CN109592680B - Super-capacitor activated carbon and three-step physical activation preparation method - Google Patents
Super-capacitor activated carbon and three-step physical activation preparation method Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 230000004913 activation Effects 0.000 title claims abstract description 42
- 239000003990 capacitor Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000011148 porous material Substances 0.000 claims abstract description 68
- 238000000034 method Methods 0.000 claims abstract description 62
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 29
- 239000007772 electrode material Substances 0.000 claims abstract description 25
- 238000009826 distribution Methods 0.000 claims abstract description 23
- 239000005539 carbonized material Substances 0.000 claims abstract description 17
- 235000013162 Cocos nucifera Nutrition 0.000 claims abstract description 6
- 244000060011 Cocos nucifera Species 0.000 claims abstract description 6
- 230000004048 modification Effects 0.000 claims abstract description 3
- 238000012986 modification Methods 0.000 claims abstract description 3
- 238000001994 activation Methods 0.000 claims description 47
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000007789 gas Substances 0.000 claims description 20
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 19
- 230000008569 process Effects 0.000 claims description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 10
- 239000001569 carbon dioxide Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- 238000010924 continuous production Methods 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 8
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000003213 activating effect Effects 0.000 description 7
- 229960004424 carbon dioxide Drugs 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 238000010248 power generation Methods 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
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- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/342—Preparation characterised by non-gaseous activating agents
- C01B32/348—Metallic compounds
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- C01B32/00—Carbon; Compounds thereof
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- C01B32/336—Preparation characterised by gaseous activating agents
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
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- C01P2006/17—Pore diameter distribution
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Abstract
The invention discloses super-capacitor activated carbon and a three-step physical activation preparation method. The method uses a coconut shell carbonized material as a raw material, and prepares the activated carbon by a three-step method of pre-activation, activation pore-forming and aperture adjustment modification. The active carbon powder prepared by the invention has the height of 0.8-1.0 cm3The pore volume per gram is 40-60%, the peak value of the main pore diameter distribution is in the range of 1-2 nm, the ratio of micropores with pore diameter distribution in the range of 0-2 nm is 55-65%, the micropores are uniformly distributed and compact, and the specific surface area reaches 1600-1900 m2(ii) in terms of/g. The method is novel and simple, can be used for preparing the active carbon for the electrode material of the super capacitor by a physical activation method, has low cost and high yield, enables the green and environment-friendly preparation method of the high-performance active carbon to be possible, and can be used for industrial continuous large-scale production. Compared with the active carbon similar products for the electrode materials of the high-performance super capacitor sold in the market at present, the key indexes of the product performance of the technology are comprehensively superior to those of the high-performance products sold in the market at present, and the technology is at the domestic and international advanced level.
Description
Technical Field
The invention belongs to the field of preparation of activated carbon materials, particularly relates to preparation of activated carbon serving as an electrode material of a super capacitor, and more particularly relates to a three-step physical activation preparation method for a microporous structure of the activated carbon serving as the electrode material of the super capacitor.
Background
Supercapacitors (SCs), a new type of energy storage device between conventional capacitors and batteries, are used. The super capacitor has the characteristics of excellent charging and discharging life, high power density, environmental friendliness and the like, and is widely applied and researched. Common application fields of the super capacitor include: consumer electronics, backup power sources, renewable energy power generation systems, rail transit, military equipment, aerospace and other fields. Among them, the electric double layer super capacitor is most widely used: the applications of electric double layer supercapacitors in general in the field of renewable energy mainly include: wind power generation variable pitch control is adopted, the stability and continuity of wind power generation are improved, and a photovoltaic power generation energy storage device is combined with a solar battery to be applied to a street lamp, a traffic indicator light and the like; the method can be applied to the aspects of forklifts, cranes, elevators, port hoisting machinery, various backup power supplies, power grid power storage and the like in the field of heavy industry; in the field of rail transit, the application of the double electric layer super capacitor mainly comprises a tramcar, a subway braking device, a heavy transport vehicle and the like.
In fact, the electrode material is the core of the supercapacitor, and the breakthrough of the supercapacitor is largely due to the electrode material. The Activated Carbon (AC) is widely applied to preparing electrode materials due to the advantages of low price, easy obtaining, wide working temperature range, large specific surface area, developed pore structure, narrow pore size distribution, high chemical stability of acid and alkali, environmental friendliness and the like. It can be seen that the breakthrough of the activated carbon technology is the key to the breakthrough of the related supercapacitor.
