CN113659136A - Organic acid radical inorganic salt pyrolytic carbon electrode material and preparation method and application thereof - Google Patents

Organic acid radical inorganic salt pyrolytic carbon electrode material and preparation method and application thereof Download PDF

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CN113659136A
CN113659136A CN202110876458.3A CN202110876458A CN113659136A CN 113659136 A CN113659136 A CN 113659136A CN 202110876458 A CN202110876458 A CN 202110876458A CN 113659136 A CN113659136 A CN 113659136A
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organic acid
electrode material
pyrolytic carbon
acid radical
inorganic salt
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CN113659136B (en
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罗雯
李子健
麦立强
武新飞
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Wuhan University of Technology WUT
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    • 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
    • H01M4/58—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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
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Abstract

The invention provides an organic acid radical inorganic salt pyrolytic carbon electrode material and a preparation method and application thereof, wherein the preparation method comprises the following steps: placing organic acid radical metal salt in a tubular furnace, and calcining under preset conditions to obtain an intermediate product A; adding hydrochloric acid into the intermediate product A, and stirring and standing to obtain an intermediate product B; and washing, centrifuging and drying the intermediate product B to obtain the organic acid radical inorganic salt pyrolytic carbon electrode material. The organic acid radical inorganic salt pyrolytic carbon electrode material is prepared by combining one-step calcination with an acid etching method, the raw materials are cheap and easy to obtain, the preparation process is simple, the obtained pyrolytic carbon material has larger interlayer spacing, can adapt to the embedding and the separation of potassium ions in the circulation process, and the mesoporous structure of the pyrolytic carbon material is beneficial to improving the electrochemical performance of the pyrolytic carbon electrode material in a potassium ion battery.

Description

Organic acid radical inorganic salt pyrolytic carbon electrode material and preparation method and application thereof
Technical Field
The invention relates to the technical field of nano materials and electrochemistry, in particular to an organic acid radical inorganic salt pyrolytic carbon electrode material and a preparation method and application thereof.
Background
The potassium ion battery can provide larger specific energy, and the Lewis acid of potassium ions is much weaker than that of lithium ions, so that the radius of solvated ions formed by potassium ions in an electrolyte solvent is much smaller than that of the lithium ions, the performance of the potassium ion battery on diffusion kinetics is more excellent, and high rate performance is hopeful to be obtained. However, the electrode material for potassium ion batteries has a great volume effect during the cycling process, and if the structural stability of the electrode material is poor, the pulverization of the electrode material and the rapid capacity fading are easily caused. Therefore, designing and constructing a negative electrode material with stable structure and high capacity is the key for the development of the potassium ion battery.
Carbon materials have been widely studied for use in potassium ion battery negative electrode materials due to their relatively low cost and relatively good structural stability. Carbon materials currently being extensively studied mainly include hard carbon, soft carbon, graphitic carbon, graphene, and other carbon-based composite materials. However, when the current commercial hard carbon material is used as a negative electrode material of a potassium ion battery, because an unstable SEI film is easily formed and an unavoidable side reaction is generated, the capacity retention rate of the hard carbon material is low, about half of the capacity can be maintained after one hundred cycles, and the hard carbon material has an unstable structure and poor rate capability and cannot bear large-current charge and discharge.
Therefore, how to design a carbon material with a larger interlayer spacing structure and good stability for application in the field of potassium ion batteries is a problem to be solved urgently at present.
Disclosure of Invention
In view of the above, the invention aims to provide a non-organic acid radical inorganic salt pyrolytic carbon electrode material, and a preparation method and an application thereof, so as to solve the problem that the existing carbon material has poor stability when being used as a potassium ion battery cathode.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a preparation method of an organic acid radical inorganic salt pyrolytic carbon electrode material comprises the following steps:
s1, placing the organic acid radical metal salt in a tubular furnace, and calcining under preset conditions to obtain an intermediate product A;
s2, adding hydrochloric acid into the intermediate product A, and stirring and standing to obtain an intermediate product B;
and S3, washing, centrifuging and drying the intermediate product B to obtain the organic acid radical inorganic salt pyrolytic carbon electrode material.
