CN103762087B - Compound porous fiber electrode material of nanocrystalline copper oxide/ferrite and its preparation method and application - Google Patents
Compound porous fiber electrode material of nanocrystalline copper oxide/ferrite and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of compound porous fiber electrode material of nanocrystalline copper oxide/ferrite and its preparation method and application, it is mainly composited by copper oxide and spinel type ferrite are biphase, and chemical formula is CuO/xRFe2O4, R is Cu, Zn, Co, Mn, Ni；The grain size of copper oxide and spinel type ferrite is nanoscale, fibre diameter is at micron order, its preparation method is first to mix the inorganic salt of copper acetate with metal Fe to be dissolved in deionized water, it is subsequently adding organic acid, it is adjusted to alkalescence with ammonia, re-evaporation is anhydrated and is obtained spinnability gel, obtains Precursors of Fibers after wire drawing；Finally carry out high temperature sintering, after cooling, obtain compound porous fiber electrode material.The application in preparing ultracapacitor of the compound porous fiber electrode material, has the advantages such as porosity height, crystal grain is tiny, electron transport ability is strong.
Description
Technical field
The invention belongs to micro nano structure electrode material and preparation thereof and applied technical field, particularly relate to a kind of compound porous fibrous material of copper oxide/ferrite that can be used as electrode material for super capacitor and its preparation method and application.
Background technology
Copper oxide (CuO) and spinel type ferrite (RFe2O4, R is Cu, Zn, Co, Mn, Ni etc.) and it is all good semi-conducting material, existing research widely and application in fields such as SOFC, catalyst, sensor, opto-electronic conversion, lithium ion battery negative materials.In recent years, many researcheres have synthesized CuO and the RFe of a series of different-shape2O4And its application in ultracapacitor has been studied, if Sun etc. is with copper nitrate and activated carbon for raw material, chemical deposition is adopted to be prepared for the hybrid super capacitor of CuO doping, capacitor specific capacity reaches 210F/g [SunGuohuaet.Physicalandelectrochemicalcharacterizationof CuO-dopedactivatedcarboninionicliquid, Electrochim.Acta., 2010,55,2,667 2672].The flower-like nanostructure CuO of the preparation such as Zhang also has good capacitive energy, its capacitance reaches 133.6F/g [ZhangHongxiaet.Preparationofflower-likeCuObyasimplechemi calprecipitationmethodandtheirapplicationaselectrodemate rialsforcapacitor, Mater.Res.Bull., 2008,43,3,221 3226].V.D.Patake etc. adopt electrodeposition process deposited oxide Copper thin film on stainless steel, during with sodium sulfate for electrolyte, its high specific capacity is up to 36F/g [V.D.Patakeet., Electrodepositedporousandamorphouscopperoxidefilmforappl icationinsupercapacitor, Mater.Chem.Phys., 2009,114,6 9].The direct growth cupric oxide nano sheet in nickel foam such as Wang is used as electrode, its specific capacity reaches as high as 569F/g [Wangguilinget., PreparationandsupercapacitanceofCuOnanosheetarraysgrowno nnickelfoam, J.PowerSources, 2011,196,5,756 5760].Additionally, open and wait the flower-shaped copper oxide synthesized by liquid phase reactor method, its specific capacity is up to 115F/g [ZhangHongxiaet., SynthesisofCuOnanocrystallineandtheirapplicationaselectr odematerialsforcapacitors, Mater.Chem.Phys.2008,108,184 187].
Although the research that copper oxide is in ultracapacitor makes first appearance, but the specific capacity of the copper oxide electrode material of prior art is relatively on the low side, also has a certain distance from industrialized production, and first charge-discharge process is irreversible limits its application.It addition, its chemical property of the copper oxide material of different-shape and composition differs greatly.Therefore, develop that a kind of preparation method is simple, preparation activity electrochemical material high, that stability is good is necessary.
