CN113086967A - Preparation method of uniform carbon-manganese oxide composite aerogel electrode material - Google Patents
Preparation method of uniform carbon-manganese oxide composite aerogel electrode material Download PDFInfo
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- CN113086967A CN113086967A CN202110386578.5A CN202110386578A CN113086967A CN 113086967 A CN113086967 A CN 113086967A CN 202110386578 A CN202110386578 A CN 202110386578A CN 113086967 A CN113086967 A CN 113086967A
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- 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
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/02—Oxides; Hydroxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/44—Raw materials therefor, e.g. resins or coal
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
Abstract
The invention discloses a preparation method of a uniform carbon-manganese oxide composite aerogel material, relates to an electrode material for an energy storage device (a battery and a capacitor), and has the advantages of simple preparation, uniform compounding, low cost, environmental friendliness, greenness, no toxicity and the like. By utilizing the unique property that the oxygen-containing functional group of the G block in the natural structure of the sodium alginate can be chelated with polyvalent metal cations to form an egg-box structure, the sodium alginate and manganese salt solution are designed to generate internal gel through emulsification, and the carbon-manganese oxide composite aerogel is constructed through freeze drying, carbonization and further oxidation at low temperature. The material provided by the invention has good performance and stable use, and is suitable for popularization.
Description
Technical Field
The invention designs a preparation method of a uniform carbon-manganese oxide composite aerogel material, belonging to the technical field of electrode materials of energy storage devices.
Background
Manufacturing high-performance electric energy storage devices is one of the key elements in developing electric vehicles and renewable energy sources. In recent years, researchers have concentrated their research on both SC (super capacitor) and LIB (lithium rechargeable battery) devices. Among them, LIBs benefit from the faraday charge storage mechanism and have a very considerable energy density; SC is stable in terms of power density, ultra-long cycle, etc., mainly due to the storage mechanism of physical surface charges. The advantages and disadvantages of SC and LIB are complementary. In the past decades, LIB has become the only energy source with the widest application range in the portable device market, and SC has also been rapidly developed in the fields of large hybrid vehicles and the like. Whether LIB or SC, the performance of the electrode material is critical to achieving high energy and power densities for all electrical energy storage devices.
Manganese is rich in earth crust and is an important transition metal element. In recent years, oxides of manganese have attracted considerable interest to researchers as electrode materials for energy storage devices. Its advantages are low cost, rich resources, no poison to environment, and high theoretical specific capacity up to 1300F/g; the material is insufficient in poor conductivity, poor in chemical property and mechanical property, easy to agglomerate in the charging and discharging process, expanded in volume and smaller in specific surface area; so we considered a solution to separate the metal oxide nanoparticles by embedding them in various carbon matrices to solve the problem of agglomeration and volume expansion of manganese oxide.
The biomass material is one of the electrode materials which are popular in recent years, and Sodium Alginate (SA) is one of the electrode materials. The sodium alginate is derived from marine organisms, and can also be used as a byproduct in the process of industrially extracting iodine and mannitol from brown algae or gulfweed. Sodium alginate is a macromolecular substance formed by connecting beta-D-mannuronic acid (M block) and alpha-L-guluronic acid (G block). The G block oxygen-containing functional group can be chelated with polyvalent metal cations to form an egg-box structure, an experiment can be skillfully designed to generate internal gel through emulsification, and the uniformly dispersed composite material is obtained through a series of processes. Patent CN109464989A reports a preparation method of sodium alginate gel beads, which utilizes the embedding property, biodegradability and other properties of sodium alginate that is easy to form gel, to prepare the material with low cost, safety, no toxicity, good adsorption property and mechanical property as adsorbent, and adopts less raw materials, and only sodium alginate, without adding other raw materials, can prepare gel beads with excellent adsorption property. The patent CN103041442A aims at the problems of low bonding strength, toxic and side effects, difficult degradation in human body and the like of the existing medical adhesives, especially bone adhesives, and provides a bone adhesive based on sodium alginate which is improved on the basis of the former and has the advantages of easy preparation, high bonding strength, excellent curing performance, good biocompatibility and the like, and takes sodium alginate, sodium carboxymethylcellulose and chondroitin sulfate as materials, and a preparation method thereof. Patent CN103087334A reports a preparation method of sodium alginate-artemisia glue composite hydrogel, which is characterized in that artemisia glue is introduced into a sodium alginate solution system, and Ca2+ is slowly released in a gluconolactone solution by utilizing microporous calcium carbonate to form the sodium alginate-artemisia glue composite hydrogel in situ, so that the performances of the sodium alginate and the artemisia glue are complementary, the water absorption performance and the mechanical performance of the sodium alginate-based composite hydrogel are enhanced, and the application range of the sodium alginate as a drug carrier and a tissue engineering material is expanded.
