CN101521119A - Preparation method of expanded graphite/metal oxide composite material - Google Patents
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- CN101521119A CN101521119A CN200910133119A CN200910133119A CN101521119A CN 101521119 A CN101521119 A CN 101521119A CN 200910133119 A CN200910133119 A CN 200910133119A CN 200910133119 A CN200910133119 A CN 200910133119A CN 101521119 A CN101521119 A CN 101521119A
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Abstract
The invention provides a preparation method of an expanded graphite/metal oxide composite material for a supercapacitor electrode. The expanded graphite is prepared from 5-99 wt% of expanded graphite and 1-95 wt% of transition metal oxide, and then the process comprises the following steps: (a) Uniformly dispersing transition metal oxide nanoparticles into an aqueous solution through a surfactant to prepare a stable dispersion of inorganic nanoparticles, wherein the weight ratio of the nanoparticles is 1-70%; (b) Dipping the expanded graphite into the stable dispersion liquid of the inorganic nano particles in the step (a), standing for 10-24 hours at room temperature, and then drying for 4-20 hours at 100-200 ℃ to obtain the expanded graphite/metal oxide composite material. The method has the advantages of simple preparation process, low cost and strong industrial application value.
Description
(I) technical field
The invention relates to the field of manufacturing of capacitor electrode materials, in particular to a preparation method of an expanded graphite/metal oxide composite material used as a super capacitor electrode material.
(II) background of the invention
The super capacitor is a novel energy storage element, and has the advantages of rapid energy storage and release, so the super capacitor can be used as a standby power supply of electronic systems such as computers and the like, a flash and ignition device in industrial equipment, and has wide application prospects in the aspects of high-power microwave and laser weapons, hybrid power supplies of electric automobiles and the like. The structural properties of the electrode material are decisive for the performance of the supercapacitor. At present, research on electrode materials of supercapacitors mainly focuses on activated carbon, carbon nanotubes, transition metal oxides, and the like. The carbon electrode material has low price and simple preparation process, but the specific capacitance is lower (50-100F/g). Metal oxide electrode materials can be divided into precious metal oxides and base metal oxides. Noble metal oxides are represented by hydrated oxidates (RuO) 2· xH 2 O), the storage of energy is realized through redox reversible reaction on the surface, the specific capacitance (720F/g) of the energy storage is far larger than that of a carbon electrode, but the application prospect of the energy storage is limited by the expensive price of noble metals. The base metal oxide is represented by manganese oxide and nickel oxide, and has a specific capacity (70-300F/g) lower than that of hydrated ruthenium oxide, but the base metal oxide is rich in resources, low in price and environment-friendly, so that the base metal oxide is prepared by the methodThere is a great potential for electrode materials.
At present, the metal oxide electrode material is mainly prepared by an electrochemical method, a thermal decomposition method or a sol-gel method, but when the metal oxide electrode material prepared by the method is used for a super capacitor, the problem of overlarge material resistance is often existed. Therefore, carbon is required to be added into the electrode material in a certain way to improve the conductivity of the material and improve the performance of the capacitor. The expanded graphite is a loose and porous material prepared from natural graphite, has good conductivity, and can be added into the anode of a rechargeable zinc-manganese battery to improve the conductivity of the electrode and prolong the service life of the battery. Therefore, by utilizing the good conductive network of the expanded graphite, the high specific capacitance and good cycle performance of the metal oxide, the expanded graphite and the metal oxide form the composite electrode, and a novel super capacitor electrode material with excellent performance is expected to be obtained.
Disclosure of the invention
The invention aims to provide a preparation method of an expanded graphite/metal oxide composite material for preparing a super capacitor and enabling the super capacitor to have high energy density and power density.
The product of the invention comprises the following components in percentage by weight: 5 to 99t percent of expanded graphite and 1 to 95 percent of metal oxide, preferably 10 to 50 percent of expanded graphite and 50 to 90 percent of metal oxide; the metal oxide is one or at least two of oxides of transition metals of Ti, zr, V, nb, ta, cr, mo, W, mn, fe, co, ir, ni, pa or Ru.