Activated carbon used as an electrode material for a supercapacitor is required to be very high, and one of the most important indexes is to have developed micropores, a large specific surface area, and a suitable pore structure, so that an electrolyte can be used and an electric double layer can be formed on the surface of a large number of micropores, thereby obtaining a supercapacitor having excellent charge and discharge characteristics. Therefore, the key to the successful obtainment of the activated carbon used as a high-performance supercapacitor electrode material and having a huge specific surface area is to ensure that a large number of micropores are uniformly and densely distributed during the preparation of the activated carbon, and control the communicated pore structure and the proper pore size ratio.
However, the existing activated carbon pore-forming technology does not rely on the activated pore-forming mechanismThe same main methods are as follows: one is a physical activation method and the other is a chemical activation method. In general, activated carbon with high performance can be obtained by a chemical method, but the activating agent used by the chemical method is usually KOH or H3PO4、ZnCl2And K2CO3The final product needs to be cleaned, which needs to be washed repeatedly, and the process is complex, so that a large amount of manpower and financial resources are consumed to remove the used activating agent when the method is used for preparation, and the quality and the stability are not always ensured; more importantly, the pollution of the activating agent is relatively large, and the activating agent is not favorable for the environment; meanwhile, the activation temperature required by the chemical activation method is usually higher, namely 700 ℃ and 1000 ℃, and the energy consumption is larger, so that the energy is not beneficial to saving energy. While H is usually used in the physical activation method2O steam and CO2Gases are used as an activating agent, and compared with an activating agent prepared by a chemical activation method, the activating agent is more green and environment-friendly, and the prepared activated carbon is more developed in micropores, free from cleaning and simple in process; although the physical activation method is generally carried out at a relatively high temperature (800-.
However, this method for preparing activated carbon is based on pore formation by reaction between water vapor and carbon as follows:
C+H2O→H2+CO△H＝123.l kJ/mol (1)
C+2H2O→2H2+CO2△H＝79.5kJ/mol (2)
the main principle of the water vapor method is that gas diffuses into the material and reacts with carbon atoms to generate hydrogen, carbon monoxide and carbon dioxide, and micropores are formed at the same time. Compared with a chemical pore-forming method, the reaction process has low efficiency, so that the prepared activated carbon has the problems of low pore volume rate and small specific surface area, thereby causing the problems of low specific capacitance, poor performance and the like when the activated carbon is used as an electrode material, further influencing the power characteristic and the energy storage characteristic of the super capacitor, and limiting the influenceFurther application of the material in the field of the super-electricity is made. Therefore, much research has been conducted on how to prepare activated carbon having a high pore volume and a high specific surface area, such as by using a strong oxidizing agent, e.g., concentrated H2SO4Concentrated HNO3、H2O2And oxidizing the functional groups on the surface of the activated carbon at a proper temperature to increase the content of oxygen-containing acid groups on the surface and increase the number of active sites in the carbonized material, so as to improve the specific pore volume and the specific surface area of the activated carbon in the pore-forming process. However, although such strong oxidizing agents have a certain effect on increasing the pore volume and the specific surface area, they are relatively expensive and are not suitable for use in industrial continuous production processes, which mainly will have a great influence on the existing activation furnace equipment and the associated furnace refractories. In a word, how to design a pore-forming process which is low in cost and can be conveniently used in an industrial continuous production process on the basis of the physical activation pore-forming is a key for making a breakthrough on the preparation of the activated carbon for the electrode material of the supercapacitor by the method.
In fact, in consideration of the fact that the basic characteristic of the weak reaction capability of the water vapor activated pore-forming process cannot be changed, if some metal ion oxides which do not cause pollution to the formation of the active carbon, have similar catalysis effects and are low in price are introduced in the early stage of the reaction pore-forming, and are pre-activated before the activation process to help greatly improve the pore-forming efficiency in the normal activation process, the problems existing in the water vapor activated pore-forming method are expected to be solved so as to improve the pore volume and the specific surface area for preparing the active carbon. In fact, consider CO2The reaction with carbon itself can also take place as follows:
C+CO2→2CO△H＝171.2kJ/mol (3)
and CO2The nature of the reaction with carbon, carbon and CO is slightly different from that of the reaction of water vapour with carbon2The reaction process is more difficult than the reaction with water vapor, i.e., the reaction with water vapor is relatively vigorous, and with CO2The reaction is weaker, so that CO2Reaction with carbon is possibleAnd particularly, under the condition that a large number of pore structures are formed in the normal pore-forming process, the formed pore structures and the pore size ratio are expected to be adjusted through the reaction of carbon and carbon dioxide, so that the high-performance activated carbon which has large pore volume, large specific surface area and proper pore structure and pore size ratio is finally obtained.