Alternatively, the organic acid group metal salt in step S1 includes p-toluenesulfonate.
Optionally, the preset condition in step S1 includes: under the protection of inert gas, the temperature rising rate of the tube furnace is within the range of 4 ℃/min to 6 ℃/min, the calcining temperature is within the range of 500 ℃ to 900 ℃, and the calcining time is within the range of 1.5h to 2.5 h.
Optionally, the stirring and standing time in the step S2 is in the range of 1.5h to 2.5 h.
Optionally, the mass fraction of hydrochloric acid in step S2 is in the range of 15% to 25%.
Alternatively, the washing in step S3 includes washing with deionized water and isopropyl alcohol in this order.
Optionally, the drying temperature of the drying in the step S3 is in the range of 75 ℃ to 85 ℃, and the drying time is in the range of 12h to 14 h.
The invention also aims to provide an organic acid radical inorganic salt pyrolytic carbon electrode material which is prepared by the preparation method of the organic acid radical inorganic salt pyrolytic carbon electrode material.
Optionally, the organic acid radical inorganic salt pyrolytic carbon electrode material is a three-dimensional micrometer spherical structure formed by orderly stacking and polymerizing two-dimensional nanosheets.
The third purpose of the invention is to provide an application of the organic acid radical inorganic salt pyrolytic carbon electrode material as a negative electrode active material in the field of potassium ion batteries.
Compared with the prior art, the organic acid radical inorganic salt pyrolytic carbon electrode material and the preparation method and application thereof provided by the invention have the following advantages:
(1) the organic acid radical inorganic salt pyrolytic carbon electrode material is prepared by combining one-step calcination with an acid etching method, the raw materials are cheap and easy to obtain, the preparation process is simple, the obtained pyrolytic carbon material has larger interlayer spacing, can adapt to the embedding and the separation of potassium ions in the circulation process, and the mesoporous structure of the pyrolytic carbon material is beneficial to improving the electrochemical performance of the pyrolytic carbon electrode material in a potassium ion battery.
(2) The organic acid radical inorganic salt pyrolytic carbon electrode material prepared by the invention is used as a potassium ion battery assembled by a negative active material, and has higher reversible specific capacity and better cycling stability.
Drawings
FIG. 1 is an XRD pattern of an organic acid radical inorganic salt pyrolytic carbon electrode material according to an embodiment of the invention;
FIG. 2 is a Raman diagram of an organic acid radical inorganic salt pyrolytic carbon electrode material according to an embodiment of the invention;
FIG. 3 is an SEM image of an organic acid radical inorganic salt pyrolytic carbon electrode material according to an embodiment of the invention;
FIG. 4 is a TEM image of an organic acid radical inorganic salt pyrolytic carbon electrode material according to an embodiment of the invention;
FIG. 5 is an electrochemical impedance spectrum of an organic acid radical inorganic salt pyrolytic carbon electrode material according to an embodiment of the invention;
FIG. 6 is a voltage distribution plot of an organic acid radical inorganic salt pyrolytic carbon electrode material according to an embodiment of the invention;
FIG. 7 is a graph of the cycling performance of an organic acid radical inorganic salt pyrolytic carbon electrode material according to an embodiment of the invention;
FIG. 8 is a graph of rate capability of an organic acid radical inorganic salt pyrolytic carbon electrode material according to an embodiment of the invention;
FIG. 9 is a graph of the large current long cycle performance of an organic acid radical inorganic salt pyrolytic carbon electrode material according to an embodiment of the invention.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below.
In the description of the present invention, it should be noted that the terms "first" and "second" mentioned in the embodiments of the present invention are only used for descriptive purposes and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. The term "in.. range" as used herein includes both end values, e.g., "in the range of 1 to 100" includes both end values of 1 and 100.