The product of the invention is made by the following method:
(1) High energy ball milling process
Adding the expanded graphite and the nano powder of the transition metal oxide into a planetary high-energy ball mill according to the proportion of 5-99 t percent of the expanded graphite and 1-95 percent of the metal oxide by weight percent for ball milling and mixing, wherein the rotating speed is 100-250 r/min, and preferably 150-250 r/min; ball powder ratio 10:1 to 30:1, preferably 10:1 to 15:1; the ball milling time is 5 to 40 hours, preferably: and (3) obtaining the expanded graphite/metal oxide composite material after 10-20 hours.
(2) Sol impregnation method
Preparing raw materials according to the proportion of 5-99 t% of expanded graphite and 1-95% of transition metal oxide in percentage by weight;
(a) Uniformly dispersing the transition metal oxide nanoparticles into an aqueous solution through a surfactant to prepare a stable dispersion liquid of inorganic nanoparticles, wherein the weight ratio of the nanoparticles is 1-70%, and preferably 10-30%;
(b) The expanded graphite is dipped into the stable dispersion liquid of the inorganic nano particles, placed for 10 to 24 hours at room temperature, and then dried for 4 to 20 hours, preferably 4 to 8 hours at 100 to 200 ℃, thus obtaining the expanded graphite/metal oxide composite material.
(3) Chemical deposition method
Adding the expanded graphite into a metal nitrate or other soluble salt solution with the concentration of 0.1-3 mol/L, wherein the weight ratio of the expanded graphite to the solution is 1: 5-20, fully stirring, performing ultrasonic dispersion for 1-20 hours, preferably 5-10 hours, then dropwise adding sodium hydroxide, potassium hydroxide or sodium carbonate solution while stirring until the pH value of the solution is more than 10, stirring for 1-4 hours, filtering and washing until the pH value is neutral, drying for 2-10 hours at 100-200 ℃, and finally calcining for 1-4 hours at 300-800 ℃ under inert atmosphere, preferably for 1-4 hours at 300-500 ℃, thus obtaining the expanded graphite/metal oxide composite material.
The invention also has the technical characteristics that:
1. the expanded graphite according to the above methods (1), (2) and (3) has an expanded volume of 10 to 600mL/g, preferably 200 to 600mL/g, and a purity of >99%;
2. the particle size of the nano transition metal oxide in the methods (1) and (2) is 5 to 1000nm, preferably 5 to 100nm;
3. the transition metal oxide in the above methods (1) and (2) is one or at least two oxides of transition metals Ti, zr, V, nb, ta, cr, mo, W, mn, fe, co, ir, ni, pa or Ru;
4. the nitrate or other soluble salt of a transition metal in the above method (3) is one or at least two of nitrates or other soluble salts of transition metals Ti, zr, V, nb, ta, cr, mo, W, mn, fe, co, ir, ni, pa or Ru.
The expanded graphite/metal oxide material is prepared into a polarized electrode according to the following steps, and electrochemical performance is tested:
fully and uniformly mixing expanded graphite/metal oxide (80 wt%) and conductive carbon black (10 wt%) in a mechanical oscillation mode, sequentially adding distilled water (5 wt%) and Polytetrafluoroethylene (PTFE) (5 wt%) emulsion, adding while mechanically stirring to ensure that the emulsion is uniform, wherein a current collector adopts foamed metal nickel, an electrode lug adopts metal nickel platinum, and the lug and the current collector are connected in a spot welding mode; mechanically coating the paste on a current collector which is cut and welded with a tab in advance, vacuum-drying the pasted pole piece at 110 ℃ for 10 hours, compacting the dried pole piece on an oil press, trimming burrs on the edge to obtain the final productElectrode (1 cm) 2 ). A polypropylene separator was inserted between two identical electrodes and pressed with a clamp. After 30% KOH electrolyte was injected into the electrode, cyclic voltammetry measurements were performed at a scan rate of 1mV/s using a platinum counter electrode and an SCE reference electrode under a voltage range of 0.0 to 0.8V and a constant current of 1 mA. The unit capacitance can be calculated by dividing the current in cyclic voltammetry by the scan rate and the mass of the electrode active material. After the completion of the charging, the circuit is opened for 1 second, and the internal resistance R is obtained from Δ V = RI from the current and voltage drop Δ V just before the circuit is opened.
According to the invention, the electrode material of the super capacitor is prepared by compounding the expanded graphite and the oxide particles, and the prepared super capacitor has high specific capacity and lower internal resistance. Meanwhile, the method uses cheap and easily-obtained expanded graphite as a raw material, has simple preparation process and low cost, and has strong industrial application value.