Summary of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, there is provided a kind of porosity high, crystal grain is tiny, there is the compound porous fiber electrode material of nanocrystalline copper oxide/ferrite of higher specific surface area and electron transport ability, correspondingly provide a kind of step simple, cost is low, production efficiency is high, the preparation method of the compound porous fiber electrode material of nanocrystalline copper oxide/ferrite that controllability is strong, and the application in preparing ultracapacitor of a kind of compound porous fiber electrode material of nanocrystalline copper oxide/ferrite is provided, the ultracapacitor of preparation will have higher specific capacity and good cycle charge discharge electrical property.
For solving above-mentioned technical problem, the technical scheme that the present invention proposes is a kind of compound porous fiber electrode material of nanocrystalline copper oxide/ferrite, described fiber electrode material is mainly composited by copper oxide and spinel type ferrite are biphase, and the chemical formulation of described fiber electrode material is:
CuO/xRFe2O4；
In above formula, x=10～40at.%, R is one or more (in the composite that x refers to, ferrite accounts for the percentage ratio of ferrite and copper oxide total mole number) in Cu, Zn, Co, Mn, Ni；
The grain size of described copper oxide and spinel type ferrite is nanoscale, and the fibre diameter of described fiber electrode material is at micron order.
In the above-mentioned compound porous fiber electrode material of nanocrystalline copper oxide/ferrite, it is preferred that the grain size of described copper oxide is 20nm～40nm, and the grain size of described spinel type ferrite is 30nm～55nm.
In the above-mentioned compound porous fiber electrode material of nanocrystalline copper oxide/ferrite, it is preferred that the fibre diameter of described fiber electrode material is 1 μm～5 μm, and Fiber Aspect Ratio is 50～1000, and the surface holes pore-size distribution of fiber electrode material is at 50nm～500nm.
Conceive as a total technology, the preparation method that the present invention also provides for a kind of above-mentioned compound porous fiber electrode material of nanocrystalline copper oxide/ferrite, comprise the following steps:
(1) copper acetate is mixed with the inorganic salt of metal Fe (described inorganic salt is preferably nitrate and/or acetate) it is dissolved in deionized water and forms mixed solution (proportioning of the inorganic salt of copper acetate and metal Fe carries out quantitative Analysis according to the x value in above-mentioned chemical formula), add organic acid until completely dissolved, with ammonia adjustment pH value to alkalescence, after stirring, at 60 DEG C～70 DEG C temperature, evaporative removal moisture obtains spinnability gel, obtains Precursors of Fibers then through after wire drawing (preferably employing roll-type spinning-drawing machine), drying (or dry)；
(2) Precursors of Fibers prepared in step (1) is carried out high temperature sintering, obtain after being cooled to room temperature with copper oxide be matrix, the compound porous fiber electrode material of nanocrystalline copper oxide/ferrite that is second-phase compound with ferrite.
Above-mentioned preparation method, in described step (1), it is preferred that
In mixed solution, the inorganic salt of metal R is also added when preparing mixed solution, or to the inorganic salt of addition metal R in mixed solution after addition organic acid, then regulate pH value with ammonia；
Described inorganic salt is nitrate and/or acetate；
Described metal R is one or more in copper, cobalt, nickel, manganese, zinc.
Above-mentioned preparation method, in described step (1), it is preferred that described organic acid is the arbitrarily ratio mixing of one or more in tartaric acid, citric acid, lactic acid, and organic acid total amount is 0.8～2.0:1 with the mol ratio of metal ion total amount in mixed solution.By the organic acid preferably added, contribute to being formed carbochain and decompose during for later stage high temperature sintering heat energy is provided, to reduce sintering temperature, reducing energy consumption.The size of grain growth and specific surface area can be effectively controlled by control organic acid and metal ion ratio.
Above-mentioned preparation method, in described step (1), it is preferred that regulates pH value to alkalescence with ammonia and refers to pH value adjustment to 9～10.After adding organic acid, add adjusting PH with base value again contribute to metal ion complexation in carbochain.
