CN112250067B - Two-step activated high-performance activated carbon, preparation method and lithium ion capacitor electrode - Google Patents
Two-step activated high-performance activated carbon, preparation method and lithium ion capacitor electrode Download PDFInfo
- Publication number
- CN112250067B CN112250067B CN202010915443.9A CN202010915443A CN112250067B CN 112250067 B CN112250067 B CN 112250067B CN 202010915443 A CN202010915443 A CN 202010915443A CN 112250067 B CN112250067 B CN 112250067B
- Authority
- CN
- China
- Prior art keywords
- activated carbon
- phosphoric acid
- drying
- activated
- carbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/342—Preparation characterised by non-gaseous activating agents
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- 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
-
- 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
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
-
- 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
- H01G11/32—Carbon-based
- H01G11/44—Raw materials therefor, e.g. resins or coal
-
- 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
- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
-
- 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 discloses a two-step activated high-performance activated carbon, a preparation method and a lithium ion capacitor electrode, wherein the preparation method comprises the following steps: adding carbonate and a carbon source base material into an aqueous solution according to a preset mass ratio, and uniformly stirring to form a uniform cream-yellow pre-crosslinked mixture; freeze-drying the pre-crosslinked mixture to obtain a mixed solid; carbonizing the mixed solid in an inert atmosphere, soaking the obtained primary carbonized product in hydrochloric acid with preset concentration, washing with deionized water, and drying to obtain nascent activated carbon; mixing the nascent state activated carbon with phosphoric acid, filtering out excessive phosphoric acid and drying to obtain nascent state activated carbon mixed with phosphoric acid; and (3) under an inert atmosphere, carrying out heat preservation treatment on the nascent state activated carbon mixed with the phosphoric acid, washing and drying to obtain the two-step activated high-performance activated carbon. The invention has the advantages of simple preparation process, low cost, environmental protection and excellent electrochemical performance.
Description
Technical Field
The invention relates to the technical field of energy, in particular to two-step activated high-performance activated carbon, a preparation method and a lithium ion capacitor electrode.
Background
The activated carbon is a carbon material which is specially treated, organic raw materials are subjected to high-temperature carbonization treatment in an air-isolated environment, and then are subjected to surface reaction by an activating agent to generate a large number of microporous structures through activation. It has great demands in the fields of sewage treatment, catalysis, catalyst loading, medical use, military industry, energy sources, particularly super capacitors and the like. At present, the global market has huge demand for activated carbon, the global market demand reaches about 280 million tons in 2017, the global market demand is increased year by year at a speed of 8-9%, and the demand for high-performance activated carbon used in the energy field is particularly vigorous. The high-performance activated carbon has very wide application in the field of energy storage, such as super capacitors, lithium ion capacitors, catalyst carriers and the like, so that the high-performance activated carbon has urgent needs and important market prospects in the field of energy sources.
A Lithium Ion Capacitor (LIC, abbreviated as LIC) is used as a combination of a Lithium Ion battery and a super Capacitor, has the characteristics of high energy density, high power density and long service life of the Lithium Ion battery and the super Capacitor, and is a warping factor in next-generation energy storage devices. At present, the anode material of the lithium ion capacitor mainly comprises activated carbon, the stability of the common commercial activated carbon is good, but the capacity is low, and the capacity of most commercial activated carbon is 30-45 mAh g-1. Therefore, even though the high-energy-density lithium ion battery cathode is introduced to improve the overall energy density in the construction of the LIC, the improvement of the overall energy density of the LIC is limited by the current situation of low capacity of the commercial activated carbon. Therefore, the development of the high-performance active carbon cathode material with simple and convenient preparation method has important significance for the development of lithium ion capacitors.
The existing preparation method of high-performance activated carbon mainly adopts a strong alkali system and a strong acid system, has harsh preparation conditions and certain dangerousness, and the post-treatment process of used substances and residues is not environment-friendly and does not accord with the concept of green development. For example: in CN1O2275937A, rice hulls are pretreated by sodium hydroxide and activated by sodium bicarbonate to generate a large amount of alkaline waste, which is not beneficial to subsequent waste treatment. Therefore, how to reduce the preparation cost of the high-performance activated carbon and reduce the pollution strength to the environment in the preparation process is an urgent technical problem to be solved.
Disclosure of Invention
The invention mainly aims to provide a two-step activated high-performance activated carbon, a preparation method and a lithium ion capacitor electrode, and aims to solve the technical problems of high preparation cost, poor electrochemical performance, complex preparation process and great environmental pollution of the high-performance activated carbon in the prior art.
In order to achieve the above object, the present invention provides a method for preparing a two-step activated high performance activated carbon, comprising the steps of:
adding carbonate and a carbon source base material into an aqueous solution according to a preset mass ratio, and uniformly stirring to form a uniform cream-yellow pre-crosslinked mixture;
freeze-drying the pre-crosslinked mixture to obtain a mixed solid;
carbonizing the mixed solid in an inert atmosphere, soaking an obtained primary carbonized product by hydrochloric acid with a preset concentration, and washing and drying by deionized water to obtain nascent activated carbon;
mixing the nascent activated carbon with phosphoric acid with a preset multiple of mass at a preset stirring speed, filtering out excessive phosphoric acid, and drying at a first preset temperature within a first preset time to obtain nascent activated carbon mixed with phosphoric acid;
and (3) under an inert atmosphere, carrying out heat preservation treatment on the nascent state activated carbon mixed with the phosphoric acid, washing and drying at a second preset temperature within a second preset time to obtain the two-step activated high-performance activated carbon.
Preferably, the step of adding the carbonate and the carbon source base material into the aqueous solution according to a preset mass ratio and uniformly stirring to form a uniform milky yellow cross-linked mixture comprises the following steps:
mixing carbonate and a carbon source base material according to the weight ratio of (15-0.5): 1, and ultrasonically mixing for 10-100 minutes by adopting an ultrasonic mixer with the power of 300-600W to form a uniform creamy yellow pre-crosslinking mixture.
Preferably, the step of mixing the nascent activated carbon with a preset multiple mass of phosphoric acid at a preset stirring speed, filtering out excessive phosphoric acid and drying at a first preset temperature within a first preset time to obtain nascent activated carbon mixed with phosphoric acid comprises:
mixing the nascent state activated carbon and phosphoric acid with the mass of 1-10 times at 300-1000 rpm, stirring for 5-30 minutes, filtering out excessive phosphoric acid by vacuum filtration, and drying for 1-10 hours at 80 ℃.