In the description of embodiments of the present application, the description of the term "some embodiments" means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. Throughout this specification, the schematic representations of the terms used above do not necessarily refer to the same implementation or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
Lithium ion batteries are widely applied to the fields of portable electronic products such as smart phones and new energy automobiles at present, however, due to the shortage of lithium resources and the uneven distribution of the lithium resources in the earth crust, the application of the lithium ion batteries in a large energy storage system is hindered. The potassium and lithium elements are located in the same main group in the periodic table of the elements, have physical and chemical properties similar to those of lithium, and the charge and discharge principles of the corresponding ion batteries are basically consistent, so that the lithium-ion battery is an environment-friendly new-generation high-energy-density energy storage raw material. The abundance of the potassium element in the crust is very high, which accounts for about 1.5 percent of the storage amount of the crust element and is higher than the lithium element by more than three orders of magnitude, and the potassium element is uniformly distributed in the crust, thereby ensuring sufficient raw material supply. K+the/K redox potential is lower in some common non-aqueous electrolyte solvents, e.g. in PC solvent, K+Potential ratio of/K Li+The potential of/Li is 0.32V lower, in EC/DEC, K+Potential ratio of/K Li+The potential of/Li is 0.15V lower, so that the potassium ion battery can provide larger specific energy. However, the electrode material of the potassium ion battery generates a huge volume effect in the circulation process, and the crushing of the electrode material and the rapid capacity decay are easily caused.
The carbon material is widely researched and applied to the potassium ion battery cathode material due to the lower cost and the better structural stability, but the carbon material is unstable in structure and poor in rate capability. Nonmetal elements such as N, P, S, O are usually used for doping, so that more potassium storage active sites are provided for the carbon material, the capacity of the battery is improved, the wettability of the carbon material can be improved to a certain extent, and the poor contact between part of the surface of the carbon material and the electrolyte is avoided. Currently, much research is carried out on MOF materials, but the preparation process of the MOF materials is complex and the price is high. The organic acid radical metal salt (such as p-toluenesulfonate) produced in large scale has excellent three-dimensional morphology structure similar to MOF material and low cost. Therefore, how to modify the organic acid radical metal salt so that the organic acid radical metal salt can be better applied to the negative electrode material of the potassium ion battery is a research subject with practical significance.
In order to solve the above problems, an embodiment of the present invention provides a method for preparing an organic acid radical inorganic salt pyrolytic carbon electrode material, including the following steps:
s1, placing the organic acid radical metal salt in a tubular furnace, and calcining under preset conditions to obtain an intermediate product A;
s2, adding hydrochloric acid into the intermediate product A, and stirring and standing to obtain an intermediate product B;
and S3, washing, centrifuging and drying the intermediate product B to obtain the organic acid radical inorganic salt pyrolytic carbon electrode material.
The organic acid radical inorganic salt pyrolytic carbon electrode material is prepared by combining one-step calcination with an acid etching method, and the organic acid radical inorganic salt pyrolytic carbon electrode material is cheap and easily available in raw materials, simple in preparation process and suitable for large-scale commercial production. The obtained organic acid radical inorganic salt pyrolytic carbon electrode material has a hierarchical porous micron sheet structure, has larger interlayer spacing, can adapt to the embedding and the separation of potassium ions in a circulating process, and has a mesoporous structure which is beneficial to improving the electrochemical performance of the organic acid radical inorganic salt pyrolytic carbon electrode material in a potassium ion battery.
Specifically, the organic acid group metal salt in step S1 includes p-toluenesulfonate. Preferably, the tosylate in embodiments of the invention comprises iron p-toluenesulfonate or sodium p-toluenesulfonate.
The preset conditions for placing the organic acid radical metal salt in a tubular furnace for calcination comprise: under the protection of inert gas, the temperature rising rate of the tube furnace is within the range of 4 ℃/min to 6 ℃/min, the calcining temperature is within the range of 500 ℃ to 900 ℃, and the calcining time is within the range of 1.5h to 2.5 h. Preferably, the temperature rise rate of the tube furnace is 5 ℃/min, the calcining temperature is within the range of 700 ℃, and the calcining time is 2 h.
Specifically, after hydrochloric acid is added to the intermediate product a in step S2, the time for stirring and standing is in the range of 1.5h to 2.5h, and preferably, the stirring time is 2 h.
