CN110544590B - Nitrate-assisted synthesized nitrogen-doped nano carbon sheet and sodium storage application thereof - Google Patents
Nitrate-assisted synthesized nitrogen-doped nano carbon sheet and sodium storage application thereof Download PDFInfo
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- H—ELECTRICITY
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- 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
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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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
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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
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- H01M10/00—Secondary cells; Manufacture thereof
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- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The invention discloses a method for synthesizing a nitrogen-doped nano carbon sheet material by using nitrate as an auxiliary material. The method uses carrageenin which is an extract of red algae as a precursor and alkali metal nitrate (LiNO)3，NaNO3，KNO3，RbNO3，CsNO3) Is used as an activating agent and a nitrogen source and is realized by high-temperature calcination. Firstly, dissolving carrageenan in deionized water at high temperature, then adding a certain amount of alkali metal nitrate aqueous solution, fully mixing, naturally cooling to room temperature to form colloid, and then carrying out freeze drying to thoroughly remove moisture, thus obtaining the carrageenan-alkali metal nitrate precursor. And putting the precursor into a tubular furnace, heating to an optimal temperature at a certain heating rate under the protection of inert gas, preserving heat for a certain time for carbonization, and carrying out acid pickling, washing and drying to obtain the nitrogen-doped porous nano carbon sheet. The method realizes the regulation and control of carbon micro-morphology, element content and the like by controlling process conditions, obtains the nitrogen-doped carbon with a lamellar structure, a large specific surface area and abundant nitrogen elements, and can be used for sodium storage electrode materials.
Description
Technical Field
The invention belongs to the field of electrochemical energy storage, and provides a method for simultaneously introducing nitrogen atoms into the surface of carbon and modifying the microscopic morphology of the carbon to prepare a nitrogen-doped nano carbon sheet, and application of the nitrogen-doped nano carbon sheet as a negative electrode material of a sodium ion battery and a mixed sodium ion capacitor.
Background
Due to severe environmental pollution caused by the overuse of coal and oil and the increasing global energy consumption, energy storage devices having both high energy density and high power density have attracted much attention. Currently, lithium ion batteries are the primary energy storage devices due to their advantages of high energy density and high operating voltage. However, due to the use of a large amount of lithium ion batteries, lithium resources in the world face the current situation of gradual depletion, and energy storage devices rich in resources are urgently needed to be found.
Because sodium in nature has abundant resources, wide distribution and low price, an energy storage device based on sodium ions becomes one of important candidates of an energy storage system. Energy storage devices based on sodium ions mainly include sodium ion batteries and hybrid sodium ion capacitors. Sodium ion batteries, like lithium ion batteries, have a very high energy density, but a low power density. To compensate for this drawback, hybrid sodium ion capacitors with both high energy density and high power density have been developed. A hybrid sodium ion capacitor, i.e., a device employing a capacitor-type positive electrode and a battery-type negative electrode. In such a hybrid capacitor, charge enters the negative electrode by intercalation, similar to a battery; meanwhile, charges enter the anode through reversible adsorption, and the adsorption is beneficial to improving the rate performance compared with insertion, similar to a super capacitor. Because the specific capacity of the negative electrode is obviously larger than that of the positive electrode, the mass ratio of the active substances of the positive electrode and the negative electrode needs to be regulated and controlled to realize the maximum energy density of the device. The invention realizes the highest energy density of the sodium ion capacitor by fixing the loading capacity of the cathode active material and changing the loading capacity of the anode active material to find the optimal mass ratio of the anode active material and the cathode active material.