Above-mentioned preparation method, in described step (1), it is preferred that described in stir the required time be 15h～48h, and described evaporation is to adopt roto-vap operation mode, and rotating speed during rotary evaporation controls at 35r/min～55r/min.
Above-mentioned preparation method, in described step (2), it is preferred that the heating rate of high-temperature sintering process is 2 DEG C/min～10 DEG C/min, and the temperature of high temperature sintering is 600 DEG C～1100 DEG C, and the sintered heat insulating time is 2h～6h.
Conceiving as a total technology, the present invention also provides for the application in preparing ultracapacitor of the compound porous fiber electrode material of nanocrystalline copper oxide/ferrite of a kind of the invention described above.
Compared with prior art, it is an advantage of the current invention that:
(1) by adopting the collosol and gel-Technology for Heating Processing of the present invention can prepare the nanocrystalline compound porous fiber of copper oxide/ferrite, this preparation technology not only step is simple, easy to operate, and raw material sources are extensive, and cost is low；By the electrode material that the present invention prepares, second-phase ferrite is uniformly distributed in copper oxide, can form the ferrite phase that degree of crystallinity is high at a lower temperature；
(2) block or granular similar composite compared by the nanocrystalline compound porous fiber of copper oxide/ferrite that the present invention prepares, and not only porosity is high, and crystal grain is tiny, has higher specific surface area, and has higher electron transport ability；
(3) the nanocrystalline compound porous fibrous material of copper oxide/ferrite that the present invention prepares can be used for preparing combination electrode, product and there is high specific capacity, good cycle charge discharge electrical property, it is compared with single-phase copper oxide fiber, specific capacity improves more than 20%, cycle life improves more than 40%, and this be that the electrode material of the better ultracapacitor of processability provides a kind of reliable path.
Accompanying drawing explanation
Fig. 1 is the CuO/10%CuFe obtained in the embodiment of the present invention 12O4The X-ray diffractogram of compound porous fiber.
Fig. 2 is the CuO/10%CuFe obtained in the embodiment of the present invention 12O4The scanning electron microscope (SEM) photograph of compound porous fiber.
Fig. 3 is the CuO/10%CoFe obtained in the embodiment of the present invention 22O4The scanning electron microscope (SEM) photograph of compound porous fiber.
Fig. 4 is the CuO/30%Zn obtained in the embodiment of the present invention 30.5Ni0.5Fe2O4The X-ray diffractogram of compound porous fiber.
Detailed description of the invention
For the ease of understanding the present invention, below in conjunction with Figure of description and preferred embodiment, the present invention is made more comprehensively, describes meticulously, but protection scope of the present invention is not limited to embodiment in detail below.
Unless otherwise defined, the implication that all technical term used hereinafter is generally understood that with those skilled in the art is identical.Technical term used herein is intended merely to the purpose describing specific embodiment, is not intended to limit the scope of the invention.
Unless otherwise specified, hereinafter used any raw material, reagent etc. all can be buied from market and maybe can be prepared by known method.
Embodiment 1:
A kind of nanocrystalline copper oxide/ferrite compound porous fiber electrode material of the present invention, this fiber electrode material is mainly composited by copper oxide and spinel type ferrite are biphase, and the chemical formulation of this fiber electrode material is:
CuO/10%CuFe2O4；
In this fiber electrode material, the grain size of copper oxide is 20nm～40nm, and the grain size of spinel type ferrite is 30nm～55nm；The fibre diameter of this fiber electrode material is 1 μm～5 μm, and Fiber Aspect Ratio is 50～1000, and the surface holes pore-size distribution of fiber electrode material is at 50nm～500nm.