Wherein the mass fraction of the hydrochloric acid is in the range of 15% to 25%, and preferably the mass fraction of the hydrochloric acid is 20%.
In step S3, intermediate product B is washed, including washing with deionized water and isopropanol in that order.
The drying temperature of the drying in the step S3 is in the range of 75 ℃ to 85 ℃, the drying time is in the range of 12h to 14h, and preferably, the drying is carried out for 13h at 80 ℃.
The embodiment of the invention adopts a one-step calcination method combined with an acid etching method, realizes the preparation of the organic acid radical inorganic salt pyrolytic carbon electrode material with large interlayer spacing, high specific surface area and graded pore size distribution by regulating and controlling calcination temperature parameters, has low and easily obtained raw materials, simple synthesis steps and is suitable for large-scale production.
The invention also aims to provide an organic acid radical inorganic salt pyrolytic carbon electrode material which is prepared by the preparation method of the organic acid radical inorganic salt pyrolytic carbon electrode material. The organic acid radical inorganic salt pyrolytic carbon electrode material is a three-dimensional micron spherical structure formed by orderly stacking and polymerizing two-dimensional nano sheets, and sulfur elements are uniformly distributed in micron spheres. The nano-sheet with larger interlayer spacing can adapt to huge volume change caused by the embedding and the removing of potassium ions in the circulating process, has good structural stability, can provide high capacity retention rate and high rate capability, and in addition, the doping of sulfur element can provide more active sites for the storage of potassium ions and provide higher capacity.
The third purpose of the invention is to provide an application of the organic acid radical inorganic salt pyrolytic carbon electrode material as a negative electrode active material in the field of potassium ion batteries. The potassium ion battery assembled by taking the organic acid radical inorganic salt pyrolytic carbon as the negative active material can show high capacity, high capacity retention rate, excellent rate performance and smaller electrochemical impedance.
On the basis of the above examples, the present invention is further illustrated below with reference to a method for preparing an organic acid radical inorganic salt pyrolytic carbon electrode material. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are examples of experimental procedures not specified under specific conditions, generally according to the conditions recommended by the manufacturer. Unless otherwise indicated, percentages and parts are by mass.
Example 1
The embodiment provides a preparation method of an organic acid radical inorganic salt pyrolytic carbon electrode material, which comprises the following steps:
1) under the nitrogen atmosphere, 2g of iron p-toluenesulfonate is placed in a porcelain boat, heated from room temperature to 700 ℃ in a tube furnace at the heating rate of 5 ℃/min and kept for 2 hours, and then cooled to room temperature along with the tube furnace to obtain an intermediate product A;
2) adding hydrochloric acid with the mass fraction of 20% into the fired intermediate product A, and stirring for 2 hours at room temperature to obtain an intermediate product B;
3) and respectively washing and centrifuging the intermediate product B by using deionized water and isopropanol for 3 times, and drying in an oven at 80 ℃ overnight to finally obtain the organic acid radical inorganic salt pyrolytic carbon electrode material.
The organic acid radical inorganic salt pyrolytic carbon electrode material prepared in example 1 was subjected to performance tests, and results shown in fig. 1-4 were obtained.
Fig. 1 is an X-ray diffraction (XRD) pattern of the organic acid radical inorganic salt pyrolytic carbon electrode material, and it can be seen from fig. 1 that two distinct broad diffraction peaks can be observed at about 24 ° and 45 ° 2 θ, corresponding to two crystal planes (002) and (101) of graphite, respectively, but as can be seen from fig. 1, the diffraction peak corresponding to the crystal plane (101) is lower, which means that the obtained product has an amorphous structure and a low degree of graphitization.
FIG. 2 is a Raman spectrum analysis (Raman) graph of the organic acid radical inorganic salt pyrolytic carbon electrode material of example 1, and it can be seen from FIG. 2 that the organic acid radical inorganic salt pyrolytic carbon electrode material shows distinct D peak and G peak, and the D peak represents the edge of the graphite sheetThe vibration of disordered carbon, the G peak, represents the C-C bond in-plane stretching vibration of graphitic carbon. The graphitization degree of the carbon material can be determined by the relative intensity ratio R (R ═ I) of the D peak and the G peakD/IG) The carbon material has a high R value, represents that the carbon material has more defects, has low graphitization degree, and is beneficial to providing active sites for the storage of potassium ions, thereby providing higher battery capacity.