Electrode materials are the most important part of energy storage devices, and mainly comprise carbon materials, metal oxides, alloys, metal sulfides and the like. Carbon materials have low cost, high conductivity and cycling stability, and have become the main electrode materials of energy storage devices at present. In the carbon material, the high specific surface area, the hierarchical pore structure and the lamellar graphene structure can be beneficial to the transmission and adsorption of electrolyte ions, so that high electrochemical performance is obtained. In addition, heterogeneous heteroatoms such as nitrogen, sulfur, phosphorus and other elements introduced into the carbon material can generate defects on the surface of the carbon material, and the defects and electrolyte ions generate oxidation-reduction reaction, so that the electrochemical energy storage capacity of the carbon material is greatly improved. Suitable precursors and activators are of utmost importance in order to obtain heteroatom-doped porous sheet carbon materials. According to the invention, the alkali metal nitrate is used as an activating agent and a nitrogen source, so that the morphology of the carbon material is regulated, and the nitrogen atoms are introduced into the carbon skeleton, thereby realizing excellent sodium storage performance.
Disclosure of Invention
The invention aims to obtain a nitrogen-doped carbon material with a higher specific surface area and a sheet structure by a nitrate-assisted synthesis method, wherein the nitrogen-doped carbon material adopts carrageenan which is an extract of marine organism red algae as a raw material, the prepared carbon material has excellent electrochemical performance, and the carbon material is applied to a sodium ion battery and a mixed sodium ion capacitor to achieve the highest energy density by adjusting the mass ratio of active substances of a positive electrode and a negative electrode of the sodium ion capacitor.
The technical scheme adopted by the invention for solving the technical problem is as follows:
(1) adding a certain amount of carrageenan powder into deionized water with the mass of 40 times, completely dissolving in an oil bath at 80 ℃, keeping the temperature constant, and adding a certain amount of alkali metal nitrate activator aqueous solution, wherein the mass ratio of the carrageenan to the activator is 10: 1-1: 1. Fully stirring to uniformly mix the carrageenan solution and the activator solution, naturally cooling to room temperature to form a carrageenan-alkali metal nitrate colloid, and then putting the colloid into a freeze dryer for drying so as to completely remove moisture, thereby obtaining a substance labeled crop material A;
(2) and moving the material A into a tubular furnace, heating to 400-1200 ℃ at a heating rate of 3 ℃/min under the protection of inert gas, and preserving heat for 0-8 h to ensure that the material A is fully carbonized and activated and the introduction of nitrogen element is completed. Continuously stirring the carbonized and activated sample in 2mol/L diluted hydrochloric acid for 24 hours to remove impurities, then carrying out suction filtration by using a large amount of deionized water, drying the sample, and then recording the dried sample as a material B;
(3) the material B is applied to electrode materials of a sodium ion battery and a mixed sodium ion capacitor, and the maximized energy density is obtained by adjusting the mass ratio of the positive electrode active substance to the negative electrode active substance of the sodium ion capacitor.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention uses the extract of the marine organism-red algae as the raw material, has wide source and is beneficial to large-scale preparation. Meanwhile, the carrageenan contains a small amount of sulfur element, so that the self-doping of hetero atoms is realized. In addition, the unique double-helix structure characteristic of the carrageenan determines that the carrageenan is beneficial to element doping during carbonization;
(2) the invention uses alkali metal nitrate as an activator, and the alkali metal nitrate also plays a role of a nitrogen source. Under the action of alkali metal nitrate, carrageenan is carbonized and activated at high temperature to obtain the porous flaky nanocarbon appearance, and meanwhile, a large amount of nitrogen elements are successfully introduced to be matched with sulfur elements contained in the carrageenan, so that the electrochemical performance of the carrageenan is improved;
(3) the prepared nitrogen-doped nano carbon sheet is applied to electrode materials of sodium ion batteries and mixed sodium ion capacitors, and the sheet porous structure of the nitrogen-doped nano carbon sheet is beneficial to the rapid transmission of electrolyte, so that the nitrogen-doped nano carbon sheet shows high specific capacity and excellent rate capability when applied to electrodes of the sodium ion batteries. The introduced nitrogen element and the internal sulfur element are subjected to redox reaction with sodium ions to generate pseudo capacitance, so that the sodium ion battery has higher specific capacity. In addition, the quality of the anode of the mixed sodium ion capacitor is regulated and controlled, so that a device with high energy density and power density is obtained.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) photograph of the nitrogen-doped nanocarbon plate of example 1.