Disclosure of Invention
Aiming at the problems, the invention compounds the alginic acid manganese hydrogel with manganese salt through the specific chelation of sodium alginate. Through a series of processes such as freeze drying, nitrogen heat treatment, oxygen heat treatment and the like, the carbon-manganese oxide composite aerogel material serving as an electrode material of an electrochemical element is finally obtained.
The method for preparing the carbon-manganese oxide composite aerogel material provided by the invention takes sodium alginate and manganese salt as raw materials and mainly comprises the following steps:
step (1) preparation of sodium alginate aqueous solution: mixing sodium alginate solid powder with deionized water in a certain proportion, and uniformly stirring by using a magnetic stirrer;
step (2) preparation of manganese salt solution: mixing manganese salt and deionized water according to a certain proportion, and uniformly stirring by using a magnetic stirrer;
step (3) preparation of manganese alginate hydrogel: dropwise adding the sodium alginate solution obtained in the step A into a manganese salt solution, and crosslinking the solution for a period of time to obtain manganese alginate hydrogel which is washed by deionized water;
step (4), preparation of manganese alginate aerogel: c, freezing and drying the manganese alginate hydrogel obtained in the step C to obtain manganese alginate aerogel;
step (5), preparing the carbon-manganese oxide aerogel: and D, respectively carrying out heat treatment on the manganese alginate aerogel obtained in the step D in a nitrogen atmosphere and an air atmosphere to obtain the carbon-manganese oxide composite aerogel material.
Preferably, in the step (1), the mass fraction of the sodium alginate in the solution is 0.8% -3%;
preferably, in the step (1), the rotation speed of the magnetic stirring is 300-;
preferably, in the step (2), the manganese salt can be one or more of manganese nitrate, manganese chloride, manganese formate, manganese acetate and manganese sulfate, and the molar concentration of the manganese salt in the solution is 0.15-0.4 mol/L;
preferably, in the step (3), the crosslinking time of the sodium alginate and the manganese salt is 0.5-8 h;
preferably, in the step (4), the freeze-drying time of the manganese alginate hydrogel is 12-48 h;
preferably, in the step (5), the heat treatment temperature of the manganese alginate aerogel in the nitrogen atmosphere is 600-1000 ℃;
preferably, in the step (5), the heat treatment time of the manganese alginate aerogel in the nitrogen atmosphere is 1-3 h;
preferably, in the step (5), the heat treatment temperature of the manganese alginate aerogel in the oxygen atmosphere is 250-350 ℃;
preferably, in the step (5), the heat treatment time of the manganese alginate aerogel in the oxygen atmosphere is 2-8 h; the obtained material has excellent performance in electrochemical tests of the supercapacitor, the retention rate of long-cycle capacitance of more than 10000 circles is more than 90%, and the capacity is 220-350F/g.
The invention has the following advantages:
(1) the biomass raw material sodium alginate is used as a carbon source, the yield is rich, the preparation is simple, the compounding is uniform, the cost is low, and the characteristic of chelating with metal is utilized to design a composite material as the electrode material of the super capacitor so as to overcome the defect of metal oxide.
(2) The aerogel material has a unique 3D net-shaped structure and a large number of mesopores, and is beneficial to the transmission of particles and the infiltration of electrolyte.
(3) The material characteristics are ingeniously utilized, the metal oxide is dispersed very uniformly, the stability of the electrode material is facilitated, and the service life of the material can be prolonged.
(4) All the raw materials are safe and nontoxic, and meet the requirement of green chemistry.
Detailed Description
The present invention is illustrated by way of specific examples, but is not intended to be limited thereto.
Example 1: 1g of sodium alginate solid powder was weighed and placed in a beaker. Adding 98ml of deionized water into the beaker, and stirring for 12 hours at room temperature at the rotating speed of 500r/min by using a magnetic stirrer until the sodium alginate is fully dissolved and uniformly stirred to obtain a2 wt% sodium alginate aqueous solution A. Measuring 19.75ml of 50% manganese nitrate aqueous solution, adding 230.24ml of deionized water, and stirring for 2 hours at room temperature at the rotating speed of 400r/min by using a magnetic stirrer to fully and uniformly stir so as to obtain 0.34mol/L manganese nitrate aqueous solution B. Next, the solution a was dropped into the solution B dropwise using a disposable syringe with stirring, and stirring was continued for 6 hours to sufficiently crosslink. After the crosslinking, the manganese alginate hydrogel is obtained. Fully washing the manganese alginate hydrogel by using deionized water in a suction filtration mode to wash out foreign ions such as sodium ions, nitrate ions and the like. After washing, the hydrogel is frozen and dried for 48 hours at the temperature of 90 ℃ below zero to ensure that the moisture is completely dried, and the manganese alginate aerogel is obtained. Carbonizing the manganese alginate aerogel in a tubular resistance furnace under the nitrogen atmosphere, heating to 600 ℃ at the heating rate of 5 ℃/min, and keeping for 2 hours to obtain the carbon-manganous oxide aerogel. And (3) further carrying out thermal treatment on the obtained sample by using oxygen, heating to 250 ℃ at the heating rate of 5 ℃/min, and keeping for 8 hours to finally obtain the carbon-manganous oxide aerogel.