Fig. 3 is a Scanning Electron Microscope (SEM) image of the organic acid radical inorganic salt pyrolytic carbon electrode material described in example 1, and it can be seen from fig. 3 that the organic acid radical inorganic salt pyrolytic carbon electrode material is a three-dimensional microsphere structure formed by vertical stacking and polymerization of two-dimensional nanosheets, the diameter of the three-dimensional microsphere structure is about 20 μm, and the porous three-dimensional structure of the organic acid radical inorganic salt pyrolytic carbon electrode material is beneficial to maintaining good structural stability in the processes of intercalation and deintercalation of potassium ions, so that a higher capacity retention rate can be obtained.
Fig. 4 is a Transmission Electron Microscope (TEM) image of the organic acid radical inorganic salt pyrolytic carbon electrode material of example 1, and it can be seen from fig. 4 that the nanosheets have a porous structure as a constituent unit of the microspheres, and the nanosheets have rough surfaces and a large number of defects, which are beneficial to being used as active sites for potassium ion storage, thereby providing higher capacity.
The organic acid radical inorganic salt pyrolytic carbon electrode material prepared in example 1 was used as a negative electrode active material, and the ratio of the active material: conductive agent (acetylene black): preparing slurry by using a binder (sodium carboxymethylcellulose) in a ratio of 8:1:1, coating the slurry on a current collector copper foil, drying to obtain a negative electrode, taking metal potassium as a counter electrode, selecting 0.8M KPF6/EC: DEC in a ratio of 1:1 (vol%) as an electrolyte, GF/D glass fiber as a diaphragm, and assembling a CR2016 type stainless steel battery shell into a button type half battery. The button half-cells were tested and the resulting graphs shown in figures 5-7 were obtained.
Fig. 5 is an electrochemical impedance spectrum of the organic acid radical inorganic salt pyrolytic carbon electrode material, and it can be known from nyquist plot data shown in fig. 5 that electrolyte resistance and SEI film migration resistance after cycling are significantly reduced, which means that a potassium ion battery system after cycling is more stable.
FIG. 6 shows the voltage of organic acid radical inorganic salt pyrolytic carbon electrode materialDistribution diagram, shown in figure 6, of the organic acid radical inorganic salt pyrolytic carbon electrode material at 100mA g-1The charge-discharge curve under the conditions of current density and voltage window of 0.01-3.0V shows that the first discharge specific capacity of the pyrolytic carbon electrode material is 743.78mA h g-1The first coulombic efficiency was 32.5%, and the irreversible capacity of the initial cycle was mainly due to SEI formation and K+Is inserted irreversibly.
FIG. 7 is a graph of the cycle performance of the organic acid radical inorganic salt pyrolytic carbon electrode material, as shown in FIG. 7, the organic acid radical inorganic salt pyrolytic carbon electrode material electrode is at 100mAg-1Under the current density, the lithium ion battery shows good cycling stability, and the initial charging specific capacity is 241.8mA h g-1After 100 cycles, the charging and discharging specific capacity is kept at 150mA h g-1And the better circulation stability is reflected.
The test results show that the organic acid radical inorganic salt pyrolytic carbon electrode material has excellent electrochemical performance and is a high-performance potassium ion battery cathode material.
Example 2
This example provides a method for preparing organic acid radical inorganic salt pyrolytic carbon electrode material, which is different from example 1 in that:
in the step 1), 2g of iron p-toluenesulfonate is placed in a porcelain boat in a nitrogen atmosphere, heated from room temperature to 500 ℃ at a heating rate of 5 ℃/min in a tubular furnace and kept for 2 hours;
the remaining steps and parameters were the same as in example 1.