According to the thought, the scheme provides a three-step green and environment-friendly preparation process taking water vapor as a main activation method, and water vapor and CO are utilized2In the process of carrying out normal activation on the mixed gas, a catalytic pre-activation process is introduced at the early stage, metal ion oxide is added, and a large number of active points are formed by reaction with a carbonized material before the normal activation process through the catalytic action; then, on the basis of a large number of active points, a normal pore-forming process is carried out, so that the activation pore-forming reaction process is greatly enhanced, the pore-forming efficiency is improved, and the pore volume is increased; further, a post-reaction process is introduced at a later stage, i.e. using CO2A relatively weak reaction with C to utilize CO2The purposes of modifying the pore structure and adjusting the pore diameter ratio in the atmosphere are achieved. Finally, the preparation process of the three-step physical activation method is utilized to successfully solve the problem of preparing the activated carbon which has large micropore capacity and high specific surface area and has the basic pore structure and the pore diameter ratio suitable for the electrode material of the super capacitor by utilizing the green and environment-friendly water vapor physical activation method. The three-step method can be realized in one activation furnace by controlling the conditions of atmosphere, temperature and the like of different stages, so the three-step method can also be used for continuous large-scale production process.
Disclosure of Invention
The invention aims to provide a three-step method physical activation preparation method suitable for using active carbon for a high-performance supercapacitor electrode material, and the active carbon meeting the use requirement of the high-performance supercapacitor electrode material is prepared by aiming at the problems that the existing physical activation pore-forming method for industrially preparing the active carbon is low in pore-forming efficiency, and micropores with proper pore structures, proper and uniform pore diameter proportion and densely distributed are difficult to obtain, so that the active carbon cannot be used as the high-performance supercapacitor electrode material.
The technical scheme adopted by the invention is as follows:
a three-step physical activation method for preparing super-capacitor activated carbon, wherein the prepared activated carbon has a height of 0.8-1.0 cm3The pore volume per gram is 40-60%, the peak value of the main pore diameter distribution is 1-2 nm, the proportion is 65-70%, and the specific surface area is 1600-1900 m2(ii)/g, the average pore diameter is about 3.0 nm. The preparation method of the activated carbon and the microporous structure by the three-step physical activation method comprises the following preparation steps:
the method comprises the following steps: adding a metal oxide catalyst into the carbonized material, and performing a pre-activation process in a high-temperature furnace at 600-800 ℃ for 1-4 h to obtain a pre-activated sample;
step two: and (3) continuously carrying out pore-forming reaction on the pre-activated sample at the high temperature of 850-950 ℃ for 3-5 hours in the mixed atmosphere of water vapor and carbon dioxide and in the presence of a proper amount of oxygen to obtain a primary pore-forming sample.
Step three: then controlling the primary pore-forming sample in CO2And (3) carrying out reaction for 3-5 h at a low temperature of 600-800 ℃ in the atmosphere (relative to the high temperature in the second step), and adjusting and modifying the pore diameter to obtain the activated carbon for the electrode material of the supercapacitor, which has a large number of micropores and reasonable pore diameter distribution.
The specific raw materials used in this production method and the specific conditions to be controlled are preferably:
(1) step one, the carbonized material is coconut shell carbonized material
(2) The oxide catalyst used in the preactivation process in the first step can be oxides of one or more metal ions such as Zn, Nb, Ca, Si, Ta, V, Fe, Cu and the like. The weight ratio of the carbon material to the carbonized material is controlled to be 1-3 wt%.
(3) In the second pore-forming step, CO2The mol ratio of the oxygen to the water vapor is 2: 8-4: 6, the volume ratio of the oxygen to the total gas is 10-40%, and the total amount of the introduced gas is 0.02-0.035 m3Min-kg (the unit is the amount of gas introduced per 1kg of the carbonized material).
(4) Aperture in the third stepCO introduced during the adjustment and modification process2The total gas amount is 0.02-0.03 m3Kg/min (the unit is CO per 1kg of the carbonized material)2The amount of gas).