Fig. 2 is a Scanning Electron Microscope (SEM) photograph of the nitrogen-doped nanocarbon plate of example 2.
FIG. 3 is a Scanning Electron Microscope (SEM) photograph of the nitrogen-doped nanocarbon plate of example 3.
FIG. 4 is a Transmission Electron Microscope (TEM) photograph of the nitrogen-doped nanocarbon plate of example 1.
FIG. 5 is a Transmission Electron Microscope (TEM) photograph of the nitrogen-doped nanocarbon plate of example 2.
FIG. 6 is a Transmission Electron Microscope (TEM) photograph of a nitrogen-doped nanocarbon plate of example 3.
Fig. 7 is a capacity plot for the assembled sodium ion battery of example 4 at different current densities.
FIG. 8 shows the assembled sodium ion battery of example 4 at 2A g-1Current density of 500 cycles.
FIG. 9 is a plot of cyclic voltammograms of the assembled hybrid sodium ion capacitor of example 5 at a scan rate of 10 mV/s.
FIG. 10 shows the assembled hybrid sodium ion capacitor of example 5 at 1A g-1Constant current charge and discharge curve diagram under the current density.
Figure 11 is a graph of energy density versus power density for different current densities for the assembled hybrid sodium ion capacitor of example 5.
Detailed Description
The present invention is illustrated by way of the following specific examples, which are not intended to be limiting.
Example 1
(1) Accurately weighing 2g k type carrageenan powder, adding into a beaker filled with 80ml of deionized water, then heating in a constant temperature oil bath at 80 ℃, and continuously stirring until the carrageenan is completely dissolved to form a viscous carrageenan solution which is marked as solution A;
(2) weighing 1.34 g KNO3Powder, dissolved in 15ml deionized water, and recorded as solution B;
(3) solution B was added dropwise to solution a under an oil bath at 80 ℃. And continuously stirring the mixed solution for 5min to make KNO3The dispersion is uniform in carrageenan solution. Then naturally cooling to room temperature, and using carrageenan-KNO3The solution forms a colloid;
(4) putting the colloid into a freeze dryer for drying for 100 h to completely remove water;
(5) the dried sample was placed in a tube furnace at 50 ml/min N2Heating to 600 ℃ at the speed of 3 ℃/min under the protection of atmosphere, and preserving heat for 1h at the temperature;
(6) after naturally cooling to room temperature, putting the product into 200ml of 2M dilute hydrochloric acid, and washing for 24 hours on a magnetic stirrer;
(7) thoroughly washing with deionized water, filtering, and drying in an oven at 80 ℃ for 12 h to obtain the nitrogen-doped nano carbon sheet.
Example 2: the method of this example is substantially the same as example 1, except that: replacement of activator with NaNO3。
Example 3: the method of this example is substantially the same as example 1, except that: replacement of activator with LiNO3。
Example 4
(1) Mixing the nitrogen-doped nano carbon sheet prepared in the embodiment 1-3 with conductive carbon black and PVDF binder in a mass ratio of 75:15:10, adding a proper amount of 1-methyl-2-pyrrolidone solution, and fully grinding to form uniform liquid;
(2) uniformly coating the liquid on a copper foil, drying the copper foil in an oven at 80 ℃ for 12 hours, and then cutting the copper foil into an electrode wafer on a slicing machine;
(3) assembling a sodium ion half cell in a glove box filled with argon, using the prepared electrode slice as a negative electrode, a sodium slice as a positive electrode, a sodium perchlorate solution as electrolyte and a polyethylene film as a diaphragm;
(4) and (4) carrying out performance test on the assembled sodium ion half-cell by using an electrochemical workstation, wherein the test result is shown in figures 7-8.
As can be seen from FIG. 7, the samples carbonized-activated carrageenan using three activators at a lower current density of 50mA g-1 The highest discharge specific capacity can reach 410 mAh g-1The capacity values of examples 1 and 2 decayed less as the current density increased, even at a high current density of 10A g-1 Next, the specific capacity of example 1 was still 130 mAh g-1 About, the specific capacity of example 2 was still maintained at 100 mAh g-1. The difference is that: example 3 the capacity fade at high current densities was severe at 10A g-1It has only about 16 mAh g-1The specific capacity of (A). This indicates that lithium nitrate has a lower activating capacity than sodium nitrate and potassium nitrate. As can be seen from fig. 8, at 2A g-1The capacity retention rate of the sodium ion half-cell prepared by the sample of the example 1 after 500 cycles of charge and discharge is about 74%, the capacity loss is mainly concentrated in the first 20 cycles, and the specific capacity and the change trend of the example 2 are basically the same as those of the example 1. The sodium ion half cell prepared from the sample of example 3 had a capacity retention of about 70% after 500 cycles of cycling, and the capacity decayed throughout the cycling. It is clear that both example 1 and example 2 have significantly higher specific capacities during cycling than example 3.
Example 5
(1) Mixing the prepared nitrogen-doped nano carbon sheet, conductive carbon black and PVDF binder according to the mass ratio of 75:15:10, adding a proper amount of 1-methyl-2-pyrrolidone solution, and fully grinding to form uniform liquid. Uniformly coating the liquid on a copper foil, drying the copper foil in an oven at 80 ℃ for 12 hours, and then cutting the copper foil into an electrode wafer on a slicing machine;
(2) a sodium ion half cell was assembled with this electrode sheet according to the method of example 4. Pre-charging the assembled sodium ion half-cell on an electrochemical workstation for 3 cycles to fully activate active substances, and after the pre-charging and the pre-discharging are completed, disassembling the cell in a glove box and taking out an electrode plate for later use;
(3) mixing methyl cellulose, KOH and NaHCO3Uniformly mixing the components in a mass ratio of 1:2:10, carbonizing and activating the components at 800 ℃ under the protection of inert gas, preserving heat for 4 hours, washing the products with dilute hydrochloric acid and deionized water respectively, and drying the products to obtain the three-dimensional porous nano carbon with a sheet structure and a very high specific surface area (2182 m)2 g-1) These characteristics determine that it possesses better electrochemical performance;
(4) mixing three-dimensional porous nano carbon, conductive carbon black and PVDF binder according to a mass ratio of 75:15:10, adding a proper amount of 1-methyl-2-pyrrolidone solution, and fully grinding to form uniform liquid. Uniformly coating the liquid on an aluminum foil, drying the aluminum foil in an oven at the temperature of 80 ℃ for 12 hours, and then cutting the aluminum foil into electrode wafers on a slicing machine;
(5) a mixed sodium ion capacitor is assembled in the glove box. An electrode plate which is made of a nitrogen-doped nano carbon sheet and is subjected to pre-charging and pre-discharging for 3 cycles is used as a negative electrode, an electrode plate which is made of three-dimensional porous nano carbon is used as a positive electrode, a sodium perchlorate solution is used as an electrolyte, and a polyethylene film is used as a diaphragm. In order to enable the mixed sodium ion capacitor to achieve the optimal energy-power density combination, the mass ratio of the nitrogen-doped nano carbon sheet to the three-dimensional porous nano carbon is adjusted to prepare various mixed sodium ion capacitors. Marking the mixed sodium ion battery according to the mass ratio of the nitrogen-doped nano carbon sheet to the three-dimensional porous nano carbon, such as: 1-2 represents that the mass ratio of the nitrogen-doped nano carbon sheet to the three-dimensional porous nano carbon is 1: 2;
(6) the prepared mixed sodium ion capacitor is tested by an electrochemical workstation, and the test results are shown in fig. 9-11.
As can be seen from FIG. 9, the cycling of the assembled hybrid sodium ion capacitor of example 5 at a scan rate of 10mV/sThe voltammograms (CV) resemble rectangles, indicating that these hybrid sodium ion capacitors have double layer capacitance properties. Since the CV curve obtained here is based on the total mass of the positive and negative electrode active materials, it is apparent that the CV area of the 1-2 capacitor is the largest, indicating that it has the highest specific mass capacity. As can be seen from fig. 10, the assembled hybrid sodium ion capacitor of example 5 is at 1A g-1 The constant current charging and discharging curve under the current density of the transformer is basically in a symmetrical triangle, and the high coulombic efficiency and the long discharging time are proved.
The performance of a hybrid sodium ion capacitor is generally evaluated by an energy-power density combination, which is calculated based on the following formula:
E=P×t；
P= V ave ×I/m；
V ave =(V max +V min )/2。
twhich represents the time of the discharge, is,Iwhich is representative of the current of the discharge,mrepresents the total mass of active material of the positive and negative electrodes,V max andV min respectively representing a discharge start voltage and an end voltage. It can be seen from fig. 11 that the assembled hybrid sodium ion capacitor of example 5 has an excellent energy-power density combination. In particular 1-2 capacitors, at a power density of 329W kg-1 It appeared at 110.8 Wh kg-1The energy density of (1) even at 9312W kg-1Still exhibits 46.6 Wh kg at the power density of-1The energy density of (2) indicates that it combines high energy density and power density.
Claims (4)
1. The nitrate-assisted method for synthesizing the nitrogen-doped nano carbon sheet is characterized by comprising the following steps of:
(1) mixing, namely adding hydrophilic carrageenan powder extracted from red algae plants into hot water of 80 ℃, stirring until the carrageenan is completely dissolved, adding a solution in which a metal nitrate activator is dissolved, continuously stirring for a certain time, and naturally cooling to room temperature to form colloid; (2) drying, namely freeze-drying the colloid for a period of time to completely remove water; (3) carbonizing, namely putting the dried sample into a tubular furnace, heating and keeping under the protection of inert gas to fully carbonize and activate the sample; (4) cleaning: and stirring the activated sample in 200ml of 2M diluted hydrochloric acid for 24 hours, then carrying out suction filtration by using a large amount of deionized water until the sample is neutral, and drying the sample in an oven at the temperature of 80 ℃ to obtain the nitrogen-doped porous nano carbon sheet.
2. The method for synthesizing the nitrogen-doped nanocarbon plate with the assistance of the nitrate according to claim 1, is characterized in that: in the step (1), the precursor of the red algae plant extract is as follows:ka carrageenan-type food additive, which is prepared from carrageenan,ia carrageenan-type food additive, which is prepared from carrageenan,λthe carrageenin is characterized in that the metal nitrate with the functions of the activator and the nitrogen source in the step (1) is LiNO3，NaNO3，KNO3，RbNO3Or CsNO3And regulating the mass ratio of the precursor to the activator to be 10: 1-1: 1.
3. The method for synthesizing the nitrogen-doped nanocarbon plate with the assistance of the nitrate according to claim 1, is characterized in that: in the step (3), the temperature of carbonization and activation is 400-1200 ℃, and the heating rate is 1-10 ℃ for min-1And the heat preservation time is 0-8 h.
4. The nitrate-assisted synthesis method of nitrogen-doped nanocarbon plates according to any one of claims 1 to 3, wherein: the nitrogen-doped nano carbon sheet material can be applied to electrode materials of sodium ion batteries and mixed sodium ion capacitors.
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| CN105110314A (en) * | 2015-07-28 | 2015-12-02 | 大连理工大学 | Metal oxide hollow nanometer particle-embedded nitrogen-doped nanometer foamy carbon synthesis method |
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