The preparation method of the compound porous fiber electrode material of nanocrystalline copper oxide/ferrite of above-mentioned the present embodiment, specifically includes following steps:
(1) by 3.993g copper acetate and 1.616gFe (NO3)3·9H2O mixing is dissolved in the deionized water of 250mL and forms mixed solution, add about 3.6022g tartaric acid (tartaric total amount is 1:1 with the mol ratio of metal ion total amount in mixed solution) until completely dissolved, pH value is regulated to 9.5 with ammonia, then magnetic agitation 20h under room temperature, it is mixing uniformly to form stable colloidal sol, at 70 DEG C of temperature, rotate evaporative removal moisture again obtain the spinnability gel of certain viscosity (such as 0.05mPa/S～0.4mPa/S), gel is gone to roll-type spinning-drawing machine drawing filamentation again, it is put in baking oven subsequently at 90 DEG C and dries 24h, obtain Precursors of Fibers；
(2) Precursors of Fibers prepared in step (1) is placed in Muffle furnace and carries out high temperature sintering, it is warmed up to 900 DEG C with the heating rate of 2 DEG C/min, it is cooled to room temperature after sintered heat insulating 4h, obtains the compound porous fiber electrode material of nanocrystalline copper oxide/ferrite of above-mentioned the present embodiment 1.
The X-ray diffractogram of the compound porous fiber electrode material of nanocrystalline copper oxide/ferrite that the present embodiment obtains as it is shown in figure 1, as seen from Figure 1, includes CuO and CuFe in its constituent2O4, its microscopic appearance is as shown in Figure 2；The compound porous fiber electrode material of nanocrystalline copper oxide/ferrite of above-mentioned the present embodiment is prepared into the electrode material in ultracapacitor, and its capacitive property and Electrochemical results are as shown in table 1 below.
Table 1: the Electrochemical results of the embodiment of the present invention 1 the electrode obtained material
| Sample | Existing CuO | The CuO/10at.%CuFe of embodiment 12O4 |
| Specific capacity (F/g) first | 116.3 | 187.8 |
| Cycle life (secondary) | 1100 | 1546 |
Embodiment 2:
A kind of nanocrystalline copper oxide/ferrite compound porous fiber electrode material of the present invention, this fiber electrode material is mainly composited by copper oxide and spinel type ferrite are biphase, and the chemical formulation of this fiber electrode material is:
CuO/10%CoFe2O4；
In this fiber electrode material, the grain size of copper oxide is 20nm～40nm, and the grain size of spinel type ferrite is 30nm～55nm；The fibre diameter of this fiber electrode material is 1 μm～5 μm, and Fiber Aspect Ratio is 50～1000, and the surface holes pore-size distribution of fiber electrode material is at 50nm～500nm.
The preparation method of the compound porous fiber electrode material of nanocrystalline copper oxide/ferrite of above-mentioned the present embodiment, specifically includes following steps:
(1) by 3.5937g copper acetate and 1.616gFe (NO3)3·9H2O mixing is dissolved in the deionized water of 250mL and forms mixed solution, add about 2.5215g tartaric acid and 1.0810g lactic acid (in tartaric acid, lactic acid and mixed solution the mol ratio of metal ion total amount respectively 0.7:0.5:1) until completely dissolved, after magnetic agitation 2h, add 0.5821gCo (NO3)2·6H2O, pH value is regulated to 9.0 with ammonia, then magnetic agitation 24h under room temperature, it is mixing uniformly to form stable colloidal sol, at 60 DEG C of temperature, rotate evaporative removal moisture again obtain the spinnability gel of certain viscosity (0.01～0.2mPa/S), gel is gone to roll-type spinning-drawing machine drawing filamentation again, is put in baking oven subsequently at 110 DEG C and dries 24h, obtain Precursors of Fibers；
(2) Precursors of Fibers prepared in step (1) is placed in Muffle furnace and carries out high temperature sintering, it is warmed up to 600 DEG C with the heating rate of 6 DEG C/min, it is cooled to room temperature after sintered heat insulating 6h, obtains the compound porous fiber electrode material of nanocrystalline copper oxide/ferrite of above-mentioned the present embodiment 2.