Preferably, the step of performing heat preservation treatment on the nascent activated carbon mixed with phosphoric acid under an inert atmosphere, washing and drying at a second preset temperature within a second preset time to obtain the two-step activated high-performance activated carbon comprises:
under inert atmosphere, raising the temperature of the nascent state activated carbon mixed with phosphoric acid to 900 ℃ at the heating rate of 1-10 ℃/min, carrying out heat preservation treatment at 900 ℃ for 0.5-4h, washing and drying at 80 ℃ for 1-10 h to obtain the two-step activated high-performance activated carbon.
Preferably, the preset concentration is 5-15 wt%; the soaking time of the soaking treatment is 5-20 hours, and the deionized water is used for washing and drying for 1-10 hours at the temperature of 80 ℃; the carbonate is one or more of sodium bicarbonate, sodium carbonate, potassium bicarbonate, potassium carbonate, ammonium bicarbonate, calcium carbonate, magnesium carbonate, zinc carbonate and copper carbonate; the carbon source base material is one or more of organic materials with high carbon content such as sucrose, glucose, chitosan, melamine, sodium alginate, dopamine, starch, flour and the like; the carbonization temperature of the carbonization treatment is 700-850 ℃, the carbonization time is 1-5 hours, and the temperature rise rate is 1-10 ℃/min; the inert atmosphere is argon or nitrogen; the phosphoric acid is 89 mass percent.
Preferably, the preset concentration is 10 wt%; the soaking time of the soaking treatment is 10 hours; the first preset time is 2 hours; the preset stirring speed is 600 revolutions per minute; the carbon source base material is chitosan, wherein the degree of deacetylation is 96.5%; the carbonate is analytically pure sodium bicarbonate; the carbonization time of the carbonization treatment is 2h, and the heating rate is 3 ℃/min; the preset multiple is 5 times.
Preferably, the power of the ultrasonic mixer is 300W, and the mixing time of the ultrasonic mixer is 30 minutes.
Preferably, after the step of subjecting the nascent activated carbon mixed with phosphoric acid to heat preservation treatment under inert atmosphere, washing and drying to obtain two-step activated high-performance activated carbon, the method further comprises the following steps:
and (3) activating the high-performance activated carbon, the conductive carbon black and the polyvinylidene fluoride by two steps according to the following formula (7-9): (1-0.5): (2-0.5) preparing the mixture into slurry;
and coating the slurry on a carbon-coated aluminum foil, and drying at 80 ℃ for 10-20 hours to obtain the electrode.
In addition, in order to achieve the above object, the present invention also provides a two-step activated high performance activated carbon prepared according to the above-described two-step activated high performance activated carbon preparation method.
In addition, in order to achieve the above object, the present invention also provides a lithium ion capacitor electrode, wherein the above two-step activated high performance activated carbon is used as a positive electrode material of the lithium ion capacitor electrode.
The invention at least comprises the following beneficial effects:
adding carbonate and a carbon source base material into an aqueous solution according to a preset mass ratio, and uniformly stirring to form a uniform milky yellow cross-linked mixture, wherein the carbonate serving as an activating agent has two activation modes in the first-step activation: physical activation and chemical activation, wherein the physical activation generated in a low-temperature area can generate a large amount of macroporous structures to form a thinner carbon wall structure, an activating agent is more fully contacted with a carbon material, the thinner carbon wall is beneficial to full activation reaction and subsequent chemical activation, and the used carbonate and carbon source base materials are low in price and easy to obtain and have small environmental pollution; freeze-drying the pre-crosslinked mixture to obtain a mixed solid, carbonizing the mixed solid in an inert atmosphere to obtain a primary carbonized product, soaking the obtained primary carbonized product in hydrochloric acid with a preset concentration, washing and drying the primary carbonized product with deionized water to obtain nascent activated carbon, mixing the nascent activated carbon with phosphoric acid with a preset multiple quality at a preset stirring speed, filtering out excessive phosphoric acid and drying to obtain nascent activated carbon mixed with phosphoric acid, wherein the specific surface area of the activated carbon can be greatly improved by adopting phosphoric acid activation, and the pore structure is optimized; and (2) carrying out heat preservation treatment on the nascent state activated carbon mixed with the phosphoric acid in an inert atmosphere, washing and drying to obtain the two-step activated high-performance activated carbon, wherein the conditions are mild, the environmental pollution is small, the used activating agent and carbon source base materials are cheap and easy to obtain, the cost is low, the operation is simple and convenient, the method is suitable for large-scale industrial production, and the obtained two-step activated high-performance activated carbon has excellent electrochemical performance.
Drawings
FIG. 1 is a schematic flow diagram of a first embodiment of a two-step activated high performance activated carbon production process of the present invention;
FIG. 2 is a schematic flow chart of a third example of the method for producing a two-step activated high-performance activated carbon according to the present invention;
FIG. 3 is a scanning micrograph of a two-step activated high performance activated carbon prepared in example 2;
FIG. 4 shows that the two-step activated high performance activated carbon prepared in example 2 was used as the positive electrode of a lithium ion capacitor at 5A g-1A cyclic plot at current density of;
fig. 5 is a comparison of specific surface areas of two-step activated high performance activated carbons prepared in example 2 and comparative example 3.
Detailed Description
The present invention is further described in detail below with reference to the drawings and examples so that those skilled in the art can practice the invention with reference to the description.
It is to be noted that the experimental methods described in the following embodiments are all conventional methods unless otherwise specified, and the reagents and materials are commercially available unless otherwise specified.
Referring to fig. 1, fig. 1 is a schematic flow chart of a first embodiment of a two-step activated high performance activated carbon preparation method of the present invention, and proposes the first embodiment of the two-step activated high performance activated carbon preparation method of the present invention.
In a first embodiment, the method for preparing the two-step activated high-performance activated carbon comprises the following steps:
step S10, adding carbonate and carbon source base materials into the aqueous solution according to a preset mass ratio, and uniformly stirring to form a uniform milky yellow cross-linked mixture.
It is understood that the preset mass ratio is generally (15-0.5): 1, mixing carbonate and a carbon source base material according to the weight ratio of (15-0.5): 1, ultrasonic mixing for 10-100 minutes by adopting ultrasonic waves with the power of 300-600W, generating a pre-crosslinking effect by utilizing the interaction of oxygen-containing functional groups and nitrogen-containing functional groups of chitosan under the combined action of an alkaline environment and ultrasonic vibration to form an even cream-yellow pre-crosslinking mixture, and wrapping carbonate inside the chitosan pre-crosslinking mixture so as to ensure the even mixing of the carbonate and a carbon source and the even generation of subsequent carbonization and activation in the whole mixture.
