CN113644228A - Potassium ion battery carbon-nitrogen-based polymer negative electrode material and preparation method and application thereof - Google Patents
Potassium ion battery carbon-nitrogen-based polymer negative electrode material and preparation method and application thereof Download PDFInfo
- Publication number
- CN113644228A CN113644228A CN202110923488.5A CN202110923488A CN113644228A CN 113644228 A CN113644228 A CN 113644228A CN 202110923488 A CN202110923488 A CN 202110923488A CN 113644228 A CN113644228 A CN 113644228A
- Authority
- CN
- China
- Prior art keywords
- nitrogen
- carbon
- ion battery
- based polymer
- potassium ion
- 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.)
- Granted
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/137—Electrodes based on electro-active polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1399—Processes of manufacture of electrodes based on electro-active polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a carbon-nitrogen-based polymer negative electrode material of a potassium ion battery, and a preparation method and application thereof. The preparation method comprises the following steps: using hexa-aminobenzene tri-hydrochloride and cyclohexadecanone octahydrate as monomers, polymerizing the monomer solution through acid catalytic condensation reaction under the protection of nitrogen or inert gas and under the heating condition to prepare the carbon-nitrogen-based polymer, and then performing low-temperature heat treatment under the protection of nitrogen or inert gas to obtain the carbon-nitrogen-based polymer cathode material of the potassium ion battery. The room temperature conductivity of the carbon-nitrogen-based polymer negative electrode material is improved by 2 orders of magnitude and reaches 2.82×10‑5S/cm; in the application process of preparing the electrode, only a small amount of conductive agent (less than or equal to 10%) needs to be added; the prepared potassium ion battery cathode can obtain 329mAh g‑1The product has good cycle performance, and the capacity retention rate is 99.5 percent when the product is cycled for 120 times under the condition of 150 mA/g.
Description
Technical Field
The invention belongs to the technical field of potassium ion battery materials, and particularly relates to a carbon-nitrogen-based polymer negative electrode material of a potassium ion battery, and a preparation method and application thereof.
Background
The shortage of fossil energy and the pollution caused by the massive combustion of the fossil energy are increasingly paid attention to by people. The development and utilization of the conversion and storage technology of clean energy to realize the replacement of fossil energy by clean energy becomes an important way to cope with sharp climate deterioration and severe air pollution. The development of secondary battery technology with abundant resources and low cost has very important significance; especially, under the background of the great and long-term goal of realizing 'carbon neutralization' proposed by the nation, the research and development of secondary battery technology with abundant resources, low cost and excellent performance is more important for realizing the replacement of fossil energy by electric energy. The existing lithium ion battery plays an important role in a plurality of fields, but the natural lithium resource is limited (lithium only accounts for 0.0017 percent of the total amount of the earth shell elements), and the resource distribution is uneven, so that the development of a resource-rich secondary battery system is urgently needed.
The potassium ion battery has the advantages of rich potassium resources (potassium accounts for 1.58 percent of the total amount of the shell elements), low cost, high energy density and the like, and has important requirements in a plurality of fields, particularly the large-scale energy storage field. However, lithium ions with a smaller radius than lithium ions with a smaller radius
Potassium ion
The radius of the ions is much larger, meanwhile, the mass of potassium ions is heavier than that of lithium ions, and the electrode material is embedded to cause larger volume expansion, thereby influencing the transport dynamics and the electrode cycling stability. Carbon-based materials show a good application prospect in terms of the negative electrode, but the theoretical capacity of the carbon-based materials is low. For example, commercial graphite can form intercalation compounds with potassium ions to achieve potassium ion storage, although its theoretical potassium storage capacity is only 279mAh/g, and the specific capacity in practical applications is typically less than 250 mAh/g. In addition, because the radius of potassium ions is far larger than that of lithium ions, the potassium ions are embedded into the electrode material and have larger volumeThe expansion causes damage to the electrode structure and is easy to cause rapid attenuation of the specific capacity of potassium storage of the electrode, so that the development of a potassium ion battery cathode material with high specific capacity and stable circulation is very necessary.