The microscopic appearance of the compound porous fiber electrode material of nanocrystalline copper oxide/ferrite that the present embodiment obtains is as shown in Figure 3；The compound porous fiber electrode material of nanocrystalline copper oxide/ferrite of above-mentioned the present embodiment is prepared into the electrode material in ultracapacitor, and its capacitive property and Electrochemical results are as shown in table 2 below.
Table 2: the Electrochemical results of the embodiment of the present invention 2 the electrode obtained material
| Sample | Existing CuO | The CuO/10%at.CoFe of embodiment 22O4 |
| Specific capacity (F/g) first | 116.3 | 140.7 |
| Cycle life (secondary) | 1100 | 1567 |
Embodiment 3:
A kind of nanocrystalline copper oxide/ferrite compound porous fiber electrode material of the present invention, this fiber electrode material is mainly composited by copper oxide and spinel type ferrite are biphase, and the chemical formulation of this fiber electrode material is:
CuO/30%(Zn0.5Ni0.5)Fe2O4；
In this fiber electrode material, the grain size of copper oxide is 20nm～40nm, and the grain size of spinel type ferrite is 30nm～55nm；The fibre diameter of this fiber electrode material is 1 μm～5 μm, and Fiber Aspect Ratio is 50～1000, and the surface holes pore-size distribution of fiber electrode material is at 50nm～500nm.
The preparation method of the compound porous fiber electrode material of nanocrystalline copper oxide/ferrite of above-mentioned the present embodiment, specifically includes following steps:
(1) by 2.7951g copper acetate and 4.848gFe (NO3)3·9H2O mixing is dissolved in the deionized water of 200mL and forms mixed solution, adds about 6.0520g citric acid (citric acid and the mol ratio respectively 0.8:1 of metal ion total amount in mixed solution) until completely dissolved, adds 0.6585gZn (C after magnetic agitation 2h4H6O4)·2H2O and 0.7465gNi (C4H6O4)·4H2O, pH value is regulated to 9.0 with ammonia, then magnetic agitation 48h under room temperature, it is mixing uniformly to form stable colloidal sol, at 70 DEG C of temperature, rotate evaporative removal moisture again obtain the spinnability gel of certain viscosity (0.1～0.5mPa/S), gel is gone to roll-type spinning-drawing machine drawing filamentation again, is put in baking oven subsequently at 110 DEG C and dries 24h, obtain Precursors of Fibers；
(2) Precursors of Fibers prepared in step (1) is placed in Muffle furnace and carries out high temperature sintering, it is warmed up to 800 DEG C with the heating rate of 8 DEG C/min, it is cooled to room temperature after sintered heat insulating 3h, obtains the compound porous fiber electrode material of nanocrystalline copper oxide/ferrite of above-mentioned the present embodiment 3.
The X-ray diffractogram of the compound porous fiber electrode material of nanocrystalline copper oxide/ferrite that the present embodiment obtains as shown in Figure 4, from fig. 4, it can be seen that its constituent includes CuO and (ZnNi) Fe2O4；The compound porous fiber electrode material of nanocrystalline copper oxide/ferrite of above-mentioned the present embodiment is prepared into the electrode material in ultracapacitor, and its capacitive property and Electrochemical results are as shown in table 3 below.
Table 3: the Electrochemical results of the embodiment of the present invention 3 the electrode obtained material
| Sample | Existing CuO | CuO/30at.% (the Zn of embodiment 30.5Ni0.5)Fe2O4 |
| Specific capacity (F/g) first | 116.3 | 227.2 |
| Cycle life (secondary) | 1100 | 1723 |
Embodiment 4:
A kind of nanocrystalline copper oxide/ferrite compound porous fiber electrode material of the present invention, this fiber electrode material is mainly composited by copper oxide and spinel type ferrite are biphase, and the chemical formulation of this fiber electrode material is:
CuO/20%(Co0.8Mn0.2)Fe2O4；
In this fiber electrode material, the grain size of copper oxide is 20nm～40nm, and the grain size of spinel type ferrite is 30nm～55nm；The fibre diameter of this fiber electrode material is 1 μm～5 μm, and Fiber Aspect Ratio is 50～1000, and the surface holes pore-size distribution of fiber electrode material is at 50nm～500nm.