Example 2: and (3) increasing the mass fraction of the sodium alginate solution to 2 wt%, replacing manganese salt with manganese chloride, increasing the concentration of the manganese salt solution to 0.35mol/L, increasing the heat treatment temperature of the nitrogen atmosphere to 700 ℃, increasing the treatment time to 2.5h, and obtaining the carbon/trimanganese tetroxide aerogel material under the same other conditions as in case 1.
Example 3: and (3) increasing the mass fraction of the sodium alginate solution to 2.5 wt%, replacing manganese formate with manganese salt, increasing the concentration of the manganese salt solution to 0.4mol/L, increasing the heat treatment temperature to 800 ℃ in a nitrogen atmosphere, increasing the heat treatment temperature to 300 ℃ in an oxygen atmosphere, reducing the heat treatment time to 4h, and obtaining the carbon/manganous oxide aerogel material under the same conditions as in case 1.
Example 4: and (3) increasing the mass fraction of the sodium alginate solution to 2.6 wt%, replacing manganese salt with manganese acetate, increasing the concentration of the manganese salt solution to 0.42mol/L, increasing the heat treatment temperature to 900 ℃ in a nitrogen atmosphere, increasing the heat treatment temperature to 350 ℃ in an oxygen atmosphere, and reducing the heat treatment time to 5.5h under the same other conditions as in case 1 to obtain the carbon/manganous oxide aerogel material.
Although some embodiments of the present invention have been described in detail, the present invention is not limited to the embodiments, and those skilled in the art can make equivalent modifications or substitutions without departing from the spirit of the present invention, and such equivalent modifications or substitutions are included in the scope of the present invention defined by the claims.
Claims (9)
1. The preparation method of the carbon-manganese oxide composite aerogel is characterized by comprising the following process steps of:
step (1) preparation of sodium alginate aqueous solution: mixing sodium alginate solid powder with deionized water in a certain proportion, and uniformly stirring by using a magnetic stirrer;
step (2) preparation of manganese salt solution: mixing manganese salt and deionized water according to a certain proportion, and uniformly stirring by using a magnetic stirrer;
step (3) preparation of manganese alginate hydrogel: dropwise adding the sodium alginate solution obtained in the step (1) into a manganese salt solution, and crosslinking the solution for a period of time to obtain manganese alginate hydrogel, and washing the manganese alginate hydrogel with deionized water;
step (4), preparation of manganese alginate aerogel: freezing and drying the manganese alginate hydrogel obtained in the step (3) to obtain manganese alginate aerogel;
step (5), preparing the carbon-manganese oxide aerogel: and (4) respectively carrying out heat treatment on the manganese alginate aerogel obtained in the step (4) in a nitrogen atmosphere and an air atmosphere to obtain the carbon-manganese oxide composite aerogel material.
2. The preparation method of the carbon-manganese oxide composite aerogel according to claim 1, wherein in the step (1), the mass fraction of the sodium alginate in the solution is 0.8% -3%.
3. The method for preparing carbon-manganese oxide composite aerogel according to claim 1, wherein in the step (1), the rotation speed of the magnetic stirring is 300-500r/min, and the stirring time is 6-12 h.
4. The method for preparing carbon-manganese oxide composite aerogel according to claim 1, wherein in the step (2), the manganese salt can be one or more of manganese nitrate, manganese chloride, manganese formate, manganese acetate and manganese sulfate.
5. The method for preparing carbon-manganese oxide composite aerogel according to claim 1, wherein in the step (2), the molar concentration of the manganese salt in the solution is 0.15-0.4 mol/L.
6. The preparation method of the carbon-manganese oxide composite aerogel according to claim 1, wherein in the step (3), the crosslinking time of the sodium alginate and the manganese salt is 0.5-8 h.
7. The preparation method of the carbon-manganese oxide composite aerogel according to claim 1, wherein in the step (4), the freeze-drying time of the manganese alginate hydrogel is 12-48 h.
8. The preparation method of the carbon-manganese oxide composite aerogel as claimed in claim 1, wherein in the step (5), the heat treatment temperature of the manganese alginate aerogel in the nitrogen atmosphere is 600-1000 ℃, and the heat treatment time is 1-3 h.
9. The preparation method of the carbon-manganese oxide composite aerogel as claimed in claim 1, wherein in the step (5), the heat treatment temperature of the manganese alginate aerogel in the oxygen atmosphere is 250-350 ℃; the heat treatment time is 2-8 h.
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| CN113603076A (en) * | 2021-08-10 | 2021-11-05 | 北京化工大学 | Preparation method of sodium alginate-based porous carbon aerogel electrode material |
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Application publication date: 20210709 |