CN110289179B - Preparation method of active metal oxide-carbonized bacterial cellulose electrode material - Google Patents
Preparation method of active metal oxide-carbonized bacterial cellulose electrode material Download PDFInfo
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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
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- 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
- H01G11/40—Fibres
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- H—ELECTRICITY
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- 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
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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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- 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 preparation method of an active metal oxide-carbonized bacterial cellulose electrode material. According to the method, firstly, an electrochemical oxidation method is adopted to carry out surface hydrophilic treatment on carbonized bacterial cellulose, then an ethanol solution of active metal nitrate is soaked, after ethanol in the material is volatilized, ammonia gas is introduced into a nitrate-carbonized bacterial cellulose membrane, and the light and flexible active metal oxide-carbonized bacterial cellulose membrane composite material is obtained through gas precipitation. In the composite material prepared by the invention, the nickel oxide has higher dispersibility, can inhibit the agglomeration of active materials such as nickel oxide and the like in a three-dimensional structure of carbonized bacterial cellulose, and is suitable for the field of super capacitors.
Description
Technical Field
The invention belongs to the technical field of preparation of composite materials, and relates to a preparation method of an active metal oxide-carbonized bacterial cellulose electrode material.
Background
The bacterial cellulose is natural fiber produced through microbial fermentation, has excellent physical, chemical and mechanical properties such as biodegradability, good three-dimensional network structure, higher chemical purity, better mechanical strength and the like compared with artificially synthesized cellulose, and is generally applied to the industries such as electrochemistry, medicine, food and the like. The synthesis of bacterial cellulose only needs cheap raw materials, such as glucose, sucrose, waste biomass acidolysis solution and the like, and the raw materials are renewable resources, and the microbial synthesis efficiency is far higher than that of artificial synthesis, so that the method is a green preparation method, and the method becomes a research hotspot of novel biological materials. The three-dimensional net formed by the bacterial cellulose nano-fibers has a relatively uniform micron-sized porous structure, and the three-dimensional space effect of the three-dimensional net can promote the efficient transmission of substances in the three-dimensional net. The size effect of the nano-fiber can provide active sites for deposition of a plurality of substances, and a plurality of effective nano-active substances can be loaded on the surface of the fiber.
At present, the compounding of the bacterial cellulose and the metal oxide active substance is mostly carried out in solution, the appearance and the size of the active substance are difficult to be effectively controlled, and the energy density and the power density of the prepared composite material are lower. Lumin et al use a co-mixing precipitation method to load Fe on the surface of bacterial cellulose3O4The particles are applied to the adsorption of heavy metal cadmium ions (Lumin, Yonghui, Weidezhou, bacterial cellulose loaded with nano Fe3O4Preparation and adsorption of Cd2+Study (J)]Safety and environmental bulletin, 2011,11(5): 22-25). Leika et al used an in-situ growth method to compound nanogold with bacterial cellulose and tested the catalytic performance. However, in the composite material prepared by the above method, the metal particles are easy to agglomerate, and the size is not uniform (lei jia, qiu tianli, jiang wei. bacterial cellulose/nano gold composite film in-situ controllable preparation and catalytic performance research [ J]Non-ferrous metals: a smelting part 2016(9) and 42-47).
Disclosure of Invention
The invention provides a preparation method of an active metal oxide-carbonized bacterial cellulose electrode material, aiming at the problems that in the prior art, when metal active oxides are deposited in situ by carbonized bacterial cellulose, active substances are easy to agglomerate in a three-dimensional space structure, so that the electrochemical activity of a composite material is inhibited, and the like.
