CN104299795A - Porous nano composite electrode material and manufacturing method and application of porous nano composite electrode material - Google Patents
Porous nano composite electrode material and manufacturing method and application of porous nano composite electrode material Download PDFInfo
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- CN104299795A CN104299795A CN201410528778.XA CN201410528778A CN104299795A CN 104299795 A CN104299795 A CN 104299795A CN 201410528778 A CN201410528778 A CN 201410528778A CN 104299795 A CN104299795 A CN 104299795A
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- electrode material
- porous nano
- preparation
- metal ion
- nano composite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention provides a porous nano composite electrode material and a manufacturing method and application of the porous nano composite electrode material, and belongs to the field of electrode material manufacturing. Metal ions are dissolved in water, multi-element organic acid is added for reacting, centrifugation, washing and stoving are carried out, burning is carried out in air, and the porous nano composite electrode material is obtained. The electrode material with the high specific capacitance performance and the excellent stability can be obtained with a simple method and a small number of chemical reagents. The porous nano composite electrode material is used as electrode materials of a supercapacitor.
Description
Technical field
The invention belongs to the preparation field of electrode material, especially a kind of porous nano combination electrode material and preparation method thereof and application.
Background technology
Ultracapacitor is as a kind of clean and effective, emerging energy storage device, and performance is significantly better than traditional capacitor, and it has higher specific capacity than traditional capacitor, and storable capacitance reaches thousands of farad in theory, is the decades of times of traditional capacitor capacity; Ultracapacitor has higher power density than battery, can abrupt release ultrahigh current, for high-power output; In addition, it also has that charge efficiency is high, the charging interval is short, service life cycle is long and the feature such as environmental pollution is little; At present, ultracapacitor has been applied to the aspects such as mobile communication, electronics, electric automobile and science and techniques of defence.
Ultracapacitor primarily of electrode material, electrolyte, barrier film and collector etc. four part composition, wherein, electrode material is the key factor affecting its performance; Therefore, finding more preferably electrode system and electrode material has become the important channel of improving ultracapacitor performance, and the classical electrode material for ultracapacitor is RuO
2hydrate, it has good capacitance characteristic, is electrode material more satisfactory at present, but as the compound of noble metal, RuO
2expensive and poisonous, this significantly limit its scale application.
Summary of the invention
For Shortcomings in prior art, the present invention selects traditional organic acids to be part, to common transition metal ions, as Cu
2+, Mn
2+, Fe
2+deng, the complex coordination while of carrying out, obtains the compound complex containing different metal element, then through high-temperature calcination, obtains a kind of porous nano combination electrode material; Loose structure effectively can increase the surface area of material, makes it have abundant charge storage or reaction site, and the electrode material obtained has outstanding ratio capacitance performance, and has good stability; The method economy is green, and technique is simple, is easy to scale.
The present invention realizes above-mentioned technical purpose by following technological means.
A preparation method for porous nano combination electrode material, comprises the steps:
By soluble in water for the metal ion of any mol ratio, add organic acid ethanolic solution and react, then carry out hydro-thermal reaction, centrifugal, washing, dry, calcine in atmosphere.
In such scheme, described metal ion is Cu
2+, Mn
2+, Fe
2+, Fe
3+, Zn
2+, Co
2+, Ni
2+in one or both.
Further, described metal ion is provided by its soluble-salt, and described soluble-salt is the hydrochloride of metal ion, sulfate, nitrate or acetate.
In such scheme, be any mol ratio during described two metal ion species mixing, the total concentration of described metal ion in water is 0.05 ~ 0.3mol/L, and described organic acid in ethanol concentration is 0.2 ~ 0.8mol/L, and described organic acid and the total amount of substance ratio of metal ion are 1:1 ~ 10:1.
Further, described organic acid is tartaric acid, citric acid or malic acid.
In such scheme, described organic acid and the total amount of substance ratio of metal ion are 6.25:1.
In such scheme, described mixing time is 2min ~ 5h, and described hydrothermal temperature is 180 DEG C, and the hydro-thermal reaction time is 16 ~ 24h, and described calcining heat is 300 ~ 600 DEG C, and calcination time is 10min ~ 2h.
The porous nano combination electrode material prepared according to the method described above.
Further, described porous nano combination electrode material is porous laminated, and mean pore size is 5nm.
Above-mentioned porous nano combination electrode material is as the application of electrode material for super capacitor.