(IV) detailed description of the preferred embodiments
The invention will be further illustrated with reference to the following specific examples: the nanometal oxides in the following embodiments can be purchased commercially or as described in [ journal Park, et al ultra-large-scale synthesis of monodisperse nanocrystals, nature Materials,2004,3:891; guoliqin, etc., preparation of nano nickel oxide and its application, chemical Engineers, 2006, 130 (7): 28], etc., and the like.
Example 1:
0.5g of expanded graphite (expanded volume 200 mL/g) and 9.5g of nano nickel oxide (average particle size 5 nm) were mixed in a planetary high-energy ball mill using steel balls and ball pots at a revolution of 100rpm, a ball powder ratio of 10: 1. ball milling was carried out for 40 hours. The electrode was taken out and dried at 100 ℃ to prepare a polarized electrode for electrochemical performance test, and the obtained results are shown in Table 1.
Example 2:
5g of expanded graphite (expansion volume 600 mL/g) and 5g of nano manganese oxide (average particle size 1000 nm) are mixed in a planetary high-energy ball mill by using steel grinding balls and ball tanks, wherein the rotation speed is 250rpm, the ball powder ratio is 30: 1. ball milling was carried out for 5 hours. The electrode was taken out and dried at 100 ℃ to prepare a polarized electrode for electrochemical performance test, and the obtained results are shown in Table 1.
Example 3:
3g of expanded graphite (expansion volume 400 mL/g) and 7g of nano manganese oxide (average particle size 50 nm) were mixed in a planetary high-energy ball mill using steel balls and ball pots at a revolution of 250rpm, a ball powder ratio of 10: 1. ball milling was carried out for 10 hours. Taking out the electrode, drying the electrode at 100 ℃ to prepare a polarized electrode, and carrying out electrochemical performance test on the polarized electrode, wherein the obtained results are listed in Table 1.
Example 4:
using an ultrasonic disperser and cetyl trimethyl ammonium bromide as a surfactant, 1g of nano molybdenum oxide (average particle size of 100 nm) is uniformly dispersed into 100g of aqueous solution, then 9g of expanded graphite (expansion volume of 300 mL/g) is immersed into the dispersion, the dispersion is placed at room temperature for 10 hours and dried at 100 ℃ for 20 hours, and the expansion volume is taken out to prepare a polarizing electrode for electrochemical performance test, and the test results are listed in table 1.
Example 5:
using an ultrasonic disperser and cetyl trimethyl ammonium bromide as a surfactant, 7g of nano ruthenium oxide (with an average particle size of 50 nm) is uniformly dispersed into 10g of aqueous solution, then 2g of expanded graphite (with an expanded volume of 400 mL/g) is immersed into the dispersion, the dispersion is left at room temperature for 24 hours and then dried at 200 ℃ for 4 hours, and after being taken out, a polarizing electrode is prepared for electrochemical performance test, and the test results are listed in table 1.
Example 6:
5g of expanded graphite (expanded volume 400 mL/g) is added into 100mL of 0.1mol/L nickel nitrate solution and fully stirred, then ultrasonic dispersion is carried out for 1 hour, then 1mol/L sodium hydroxide solution is dropwise added under stirring until pH =10 is completely dropwise added, stirring is carried out for 4 hours, filtering and washing are carried out until the pH value is neutral, and after drying at 100 ℃ for 2 hours, calcination is carried out at 400 ℃ for 4 hours under an inert atmosphere. The obtained mixture was formed into a polarizable electrode to be subjected to electrochemical performance tests, and the results thereof are shown in table 1.
Example 7:
4g of expanded graphite (expanded volume 400 mL/g) was added to 20mL of 1mol/L nickel nitrate solution, and after sufficient stirring, the mixture was ultrasonically dispersed for 20 hours, then 0.1mol/L sodium carbonate solution was added dropwise with stirring until pH =10 was added dropwise, and after that, the mixture was stirred for 1 hour, filtered and washed until the pH was neutral, dried at 100 ℃ for 10 hours, and then calcined at 800 ℃ for 1 hour under an inert atmosphere. The obtained mixture was formed into a polarizable electrode to be subjected to electrochemical performance tests, and the results thereof are shown in table 1.