There are two activation modes of the carbonate used in the first step of activation. In a low-temperature area, a large amount of gas is generated by decomposing carbonate to form a large amount of air holes, belonging to physical activation; in the high temperature area, the generated carbonate, oxide and peroxide can react with the nascent state active carbon to form a large amount of micro-mesopores, belonging to chemical activation. The physical activation generated in the low-temperature area can generate a large amount of macroporous structures to form a thinner carbon wall structure, the activator is more fully contacted with the carbon material, and the thinner carbon wall is beneficial to full activation reaction and later chemical activation.
Step S20, freeze drying the pre-crosslinked mixture to obtain a mixed solid.
And step S30, carbonizing the mixed solid in an inert atmosphere, soaking the obtained primary carbonized product in hydrochloric acid with preset concentration, and washing and drying the product by using deionized water to obtain the nascent activated carbon.
It should be noted that, usually, the preset concentration is 5 to 15wt%, for example, 10wt%, the cream-yellow pre-crosslinked mixture is freeze-dried, the obtained mixed solid is a white fluffy uniformly mixed solid of chitosan and carbonate, the white fluffy uniformly mixed solid of chitosan and carbonate is carbonized in an inert atmosphere, the mixture is soaked in 5 to 15wt% hydrochloric acid for 5 to 20 hours, and then washed with deionized water, and dried at 80 ℃ for 5 hours, so as to obtain the nascent state activated carbon.
And step S40, mixing the nascent activated carbon with phosphoric acid with the mass of a preset multiple at a preset stirring speed, filtering out excessive phosphoric acid, and drying at a first preset temperature within a first preset time to obtain the nascent activated carbon mixed with the phosphoric acid.
Understandably, the preset multiple mass is 1-10 times of the mass generally; the preset stirring speed is 300-1000 rpm; the first predetermined time is 1-10 hours, such as 2 hours; the first preset temperature is 80 ℃.
And step S50, carrying out heat preservation treatment on the nascent state activated carbon mixed with the phosphoric acid in an inert atmosphere, washing and drying at a second preset temperature within a second preset time to obtain the two-step activated high-performance activated carbon.
It will be appreciated that the second predetermined time is from 1 to 10 hours, such as 5 hours; the second preset temperature is 80 ℃; stirring and mixing the nascent state activated carbon and 1-10 times of phosphoric acid by mass at the rotating speed of 300-1000 rpm, stirring for 5-30 minutes, filtering out excessive phosphoric acid by vacuum filtration, and drying for 1-10 hours at 80 ℃. Under inert atmosphere, the nascent state activated carbon mixed with phosphoric acid is heated to 900 ℃ at the heating rate of 1-10 ℃/min (for example, 5 ℃/min), and is subjected to heat preservation treatment at 900 ℃ for 0.5-4h, washed and dried at 80 ℃ for 1-10 h to obtain the two-step activated high-performance activated carbon.
Further, the preset concentration is 5-15 wt%; the soaking time of the soaking treatment is 5-20 hours, and the deionized water is used for washing and drying for 1-10 hours at the temperature of 80 ℃; the carbonate is one or more of sodium bicarbonate, sodium carbonate, potassium bicarbonate, potassium carbonate, ammonium bicarbonate, calcium carbonate, magnesium carbonate, zinc carbonate and copper carbonate; the carbon source base material is one or more of organic materials with high carbon content such as sucrose, glucose, chitosan, melamine, sodium alginate, dopamine, starch, flour and the like; the carbonization temperature of the carbonization treatment is 700-850 ℃, the carbonization time is 1-5 hours, and the temperature rise rate is 1-10 ℃/min; the inert atmosphere is argon or nitrogen; the phosphoric acid is 89% by mass.
In the specific implementation, the carbonate and the carbon source base material are added into water according to a certain proportion, uniformly mixed by ultrasonic, and carbonized at high temperature (700-850 ℃) to form the nascent state activated carbon after being freeze-dried. The obtained activated carbon is washed and dried, then soaked by excessive phosphoric acid (89%), filtered, dried and then kept at 900 ℃ for 0.5-4 h. The carbonate can be decomposed to form a large amount of gas during the first step of activation, and multi-level physical activation is carried out on the nascent state activated carbon; and then decomposing the generated carbonates such as sodium carbonate and potassium carbonate, oxides such as potassium oxide, sodium oxide, magnesium oxide, copper oxide and calcium oxide, and peroxides such as potassium peroxide and sodium peroxide and the nascent state activated carbon at the temperature of 200-600 ℃ to generate multi-stage chemical reaction to cooperatively form a large number of micropores, and the specific surface area of the activated carbon is increased. And then, phosphoric acid is used for secondary activation at the high temperature of 900 ℃, the specific surface area of the activated carbon is further greatly improved, and a certain amount of phosphorus (P) element is doped, so that the activated carbon has more active sites, the conductivity and the wettability are improved, and the interface resistance is reduced. The activated carbon is applied to a lithium ion capacitor cathode material, and shows higher capacity and excellent cycle performance compared with commercial activated carbon.
In this embodiment, carbonate and carbon source base material are added into the aqueous solution according to a predetermined mass ratio and stirred uniformly to form a uniform creamy yellow pre-crosslinked mixture, and carbonate as an activating agent has two activation modes in the first activation step: physical activation and chemical activation, wherein the physical activation generated in a low-temperature area can generate a large amount of macroporous structures to form a thinner carbon wall structure, an activating agent is more fully contacted with a carbon material, the thinner carbon wall is beneficial to full activation reaction and subsequent chemical activation, and the used carbonate and carbon source base materials are low in price and easy to obtain and have small environmental pollution; freeze-drying the pre-crosslinked mixture to obtain a mixed solid, carbonizing the mixed solid in an inert atmosphere to obtain a primary carbonized product, soaking the obtained primary carbonized product in hydrochloric acid with a preset concentration, washing and drying the primary carbonized product with deionized water to obtain nascent activated carbon, mixing the nascent activated carbon with phosphoric acid with a preset multiple quality at a preset stirring speed, filtering out excessive phosphoric acid and drying to obtain nascent activated carbon mixed with phosphoric acid, wherein the specific surface area of the activated carbon can be greatly improved by adopting phosphoric acid activation, and the pore structure is optimized; and (2) carrying out heat preservation treatment on the nascent activated carbon mixed with the phosphoric acid in an inert atmosphere, washing and drying to obtain the two-step activated high-performance activated carbon, wherein the conditions are mild, the environmental pollution is small, the used activating agent and carbon source base materials are cheap and easy to obtain, the cost is low, and the operation is simple and convenient and is suitable for large-scale industrial production.