The organic acid radical inorganic salt pyrolytic carbon electrode material obtained in example 2 was used as a negative electrode active material and assembled into a button type half cell in the above-described manner for testing. The results are as follows: at 100mA g-1Under the current density, the first discharge specific capacity is 417.9mA h/g, the first charge specific capacity is 212.8mAh/g, the discharge specific capacity is 126.4mA h/g after 100 cycles, and the capacity retention rate is about 49.4%.
Example 3
This example provides a method for preparing organic acid radical inorganic salt pyrolytic carbon electrode material, which is different from example 1 in that:
in the step 1), 2g of iron p-toluenesulfonate is placed in a porcelain boat in a nitrogen atmosphere, heated from room temperature to 600 ℃ at a heating rate of 5 ℃/min in a tubular furnace and kept for 2 hours;
the remaining steps and parameters were the same as in example 1.
The organic acid radical inorganic salt pyrolytic carbon electrode material obtained in example 3 was used as a negative electrode active material and assembled into a button type half cell in the above-described manner for testing. The results are as follows: at 100mA g-1Under the current density, the first discharge specific capacity is 524.6mA h/g, the charge specific capacity is 218.1mA h/g, the discharge specific capacity after 100 cycles is 90.4m Ah/g, and the capacity retention rate is about 41%.
Example 4
This example provides a method for preparing organic acid radical inorganic salt pyrolytic carbon electrode material, which is different from example 1 in that:
in the step 1), 2g of iron p-toluenesulfonate is placed in a porcelain boat in a nitrogen atmosphere, heated from room temperature to 800 ℃ at a heating rate of 5 ℃/min in a tubular furnace and kept for 2 hours;
the remaining steps and parameters were the same as in example 1.
The organic acid radical inorganic salt pyrolytic carbon electrode material obtained in example 4 was used as a negative electrode active material and assembled into a button type half cell in the above-described manner for testing. The results are as follows: at 100mA g-1Under the current density, the first discharge specific capacity is 505.9m Ah/g, the charge specific capacity is 186.5mA h/g, the discharge specific capacity after 100 cycles is 127.2mA h/g, and the capacity retention rate is about 55.61%.
Example 5
This example provides a method for preparing organic acid radical inorganic salt pyrolytic carbon electrode material, which is different from example 1 in that:
in the step 1), 2g of iron p-toluenesulfonate is placed in a porcelain boat in a nitrogen atmosphere, and is heated to 900 ℃ from room temperature at the heating rate of 5 ℃/min in a tubular furnace and is kept for 2 hours;
the remaining steps and parameters were the same as in example 1.
Organic acid radical inorganic salt pyrolytic carbon electrode material obtained in example 5 is used as a negative electrodeActive material, and assembled into button half cell according to the above method, and tested. The results are as follows: at 100mA g-1Under the current density, the initial discharge specific capacity can be 564.0mA h/g, the charge specific capacity is 136.6mA h/g, the discharge specific capacity after 100 cycles is 133.4mA h/g, and the capacity retention rate is about 74.4%.
Example 6
The embodiment provides a preparation method of an organic acid radical inorganic salt pyrolytic carbon electrode material, which comprises the following steps:
1) under the nitrogen atmosphere, 2g of sodium p-toluenesulfonate is placed in a porcelain boat, is heated to 700 ℃ from room temperature in a tubular furnace at the heating rate of 5 ℃/min, is kept at the temperature of 700 ℃ for 2 hours, and is cooled to the room temperature along with the furnace;
2) adding hydrochloric acid with the mass fraction of 20% into the fired intermediate product, and stirring for 2 hours at room temperature;
3) and respectively washing and centrifuging the sample for 3 times by using deionized water and isopropanol, and drying in an oven at 80 ℃ overnight to finally obtain the organic acid radical inorganic salt pyrolytic carbon electrode material.
Using the organic acid radical inorganic salt pyrolytic carbon electrode material obtained in example 6 as an example, at 100mA g-1Under the current density, the first discharge specific capacity can reach 529.3mAh/g, the charge specific capacity is 271.4mAh/g, and the discharge specific capacity after 50 cycles is 264.7 mAh/g.