Compared with the background art, the invention has the beneficial effects that:
the method is novel and simple, can be used for preparing the active carbon for the electrode material of the super capacitor by a physical activation method, has low cost and high yield, enables the green and environment-friendly preparation method of the high-performance active carbon to be possible, and can be used for industrial continuous large-scale production. The prepared activated carbon powder not only has huge specific surface area, but also can control activated carbon micropores to have certain pore size distribution, and meets the basic requirements of the supercapacitor electrode material on microstructure and pore size distribution in use. The specific surface area of the activated carbon sample prepared by the three-step method can reach 1900m2Per gram, pore volume up to 0.8-1.0 cm3The pore volume ratio reaches 40-60%, the main pore diameter distribution peak value is micropores with the range of 1-2 nm, the range of the micropores with the pore diameter of 0-2 nm reaches 55-65%, and the micropores are uniformly distributed and compact. Compared with the active carbon similar products for the electrode materials of the high-performance super capacitor sold in the market at present, the key indexes of the product performance of the technology are comprehensively superior to those of the high-performance products sold in the market at present, and the technology is at the domestic and international advanced level.
Drawings
FIG. 1 is a BET test chart of the pore size distribution of activated carbon prepared by the physical activation three-step pore-forming method in example 1.
FIG. 2 is a BET test chart of the pore size distribution of activated carbon prepared by the physical activation three-step pore-forming method of example 2.
FIG. 3 is a BET test chart of the pore size distribution of activated carbon prepared by the physical activation three-step pore-forming method of example 3.
Detailed Description
The technical solutions of the present invention are described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without any inventive step, are within the scope of protection of the present invention.
Example 1:
the preparation method comprises the following steps:
the method comprises the following steps: adding an oxide catalyst ZnO into the coconut shell carbonized material, controlling the weight ratio of the oxide catalyst ZnO to the carbonized material at 1 wt%, and performing a pre-activation process in a pre-activation furnace at 700 ℃ for 4h to obtain a pre-activated sample.
Step two: and (3) continuously carrying out activation reaction on the pre-activated sample at the high temperature of 900 ℃ in the mixed atmosphere of water vapor and carbon dioxide, and preserving the heat for 2.5 hours to obtain the activated sample. Wherein, CO2The mol ratio of the oxygen to the water vapor is 2:8, the volume ratio of the oxygen to the whole gas is 30 percent, and the total amount of the introduced gas is 0.02m3And/min-kg, obtaining a primary pore-forming sample.
Step three: controlling the initial pore-forming sample in CO2Reacting at 600 deg.C for 5 hr under atmosphere, adjusting and modifying aperture, introducing CO2The total gas amount is 0.03m3And/min kg, finally obtaining the activated carbon for the electrode material of the super capacitor, which has a large number of micropores and reasonable pore size distribution. The obtained carbon has pore size distribution as shown in FIG. 1 and Table 1, and specific surface area of 1690m2Per g, pore volume 0.947cm3The volume ratio of the active carbon is 53.7 percent, and the micropore volume is 0.554cm3In terms of pore volume, 58.5%.
Example 2:
the preparation method comprises the following steps:
the method comprises the following steps: adding an oxide catalyst CaO into the coconut shell carbonized material, controlling the weight ratio of the oxide catalyst CaO to the carbonized material at 2 wt%, and performing a pre-activation process in a pre-activation furnace at 750 ℃ for 3h to obtain a pre-activated sample.
Step two: and (3) continuously carrying out activation reaction on the pre-activated sample at the high temperature of 900 ℃ in the mixed atmosphere of water vapor and carbon dioxide, and preserving the heat for 3 hours to obtain the activated sample. Wherein, CO2The mol ratio of the oxygen to the water vapor is 3:6, the volume ratio of the oxygen to the whole gas is 25 percent, and the total amount of the introduced gas is 0.025m3And/min-kg, obtaining a primary pore-forming sample.
Step three: controlling the initial pore-forming sample in CO2Reacting at 700 deg.C for 4 hr under atmosphere, adjusting and modifying pore diameter, introducing CO2The total gas amount is 0.025m3And/min kg, finally obtaining the activated carbon for the electrode material of the super capacitor, which has a large number of micropores and reasonable pore size distribution. The pore size distribution of the obtained carbon is shown in FIG. 2 and Table 1, and the specific surface area is 1910m2Per g, pore volume 1.058cm3The volume ratio of the active carbon is 56.8 percent, and the micropore volume is 0.617cm3In terms of pore volume, 58.3%.
Example 3:
the preparation method comprises the following steps:
the method comprises the following steps: adding an oxide catalyst CaO into the coconut shell carbonized material, controlling the weight ratio of the oxide catalyst CaO to the carbonized material at 3wt%, and performing a pre-activation process in a pre-activation furnace at 800 ℃ for 2h to obtain a pre-activation sample.