The preparation method of the compound porous fiber electrode material of nanocrystalline copper oxide/ferrite of above-mentioned the present embodiment, specifically includes following steps:
(1) by 3.1944g copper acetate and 0.9313gCo (NO3)2·6H2O、0.1961gMn(C4H6O4)·4H2O、3.232gFe(NO3)3·9H2O mixing is dissolved in the deionized water of 250mL and forms mixed solution, add about 3.362g tartaric acid and 2.3536g citric acid (tartaric acid until completely dissolved, citric acid and the mol ratio respectively 0.8:0.4:1 of metal ion total amount in mixed solution), pH value is regulated to 10.0 with ammonia, then magnetic agitation 15h under room temperature, it is mixing uniformly to form stable colloidal sol, at 65 DEG C of temperature, rotate evaporative removal moisture again obtain the spinnability gel of certain viscosity (0.2～0.7mPa/S), gel is gone to roll-type spinning-drawing machine drawing filamentation again, it is put in baking oven subsequently at 100 DEG C and dries 24h, obtain Precursors of Fibers；
(2) Precursors of Fibers prepared in step (1) is placed in Muffle furnace and carries out high temperature sintering, it is warmed up to 1100 DEG C with the heating rate of 10 DEG C/min, it is cooled to room temperature after sintered heat insulating 4h, obtains the compound porous fiber electrode material of nanocrystalline copper oxide/ferrite of above-mentioned the present embodiment 4.
Table 4: the Electrochemical results of the embodiment of the present invention 4 the electrode obtained material
| Sample | Existing CuO | CuO/20% (the Co of embodiment 40.8Mn0.2)Fe2O4 |
| Specific capacity (F/g) first | 116.3 | 207.8 |
| Cycle life (secondary) | 1100 | 1534 |
Embodiment 5:
A kind of nanocrystalline copper oxide/ferrite compound porous fiber electrode material of the present invention, this fiber electrode material is mainly composited by copper oxide and spinel type ferrite are biphase, and the chemical formulation of this fiber electrode material is:
CuO/40%(Zn0.5Ni0.5)Fe2O4；
In this fiber electrode material, the grain size of copper oxide is 20nm～40nm, and the grain size of spinel type ferrite is 30nm～55nm；The fibre diameter of this fiber electrode material is 1 μm～5 μm, and Fiber Aspect Ratio is 50～1000, and the surface holes pore-size distribution of fiber electrode material is at 50nm～500nm.
The preparation method of the compound porous fiber electrode material of nanocrystalline copper oxide/ferrite of above-mentioned the present embodiment, specifically includes following steps:
(1) by 2.9948g copper acetate and 8.08gFe (NO3)3·9H2O mixing is dissolved in the deionized water of 200mL and forms mixed solution, add about 3.3020g tartaric acid, 11.5577g citric acid and 2.9726g lactic acid (tartaric acid, citric acid and lactic acid and the mol ratio of metal ion total amount respectively 0.4:1:0.6:1 in mixed solution) until completely dissolved, after magnetic agitation 2h, add 2.9749gZn (NO3)2·6H2O and 2.9079gNi (NO3)2·6H2O, pH value is regulated to 9.0 with ammonia, then magnetic agitation 48h under room temperature, it is mixing uniformly to form stable colloidal sol, at 70 DEG C of temperature, rotate evaporative removal moisture again obtain the spinnability gel of certain viscosity (0.05～0.3mPa/S), gel is gone to roll-type spinning-drawing machine drawing filamentation again, is put in baking oven subsequently at 110 DEG C and dries 24h, obtain Precursors of Fibers；
(2) Precursors of Fibers prepared in step (1) is placed in Muffle furnace and carries out high temperature sintering, it is warmed up to 800 DEG C with the heating rate of 8 DEG C/min, it is cooled to room temperature after sintered heat insulating 2h, obtains the compound porous fiber electrode material of nanocrystalline copper oxide/ferrite of above-mentioned the present embodiment 5.
Table 5: the Electrochemical results of the embodiment of the present invention 5 the electrode obtained material
| Sample | Existing CuO | CuO/40% (the Zn of embodiment 50.5Ni0.5)Fe2O4 |
| Specific capacity (F/g) first | 116.3 | 213.4 |
| Cycle life (secondary) | 1100 | 1437 |
Claims (8)
1. a preparation method for the compound porous fiber electrode material of nanocrystalline copper oxide/ferrite, comprises the following steps:
(1) inorganic salt of copper acetate with metal Fe is mixed it is dissolved in deionized water formation mixed solution, add organic acid until completely dissolved, with ammonia adjustment pH value to alkalescence, after stirring, at 60 DEG C～70 DEG C temperature, evaporative removal moisture obtains spinnability gel, then through obtaining Precursors of Fibers after wire drawing；In this step, in mixed solution, also add the inorganic salt of metal R when preparing mixed solution, or to the inorganic salt of addition metal R in mixed solution after addition organic acid, then regulate pH value with ammonia；Described inorganic salt is nitrate and/or acetate；Described metal R is one or more in copper, cobalt, nickel, manganese, zinc；
(2) Precursors of Fibers prepared in step (1) is carried out high temperature sintering, after being cooled to room temperature, obtain the compound porous fiber electrode material of nanocrystalline copper oxide/ferrite；
Described nanocrystalline copper oxide/ferrite compound porous fiber electrode material is mainly composited by copper oxide and spinel type ferrite are biphase, and the chemical formulation of described fiber electrode material is: CuO/xRFe2O4；
In above formula, x=10～40at.%, R is one or more in Cu, Zn, Co, Mn, Ni；
The grain size of described copper oxide and spinel type ferrite is nanoscale, and the fibre diameter of described fiber electrode material is at micron order.
2. preparation method according to claim 1, it is characterised in that: the grain size of described copper oxide is 20nm～40nm, and the grain size of described spinel type ferrite is 30nm～55nm.
3. preparation method according to claim 1 and 2, it is characterised in that: the fibre diameter of described fiber electrode material is 1 μm～5 μm, and Fiber Aspect Ratio is 50～1000, and the surface apertures of fiber electrode material is distributed in 50nm～500nm.
4. preparation method according to claim 1, it is characterised in that: in described step (1),
Described organic acid is the arbitrarily ratio mixing of one or more in tartaric acid, citric acid, lactic acid, and organic acid total amount is 0.8～2.0:1 with the mol ratio of metal ion total amount in mixed solution.
5. preparation method according to claim 1, it is characterised in that: in described step (1),
Regulate pH value to alkalescence with ammonia to refer to pH value adjustment to 9～10.
6. preparation method according to claim 1, it is characterised in that: in described step (1),
Described to stir the required time be 15h～48h, and described evaporation is to adopt roto-vap operation mode, and rotating speed during rotary evaporation controls at 35r/min～55r/min.
7. preparation method according to claim 1, it is characterised in that: in described step (2),
The heating rate of high-temperature sintering process is 2 DEG C/min～10 DEG C/min, and the temperature of high temperature sintering is 600 DEG C～1100 DEG C, and the sintered heat insulating time is 2h～6h.
8. the compound porous fiber electrode material of nanocrystalline copper oxide/ferrite that a preparation method as according to any one of claim 1～7 obtains application in preparing ultracapacitor.
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| EP2181472A1 (en) * | 2007-08-16 | 2010-05-05 | Forschungszentrum Jülich Gmbh | Method for production of a high-temperature fuel cell |
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