Most of the reported potassium ion batteries are inorganic electrode materials, and the organic polymer type is still less. Compared with inorganic cathode materials, the organic polymer electrode material has unique advantages: firstly, the polymer electrode material (the main components are C, N, O and H) has strong resource sustainability and does not contain toxic elements. Secondly, the polymer has stronger designability, and on one hand, a specific electrochemical active unit can be accessed into a polymer network, so that an electrode material with rich storage activity is obtained; on the other hand, the structure has larger controllable space in the aspect of morphology, and samples with different dimensions and different morphologies are easily synthesized according to requirements, so that better functionalization is realized. In addition, compared with a small-molecule organic electrode, the organic polymer also effectively avoids dissolving in the electrolyte, so that better circulation stability can be kept. However, the practical application of organic electrodes still needs to solve some problems, on one hand, how to design polymers with activity of storing potassium ions; secondly, how to improve the room-temperature conductivity of the polymer, thereby effectively releasing the potassium storage potential of the polymer and reducing the use of conductive agent components; and how to ensure the stability of the electrode material. Roman R.Kapaev et al reported a carbon-nitrogen based polymer as a potassium storage positive electrode material in 2019 (reference: J.Mater.chem.A., 2019,7, 22596--1. However, because the conductivity is poor, 40% of conductive agent needs to be added in the electrode preparation process, and because the conductive agent is not an active substance for storing potassium, the use of a large proportion of conductive agent can cause the reduction of the specific energy of the battery, which is not beneficial to the practical application of the device. In addition, the carbon-nitrogen-based polymer as a potassium storage negative electrode material is not reported in a public way at present.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide a carbon-nitrogen-based polymer negative electrode material of a potassium ion battery.
The invention also provides a preparation method of the carbon-nitrogen-based polymer negative electrode material of the potassium ion battery.
The invention also provides application of the carbon-nitrogen-based polymer negative electrode material of the potassium ion battery.
The purpose of the invention is realized by the following technical scheme:
the preparation method of the carbon-nitrogen-based polymer negative electrode material of the potassium ion battery comprises the following steps: using hexa-aminobenzene tri-hydrochloride and cyclohexadene octahydrate as monomers, polymerizing a monomer solution through an acid-catalyzed condensation reaction under the protection of nitrogen or inert gas and under a heating condition to obtain a carbon-nitrogen-based polymer, and then performing low-temperature heat treatment under the protection of nitrogen or inert gas to obtain the carbon-nitrogen-based polymer cathode material of the potassium ion battery.
According to the invention, a carbon-nitrogen-based polymer material is synthesized, and the room-temperature conductivity of the polymer negative electrode material can be improved by 2 orders of magnitude to 2.82 multiplied by 10 by carrying out simple low-temperature (300-500 ℃) heat treatment on the synthesized carbon-nitrogen-based polymer material-5S/cm; in the application process of preparing the electrode, only a small amount of conductive agent (less than or equal to 10%) needs to be added; the prepared potassium ion battery cathode can obtain 329mAh g-1The reversible specific capacity of the composite material is high, the composite material has good cycle performance, the capacity retention rate reaches 99.5 percent after the composite material is cycled for 120 times under the condition of 150mA/g, and the composite material is superior to the prior art.
The molar ratio of the hexaaminobenzene trihydrochloride to the cyclohexanehexone octahydrate is 1: 0.5-1.5, preferably 1: 1.
the heating conditions (i.e. the temperature of the acid-catalyzed condensation reaction) are 100-200 ℃, preferably 110-190 ℃, such as 120 ℃, 180 ℃ and the like; the time of the acid-catalyzed condensation reaction is 2-100 h, preferably 24-72 h, such as 24h, 36h, 72h and the like.
The solvent used in the monomer solution is at least one of N-methyl pyrrolidone, mesitylene and 1, 4-dioxane.
The acid catalyst for the acid-catalyzed condensation reaction is at least one of sulfuric acid and acetic acid. The mass fraction of sulfuric acid is preferably 95% to 98%.
The temperature of the low-temperature heat treatment is 300-500 ℃, and preferably 350 ℃; the heating rate is 5 ℃/min; the heat preservation time is 0.5-10 h, preferably 2 h.
The inert atmosphere is one of argon and helium.
Specifically, the preparation method of the carbon-nitrogen-based polymer negative electrode material of the potassium ion battery comprises the following steps:
a. adding hexa-aminobenzene tri-hydrochloride and cyclohexadecanone octahydrate monomers into a reaction vessel, introducing nitrogen or inert gas for protection, placing the mixture into an ice water bath, then adding a solvent, then adding an acid catalyst, stirring uniformly, and heating to a reaction temperature for carrying out acid catalytic condensation reaction;
b. after the reaction is finished, cooling to normal temperature, separating and drying to obtain a carbon-nitrogen-based polymer; and carrying out low-temperature heat treatment on the obtained carbon-nitrogen-based polymer under the protection of nitrogen or inert gas to obtain the carbon-nitrogen-based polymer negative electrode material of the potassium ion battery.