Example 8:
5g of expanded graphite (expansion volume 400 mL/g) is added into 50mL of a 3mol/L cobalt nitrate solution, the mixture is fully stirred, the mixture is ultrasonically dispersed for 10 hours, then 3mol/L of a potassium hydroxide solution is dropwise added under stirring until the pH value is =10, the mixture is stirred for 1 hour after the dropwise addition is finished, the mixture is filtered and washed until the pH value is neutral, and the mixture is dried at 100 ℃ for 5 hours and then calcined at 400 ℃ for 1 hour under an inert atmosphere. The obtained mixture was formed into a polarized electrode and subjected to electrochemical performance test, and the results are shown in Table 1.
TABLE 1 results of electrochemical testing of expanded graphite/oxide composites
| Examples | Unit capacitor F/g | Internal resistance Ω |
| Example 1 | 295 | 0.24 |
| Example 2 | 264 | 0.38 |
| Example 3 | 240 | 0.34 |
| Example 4 | 265 | 0.25 |
| Example 5 | 620 | 0.34 |
| Example 6 | 257 | 0.21 |
| Example 7 | 248 | 0.39 |
| Example 8 | 148 | 0.32 |
Claims (6)
1. A preparation method of an expanded graphite/metal oxide composite material is characterized by comprising the following steps: the expanded graphite is prepared from 5-99 wt% of expanded graphite and 1-95 wt% of transition metal oxide, and then the process comprises the following steps:
(a) Uniformly dispersing transition metal oxide nanoparticles into an aqueous solution through a surfactant to prepare a stable dispersion of inorganic nanoparticles, wherein the weight ratio of the nanoparticles is 1-70%;
(b) Dipping the expanded graphite into the stable dispersion liquid of the inorganic nano particles in the step (a), standing for 10-24 hours at room temperature, and then drying for 4-20 hours at 100-200 ℃ to obtain the expanded graphite/metal oxide composite material.
2. The method for producing an expanded graphite/metal oxide composite material according to claim 1, characterized in that: the weight ratio of the nano particles in the step (a) is 10-30%.
3. The method for producing an expanded graphite/metal oxide composite material according to claim 2, characterized in that: the drying time of drying at 100-200 ℃ in the step (b) is 4-8 hours.
4. The method for producing an expanded graphite/metal oxide composite material according to claim 3, characterized in that: the expansion volume of the expanded graphite is 10-600 mL/g, and the purity is more than 99%.
5. The method for preparing an expanded graphite/metal oxide composite material according to claim 4, wherein: the grain diameter of the transition metal oxide is 5-1000 nm.
6. The method for producing an expanded graphite/metal oxide composite material according to claim 5, characterized in that: the transition metal oxide is one or at least two of oxides of Ti, zr, V, nb, ta, cr, mo, W, mn, fe, co, ir, ni, pa or Ru.
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| CN2009101331195A CN101521119B (en) | 2007-04-20 | 2007-04-20 | Preparation method of expanded graphite/metal oxide composite material |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102553571A (en) * | 2010-12-08 | 2012-07-11 | 海洋王照明科技股份有限公司 | Expandable graphite based composite material, its preparation method and application thereof |
| CN110551324A (en) * | 2019-09-26 | 2019-12-10 | 山东一诺威新材料有限公司 | Preparation method and application of nanoscale transition metal oxide loaded expanded graphite particles |
| CN117275794A (en) * | 2023-10-17 | 2023-12-22 | 四川永星电子有限公司 | Conductive carbon black material for carbon-based resistor paste, preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP3450894B2 (en) * | 1994-03-28 | 2003-09-29 | 松下電器産業株式会社 | Alkaline manganese battery |
| US6828064B1 (en) * | 1998-01-07 | 2004-12-07 | Eveready Battery Company, Inc. | Alkaline cell having a cathode incorporating enhanced graphite |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102553571A (en) * | 2010-12-08 | 2012-07-11 | 海洋王照明科技股份有限公司 | Expandable graphite based composite material, its preparation method and application thereof |
| CN102553571B (en) * | 2010-12-08 | 2013-10-09 | 海洋王照明科技股份有限公司 | Preparation method of expandable graphite based composite material |
| CN110551324A (en) * | 2019-09-26 | 2019-12-10 | 山东一诺威新材料有限公司 | Preparation method and application of nanoscale transition metal oxide loaded expanded graphite particles |
| CN117275794A (en) * | 2023-10-17 | 2023-12-22 | 四川永星电子有限公司 | Conductive carbon black material for carbon-based resistor paste, preparation method and application thereof |
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