn oxide is the electric capacity of the capacitor of electrode assembling.
Accompanying drawing 4 is the cyclic voltammetry curves that adopt the poroid nanostructure Mn-Mo-Fe-O oxide electrode of three dimensional network of electrochemistry three electrode test systems test, can analyze the capacitive property of this electrode thus.With mesh nanostructure Mn-Mo-Fe-O oxide electrode is work electrode, and saturated calomel electrode (SCE) is a reference electrode, and platinized platinum is an auxiliary electrode, and electrolyte is 25 ℃ 0.5 moldm -3Na 2SO 4Solution, sweep speed are 10 mVs -1, utilize cyclic voltammetry curve that the CHI660B electrochemical workstation records as shown in Figure 3.Show that the Mn-Mo-Fe-O oxide electrode is rectangular characteristic preferably at 0 ~ 1 V potential region, cathodic process and anodic process substantial symmetry, show the pseudo-capacitance feature of pure capacitor, illustrate that electrode is with constant current charge-discharge in this potential range, and the size of reversible pseudo-capacitance is relevant with current potential, and this is the key character of difference electric double layer capacitance; A pair of faint redox peak appears in the CV curve between 0.4 ~ 0.6 V, the corresponding Mn in this peak 4+/ Mn 3+Conversion process; This electrode charge and discharge is functional, and the electric capacity that is produced in 0 ~ 1 V potential region work mainly is faraday's electric capacity that the electroactive material redox reaction is produced.So the formation of this tridimensional nano net structure Mn-Mo-Fe-O oxide electrode electric capacity has electric double layer capacitance and two kinds of Charge Storage mechanism of pseudo capacitance at least, its capacitive property depends on the bigger serface electric double layer that tridimensional nano net structure forms on the one hand, depends on Mn(IV in the electrochemical window on the one hand) with the Mn(III) between reversible fast redox farad the react.And according to capacitor energy storage computing formula E=C (Δ V) 2/ 2, square being directly proportional of the ratio electric capacity of energy storage density and capacitor and operating potential window, this Mn-Mo-Fe-O oxide electrode potential window is 1V, illustrates that its energy storage density is very high.According to the quality of ultracapacitor than electric capacity (C St), the quality that by formula calculates the Mn-Mo-Fe-O oxide electrode compares capacitor C St515.22 Fg have been reached -1Repeatedly the volt-ampere curve test of circulation shows that also the capacitance of the rear electrode that repeatedly circulates still can remain on more than 95%, illustrates with the Mn-Mo-Fe-O oxide to be that the ultracapacitor of electrode active material has better cycle performance and electric capacity stability.
Embodiment 1
Adopt two mesh nano-structure manganese series oxides electrodes to be assembled into symmetrical manganese series oxides ultracapacitor, the electrolytical aqueous solution of inorganic matter such as used for electrolyte KCl.With the Mn-Mo-Fe-O oxide electrode therebetween of two poroid nanostructures of three dimensional network to be soaked with 2 moldm -3The glass fibre membrane barrier film of KCl electrolyte solution is assembled into the monolithic capacitor of symmetrical structure, tests its cyclic voltammetry curve at-0.5 ~ 0.5V voltage range under room temperature, and sweep speed is 5mVs -1Test result as shown in Figure 6, Mn-Mo-Fe-O oxide monomer ultracapacitor-0.5 ~+have rectangular characteristic preferably in the 0.5V potential window scope, and it is symmetrical substantially with respect to zero current line, there is not tangible redox peak, the current response value is almost constant, show cathodic process and anodic process substantial symmetry, illustrate that this ultracapacitor discharges and recharges with constant rate of speed, the potential change of electrode is to the not significantly influence of capacity of electrode, electrode has typical capacitance characteristic, and the charge-exchange between electrode and the electrolyte is carried out with constant speed.From then on when the scanning direction changes, there is current response fast at the two ends of curve as can be seen, and electric current generation fast steering illustrates that the internal resistance of electrode is less, and electrode charge and discharge process has dynamics invertibity preferably.According to the quality of ultracapacitor than electric capacity (C St), the quality that by formula calculates the Mn-Mo-Fe-O oxide electrode compares capacitor C St515.22 Fg have been reached -1And according to capacitor energy storage computing formula E=C (Δ V) 2/ 2, square being directly proportional of the ratio electric capacity of energy storage density and capacitor and operating potential window, this Mn-Mo-Fe-O oxide electrode potential window is 1V, illustrates that its energy storage density is very high, energy density can reach 71.59WhKg -1, be higher than the RuO that the cathode electrodeposition method makes 2Energy density 66.35 WhKg that membrane electrode records at its potential window 0 ~ 0.8V -1, comparatively speaking be lower than slightly with the MnO of sol-gal process than the electrodeposition process preparation 2Energy density 78.52 WhKg that record at its potential window 0 ~ 0.9V -1
Embodiment 2
Adopt two poroid nano-structure manganese series oxides electrodes of three dimensional network to be assembled into symmetrical manganese series oxides ultracapacitor, used for electrolyte organic electrolyte.With the Mn-Fe-V-O anodizing thing electrode therebetween of two mesh nanostructures to be soaked with 1.36 moldm -3MgCl 2The glass fibre membrane barrier film of/EtOH organic electrolyte solution is assembled into the monolithic capacitor of symmetrical structure.The MgCl of present embodiment 2/ EtOH organic electrolyte solution is with inorganic electrolyte MgCl 2Be dissolved in the organic solvent absolute ethyl alcohol (EtOH) and make.This capacitor that adopts organic electrolyte-0.5 ~+0.5V potential window scope in cyclic voltammetry curve also have rectangular characteristic preferably, and it is symmetrical substantially with respect to zero current line, there is not tangible redox peak, the current response value is almost constant, cathodic process and anodic process substantial symmetry, this shows that this electrode capacitor discharges and recharges with constant rate of speed, and the potential change of electrode is to the not significantly influence of capacity of electrode, and electrode has typical capacitance characteristic.Explanation simultaneously, the charge-exchange between electrode and the electrolyte is carried out with constant speed.When the scanning direction of cyclic voltammetry curve changes, current response is fast arranged, electric current generation fast steering illustrates that the internal resistance of electrode is less, and electrode charge and discharge process has dynamics invertibity preferably.The ultracapacitor of this type of symmetrical structure is because of differences such as organic electrolyte electrolyte ingredient, concentration, organic solvents, quality than electric capacity about 50 ~ 350 Fg -1Scope, the having good stability of electric capacity.
Embodiment 3
Assemble asymmetrical manganese series oxides ultracapacitor, promptly electrode adopts the manganese series oxides electrode of mesh nanostructure, and electrode is adopted other electrode such as activated carbon electrodes.With the Mn-Mo-V-O oxide electrode of mesh nanostructure and activated carbon electrodes therebetween to be soaked with 0.5 moldm -3Na 2SO 4The glass fibre membrane barrier film of electrolyte solution is assembled into the monolithic capacitor of unsymmetric structure.The activated carbon electrodes of present embodiment mixes active carbon oven dry with electrically conductive graphite, polytetrafluoroethylene etc., is pressed into moulding preparation on the nickel foam.The poroid nano-structure manganese series oxides ultracapacitor of the three dimensional network of this unsymmetric structure has and the similar cyclic voltammetry curve shape of the manganese series oxides ultracapacitor of symmetrical structure,-0.5 ~+rectangular characteristic preferably had in the 0.5V potential window scope, and it is symmetrical substantially with respect to zero current line, there is not tangible redox peak, the current response value is almost constant, cathodic process and anodic process substantial symmetry, show that ultracapacitor still discharges and recharges with constant rate of speed, the potential change of electrode is to the not significantly influence of capacity of electrode, electrode has typical capacitance characteristic, and electrode charge and discharge process has dynamics invertibity preferably.The ultracapacitor of this type of unsymmetric structure is because of differences such as the composition of other electrodes such as activated carbon electrodes, manufacture crafts, quality than electric capacity about 60 ~ 180 Fg -1Scope, electric capacity has good stability.