The technical scheme of the invention is as follows:
the preparation method of the active metal oxide-carbonized bacterial cellulose electrode material comprises the following steps of taking bacterial cellulose as a raw material, pre-fixing a three-dimensional structure of the cellulose through high-temperature calcination to obtain light and flexible carbonized bacterial cellulose, performing surface hydrophilic treatment by adopting a potentiostatic method, soaking a metal oxide precursor solution, volatilizing a solvent to uniformly distribute a metal oxide precursor on the surface of a fiber, introducing gas into a three-dimensional network structure of the fiber, and realizing efficient conversion of the metal oxide precursor to the metal oxide by adopting a gas precipitator to prepare the carbonized bacterial cellulose-based metal oxide composite material with high dispersibility, wherein the preparation method specifically comprises the following steps:
step 1, performing surface oxidation on carbonized bacterial cellulose by using a constant potential anodic oxidation method, wherein the oxidation potential is 2-5V, and the oxidation time is 100-300 s, so as to obtain hydrophilic flexible carbonized bacterial cellulose;
step 2, soaking the hydrophilic flexible carbonized bacterial cellulose in an ethanol solution of active metal nitrate, and removing ethanol after complete soaking to obtain active metal nitrate-carbonized bacterial cellulose;
and 3, heating ammonia water by adopting a gas precipitation method, and reacting the generated ammonia gas with the active metal nitrate on the surface of the carbonized bacterial cellulose fiber through the active metal nitrate-carbonized bacterial cellulose to obtain the flexible active metal oxide-carbonized bacterial cellulose electrode material.
Preferably, in the step 1, the carbonized bacterial cellulose is prepared by static culture and high-temperature calcination, and specifically, the bacterial cellulose membrane obtained by static culture is calcined at 700-1000 ℃.
Preferably, in the step 2, the soaking time is 1-2 h.
Preferably, in step 2, the active metal is nickel, iron, manganese or cobalt.
Preferably, in the step 2, the concentration of the ethanol solution of the active metal nitrate is 0.02-0.1M.
In the step 3, ammonia gas is used as a gas precipitator for the conversion of the metal nitrate to the metal oxide, and the temperature of a gas precipitation system is 110-130 ℃.
Compared with the prior art, the invention has the following advantages:
(1) the carbonized bacterial cellulose is formed by carbonizing natural fibers generated in a microbial fermentation process, the diameter size of the carbonized bacterial cellulose is smaller than 100nm, the carbonized bacterial cellulose belongs to nano-scale fibers, the size of the carbonized bacterial cellulose is only 1/10 of artificial synthetic fibers, a three-dimensional net formed by the nano-fibers has a relatively uniform micro-scale porous structure, a three-dimensional space effect can promote efficient transmission of substances in the carbonized bacterial cellulose, the size effect of the nano-fibers can provide active sites for deposition of a plurality of substances, the three-dimensional structure is fixed through high-temperature calcination, and convenience is provided for loading of nano-active substances on the surfaces of the fibers;
(2) the surface of the carbonized bacterial cellulose is subjected to hydrophilic treatment by adopting a constant potential anodic oxidation method, and the modified hydrophilic carbonized bacterial cellulose provides a better active site for the attachment of a metal oxide precursor;
(3) the active metal oxide-carbonized bacterial cellulose composite material prepared by oxidizing the active metal nitrate with ammonia gas has the advantages of light weight, flexibility and the like, the metal oxide has high dispersity, and the composite material has high capacity density, and is suitable for the fields of supercapacitors and the like.
Drawings
FIG. 1 is a flow chart of the preparation of the active metal oxide-carbonized bacterial cellulose electrode material of the present invention.
Fig. 2 is a flexible display of carbonized bacterial cellulose.
Fig. 3 is an XPS spectrum (a) of nickel oxide-carbonized bacterial cellulose, a narrow spectrum (b) of Ni element, a narrow spectrum (c) of carbon element, and a narrow spectrum (d) of oxygen element.
FIG. 4 is a transmission electron microscope photograph of nickel oxide-carbonized bacterial cellulose.
FIG. 5 is a charge/discharge curve diagram of carbonized bacterial cellulose and nickel oxide-carbonized bacterial cellulose under the condition of 0.2A/g.
Fig. 6 is an SEM image of the prepared nickel oxide-carbonized bacterial cellulose composite materials prepared in example 1(a), comparative example 1(b) and comparative example 2 (c).
Detailed Description
The present invention will be described in further detail with reference to the following examples and the accompanying drawings.
The carbonized bacterial cellulose adopted in the following embodiments of the invention is prepared by the following steps: adding glucose, disodium hydrogen phosphate, citric acid, yeast extract powder and peptone into water, dissolving, mixing uniformly, adjusting pH to 6.0, performing wet sterilization at 121 ℃ for 30min, inoculating seed liquid with an inoculum size of 10%, culturing for 48h to obtain a bacterial cellulose crude membrane, heating in 0.3% sodium hydroxide solution at 85 ℃ for 2h, washing with deionized water to neutrality to obtain a bacterial cellulose membrane, and freeze-drying for later use. And calcining the bacterial cellulose membrane at high temperature of 700-1000 ℃ in an inert atmosphere to obtain the flexible carbonized bacterial cellulose.