With continued reference to fig. 1, a second embodiment of the method for producing a two-step activated high-performance activated carbon according to the present invention is presented based on the above-described first embodiment.
In this embodiment, the step S10 includes:
mixing carbonate and a carbon source base material according to the weight ratio of (15-0.5): 1, and ultrasonically mixing for 10-100 minutes by adopting an ultrasonic mixer with the power of 300-600W to form a uniform creamy yellow pre-crosslinking mixture.
In this embodiment, in the step S10, the soaking time of the soaking treatment is 5 to 20 hours, and the deionized water is washed and dried at 80 ℃ for 1 to 10 hours.
In this embodiment, the step S40 includes:
mixing the nascent state activated carbon and phosphoric acid with the mass of 1-10 times at 300-1000 rpm, stirring for 5-30 minutes, filtering out excessive phosphoric acid by vacuum filtration, and drying for 1-10 hours at 80 ℃.
In this embodiment, the step S50 includes:
under inert atmosphere, raising the temperature of the nascent state activated carbon mixed with phosphoric acid to 900 ℃ at the heating rate of 1-10 ℃/min, carrying out heat preservation treatment at 900 ℃ for 0.5-4h, washing and drying to obtain the two-step activated high-performance activated carbon.
In this embodiment, in the step S30, the carbonization temperature of the carbonization treatment is 700 to 850 ℃, the carbonization time is 1 to 5 hours, and the temperature increase rate is 1 to 10 ℃/min.
In this embodiment, in the steps S30 and S50, the inert atmosphere is argon or nitrogen.
In this embodiment, in the step S40, the phosphoric acid is 89% by mass.
In the embodiment, the system and the method for preparing the high-performance activated carbon by two-step activation of carbonate and phosphoric acid are different from the traditional strong acid and strong base activation system, the conditions are mild, and the method is a green and environment-friendly preparation method; in the second step of activation treatment, high-concentration phosphoric acid with the mass concentration of 89% is adopted and is finally filtered and recycled, and the filtered and recycled phosphoric acid can be recycled, so that the environmental pollution and waste are greatly reduced, and the cost is saved; and compared with dilute phosphoric acid, the use of concentrated phosphoric acid has the advantages that: the consumption of phosphoric acid is small, the residue is less, the subsequent treatment is convenient, and the activation effect of the concentrated phosphoric acid is better; the specific surface area of the activated carbon can be greatly improved by adopting phosphoric acid activation, the pore structure is optimized, most of the obtained pore diameter distribution is 1-4 nm, and the PF (positive electrode active carbon) can be just prepared6-Anion by anion, the pore size distribution of the activated carbon prepared by the method of this example is more suitable for use as an electrode material for lithium ion capacitors and conventional supercapacitors than commercial activated carbon having a pore size mainly below 1 nm.
Referring to fig. 2, fig. 2 is a schematic flow chart of a third embodiment of the method for preparing the two-step activated high-performance activated carbon according to the present invention, and the third embodiment of the method for preparing the two-step activated high-performance activated carbon according to the present invention is proposed based on the second embodiment.
In the third embodiment, the set power of the ultrasonic mixer is 300W, and the set mixing time of the ultrasonic mixer is 30 minutes; the preset concentration is 10 wt%; the soaking time of the soaking treatment is 10 hours; the first preset time is 2 h; the preset stirring speed is 600 revolutions per minute; the carbon source base material is chitosan, wherein the degree of deacetylation is 96.5%; the carbonate is analytically pure sodium bicarbonate; the carbonization time of the carbonization treatment is 2h, and the heating rate is 3 ℃/min; the preset multiple is 5 times.
In the third embodiment, after the step S50, the method further includes:
step S60, the two-step activated high-performance activated carbon, the conductive carbon black and the polyvinylidene fluoride are mixed according to the ratio of (7-9): (1-0.5): (2-0.5) to prepare a slurry.
And step S70, coating the slurry on a carbon-coated aluminum foil, and drying at 80 ℃ for 10-20 hours to obtain the electrode.
In the specific implementation, the obtained two-step activated high-performance activated carbon, conductive carbon black and polyvinylidene fluoride (poly (vinylidene fluoride), abbreviated as PVDF) are mixed according to the proportion of (7-9): (1-0.5): (2-0.5) (e.g., 8: 1: 1) in a mass ratio, coating the slurry on a carbon-coated aluminum foil, and drying at 80 ℃ for 10-20 hours (e.g., 12 hours) to obtain an electrode. The two-step activated high-performance activated carbon is used as the anode material of the lithium ion capacitor and is used at 50mA g-1Has a specific capacity at a current density of more than 87.5mAh g-1At more than 1000mA g-1Over 5000 cycles at a current density of over, the capacity remains above 100% of the initial value. And the mass ratio of the anode to the cathode is (1-4): 1, the positive and negative electrodes are assembled into a full battery, and the energy density can reach 170Wh kg to the maximum-1。
The technical solutions of the present invention are further described in detail below with reference to specific examples and drawings, it should be understood that the following examples are merely illustrative of the present invention and are not intended to limit the present invention.
Example 1:
(1) 4g of chitosan and 4g of sodium bicarbonate were added to 50mL of water and ultrasonically dispersed with ultrasonic waves at a power of 300W for 30 minutes.
(2) Putting the obtained milky yellow jelly-like mixture into a freeze dryer, and freeze-drying for 36 h.
(3) And (3) putting the material obtained in the step (2) into a high-temperature furnace, keeping the temperature at 700 ℃ for 2 hours by taking argon or nitrogen as a protective gas at the heating rate of 3 ℃/minute, and washing the material to be neutral by using 10wt% of dilute hydrochloric acid and deionized water.
(4) And (4) drying the black solid obtained in the step (3) at 80 ℃ for 5 hours to obtain the nascent state activated carbon activated by the sodium bicarbonate.
(5) 1.5g of the sodium hydrogencarbonate-activated nascent activated carbon obtained in the step (4) was put into 7.5g of 89% concentrated phosphoric acid and magnetically stirred for 10 minutes.
(6) The excess phosphoric acid was filtered off with suction and dried at 80 ℃ for 2 h.
(7) And (3) putting the dried sodium bicarbonate activated carbon into a high-temperature furnace, and keeping the temperature for 1h by using argon or nitrogen as shielding gas at the heating rate of 3 ℃/min.
(8) And (4) washing the black powder obtained in the step (7) to be neutral by using deionized water, and drying to obtain the two-step activated high-performance activated carbon.