Claims (5)

1. ultracapacitor with mesh nano-structure manganese series oxides electrode assembling, it is characterized in that: described ultracapacitor comprises that at least one has the manganese series oxides electrode of unique mesh nanostructure; The manganese series oxides electrode of described unique mesh nanostructure and electrode of the same race or activated carbon electrodes therebetween are to be soaked with the barrier film of electrolyte solution, and bag is with shell and draw negative pole and positive wire, is assembled into ultracapacitor;
Described manganese series oxides electrode with unique mesh nanostructure, this manganese series oxides are Mn-O or Mn-Mo-O or Mn-Mo-Fe-O or Mn-Mo-V-O or Mn-Fe-V-O; Mn ?O oxide aperture distribution be 3.6～9.4nm; And Mn ?Mo ?O, Mn ?Mo ?V ?O, Mn ?Fe ?V ?O oxide aperture distribution be 0.85～2.5nm; Mn ?Mo ?Fe ?O oxide aperture distribution 0.5～2.5nm.
2. ultracapacitor according to claim 1 is characterized in that: described capacitor diaphragm is glass fibre membrane or polypropylene film or agar membrane barrier film.
3. ultracapacitor according to claim 1 is characterized in that: electrolyte is a water based inorganic electrolyte in the described capacitor, or organic electrolyte, or inorganic and organic mixed electrolytic solution, or solid electrolyte or gel electrolyte.
4. ultracapacitor according to claim 1 is characterized in that: the electrode of described capacitor and barrier film are plain film or plain film are carried out around volume.
5. a kind of ultracapacitor according to claim 1 is characterized in that: described capacitor is the monolithic capacitor of two electrodes assembling, or the multielectrode capacitance device of a plurality of electrode assembling.
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CN101286418A (en) * 2008-04-30 2008-10-15 清华大学深圳研究生院 A manganese bioxide electrochemical super capacitor
CN101399120A (en) * 2008-10-30 2009-04-01 上海大学 Novel hybrid supercapacitor

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CN101230468A (en) * 2007-11-01 2008-07-30 北京科技大学 Meshed nano-structure manganese series oxides coating and method for preparing same
CN101286418A (en) * 2008-04-30 2008-10-15 清华大学深圳研究生院 A manganese bioxide electrochemical super capacitor
CN101399120A (en) * 2008-10-30 2009-04-01 上海大学 Novel hybrid supercapacitor

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