Example 1
Step 1, oxidizing the surface of the carbonized bacterial cellulose fiber by a constant potential anodic oxidation method, wherein the oxidation potential and the oxidation time are respectively 2V and 300s, and obtaining the hydrophilic flexible carbonized bacterial cellulose material.
And 2, soaking the hydrophilic flexible carbonized bacterial cellulose material in a 0.02M nickel nitrate solution for 2 hours, and then volatilizing ethanol at the temperature of 60 ℃ to obtain the nickel nitrate-carbonized bacterial cellulose material.
And 3, covering the flexible nickel nitrate-carbonized bacterial cellulose membrane material in a closed ammonia water beaker, enabling ammonia gas to permeate through the nickel nitrate-carbonized bacterial cellulose membrane at the temperature of 110 ℃, and enabling the ammonia gas to react with nickel nitrate on the surface of the carbonized bacterial cellulose fiber to obtain the flexible nickel oxide-carbonized bacterial cellulose material.
Example 2
Step 1, oxidizing the surface of the carbonized bacterial cellulose fiber by a constant potential anodic oxidation method, wherein the oxidation potential and the oxidation time are respectively 5V and 100s, and obtaining the hydrophilic flexible carbonized bacterial cellulose material.
And 2, soaking the hydrophilic flexible carbonized bacterial cellulose material in 0.05M nickel nitrate solution for 1h, and volatilizing ethanol at the temperature of 60 ℃ to obtain the nickel nitrate-carbonized bacterial cellulose material.
And 3, covering the flexible nickel nitrate-carbonized bacterial cellulose membrane material in a closed ammonia water beaker, enabling ammonia gas to permeate through the nickel nitrate-carbonized bacterial cellulose membrane at the temperature of 120 ℃, and enabling the ammonia gas to react with nickel nitrate on the surface of the carbonized bacterial cellulose fiber to obtain the flexible nickel oxide-carbonized bacterial cellulose material.
Example 3
Step 1, oxidizing the surface of the carbonized bacterial cellulose fiber by a constant potential anodic oxidation method, wherein the oxidation potential and the oxidation time are respectively 5V and 300s, and obtaining the hydrophilic flexible carbonized bacterial cellulose material.
And 2, soaking the hydrophilic flexible carbonized bacterial cellulose material in a 0.1M nickel nitrate solution for 1h, and volatilizing ethanol at the temperature of 60 ℃ to obtain the nickel nitrate-carbonized bacterial cellulose material.
And 3, covering the flexible nickel nitrate-carbonized bacterial cellulose membrane material in a closed ammonia water beaker, enabling ammonia gas to permeate through the nickel nitrate-carbonized bacterial cellulose membrane at the temperature of 130 ℃, and enabling the ammonia gas to react with nickel nitrate on the surface of the carbonized bacterial cellulose fiber to obtain the flexible nickel oxide-carbonized bacterial cellulose material.
Example 4
Step 1, oxidizing the surface of the carbonized bacterial cellulose fiber by a constant potential anodic oxidation method, wherein the oxidation potential and the oxidation time are respectively 5V and 300s, and obtaining the hydrophilic flexible carbonized bacterial cellulose material.
And 2, preparing, namely soaking the hydrophilic flexible carbonized bacterial cellulose material in a nickel nitrate solution with the concentration of 0.1M for 2h, and volatilizing ethanol at the temperature of 60 ℃ to obtain the nitrate-carbonized bacterial cellulose material.
And 3, covering the flexible nickel nitrate-carbonized bacterial cellulose membrane material in a closed ammonia water beaker, enabling ammonia gas to permeate through the nickel nitrate-carbonized bacterial cellulose membrane at the temperature of 130 ℃, and enabling the ammonia gas to react with nickel nitrate on the surface of the carbonized bacterial cellulose fiber to obtain the flexible nickel oxide-carbonized bacterial cellulose material.