Example 2:
(1) 4g of chitosan and 4g of sodium bicarbonate were added to 50mL of water and ultrasonically dispersed for 30 minutes by using ultrasonic waves with a power of 300W.
(2) Putting the obtained milky yellow jelly-like mixture into a freeze dryer, and freeze-drying for 36 h.
(3) And (3) putting the material obtained in the step (2) into a high-temperature furnace, keeping the temperature at 750 ℃ for 2h by using argon or nitrogen as a protective gas at the heating rate of 3 ℃/min, and washing the material to be neutral by using 10wt% of dilute hydrochloric acid and deionized water.
(4) And (4) drying the black solid obtained in the step (3) at 80 ℃ for 5 hours to obtain the nascent state activated carbon activated by the sodium bicarbonate.
(5) 1.5g of the sodium hydrogencarbonate-activated nascent activated carbon obtained in the step (4) was put into 7.5g of 89% concentrated phosphoric acid and magnetically stirred for 10 minutes.
(6) The excess phosphoric acid was filtered off with suction and dried at 80 ℃ for 2 h.
(7) And (3) putting the dried sodium bicarbonate activated carbon into a high-temperature furnace, and keeping the temperature for 1h by using argon or nitrogen as shielding gas at the heating rate of 3 ℃/min.
(8) And (4) washing the black powder obtained in the step (7) to be neutral by using deionized water, and drying to obtain the two-step activated high-performance activated carbon.
As shown in fig. 3, fig. 3 is a scanning micrograph of the two-step activated high performance activated carbon prepared in example 2. As shown in FIG. 4, FIG. 4 shows that the two-step activated high performance activated carbon prepared in example 2 was used as a lithium ion capacitor anode at 5A g-1Current density of (a).
Example 3:
(1) 4g of chitosan and 4g of sodium bicarbonate were added to 50mL of water and ultrasonically dispersed for 30 minutes by using ultrasonic waves with a power of 300W.
(2) Putting the obtained milky yellow jelly-like mixture into a freeze dryer, and freeze-drying for 36 h.
(3) And (3) putting the material obtained in the step (2) into a high-temperature furnace, keeping the temperature at 800 ℃ for 2h by using argon or nitrogen as a protective gas at the heating rate of 3 ℃/min, and washing the material to be neutral by using 10wt% of dilute hydrochloric acid and deionized water.
(4) And (4) drying the black solid obtained in the step (3) at 80 ℃ for 5 hours to obtain the nascent state activated carbon activated by the sodium bicarbonate.
(5) 1.5g of the sodium hydrogencarbonate-activated nascent activated carbon obtained in the step (4) was put into 7.5g of 89% concentrated phosphoric acid and magnetically stirred for 10 minutes.
(6) The excess phosphoric acid was filtered off with suction and dried at 80 ℃ for 2 h.
(7) And (3) putting the dried sodium bicarbonate activated carbon into a high-temperature furnace, and keeping the temperature for 1h by using argon or nitrogen as shielding gas at the heating rate of 3 ℃/min.
(8) And (4) washing the black powder obtained in the step (7) to be neutral by using deionized water, and drying to obtain the two-step activated high-performance activated carbon.
Example 4:
(1) 4g of chitosan and 4g of sodium bicarbonate were added to 50mL of water and ultrasonically dispersed for 30 minutes by using ultrasonic waves with a power of 300W.
(2) Putting the obtained milky yellow jelly-like mixture into a freeze dryer, and freeze-drying for 36 h.
(3) And (3) putting the material obtained in the step (2) into a high-temperature furnace, keeping the temperature of the material at 850 ℃ for 2 hours by taking argon or nitrogen as a protective gas at the heating rate of 3 ℃/minute, and washing the material to be neutral by using 10wt% of dilute hydrochloric acid and deionized water.
(4) And (4) drying the black solid obtained in the step (3) at 80 ℃ for 5 hours to obtain the nascent state activated carbon activated by the sodium bicarbonate.
(5) 1.5g of the sodium hydrogencarbonate-activated nascent activated carbon obtained in the step (4) was put into 7.5g of 89% concentrated phosphoric acid and magnetically stirred for 10 minutes.
(6) The excess phosphoric acid was filtered off with suction and dried at 80 ℃ for 2 h.
(7) And (3) putting the dried sodium bicarbonate activated carbon into a high-temperature furnace, and keeping the temperature for 1h by using argon or nitrogen as shielding gas at the heating rate of 3 ℃/min.
(8) And (4) washing the black powder obtained in the step (7) to be neutral by using deionized water, and drying to obtain the two-step activated high-performance activated carbon.
(9) And (3) carrying out two-step activation on the high-performance activated carbon obtained in the step (8), conductive carbon black and polyvinylidene fluoride according to the weight ratio of (7-9): (1-0.5): (2-0.5) to prepare a slurry.
(10) And (4) coating the slurry obtained in the step (9) on a carbon-coated aluminum foil, and drying at 80 ℃ for 10-20 hours to obtain the electrode.
Example 5:
(1) 2g of chitosan and 4g of sodium bicarbonate were added to 50mL of water and ultrasonically dispersed for 10 minutes by using ultrasonic waves with a power of 300W.
(2) Putting the obtained milky yellow jelly-like mixture into a freeze dryer, and freeze-drying for 36 h.
(3) And (3) putting the material obtained in the step (2) into a high-temperature furnace, keeping the temperature at 750 ℃ for 1h by taking argon or nitrogen as a protective gas at the heating rate of 1 ℃/minute, soaking the material for 5h by using 5wt% of dilute hydrochloric acid, and washing the material to be neutral by using deionized water.
(4) And (4) drying the black solid obtained in the step (3) at the temperature of 80 ℃ for 1h to obtain the nascent state activated carbon activated by the sodium bicarbonate.
(5) 1.5g of the sodium bicarbonate activated nascent state activated carbon obtained in the step (4) was put into 1.5g of 89% concentrated phosphoric acid, and magnetically stirred for 5 minutes at a rotation speed of 300 rpm.
(6) The excess phosphoric acid was filtered off with suction and dried at 80 ℃ for 1 h.
(7) And (3) putting the dried sodium bicarbonate activated carbon into a high-temperature furnace, and keeping the temperature for 0.5h by taking argon or nitrogen as shielding gas at the heating rate of 1 ℃/min.
(8) And (4) washing the black powder obtained in the step (7) to be neutral by using deionized water, and drying to obtain the two-step activated high-performance activated carbon.