Step two: and (3) continuously carrying out an activation reaction on the pre-activated sample at the high temperature of 950 ℃ in the mixed atmosphere of water vapor and carbon dioxide, and preserving the heat for 2.5 hours to obtain the activated sample. Wherein, CO2The mol ratio of the oxygen to the water vapor is 4:6, the volume ratio of the oxygen to the whole gas is 35 percent, and the total amount of the introduced gas is 0.02m3And/min-kg, obtaining a primary pore-forming sample.
Step three: controlling the initial pore-forming sample in CO2Reacting at 800 deg.C for 3 hr under atmosphere, adjusting and modifying pore diameter, introducing CO2The total gas amount is 0.02m3And/min kg, finally obtaining the activated carbon for the electrode material of the super capacitor, which has a large number of micropores and reasonable pore size distribution. The pore size distribution of the obtained carbon is shown in FIG. 3 and Table 1, and the specific surface area is 1910m2G, pore volume 1.045cm3The volume ratio of the active carbon is 56.4 percent, and the micropore volume is 0.614cm3In terms of pore volume, 58.8%.
TABLE 1 three-step physical pore-forming method for preparing activated carbon with pore size distribution, pore ratio and specific surface area
The preparation of the active carbon is controlled by a three-step method, the active carbon microporous structure is controlled and formed by a pre-activation, pore-forming and pore diameter adjustment three-step method, the obtained active carbon has the pore volume of 0.8-1.0 cm/g, the pore volume ratio reaches 40-60%, the main pore diameter distribution peak value is in the range of 0-2 nm, the ratio reaches 55-65%, and the specific surface area reaches 1600-1910 m2And the material meets the basic requirements of the supercapacitor electrode material on microstructure and pore size distribution in use. Compared with the active carbon similar products for the electrode materials of the high-performance super capacitor sold in the market at present, the key indexes of the product performance of the technology are comprehensively superior to those of the high-performance products sold in the market at present, and the technology is at the domestic and international advanced level.
Claims (4)
1. A three-step physical activation preparation method of super-capacitor activated carbon is characterized by comprising the following preparation steps:
the method comprises the following steps: adding a metal oxide catalyst into the carbonized material, and performing a pre-activation process in a high-temperature furnace at 600-800 ℃ for 1-4 h to obtain a pre-activated sample;
step two: continuously placing the pre-activated sample in a mixed atmosphere of water vapor and carbon dioxide, controlling the presence of a proper amount of oxygen, and carrying out pore-forming reaction at the high temperature of 850-950 ℃ for 3-5 h to obtain a primary pore-forming sample; in the pore-forming process, CO2The volume ratio of the oxygen to the water vapor is 2: 8-4: 6, the volume ratio of the oxygen to all the gases is 10-40%, and the total amount of the introduced gases is 0.02-0.035 m3/min·kg；
Step three: subjecting the primary pore-forming sample to CO2Carrying out reaction for 3-5 h at a low temperature of 600-800 ℃ in the atmosphere, and adjusting and modifying the pore diameter to obtain the active carbon for the electrode material of the supercapacitor, which has a large number of micropores and reasonable pore diameter distribution;
the prepared active carbon has the height of 0.8-1.0 cm3The pore volume per gram is 50-60%, the peak value of the main pore diameter distribution is in the range of 1-2 nm, the proportion of micropores with pore diameter distribution in the range of 0-2 nm is 55-65%, and the specific surface area is 1600-1900 m2/g；
The metal oxide catalyst used in the pre-activation process in the step one is oxide of one or more metal ions of Zn, Nb, Ca, Ta, V, Fe and Cu, and the weight ratio of the oxide to the carbonized material is controlled to be 1-3 wt%.
2. The three-step physical activation preparation method of super-capacitor activated carbon as claimed in claim 1, wherein the method is a continuous process, used in industrial continuous production, and is realized by controlling temperature, time and atmosphere in a high temperature furnace in a subsection manner; or the method is divided into three separate processes according to steps, and each process can be independently carried out; all three of these three steps can be repeated as desired.
3. The three-step physical activation preparation method of super-capacitor activated carbon as claimed in claim 1, wherein the charred material in step one is coconut shell charred material.
4. The three-step physical activation preparation method of super-capacitor activated carbon according to claim 1, wherein CO introduced in the process of pore size adjustment and modification in the three steps2The total gas amount is 0.02-0.03 m3/min·kg。
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| CN113060729A (en) * | 2021-03-25 | 2021-07-02 | 浙江大学 | Method for preparing super-capacitor electrode material active carbon by adopting carbon ring layer-to-layer spacing expansion treatment |
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