The nickel oxide-carbonized bacterial cellulose material prepared in each example has better flexibility as shown in fig. 2. The XPS elemental analysis of the nickel oxide-carbonized bacterial cellulose composites obtained in the examples is shown in fig. 3, and the results show that C, O, Ni and trace N element are contained in the composites, wherein the O ═ C — O peak in C comes from electrochemical oxidation, and the Ni2p peak of nickel element almost completely matches the standard nickel element peak of analytically pure NiO. As shown in fig. 4, the transmission electron microscope image of the prepared nickel oxide-carbonized bacterial cellulose composite shows that the metal oxide is uniformly dispersed on the surface of the fiber. The charge-discharge curve of the supercapacitor assembled by the prepared carbonized bacterial cellulose and the nickel oxide-carbonized bacterial cellulose composite is shown in fig. 5, the charge-discharge curve of the carbonized bacterial cellulose is symmetrical and is in a linear triangular shape, and the charge-discharge curve shows that the carbonized bacterial cellulose has highly reversible electrochemical behavior. The charge/discharge curve of the nickel oxide-carbonized bacterial cellulose compound is asymmetric, which shows that the nickel oxide has better energy storage performance, the charge/discharge capacity of the compound is 307.1mAh, and the charge/discharge capacity of the carbonized bacterial cellulose is 100.9mAh, which shows that the charge/discharge capacity of the compound is higher.
Comparative example 1
This comparative example is essentially the same as example 1, except that the potentiostatic anodization process of step 1 was not carried out. The SEM image of the prepared material is shown in fig. 6 (b).
Comparative example 2
Different from the embodiment, the bacterial cellulose membrane is soaked in the nitrate ethanol solution, freeze-dried and then calcined at a high temperature of 800 ℃ to prepare the carbonized metal oxide-bacterial cellulose electrode material, and the SEM picture of the carbonized metal oxide-bacterial cellulose electrode material is shown in FIG. 6 (c).
FIG. 6 (a) is an SEM image (example) of an electrode material prepared by performing a constant potential anodizing operation; (b) SEM image of electrode material prepared without potentiostatic anodization (comparative example 1); (c) SEM image of electrode material prepared by soaking in metal nitrate and then freeze-drying and carbonizing (comparative example 2). As can be seen from the figure, the electrode material prepared by the method can maintain a three-dimensional network structure, metal oxide particles are uniformly loaded in fibers, while the electrode material prepared by constant potential anodic oxidation operation is not adopted.
Claims (7)
1. The preparation method of the active metal oxide-carbonized bacterial cellulose electrode material is characterized by comprising the following steps:
step 1, performing surface oxidation on carbonized bacterial cellulose by using a constant potential anodic oxidation method, wherein the oxidation potential is 2-5V, and the oxidation time is 100-300 s, so as to obtain hydrophilic flexible carbonized bacterial cellulose;
step 2, soaking the hydrophilic flexible carbonized bacterial cellulose in an ethanol solution of active metal nitrate, and removing ethanol after complete soaking to obtain active metal nitrate-carbonized bacterial cellulose;
and 3, heating ammonia water by adopting a gas precipitation method, and reacting the generated ammonia gas with the active metal nitrate on the surface of the carbonized bacterial cellulose fiber through the active metal nitrate-carbonized bacterial cellulose to obtain the flexible active metal oxide-carbonized bacterial cellulose electrode material.
2. The method according to claim 1, wherein in step 1, the carbonized bacterial cellulose is prepared by static culture and high-temperature calcination.
3. The preparation method according to claim 1 or 2, wherein in the step 1, the carbonized bacterial cellulose is prepared by calcining a bacterial cellulose membrane obtained by static culture at 700-1000 ℃.
4. The preparation method according to claim 1, wherein in the step 2, the soaking time is 1-2 h.
5. The method according to claim 1, wherein in step 2, the active metal is nickel, iron, manganese or cobalt.
6. The method according to claim 1, wherein in the step 2, the concentration of the ethanol solution of the active metal nitrate is 0.02-0.1M.
7. The preparation method according to claim 1, wherein in the step 3, ammonia gas is used as a gas precipitator for the conversion of the metal nitrate into the metal oxide, and the temperature of the gas precipitation system is 110-130 ℃.
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