(9) And (3) mixing the two-step activated high-performance activated carbon obtained in the step (8), conductive carbon black and polyvinylidene fluoride according to the weight ratio of 7: 1: 2 is prepared into slurry.
(10) And (4) coating the slurry obtained in the step (9) on a carbon-coated aluminum foil, and drying at 80 ℃ for 10 hours to obtain the electrode.
Example 6:
(1) 60g of chitosan and 4g of sodium bicarbonate are added to 50mL of water and dispersed ultrasonically for 100 minutes by using ultrasonic waves with the power of 600W.
(2) Putting the obtained milky yellow jelly-like mixture into a freeze dryer, and freeze-drying for 36 h.
(3) And (3) putting the material obtained in the step (2) into a high-temperature furnace, keeping the temperature at 750 ℃ for 5 hours by taking argon or nitrogen as a protective gas at the heating rate of 10 ℃/minute, soaking the material in 15wt% of dilute hydrochloric acid for 20 hours, and washing the material to be neutral by deionized water.
(4) And (4) drying the black solid obtained in the step (3) at the temperature of 80 ℃ for 10 hours to obtain the nascent state activated carbon activated by the sodium bicarbonate.
(5) 1.5g of the sodium bicarbonate activated nascent state activated carbon obtained in the step (4) was put into 15g of 89% concentrated phosphoric acid, and magnetically stirred for 30 minutes at a rotation speed of 1000 rpm.
(6) The excess phosphoric acid was filtered off with suction and dried at 80 ℃ for 10 h.
(7) And (3) putting the dried sodium bicarbonate activated carbon into a high-temperature furnace, and keeping the temperature for 4 hours by taking argon or nitrogen as shielding gas at the heating rate of 10 ℃/minute.
(8) And (4) washing the black powder obtained in the step (7) to be neutral by using deionized water, and drying to obtain the two-step activated high-performance activated carbon.
(9) And (3) mixing the two-step activated high-performance activated carbon obtained in the step (8), conductive carbon black and polyvinylidene fluoride according to the weight ratio of 9: 0.5: : a mass ratio of 0.5 was formulated into a slurry.
(10) And (4) coating the slurry obtained in the step (9) on a carbon-coated aluminum foil, and drying at 80 ℃ for 20 hours to obtain the electrode.
In examples 1 to 3, after the step (8) of washing the black powder obtained in (7) with deionized water to neutrality and drying to obtain the two-step activated high performance activated carbon, the step (9) of adding the two-step activated high performance activated carbon obtained in (8), the conductive carbon black and the polyvinylidene fluoride may be performed in accordance with the following formula (7-9): (1-0.5): (2-0.5) preparing the mixture into slurry; (10) and (4) coating the slurry obtained in the step (9) on a carbon-coated aluminum foil, and drying at 80 ℃ for 10-20 hours to obtain an electrode, and carrying out two steps to obtain the electrode.
Comparative example 1:
(1) 4g of chitosan and 4g of sodium bicarbonate were added to 50mL of water and ultrasonically dispersed for 30 minutes by using ultrasonic waves with a power of 300W.
(2) Putting the obtained milky yellow jelly-like mixture into a freeze dryer, and freeze-drying for 36 h.
(3) And (3) putting the material obtained in the step (2) into a high-temperature furnace, keeping the temperature at 750 ℃ for 2h by using argon or nitrogen as a protective gas at the heating rate of 3 ℃/min, and washing the material to be neutral by using 10wt% of dilute hydrochloric acid and deionized water.
(4) And (4) drying the black solid obtained in the step (3) at 80 ℃ for 5 hours to obtain the nascent state activated carbon activated by the sodium bicarbonate.
Comparative example 2:
(1) 4g of chitosan was added to 50mL of water and ultrasonically dispersed for 30 minutes by using ultrasonic waves with a power of 300W.
(2) Putting the obtained mixture into a freeze dryer, and freeze-drying for 36 h.
(3) And (3) putting the material obtained in the step (2) into a high-temperature furnace, keeping the temperature at 750 ℃ for 2h by using argon or nitrogen as a protective gas at the heating rate of 3 ℃/min, and washing the material to be neutral by using 10wt% of dilute hydrochloric acid and deionized water.
(4) And (4) drying the black solid obtained in the step (3) at 80 ℃ for 5 hours to obtain the nascent state activated carbon.
(5) 1.5g of the nascent activated carbon obtained in the step (4) was put into 7.5g of 89% concentrated phosphoric acid, and magnetically stirred for 10 minutes.
(6) The excess phosphoric acid was filtered off with suction and dried at 80 ℃ for 2 h.
(7) And (3) putting the dried nascent state activated carbon into a high-temperature furnace, and keeping the temperature for 1h by taking argon or nitrogen as a protective gas at the heating rate of 3 ℃/min.
(8) And (4) washing the black powder obtained in the step (7) to be neutral by using deionized water, and drying to obtain the phosphoric acid activated carbon.
Comparative example 3:
(1) 4g of chitosan and 4g of sodium bicarbonate were added to 50mL of water and ultrasonically dispersed for 30 minutes by using ultrasonic waves with a power of 300W.
(2) Putting the obtained milky yellow jelly-like mixture into a freeze dryer, and freeze-drying for 36 h.
(3) And (3) putting the material obtained in the step (2) into a high-temperature furnace, keeping the temperature at 750 ℃ for 2h by using argon or nitrogen as a protective gas at the heating rate of 3 ℃/min, and washing the material to be neutral by using 10wt% of dilute hydrochloric acid and deionized water.
(4) And (4) drying the black solid obtained in the step (3) at 80 ℃ for 5 hours to obtain the nascent state activated carbon activated by the sodium bicarbonate.
(5) 1.5g of the sodium hydrogencarbonate-activated nascent activated carbon obtained in the step (4) was put into 7.5g of 20% concentrated phosphoric acid and magnetically stirred for 10 minutes.
(6) The excess phosphoric acid was filtered off with suction and dried at 80 ℃ for 2 h.
(7) And (3) putting the dried sodium bicarbonate activated carbon into a high-temperature furnace, and keeping the temperature for 1h by using argon or nitrogen as shielding gas at the heating rate of 3 ℃/min.
(8) And (4) washing the black powder obtained in the step (7) to be neutral by using deionized water, and drying to obtain the two-step activated high-performance activated carbon.
(9) And (3) carrying out two-step activation on the high-performance activated carbon obtained in the step (8), conductive carbon black and polyvinylidene fluoride according to the weight ratio of (7-9): (1-0.5): (2-0.5) to prepare a slurry.
(10) And (4) coating the slurry obtained in the step (9) on a carbon-coated aluminum foil, and drying at 80 ℃ for 10-20 hours to obtain the electrode.