Advantage of the present invention:
1. raw material rich reserves, cheap, the environmental friendliness of the present invention's employing, preparation method is simple, without the need to complicated chemical reagent, is easy to scale application;
2. the porous nano combination electrode material of preparation has high ratio capacitance performance and excellent stability, has good application prospect in this field.
Accompanying drawing explanation
Fig. 1 is process flow diagram of the present invention.
X-ray diffraction (XRD) figure of porous nano combination electrode material prepared by Fig. 2 embodiment 1.
Fig. 3 is ESEM (SEM) figure of porous nano combination electrode material prepared by embodiment 1.
Fig. 4 is projection Electronic Speculum (TEM) figure of porous nano combination electrode material prepared by embodiment 1.
Fig. 5 is constant current charge-discharge (GCD) figure of porous nano combination electrode material prepared by embodiment 1.
Embodiment
Below in conjunction with accompanying drawing and specific embodiment, the present invention is further illustrated, but protection scope of the present invention is not limited to this.
Embodiment 1
Take 0.72mmol ferric nitrate and 0.48mmol manganese acetate is dissolved in 10mL deionized water completely, stir, add the tartaric acid solution that 15mL take ethanol as the 0.5mol/L of solvent, after magnetic agitation 1h, at 180 DEG C, carry out hydro-thermal reaction 16h; By pelleting centrifugation, wash 3 times, ethanol washes 2 times, dries the compound complex obtained containing Fe and Mn; This compound complex is calcined at 500 DEG C 30min in air and obtain Fe-Mn-O metal oxide porous composite construction, namely contain the compound of iron oxide and manganese oxide.
Fig. 2 show sample contains Mn
3o
4and Fe
2o
3, do not occur other dephasign peaks in addition, sample crystallinity is good, and diffraction maximum corresponds to Tetragonal Mn
3o
4with water chestnut side phase Fe
2o
3.
Fig. 3 shows that sample presents layer structure.
Fig. 4 shows that sample has and enriches vesicular texture feature.
Fig. 5 is presented at current density when being 0.5A/s, and ratio capacitance is 530mF/cm
2.
Embodiment 2
Take 0.48mmol ferric nitrate and 0.72mmol manganese acetate is dissolved in 10mL deionized water, adding with ethanol is the 15mL 0.8mol/L tartaric acid of solvent, carries out hydro-thermal reaction 16h after magnetic agitation 30min at 180 DEG C; By pelleting centrifugation, wash 3 times, ethanol washes 2 times, dries; 30min is calcined in air at 500 DEG C; Sample is when current density is 0.5A/s, and ratio capacitance is 386mF/cm
2.
Embodiment 3
Take 0.24mmol iron chloride and 0.96mmol manganese acetate is dissolved in 10mL deionized water, adding with ethanol is the 15mL 0.5mol/L citric acid of solvent, carries out hydro-thermal reaction 20h after magnetic agitation 5h at 180 DEG C; By pelleting centrifugation, wash 3 times, ethanol washes 2 times, dries; 30min is calcined in air at 600 DEG C; Sample is when current density is 0.5A/s, and ratio capacitance is 329mF/cm
2.
Embodiment 4
Take 0.38mmol ferric nitrate and 0.12mmol manganese acetate is dissolved in 10mL deionized water, adding with ethanol is the 15mL 0.3mol/L tartaric acid of solvent, carries out hydro-thermal reaction 24h after magnetic agitation 2min at 180 DEG C; By pelleting centrifugation, wash 3 times, ethanol washes 2 times, dries; 30min is calcined in air at 500 DEG C; Sample is when current density is 0.5A/s, and ratio capacitance is 294mF/cm
2.
Embodiment 5
Take 3mmol iron chloride and be dissolved in 10mL deionized water, adding with ethanol is the 15mL 0.2mol/L malic acid of solvent, carries out hydro-thermal reaction 24h after magnetic agitation 1h at 180 DEG C; By pelleting centrifugation, wash 3 times, ethanol washes 2 times, dries; 10min is calcined in air at 600 DEG C; Sample is when current density is 0.5A/s, and ratio capacitance is 151mF/cm
2.