Example 7
The embodiment provides a preparation method of an organic acid pyrolytic carbon electrode material, which comprises the following steps:
1) under the nitrogen atmosphere, 2g of p-toluenesulfonic acid is placed in a porcelain boat, heated from room temperature to 700 ℃ in a tubular furnace at the heating rate of 5 ℃/min, kept at the temperature of 700 ℃ for 2 hours, and then cooled to the room temperature along with the furnace;
2) adding hydrochloric acid with the mass fraction of 20% into the fired intermediate product, and stirring for 2 hours at room temperature;
3) and respectively washing and centrifuging the sample for 3 times by using deionized water and isopropanol, and drying in an oven at 80 ℃ overnight to finally obtain the organic acid pyrolytic carbon electrode material.
Taking the pyrolytic carbon electrode material obtained in example 7 as an example, the yield was 100mA g-1Under the current density, the first discharge specific capacity can reach 263.6mAh/g, the charge specific capacity is 93.0mAh/g, and the discharge specific capacity after 100 cycles is 85.0 mAh/g.
In summary, examples 1 to 5 are carbonization products of "iron p-toluenesulfonate" at 700 ℃, 500 ℃, 600 ℃, 800 ℃ and 900 ℃, example 6 is a carbonization product of "sodium p-toluenesulfonate" at 700 ℃, and example 7 is a carbonization product of "p-toluenesulfonate" at 700 ℃, and it can be seen that, as an organic acid radical inorganic salt, the carbonization product obtained by calcining iron p-toluenesulfonate and sodium p-toluenesulfonate at a certain range of carbonization temperature can be used as a potassium ion battery negative electrode material, and due to the fact that the carbonization product has a hierarchical porous nanosheet structure, the carbonization product can adapt to insertion and extraction of potassium ions, and therefore, excellent electrochemical performance is shown. Organic acid represented by p-toluenesulfonic acid is used as a precursor of organic acid radical inorganic salt, and a carbonized product obtained by the same experimental method does not have a nanosheet structure and has lower specific discharge capacity when used as a negative electrode material of a potassium ion battery.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.

Claims (10)

1. A preparation method of an organic acid radical inorganic salt pyrolytic carbon electrode material is characterized by comprising the following steps:
s1, placing the organic acid radical metal salt in a tubular furnace, and calcining under preset conditions to obtain an intermediate product A;
s2, adding hydrochloric acid into the intermediate product A, and stirring and standing to obtain an intermediate product B;
and S3, washing, centrifuging and drying the intermediate product B to obtain the organic acid radical inorganic salt pyrolytic carbon electrode material.
2. The method of claim 1, wherein said organic acid salt of metal in step S1 comprises p-toluenesulfonate.
3. The method according to claim 1, wherein the preset conditions in step S1 include: under the protection of inert gas, the temperature rising rate of the tube furnace is within the range of 4 ℃/min to 6 ℃/min, the calcining temperature is within the range of 500 ℃ to 900 ℃, and the calcining time is within the range of 1.5h to 2.5 h.
4. The production method according to any one of claims 1 to 3, wherein the stirring standing time in step S2 is in the range of 1.5h to 2.5 h.
5. The method according to claim 4, wherein the mass fraction of the hydrochloric acid in step S2 is in the range of 15% to 25%.
6. The method according to claim 4, wherein the washing in step S3 includes washing with deionized water and isopropanol in this order.
7. The method as claimed in claim 6, wherein the drying temperature of the drying in step S3 is in the range of 75 ℃ to 85 ℃ and the drying time is in the range of 12h to 14 h.
8. An organic acid radical inorganic salt pyrolytic carbon electrode material, which is characterized by being prepared by the preparation method of the organic acid radical inorganic salt pyrolytic carbon electrode material according to any one of claims 1 to 7.
9. The organic acid radical inorganic salt pyrolytic carbon electrode material of claim 8, wherein the organic acid radical inorganic salt pyrolytic carbon electrode material is a three-dimensional micron spherical structure formed by ordered stacking polymerization of two-dimensional nanosheets.
10. The organic acid radical inorganic salt pyrolytic carbon electrode material as claimed in claim 8 or 9, which is applied to the field of potassium ion batteries as a negative electrode active material.
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