It should be noted that, in comparative examples 1 and 2, after the two-step activated high performance activated carbon was obtained, the obtained two-step activated high performance activated carbon, conductive carbon black and polyvinylidene fluoride were also prepared in accordance with (7-9): (1-0.5): (2-0.5) preparing the mixture into slurry; and coating the obtained slurry on a carbon-coated aluminum foil, and drying at 80 ℃ for 10-20 hours to obtain the electrode.
As shown in fig. 5, fig. 5 is a comparison graph of specific surface areas of two-step activated high performance activated carbons prepared in example 2 and comparative example 3.
Table 1 comparison of the performance parameters of the products obtained in the various examples
As can be seen from the data analysis in Table 1, carbonate has a better activation effect on carbon source and can generate 766m2 g-1Has a large surface area (comparative example 1), and the specific surface area after the secondary activation of concentrated phosphoric acid can reach 1872m at the maximum2 g-1(example 3). Instead of the carbonate preliminary activation, the carbon source carbonized under the same condition is directly subjected to concentrated phosphoric acid activation treatment, and the achievable effect is very limited, and the specific surface area is only 750m2 g-1The reason why the carbonized carbon source forms a foam-like structure with a thin carbon wall after the carbonate is initially activated is that concentrated phosphoric acid can easily perform secondary action on the thin-wall structure to form a large amount of micro-mesoporous structures, thereby forming a large specific surface area (comparative example 2). The carbonized carbon source which is not activated by carbonate is large block structure concentrated phosphoric acid which can only react on the surface and has little activation effect on the inside. Also, by carrying out the same treatment with a 20% concentration phosphoric acid solution (comparative example 3), it was revealed that the effect after the treatment with a low concentration of phosphoric acid was extremely different from that of 89% concentrated phosphoric acid. This is thatBecause the low-concentration phosphoric acid is difficult to fix a sufficient amount of phosphoric acid on the surface of the nascent state active carbon for secondary activation by adopting the dipping and pumping filtration method, obvious effect is difficult to achieve after the activation.
The invention also provides the two-step activated high-performance activated carbon prepared by the preparation method of the two-step activated high-performance activated carbon. Since the two-step activated high-performance activated carbon adopts all technical solutions of all the embodiments, the two-step activated high-performance activated carbon at least has the beneficial effects brought by the technical solutions of the embodiments, and details are not repeated herein.
The invention also provides a lithium ion capacitor electrode, and the two-step activated high-performance activated carbon is used as a positive electrode material of the lithium ion capacitor electrode.
The high-performance activated carbon obtained by two-step activation has high specific capacity which can reach 87.5mAh g when being applied to a lithium ion capacitor-1The capacity of the capacitor is 1.5-2.5 times of that of the current commercial activated carbon lithium ion capacitor.
Since the lithium ion capacitor electrode adopts all technical solutions of all the embodiments, the lithium ion capacitor electrode at least has the beneficial effects brought by the technical solutions of the embodiments, and details are not repeated herein.
While embodiments of the invention have been described above, it is not limited to the applications set forth in the description and the embodiments, which are fully applicable to various fields of endeavor for which the invention may be embodied with additional modifications as would be readily apparent to those skilled in the art, and the invention is therefore not limited to the details shown and described herein without departing from the generic concept as defined by the claims and their equivalents.
Claims (7)
1. A preparation method of two-step activated high-performance activated carbon is characterized by comprising the following steps:
mixing carbonate and a carbon source base material according to the weight ratio of (15-0.5): 1, adding the mixture into an aqueous solution, uniformly stirring, and ultrasonically mixing for 10-100 minutes by adopting an ultrasonic mixer with the power of 300-600W to form a uniform cream-yellow pre-crosslinked mixture;
freeze-drying the pre-crosslinked mixture to obtain a mixed solid;
carbonizing the mixed solid in an inert atmosphere, soaking an obtained primary carbonized product by hydrochloric acid with a preset concentration, and washing and drying by deionized water to obtain nascent activated carbon;
mixing the nascent state activated carbon with phosphoric acid with a preset multiple of mass at a preset stirring speed, filtering out excessive phosphoric acid by vacuum filtration, and drying at a first preset temperature within a first preset time to obtain nascent state activated carbon mixed with phosphoric acid; the preset multiple is 1-10 times; the preset stirring speed is 300-1000 rpm, stirring is carried out for 5-30 minutes, the first preset temperature is 80 ℃, and the first preset time is 1-10 hours; the phosphoric acid is 89% by mass;
under inert atmosphere, raising the temperature of the nascent state activated carbon mixed with phosphoric acid to 900 ℃ at the heating rate of 1-10 ℃/min, carrying out heat preservation treatment at 900 ℃ for 0.5-4h, washing and drying at 80 ℃ for 1-10 h to obtain the two-step activated high-performance activated carbon.
2. The method of preparing a two-step activated high performance activated carbon of claim 1, wherein the predetermined concentration is 5-15 wt%; the soaking time of the soaking treatment is 5-20 hours, and the deionized water is used for washing and drying for 1-10 hours at the temperature of 80 ℃; the carbonate is one or more of sodium bicarbonate, sodium carbonate, potassium bicarbonate, potassium carbonate, ammonium bicarbonate, calcium carbonate, magnesium carbonate, zinc carbonate and copper carbonate; the carbon source base material is one or more of sucrose, glucose, chitosan, melamine, sodium alginate, dopamine, starch and flour; the carbonization temperature of the carbonization treatment is 700-850 ℃, the carbonization time is 1-5 hours, and the temperature rise rate is 1-10 ℃/min; the inert atmosphere is argon or nitrogen; the phosphoric acid is 89% by mass.
3. The method of preparing a two-step activated high performance activated carbon of claim 1, wherein the predetermined concentration is 10 wt%; the soaking time of the soaking treatment is 10 hours; the first preset time is 2 hours; the preset stirring speed is 600 revolutions per minute; the carbon source base material is chitosan, wherein the degree of deacetylation is 96.5%; the carbonate is analytically pure sodium bicarbonate; the carbonization time of the carbonization treatment is 2h, and the heating rate is 3 ℃/min; the preset multiple is 5 times.
4. The method of preparing a two-step activated high performance activated carbon according to claim 1, wherein the power of the ultrasonic mixer is 300W and the mixing time of the ultrasonic mixer is 30 minutes.