Embodiment 6
Take 0.6mmol Schweinfurt green and be dissolved in 10mL deionized water, adding with ethanol is the 15mL 0.4mol/L tartaric acid of solvent, carries out hydro-thermal reaction 16h after magnetic agitation 1h at 180 DEG C; By pelleting centrifugation, wash 3 times, ethanol washes 2 times, dries; 2h is calcined in air at 300 DEG C; Sample is when current density is 0.5A/s, and ratio capacitance is 317mF/cm
2.
Embodiment 7
Take 0.48mmol zinc nitrate and 0.72mmol Schweinfurt green is dissolved in 10mL deionized water, adding with ethanol is the 15mL 0.8mol/L tartaric acid of solvent, carries out hydro-thermal reaction 16h after magnetic agitation 30min at 180 DEG C; By pelleting centrifugation, wash 3 times, ethanol washes 2 times, dries; 30min is calcined in air at 500 DEG C; Sample is when current density is 0.5A/s, and ratio capacitance is 382mF/cm
2.
Cu
2+, Mn
2+, Fe
2+, Fe
3+, Zn
2+, Co
2+, Ni
2+in one or both ions all undertaken reacting by above-mentioned condition and done ratio capacitance test; the above embodiment is preferred embodiment of the present invention; but the present invention is not limited to above-mentioned execution mode; when not deviating from flesh and blood of the present invention, any apparent improvement that those skilled in the art can make, replacement or modification all belong to protection scope of the present invention.
Claims (10)
1. a preparation method for porous nano combination electrode material, is characterized in that, comprises the steps:
By soluble in water for the metal ion of any mol ratio, add organic acid ethanolic solution and stir, then carry out hydro-thermal reaction, centrifugal, washing, dry, calcine in atmosphere.
2. the preparation method of electrode material as claimed in claim 1, it is characterized in that, described metal ion is Cu
2+, Mn
2+, Fe
2+, Fe
3+, Zn
2+, Co
2+, Ni
2+in one or both.
3. the preparation method of electrode material as claimed in claim 2, it is characterized in that, described metal ion is provided by its soluble-salt, and described soluble-salt is the hydrochloride of metal ion, sulfate, nitrate or acetate.
4. the preparation method of electrode material as claimed in claim 1, it is characterized in that, the total concentration of described metal ion in water is 0.05 ~ 0.3mol/L, and described organic acid in ethanol concentration is 0.2 ~ 0.8mol/L, and described organic acid and the total amount of substance ratio of metal ion are 1:1 ~ 10:1.
5. the preparation method of electrode material as claimed in claim 4, it is characterized in that, described organic acid is tartaric acid, citric acid or malic acid.
6. the preparation method of electrode material as claimed in claim 4, it is characterized in that, described organic acid and the total amount of substance ratio of metal ion are 6.25:1.
7. the preparation method of electrode material as claimed in claim 1, it is characterized in that, described mixing time is 2min ~ 5h, described hydrothermal temperature is 180 DEG C, the hydro-thermal reaction time is 16 ~ 24h, and described calcining heat is 300 ~ 600 DEG C, and calcination time is 10min ~ 2h.
8. the porous nano combination electrode material that the preparation method as the electrode material in claim 1-7 as described in any one prepares.
9. porous nano combination electrode material as claimed in claim 8, it is characterized in that, described material porous stratiform, mean pore size is 5nm.
10. porous nano combination electrode material as claimed in claim 8 is as the application of electrode material for super capacitor.
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|---|---|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111547705A (en) * | 2020-05-12 | 2020-08-18 | 中国计量大学 | Preparation method of porous carbon electrode material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101863518A (en) * | 2010-07-01 | 2010-10-20 | 上海应用技术学院 | Co3O4 nano hollow sphere material and preparation method and application thereof |
-
2014
- 2014-10-09 CN CN201410528778.XA patent/CN104299795A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101863518A (en) * | 2010-07-01 | 2010-10-20 | 上海应用技术学院 | Co3O4 nano hollow sphere material and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| CHRISTIAN BLUTHARDT等: "Aqueous synthesis of high surface area metal oxides", 《CATALYSIS TODAY》 * |
| 贾志刚: "纳米晶构筑介孔过渡金属氧化物的合成与表征", 《中国优秀博士学位论文全文数据库工程科技I辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111547705A (en) * | 2020-05-12 | 2020-08-18 | 中国计量大学 | Preparation method of porous carbon electrode material |
| CN111547705B (en) * | 2020-05-12 | 2022-03-29 | 中国计量大学 | Preparation method of porous carbon electrode material |
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Application publication date: 20150121 |
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