The carbon-nitrogen-based polymer negative electrode material of the potassium ion battery has a graphite-like layered conjugated structure, is granular, and has a particle size of 0.1-5 microns, preferably 0.2-1 micron.
The carbon-nitrogen-based polymer negative electrode material of the potassium ion battery can be used for preparing a polymer negative electrode of the potassium ion battery.
The invention also provides a preparation method of the potassium ion battery polymer negative electrode, which comprises the following steps: the potassium ion battery carbon nitrogen-based polymer negative electrode material is used as an active substance, is stirred with a binder and a conductive agent, is coated on a current collector, and is dried in vacuum to obtain the potassium ion battery polymer negative electrode.
Wherein the conductive agent may be at least one of Ketjen Black (KB), Super P, and Acetylene Black (AB).
The binder may be at least one of carboxymethyl cellulose (CMC), Styrene Butadiene Rubber (SBR), polyacrylic acid (PAA), and sodium alginate.
The current collector is an aluminum foil or a copper foil.
The mass ratio of the active substance to the conductive agent to the binder is (95-80): (0-10): (5-10), preferably, the mass ratio is (80-90): (5-10): (5-10), such as 85: 10: 5, or 80: 10: 10, etc.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the invention firstly proposes that the conductivity of the polymer cathode material is improved by two orders of magnitude by carrying out simple low-temperature (300-500 ℃) heat treatment on the carbon-nitrogen-based polymer with lower conductivity, and the room-temperature conductivity of the original polymer is 3.17 multiplied by 10-7The S/cm is increased to 2.82 multiplied by 10 of the carbon nitrogen-based polymer negative electrode material of the potassium ion battery-5S/cm。
The polymer cathode of the potassium ion battery provided by the invention needs to be added with the conductive agent not more than 10%, and the content of the carbon nitrogen-based polymer cathode material of the potassium ion battery as the active substance is not less than 80%, so that the use of a large amount of conductive agent is avoided, and the proportion of the active substance is improved, thereby being beneficial to improving the integral energy density of the cathode electrode part.
The potassium ion battery polymer cathode provided by the invention has excellent electrochemical performance, and can obtain high reversible specific capacity of 329mAh/g under the current density of 30 mA/g; meanwhile, the high-capacity lithium ion battery has excellent cycle performance, and the capacity retention rate is 99.5 percent when the battery is cycled for 120 circles under the condition of 150mA/g current density. Therefore, the invention effectively solves the problem that the polymer cathode of the existing potassium ion battery has poor conductivity and poor electrochemical performance.
Drawings
FIG. 1 is a schematic diagram of the preparation of a carbon-nitrogen-based polymer negative electrode material of a potassium ion battery.
FIG. 2 shows a carbon-nitrogen-based polymer negative electrode material C of the potassium ion battery in example 1xXRD pattern of N-350.
FIG. 3 shows a carbon-nitrogen-based polymer negative electrode material C of the potassium ion battery in example 1xN-350 and Polymer negative electrode Material C in comparative example 1xRaman plot of N.
FIG. 4 shows a carbon-nitrogen-based polymer negative electrode material C of the potassium ion battery in example 1xN-350 scanning electron microscopy and elemental analysis plots.
Fig. 5 is a charge and discharge graph of the potassium ion batteries prepared in example 1 and example 2 and comparative example 1 and comparative example 2.
FIG. 6 is a graph showing cycle performance of the potassium ion batteries manufactured in example 1 and comparative example 1 at a current density of 150 mA/g.
Fig. 7 is a charge and discharge graph of the potassium ion batteries prepared in example 3 and comparative example 3.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto. The raw materials related to the invention can be directly purchased from the market. For process parameters not specifically noted, reference may be made to conventional techniques. The mass fraction of concentrated sulfuric acid used in the examples was 98%.
Example 1
Preparation of carbon-nitrogen-based polymer negative electrode material of potassium ion battery
a. Adding hexa-aminobenzene trihydrochloride (1g, 3.6mmol) and cyclohexanone octahydrate (1.124g, 3.6mmol) monomers into a round-bottom three-neck flask, introducing argon gas for protection, placing the flask in an ice-water bath, then adding 40mL of N-methylpyrrolidone, then adding concentrated sulfuric acid (40 mu L), stirring uniformly, continuing stirring for 2h at room temperature, then transferring the flask into an oil bath at 180 ℃ and reacting for 72 h.
b. After the reaction is finished, cooling to normal temperature, separating and drying to obtain a carbon-nitrogen-based polymer, treating the obtained product for 2h at 350 ℃ under the protection of argon to obtain the carbon-nitrogen-based polymer cathode material (C) of the potassium ion batteryxN-350)。
c. The obtained carbon nitrogen-based polymer negative electrode material sample C of the potassium ion batteryxN-350 powder compacts were tested for electrical conductivity using a powder conductivity meter.
Conductivity test of carbon-nitrogen-based polymer negative electrode material of potassium ion battery
Characterized by that, the potassium ion battery carbon nitrogen base polymer negative pole material sample CxThe room-temperature conductivity of N-350 was 2.82X 10-5S cm-1。
FIG. 1 shows a carbon-nitrogen-based polymer negative electrode of a potassium ion battery in example 1Material CxSchematic preparation of N-350.
FIG. 2 shows a carbon-nitrogen-based polymer negative electrode material C of the potassium ion battery in example 1xXRD pattern of N-350. As can be seen from the figure, it has a strong peak at 27.2 ℃, and proves that it forms a graphite-like layered conjugated structure with the interlayer spacing of
Carbon-nitrogen-based polymer negative electrode material C of potassium ion battery in example 1xThe raman plot of N-350 is shown in fig. 3. From this figure, the polymer negative electrode material CxN-350 at 1359cm-1And 1515cm-1Two oscillation peaks appeared, of which 1515cm-1And C atom sp2The hybridized in-plane stretching vibration characteristic peaks are close to each other, and the graphite-like conjugated structure is proved.
FIG. 4 shows a carbon-nitrogen-based polymer negative electrode material C of the potassium ion battery in example 1xN-350 scanning electron microscope and element analysis chart to obtain the carbon-nitrogen-based polymer negative electrode material C of the potassium ion batteryxN-350 is granular, the granularity is 0.2-1 mu m, and the atomic molar ratio of carbon to nitrogen is 2.1: 1.
preparation of potassium ion battery negative pole piece and battery assembly
The embodiment provides a method for preparing a polymer negative pole piece of a potassium ion battery and assembling the battery, which comprises the following steps:
a. mixing the obtained carbon-nitrogen-based polymer negative electrode material of the potassium ion battery, a conductive agent Super P and a binder according to a mass ratio of 80: 10: 10, mixing, wherein the binder is sodium carboxymethyl cellulose: the mass of the styrene butadiene rubber is 1: 1, dripping a few drops of deionized water, mechanically stirring to form uniform slurry, coating the slurry on an aluminum foil, and drying at 80 ℃ for 10 hours under a vacuum condition to obtain the dried electrode plate.
b. And cutting the dried electrode plate into a circular electrode plate with the diameter of 10 nm.
c. The round electrode plate obtained by the preparation is used as a negative electrode, the glass fiber diaphragm is used as a diaphragm, and the diaphragm and the metal potassium sheet are assembled into a button cell, the model of the button cell is CR2032, the electrolyte is KFSI dissolved in DME electrolyte, wherein the KFSI: DME 1: 2.5 (molar ratio).
Fourth, battery test
The battery obtained in the embodiment was subjected to constant current charge and discharge test using a battery charge and discharge tester with a test voltage interval of 0.01-3V and a test temperature of 25 ℃.
The charge/discharge curve of the potassium ion battery of example 1 at 30mA/g is shown in FIG. 5, and it can be seen that the capacity is as high as 329 mAh/g.
The cycle performance of the potassium ion battery in example 1 at a current density of 150mAh/g is shown in FIG. 6. Therefore, the prepared polymer negative pole piece has good cycle performance, 199mAh/g can be obtained under the current density of 150mA/g, after 120 cycles, the specific capacity is 198mAh/g, and the capacity retention rate is close to 100%.
Example 2
Preparation of carbon-nitrogen-based polymer negative electrode material of potassium ion battery
a. Adding hexa-aminobenzene trihydrochloride (1g, 3.6mmol) and cyclohexanone octahydrate (1.124g, 3.6mmol) monomers into a round bottom three-neck flask, introducing argon gas for protection, placing the flask into an ice-water bath, then adding 40mL of N-methylpyrrolidone, then adding 98 mass percent of concentrated sulfuric acid (40 mu L), stirring uniformly, continuing stirring at room temperature for 2h, then transferring the flask into an oil bath at 160 ℃ and reacting for 12 h.
b. After the reaction is finished, cooling to normal temperature, separating and drying to obtain a carbon-nitrogen-based polymer, treating the obtained product for 8 hours at 300 ℃ under the protection of argon gas to obtain the carbon-nitrogen-based polymer negative electrode material (C) of the potassium ion batteryxN-300)。
Preparation of potassium ion battery negative pole piece and battery assembly
The embodiment provides a method for preparing a polymer negative pole piece of a potassium ion battery and assembling the battery, which comprises the following steps:
a. mixing the obtained carbon-nitrogen-based polymer negative electrode material of the potassium ion battery, a conductive agent Super P and a binder according to a mass ratio of 80: 10: 10, mixing, wherein the binder is sodium carboxymethyl cellulose: the mass of the styrene butadiene rubber is 1: 1, dripping a few drops of deionized water, mechanically stirring to form uniform slurry, coating the slurry on an aluminum foil, and drying at 80 ℃ for 10 hours under a vacuum condition to obtain the dried electrode plate.
b. And cutting the dried electrode plate into a circular electrode plate with the diameter of 10 nm.
c. The round electrode plate obtained by the preparation is used as a negative electrode, the glass fiber diaphragm is used as a diaphragm, and the diaphragm and the metal potassium sheet are assembled into a button cell, the model of the button cell is CR2032, the electrolyte is KFSI dissolved in DME electrolyte, wherein the KFSI: DME 1: 2.5 (molar ratio).
Fourth, battery test
The battery obtained in the embodiment was subjected to constant current charge and discharge test using a battery charge and discharge tester with a test voltage interval of 0.01-3V and a test temperature of 25 ℃.
The charge/discharge curve of the potassium ion battery of example 2 at 30mA/g is shown in FIG. 5, and it can be seen that the capacity is up to 313 mAh/g.
Example 3
Preparation of carbon-nitrogen-based polymer negative electrode material of potassium ion battery
a. Adding hexa-aminobenzene trihydrochloride (1g, 3.6mmol) and cyclohexanone octahydrate (1.124g, 3.6mmol) monomers into a round bottom three-neck flask, introducing argon gas for protection, placing the flask into an ice-water bath, then adding 40mL of N-methylpyrrolidone, then adding 98 mass percent of concentrated sulfuric acid (40 mu L), stirring uniformly, continuing stirring at room temperature for 2h, then transferring the flask into an oil bath at 160 ℃ and reacting for 1 h.
b. After the reaction is finished, cooling to normal temperature, separating and drying to obtain a carbon-nitrogen-based polymer, treating the obtained product for 1h at 500 ℃ under the protection of argon gas to obtain the carbon-nitrogen-based polymer negative electrode material (C) of the potassium ion batteryxN-500)。
Preparation of potassium ion battery negative pole piece and battery assembly
The embodiment provides a method for preparing a polymer negative pole piece of a potassium ion battery and assembling the battery, which comprises the following steps:
a. mixing the obtained carbon-nitrogen-based polymer negative electrode material of the potassium ion battery, a conductive agent Super P and a binder according to a mass ratio of 85: 5: 10, mixing, wherein the binder is sodium carboxymethyl cellulose: the mass of the styrene butadiene rubber is 1: 1, dripping a few drops of deionized water, mechanically stirring to form uniform slurry, coating the slurry on an aluminum foil, and drying at 80 ℃ for 10 hours under a vacuum condition to obtain the dried electrode plate.
b. And cutting the dried electrode plate into a circular electrode plate with the diameter of 10 nm.
c. The round electrode plate obtained by the preparation is used as a negative electrode, the glass fiber diaphragm is used as a diaphragm, and the diaphragm and the metal potassium sheet are assembled into a button cell, the model of the button cell is CR2032, the electrolyte is KFSI dissolved in DME electrolyte, wherein the KFSI: DME 1: 2.5 (molar ratio).
Fourth, battery test
The battery obtained in the embodiment was subjected to constant current charge and discharge test using a battery charge and discharge tester with a test voltage interval of 0.01-3V and a test temperature of 25 ℃.
The charge/discharge curve of the potassium ion battery of example 1 at 30mA/g is shown in FIG. 5, and it can be seen that the capacity is as high as 299 mAh/g.
Comparative example 1
A polymer negative electrode material CxPreparation of N
a. Adding hexa-aminobenzene trihydrochloride (1g, 3.6mmol) and cyclohexanone octahydrate (1.124g, 3.6mmol) monomers into a round bottom three-neck flask, introducing argon gas for protection, placing the flask in an ice-water bath, then adding 40mL of N-methylpyrrolidone, then adding 98 mass percent of concentrated sulfuric acid (40 mu L), stirring uniformly, continuing stirring at room temperature for 2h, then transferring the flask into an oil bath at 180 ℃ and reacting for 72 h.
b. After the reaction is finished, cooling to normal temperature, separating and drying to obtain a carbon-nitrogen-based polymer, which is marked as CxN。
II, polymer negative electrode material CxConductivity test of N
For the carbon-nitrogen based polymer C in comparative example 1xN for conductivity testing. The tests show that C obtained in the comparative examplexThe conductivity of N was 3.17X 0-7S cm-1And C in example 1xThe room-temperature conductivity of N-350 was 2.82X 10-5S cm-1The conductivity increase is nearly 90 times.
Polymer negative electrode material C in comparative example 1xThe raman plot of N is shown in fig. 3. It can be seen that C is a comparison with example 1xN and CxThe Raman spectrogram of N-350 has no obvious change, and proves that the main structure of the carbon-nitrogen-based polymer has no obvious change before and after the heat treatment at 350 ℃.
Preparation of potassium ion battery negative pole piece and battery assembly
The preparation and the battery assembly of the negative electrode plate of the potassium ion battery in the comparative example are respectively the same as the preparation and the battery assembly of the negative electrode plate of the potassium ion battery in the example 1, except that the polymer negative electrode sample in the example 1 is a sample C subjected to heat treatment at 350 ℃xN-350, while the polymer negative electrode sample in this comparative example is sample C which was not heat-treatedxN。
Fourth, the battery test and the test method are the same as those of the example 1
As shown in FIG. 5, the specific capacity of the negative electrode plate of the potassium-ion battery prepared in example 1 is 329 mAh/g. The potassium storage specific capacity of the negative pole piece of the potassium ion battery prepared in the comparative example 1 is 39 mAh/g. Therefore, the potassium storage specific capacity of the polymer negative electrode material of the potassium ion battery can be greatly improved through low-temperature heat treatment.
As shown in fig. 6, the cycle performance of the negative electrode plate of the potassium-ion battery prepared in example 1 is good, 199mAh/g can be obtained at a current density of 150mA/g, after 120 cycles, the specific capacity is 198mAh/g, and the capacity retention rate is close to 100%. The cycle performance of the negative pole piece of the potassium ion battery prepared in the comparative example 1 is poor, and the capacity is completely attenuated to be close to 0 after 50 times of cycle. It can be seen that the potassium ion battery polymer negative electrode material prepared in example 1 obtained excellent cycle performance.
Comparative example 2
Comparative example 2 is different from example 2 only in that the temperature of low-temperature heat treatment of the resulting polymer in comparative example 2 was 200 c, whereas the temperature of low-temperature heat treatment of example 2 was 300 c, and the other synthesis conditions, battery preparation and test conditions were exactly the same as in example 2.
As shown in FIG. 5, the specific capacity of the negative electrode plate of the potassium ion battery prepared in example 2 is 313 mAh/g. The potassium storage specific capacity of the negative pole piece of the potassium ion battery prepared in the comparative example 1 is 69.4 mAh/g. Therefore, the potassium storage specific capacity of the polymer cathode material of the potassium ion battery can be greatly improved only by selecting proper temperature to carry out heat treatment on the synthesized carbon-nitrogen-based polymer.
Comparative example 3
Comparative example 3 is different from example 3 only in that the temperature of low-temperature heat treatment of the resulting polymer in comparative example 3 is 700 c, whereas the temperature of low-temperature heat treatment of example 3 is 400 c, and the rest of the synthesis conditions, battery preparation and test conditions are exactly the same as those in example 3.
As shown in fig. 7, the specific capacity of the negative electrode plate of the potassium-ion battery prepared in example 3 is 299 mAh/g. The potassium storage specific capacity of the negative pole piece of the potassium ion battery prepared in the comparative example 3 is 237 mAh/g. It can be seen that if the treatment temperature is too high, the potassium storage effect of the material is poor.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of a carbon-nitrogen-based polymer negative electrode material of a potassium ion battery is characterized by comprising the following steps: using hexa-aminobenzene tri-hydrochloride and cyclohexadecanone octahydrate as monomers, polymerizing the monomer solution through acid catalytic condensation reaction under the protection of nitrogen or inert gas and under the heating condition to prepare the carbon-nitrogen-based polymer, and then carrying out heat treatment under the protection of nitrogen or inert gas to obtain the carbon-nitrogen-based polymer cathode material of the potassium ion battery.
2. The preparation method of the carbon-nitrogen-based polymer negative electrode material of the potassium ion battery as claimed in claim 1, wherein the molar ratio of the hexaamino benzene trihydrochloride to the cyclohexanehexone octahydrate is 1: 0.5-1.5.
3. The method for preparing the carbon-nitrogen-based polymer negative electrode material of the potassium ion battery as claimed in claim 1, wherein the temperature of the acid-catalyzed condensation reaction is 100-200 ℃, and the time of the acid-catalyzed condensation reaction is 2-100 h.
4. The method for preparing the carbon-nitrogen-based polymer negative electrode material of the potassium ion battery as claimed in claim 1, wherein the solvent used in the monomer solution is at least one of N-methylpyrrolidone, mesitylene and 1, 4-dioxane.
5. The method for preparing the carbon-nitrogen-based polymer negative electrode material of the potassium ion battery as claimed in claim 1, wherein the acid catalyst for the acid-catalyzed condensation reaction is at least one of sulfuric acid and acetic acid.
6. The method for preparing the carbon-nitrogen-based polymer negative electrode material of the potassium ion battery as claimed in claim 1, wherein the temperature of the heat treatment is 300-500 ℃; the heating rate is 1-20 ℃/min; the heat preservation time is 0.5-24 h.
7. The method for preparing the carbon-nitrogen-based polymer negative electrode material of the potassium ion battery as claimed in claim 1, wherein the temperature of the heat treatment is 350 ℃; the heating rate is 5 ℃/min; the heat preservation time is 2 h.
8. The preparation method of the carbon-nitrogen-based polymer negative electrode material of the potassium ion battery as claimed in any one of claims 1 to 7, wherein the preparation method comprises the following steps:
a. adding hexa-aminobenzene tri-hydrochloride and cyclohexadecanone octahydrate monomers into a reaction vessel, introducing nitrogen or inert gas for protection, placing the mixture into an ice water bath, then adding a solvent, then adding an acid catalyst, stirring uniformly, and heating to a reaction temperature for carrying out acid catalytic condensation reaction;
b. after the reaction is finished, cooling to normal temperature, separating and drying to obtain a carbon-nitrogen-based polymer; and carrying out heat treatment on the obtained carbon-nitrogen-based polymer under the protection of nitrogen or inert gas to obtain the carbon-nitrogen-based polymer negative electrode material of the potassium ion battery.
9. The carbon-nitrogen-based polymer negative electrode material for the potassium ion battery, which is prepared by the method of any one of claims 1 to 8, is granular, has a graphite-like layered conjugated structure, and has a particle size of 0.1 to 5 μm.
10. The use of the carbon-nitrogen-based polymer negative electrode material of the potassium ion battery as defined in claim 9 for preparing a polymer negative electrode of the potassium ion battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110923488.5A CN113644228B (en) | 2021-08-12 | 2021-08-12 | Potassium ion battery carbon-nitrogen-based polymer negative electrode material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110923488.5A CN113644228B (en) | 2021-08-12 | 2021-08-12 | Potassium ion battery carbon-nitrogen-based polymer negative electrode material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113644228A true CN113644228A (en) | 2021-11-12 |
| CN113644228B CN113644228B (en) | 2022-10-14 |
Family
ID=78421055
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110923488.5A Active CN113644228B (en) | 2021-08-12 | 2021-08-12 | Potassium ion battery carbon-nitrogen-based polymer negative electrode material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113644228B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011034962A (en) * | 2009-07-07 | 2011-02-17 | Nippon Zeon Co Ltd | Method for manufacturing electrode of lithium ion secondary battery,and lithium ion secondary battery |
| JP2013043821A (en) * | 2011-08-26 | 2013-03-04 | Asahi Kasei Chemicals Corp | Nitrogen-containing carbon material, method for producing the same, and electrode for fuel cell |
| WO2017028520A1 (en) * | 2015-08-18 | 2017-02-23 | 华为技术有限公司 | C2n graphene-precious metal composite nanometer catalyst and preparation method therefor |
| CN109535421A (en) * | 2018-12-29 | 2019-03-29 | 上海师范大学 | A kind of piperazine base carbon nitrogen polymer, Its Preparation Method And Use |
| CN112531162A (en) * | 2020-12-06 | 2021-03-19 | 西北工业大学 | Water-based proton battery electrode based on aza-conjugated porous polymer and preparation method thereof |
| CN112919434A (en) * | 2021-02-09 | 2021-06-08 | 复旦大学 | Carbon-rich carbonitride as negative electrode material of secondary battery, and preparation method and application thereof |
-
2021
- 2021-08-12 CN CN202110923488.5A patent/CN113644228B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011034962A (en) * | 2009-07-07 | 2011-02-17 | Nippon Zeon Co Ltd | Method for manufacturing electrode of lithium ion secondary battery,and lithium ion secondary battery |
| JP2013043821A (en) * | 2011-08-26 | 2013-03-04 | Asahi Kasei Chemicals Corp | Nitrogen-containing carbon material, method for producing the same, and electrode for fuel cell |
| WO2017028520A1 (en) * | 2015-08-18 | 2017-02-23 | 华为技术有限公司 | C2n graphene-precious metal composite nanometer catalyst and preparation method therefor |
| CN109535421A (en) * | 2018-12-29 | 2019-03-29 | 上海师范大学 | A kind of piperazine base carbon nitrogen polymer, Its Preparation Method And Use |
| CN112531162A (en) * | 2020-12-06 | 2021-03-19 | 西北工业大学 | Water-based proton battery electrode based on aza-conjugated porous polymer and preparation method thereof |
| CN112919434A (en) * | 2021-02-09 | 2021-06-08 | 复旦大学 | Carbon-rich carbonitride as negative electrode material of secondary battery, and preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| CHEN, SC等: "Highly Tunable and Facile Synthesis of Uniform Carbon Flower Particles", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
| LEI WANG等: "Van der Waals Heterostructures Comprised of Ultrathin Polymer Nanosheets for Efficient Z-Scheme Overall Water Splitting", 《ANGEWANDTE CHEMIE-INTERNATIONAL EDITION》 * |
| SHUNQI XU等: "A Nitrogen-Rich 2D sp2 -Carbon-Linked Conjugated Polymer Framework as a High-Performance Cathode for Lithium-Ion Batteries", 《ANGEW.CHEM. INT.ED.》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113644228B (en) | 2022-10-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109301215B (en) | High-capacity silicon-carbon negative electrode active material, and preparation method and application thereof | |
| Xu et al. | Tri-functionalized polypropylene separator by rGO/MoO 2 composite for high-performance lithium–sulfur batteries | |
| CN112993256B (en) | Application of covalent organic framework material in lithium metal negative electrode protection | |
| CN108321369B (en) | Macroporous carbon/zinc oxide/sulfur composite material for lithium-sulfur battery and preparation method and application thereof | |
| CN112670507B (en) | Preparation method of lithium-sulfur battery intermediate layer of metal selenide-loaded carbon nanofiber and lithium-sulfur battery | |
| CN111446414B (en) | Covalent organic framework material, preparation method and application thereof | |
| KR102139318B1 (en) | Sodium ion battery electrode material and manufacturing method thereof | |
| CN109360946A (en) | Repeatedly mixing cladding high compacted density silicon-carbon cathode material and preparation method thereof | |
| CN109037718A (en) | A kind of biomass carbon carried transition metal oxide composite and the preparation method and application thereof | |
| CN111974430B (en) | Preparation method of monoatomic copper catalyst and application of monoatomic copper catalyst in positive electrode of lithium-sulfur battery | |
| CN113594415A (en) | Sandwich independent positive electrode for inhibiting shuttle effect of lithium-sulfur battery and preparation method thereof | |
| Yang et al. | Self-doped N Sponge Carbon as a functional interlayer for high-performance lithium-sulfur batteries | |
| CN112374484A (en) | S/CeO for preparing lithium-sulfur battery positive electrode material2Method for preparing porous biomass carbon | |
| CN114975920B (en) | Electrode material of core-shell structure graphite alkyne coated with metallic antimony, and preparation method and application thereof | |
| CN110783542A (en) | Paper towel derived carbon fiber loaded MoS 2Preparation method of micro-flower composite material and application of micro-flower composite material in lithium-sulfur battery | |
| CN111099574A (en) | Preparation method of hierarchical porous carbon aerogel for lithium ion battery cathode | |
| CN113644228B (en) | Potassium ion battery carbon-nitrogen-based polymer negative electrode material and preparation method and application thereof | |
| CN112053858B (en) | Method for preparing zinc ion hybrid capacitor by using acid activated carbon electrode material | |
| CN111276683B (en) | Silicon dioxide sulfur positive electrode rich in aluminum hydroxyl and preparation method thereof | |
| CN113321199A (en) | Polybenzoxazine-co-cresol-based polymer-derived hard carbon microspheres, and preparation method and application thereof | |
| Lang et al. | Study on the electrochemical performance of lead-acid battery with micro/nanostructure tetrabasic lead sulfate prepared via sol-gel method | |
| CN112117502B (en) | Aqueous ion battery and application thereof | |
| CN113193191B (en) | Manganous-manganic oxide nanocrystalline @3D honeycomb-shaped hierarchical porous network framework carbon composite material and preparation and application thereof | |
| CN115911382B (en) | Self-supporting SnO of foam nickel 2 Nano array@porous carbon fiber composite material and preparation method and application thereof | |
| CN111029525B (en) | Preparation method of positive pole piece of lithium-sulfur battery and product thereof |
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 |