5. The method for preparing two-step activated high performance activated carbon according to any one of claims 1 to 4, wherein the method further comprises, after the step of subjecting the nascent activated carbon mixed with phosphoric acid to heat preservation treatment under an inert atmosphere, washing and drying to obtain two-step activated high performance activated carbon:
and (3) activating the high-performance activated carbon, the conductive carbon black and the polyvinylidene fluoride by two steps according to the following formula (7-9): (1-0.5): (2-0.5) preparing the mixture into slurry;
and coating the slurry on a carbon-coated aluminum foil, and drying at 80 ℃ for 10-20 hours to obtain the electrode.
6. A two-step activated high-performance activated carbon, which is characterized by being prepared by the preparation method of the two-step activated high-performance activated carbon according to any one of claims 1 to 5.
7. A lithium ion capacitor electrode, characterized in that the two-step activated high performance activated carbon according to claim 6 is used as a positive electrode material of the lithium ion capacitor electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010915443.9A CN112250067B (en) | 2020-09-03 | 2020-09-03 | Two-step activated high-performance activated carbon, preparation method and lithium ion capacitor electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010915443.9A CN112250067B (en) | 2020-09-03 | 2020-09-03 | Two-step activated high-performance activated carbon, preparation method and lithium ion capacitor electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112250067A CN112250067A (en) | 2021-01-22 |
| CN112250067B true CN112250067B (en) | 2022-05-06 |
Family
ID=74224837
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010915443.9A Active CN112250067B (en) | 2020-09-03 | 2020-09-03 | Two-step activated high-performance activated carbon, preparation method and lithium ion capacitor electrode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112250067B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105236407A (en) * | 2015-09-14 | 2016-01-13 | 中国东方电气集团有限公司 | Double-layer capacitor electrode spherical active carbon material preparation method |
| CN105439143A (en) * | 2014-08-21 | 2016-03-30 | 中国科学院大连化学物理研究所 | Hierarchical porous activated carbon used for a super capacitor and preparation method thereof |
| CN106145110A (en) * | 2016-07-05 | 2016-11-23 | 中国矿业大学 | A kind of activated carbon two step process for preparing activated and the application in ultracapacitor thereof |
| CN109081342A (en) * | 2018-08-03 | 2018-12-25 | 成都城电电力工程设计有限公司 | A kind of biomass porous active carbon of nipa palm leaf and its preparation method and application |
-
2020
- 2020-09-03 CN CN202010915443.9A patent/CN112250067B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105439143A (en) * | 2014-08-21 | 2016-03-30 | 中国科学院大连化学物理研究所 | Hierarchical porous activated carbon used for a super capacitor and preparation method thereof |
| CN105236407A (en) * | 2015-09-14 | 2016-01-13 | 中国东方电气集团有限公司 | Double-layer capacitor electrode spherical active carbon material preparation method |
| CN106145110A (en) * | 2016-07-05 | 2016-11-23 | 中国矿业大学 | A kind of activated carbon two step process for preparing activated and the application in ultracapacitor thereof |
| CN109081342A (en) * | 2018-08-03 | 2018-12-25 | 成都城电电力工程设计有限公司 | A kind of biomass porous active carbon of nipa palm leaf and its preparation method and application |
Non-Patent Citations (3)
| Title |
|---|
| Methods for preparation and activation of activated carbon: a review;Zoha Heidarinejad等;《Environmental Chemistry Letters》;20200104;第18卷;第397页右栏第2段第7-9行、第3段第4-6行和22-24行、第398页左栏第1段第13-16行、第398页右栏第1段第6-12行、第399页左栏第2段第5-10行、第400页右栏最后一段第1-9行、第401页左栏第2段 * |
| 中等比表面积高容量活性炭电极材料制备和表征;郑祥伟等;《复旦学报（自然科学版）》;20090228;第48卷(第1期);第59页第1.2.1节、第60页表1、第62页第1段 * |
| 浸渍金属盐二次活化制备中孔沥青基球形活性炭的研究;刘小军等;《离子交换与吸附》;20080831;第24卷(第4期);第289-295页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112250067A (en) | 2021-01-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110589827B (en) | Method for preparing biomass carbon aerogel by double activation method and application thereof | |
| CN108101051B (en) | Preparation method of seaweed-based activated carbon precursor for supercapacitor | |
| CN107244664B (en) | Preparation method and application of graphene-like structure carbon electrode material | |
| CN106365163B (en) | A kind of preparation method of sisal fiber activated carbon and the application of the sisal fiber activated carbon in lithium-ion capacitor | |
| CN111477465B (en) | Preparation and application of polyaniline nanowire/three-dimensional porous graphene electrode material | |
| CN113044827A (en) | Nano carbon material composite biomass hard carbon electrode material and preparation method and application thereof | |
| CN112850708A (en) | Preparation method and application of nitrogen-doped porous carbon material with high specific surface area | |
| CN111082034B (en) | Preparation of tin/tin phosphide/carbon composite material of alkali metal ion battery cathode | |
| CN114538408A (en) | Method for preparing high electrocatalytic activity biochar through micro-aerobic pyrolysis | |
| CN114506838B (en) | Three-dimensional conductive network reinforced nickel-doped carbon aerogel material and preparation method and application thereof | |
| CN114702022A (en) | Preparation method and application of hard carbon negative electrode material | |
| CN114890403A (en) | Nitrogen-doped polymer derived carbon material and application thereof in sodium ion battery | |
| CN114400307A (en) | Tin-carbon composite material and preparation method and application thereof | |
| CN114408897A (en) | Biomass-based two-dimensional nano carbon material and preparation method thereof | |
| CN112250067B (en) | Two-step activated high-performance activated carbon, preparation method and lithium ion capacitor electrode | |
| CN109256561B (en) | Hard carbon negative electrode material, manufacturing method thereof and method for manufacturing battery by using hard carbon negative electrode material | |
| CN110690423B (en) | Heteroatom doped carbon material and preparation method and application thereof | |
| CN110459772B (en) | Preparation method of lead-carbon composite material for lead-carbon battery cathode additive | |
| CN109686945B (en) | Method for preparing carbon-coated tin-based composite material through low-temperature self-activation | |
| CN111099578B (en) | Nitrogen-doped three-dimensional graphene material | |
| CN113522368A (en) | Fe and Co Co-doped sea urchin structure hollow carbon sphere electrocatalyst and preparation method thereof | |
| CN115611262B (en) | Glycosyl hard carbon material and preparation method and application thereof | |
| CN116986581B (en) | Biomass hard carbon and preparation method and application thereof | |
| CN117550587B (en) | Negative electrode material and preparation method and application thereof | |
| CN112751013B (en) | Nitrogen-doped TiO2/GRA composite material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |