CN115849342A - Coiled nitrogen-sulfur-oxygen co-doped sodium ion battery negative electrode material and preparation method thereof - Google Patents
Coiled nitrogen-sulfur-oxygen co-doped sodium ion battery negative electrode material and preparation method thereof Download PDFInfo
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- 239000007773 negative electrode material Substances 0.000 title claims abstract description 45
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
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- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 32
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- 238000000034 method Methods 0.000 claims description 27
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Images
Abstract
The invention relates to a coil-shaped nitrogen-sulfur-oxygen co-doped sodium ion battery negative electrode material and a preparation method thereof. Through simple one-step carbonization, the nitrogen/sulfur-containing high polymer material forms a coating shell on the surface of carbon derived from hydroquinone formaldehyde resin, the structure can improve the first charge-discharge efficiency of the negative electrode material, and meanwhile, nitrogen-sulfur co-doping can improve the wettability of the negative electrode and electrolyte and shorten the transmission distance of sodium ions.
Description
Technical Field
The invention relates to the technical field of negative electrode materials of sodium ion batteries, in particular to a coiled nitrogen-sulfur-oxygen co-doped negative electrode material of a sodium ion battery and a preparation method thereof.
Background
The sustainable development and utilization of green energy are not far from the development of high-performance energy storage equipment, and in a new secondary battery system, a sodium ion battery is considered to be the most promising to replace a lithium ion battery because the sodium ion battery and the lithium ion battery have similar electrochemical mechanisms, meanwhile, the storage amount of sodium in a crust reaches 2.64 percent, which is 421 times of that of lithium, sodium ore is uniformly distributed in the global range, the extraction is not complicated, lithium carbonate serving as a main raw material of the lithium battery needs tens of thousands yuan per ton, sodium chloride serving as a main raw material of the sodium battery only needs thousands of yuan per ton, and the price of the sodium chloride is dozens of times lower than that of the lithium ore, so the sodium ion battery has advantages in the aspect of raw material cost, in addition, the sodium battery has excellent electrolyte stability, can normally work in an environment of minus 40 ℃ to 80 ℃, even in an extremely cold environment of minus 20 ℃, the capacity of about 90 percent is still kept, and the problem of continuous voyage of an electric automobile in winter is relieved to a certain extent.
Although sodium ion batteries have many advantages, the traditional high-conductivity graphite negative electrode is not suitable for the larger ion radius of sodium ions, the carbon layer spacing of the graphitized negative electrode material is small, and the larger volume expansion caused by the intercalation and deintercalation of sodium ions cannot be met, so that the negative electrode material is cracked in the charging and discharging process and the capacity of the sodium ion battery is rapidly attenuated. Hard carbon with larger carbon layer spacing is adopted as the cathode material, the wettability of the cathode material with electrolyte is poor, and the electrode conductivity is poor. Although the prior art makes some improvements on the negative electrode material, the improvement on the performance of the sodium ion negative electrode is still limited, and the negative electrode material is accompanied by side effects, such as excessive conductive material coating and excessive doping, which are easy to reduce the specific capacity of the negative electrode material.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a preparation method of a linear-shaped nitrogen-sulfur-oxygen co-doped sodium ion battery negative electrode material.
The second purpose of the invention is to provide the coil-shaped nitrogen-sulfur-oxygen co-doped sodium ion battery negative electrode material prepared by the preparation method.
The invention also aims to provide a sodium ion battery, which comprises the coil-shaped nitrogen-sulfur-oxygen co-doped sodium ion battery negative electrode material.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
in a first aspect, the invention provides a preparation method of a linear nitrogen-sulfur-oxygen co-doped sodium ion battery anode material, which comprises the following steps:
(1) Mixing hydroquinone formaldehyde resin nanobelt coils, ethylene amine and a solvent in an ice water bath, adding carbon disulfide, heating to 25-30 ℃, supplementing carbon dioxide to 1-2 MPa after the system pressure reaches saturated vapor pressure, carrying out constant temperature reaction, and separating, cleaning and drying the product;
(2) And carbonizing the dried product in an inert atmosphere to obtain the coil-shaped nitrogen-sulfur-oxygen co-doped sodium ion battery negative electrode material.
The steps are explained in detail below.
Step (1)
In this step, the source of the hydroquinone formaldehyde resin nanobelt coil is not particularly limited, and the hydroquinone formaldehyde resin nanobelt coil may be commercially available or may be prepared by itself according to a known method.
In some embodiments, the ethylene amine is a mixture of one or more acyclic polymers selected from diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and the like.
In some embodiments, the solvent is a mixed solvent of water and ethylenediamine, wherein the volume ratio of water to ethylenediamine is 1.
In some embodiments, the ratio of the mass of the hydroquinone formaldehyde resin nanoribbon coils to the molar amount of the ethylene amine is 30 to 100mg.
In some embodiments, the hydroquinone formaldehyde resin nanobelt coil has a concentration of 0.375 to 1.25g/L in the solvent.
In some embodiments, the molar ratio of ethylene amine to carbon disulfide is 1.
Carbon dioxide is added into the system, so that on one hand, the pressure of the system can be increased, the ethylene amine and the carbon disulfide are promoted to permeate into the pores of the phenolic resin matrix, and the polymerization and the matrix are tightly combined; on the other hand, carbon dioxide is used as a raw material to participate in the reaction, and the ethylene amine has the function of adsorbing the carbon dioxide and can partially react with the carbon dioxide to increase the carbon content of the final product.
The separation method is not particularly limited, and a centrifugal separation method may be employed.
The washing method is not particularly limited, and washing methods known in the art may be employed, and the washing solvent may be an alcohol, such as ethanol.
The drying temperature is not particularly limited, and the drying may be carried out at 60 to 80 ℃ and the drying time is not particularly limited until the weight is constant.
Step (2)
In this step, the inert gas may be nitrogen, argon, helium, or the like.
In some embodiments, the carbonization treatment has the following process parameters: heating to 500-900 ℃ at the speed of 5 ℃/min, and then preserving heat for 1.5-3 h.
As shown in FIG. 1, the principle of the preparation process of the invention is as follows:
according to the invention, the hydroquinone formaldehyde resin nanobelt coil is taken as a resin substrate, ethylene amine substances, carbon disulfide and carbon dioxide are promoted to be polymerized on the surface of the substrate in situ in a high-pressure reaction kettle (a high-molecular polymer containing nitrogen and sulfur grows on the surface of the hydroquinone formaldehyde resin nanobelt coil in situ), a carbon precursor raw material containing sulfur/nitrogen elements is obtained, the high-molecular polymer is pyrolyzed and converted into a nitrogen-sulfur-oxygen co-doped hard carbon material by a simple one-step carbonization method, the material still maintains a ribbon coil structure, the inner part of the material is a carbon skeleton derived from the hydroquinone formaldehyde resin, and the outer coating layer is a nitrogen-sulfur-oxygen doped hard carbon shell layer.
In order to solve the problem that the negative electrodes such as graphite, hard carbon and the like are not suitable for the sodium ion battery, the negative electrode material is modified by adopting the processes of negative electrode structure design, heteroatom doping, negative electrode material surface coating and the like, but the improvement of the performance of the sodium ion negative electrode by a single strategy is limited, and the negative electrode material is accompanied by side effects, such as excessive conductive material coating and excessive doping, which are easy to reduce the specific capacity of the negative electrode material. Based on the structure, the invention provides the linear nitrogen-sulfur-oxygen co-doped sodium ion battery cathode material, the structure avoids the damage of volume expansion to the electrode material, the mutually communicated carbon structure network is favorable for quick charge transfer, the sodium ion diffusion path is shortened, and the diffusion resistance is reduced. Meanwhile, in-situ nitrogen, sulfur and oxygen co-doping of the cathode material is realized, the conductivity of the hard carbon cathode material can be obviously improved by doping nitrogen, more defect sites can be manufactured on the surface of hard carbon by doping sulfur/oxygen and other elements, the interlayer distance of carbon atoms is increased, the wettability of the cathode and electrolyte is improved, the transmission distance of sodium ions is shortened, and the mass transfer efficiency of the sodium ions is accelerated. Therefore, the cathode material has good rate performance and excellent cycle stability. The preparation method overcomes the limitation of a single negative electrode modification strategy, is simple and is suitable for large-scale industrial production.
In a specific embodiment, the preparation method of the coil-shaped nitrogen-sulfur-oxygen co-doped sodium ion battery negative electrode material specifically comprises the following steps:
preparing a mixed solvent of water and ethylenediamine according to a certain proportion, adding the mixed solvent into a polytetrafluoroethylene lining of a high-pressure reaction kettle, adding a certain amount of hydroquinone formaldehyde resin nanoribbon coils and a certain amount of ethylene amine, sealing the reaction kettle, and magnetically stirring the mixture under the condition of ice-water bath. Slowly injecting a certain amount of carbon disulfide through a reserved feeding port of a reaction kettle cover by using an injector, then heating to 25 ℃, supplementing a certain amount of carbon dioxide to 1MPa after the system pressure reaches saturated vapor pressure, stirring for 2 hours at constant temperature under the pressure, after the reaction is finished, performing centrifugal separation and ethanol cleaning on a product, and drying at 60-80 ℃ to constant weight. And under the protection of inert gas, performing one-step carbonization treatment on the dried sample, and slowly cooling to room temperature after the carbonization is finished to obtain the coil-shaped nitrogen-sulfur-oxygen co-doped negative electrode material.
In a second aspect, the invention provides a linear-shaped nitrogen-sulfur-oxygen co-doped sodium ion battery negative electrode material, which is prepared according to the method;
the negative electrode material of the coil-shaped nitrogen-sulfur-oxygen co-doped sodium ion battery is hard carbon with a ribbon coil structure, the hard carbon is of a core-shell structure, the inner core is a carbon skeleton derived from hydroquinone formaldehyde resin, and the surface of the inner core is coated with a nitrogen-sulfur-oxygen doped carbon shell layer.
In a third aspect, the invention provides a sodium ion battery, which comprises the coil-shaped nitrogen-sulfur-oxygen co-doped sodium ion battery negative electrode material.
The negative electrode material is coated on a negative electrode sheet as a negative electrode active material layer to form a negative electrode, and the sodium ion battery may have a structure and components conventional in the art, for example, a positive electrode, an electrolyte, a separator, an aluminum plastic film, and the like, in addition to the negative electrode. There is no particular limitation on the positive electrode, the electrolyte, the separator, and the aluminum plastic film, nor on the structure and assembly method of the sodium battery, and any structure and assembly method known in the art that can be used for the sodium battery may be employed.
The sodium ion battery has the same advantages as the coil-shaped nitrogen-sulfur-oxygen co-doped sodium ion battery cathode material, and the description is omitted.
Has the advantages that:
(1) The nitrogen-sulfur-oxygen co-doped cathode material prepared by the invention has a coil-shaped structure, and the structure can effectively buffer the volume expansion in the process of sodium ion sodium intercalation and deintercalation. The nitrogen-sulfur-doped shell-coated hard carbon material can inhibit the formation of an SEI film on the surface of a negative electrode and improve the first charge-discharge efficiency of the negative electrode material. The in-situ nitrogen-sulfur-oxygen co-doping can introduce a defect structure on the surface of the carbon material, improve the wettability of the cathode and electrolyte, simultaneously improve the conductivity of the electrode, accelerate the mass transfer efficiency of sodium ions, and the nitrogen-sulfur-oxygen co-doping cathode material has good rate performance and excellent cycling stability.
(2) The preparation method is simple, has a novel structure, can be used for large-scale production, and has excellent industrial prospect.
The present invention has been described in detail hereinabove, but the above embodiments are merely illustrative in nature and are not intended to limit the present invention. Furthermore, there is no intention to be bound by any theory presented in the preceding prior art or the summary or the following examples.
Unless expressly stated otherwise, a numerical range throughout this specification includes any sub-range therein and any numerical value incremented by the smallest sub-unit within a given value. Unless expressly stated otherwise, numerical values throughout this specification represent approximate measures or limitations to the extent that such deviations from the given values, as well as embodiments having approximately the stated values and having the exact values stated, are included. Other than in the operating examples provided at the end of the detailed description, all numbers expressing quantities or conditions of parameters (e.g., quantities or conditions) used in this specification, including the appended claims, are to be understood as being modified in all instances by the term "about" whether or not "about" actually appears before the number. "about" means that the numerical value so described is susceptible to slight imprecision (with some approach to exactness in that value; approximately or reasonably close to that value; approximately). As used herein, "about" refers to at least variations that can be produced by ordinary methods of measuring and using such parameters, provided that the imprecision provided by "about" is not otherwise understood in the art with this ordinary meaning. For example, "about" can include variations of less than or equal to 10%, less than or equal to 5%, less than or equal to 4%, less than or equal to 3%, less than or equal to 2%, less than or equal to 1%, or less than or equal to 0.5%.
Drawings
FIG. 1 is a schematic diagram of the preparation of a negative electrode material of a wire-wound nitrogen-sulfur-oxygen co-doped sodium ion battery.
FIG. 2 is a schematic structural diagram of a high-pressure reactor used in the present invention.
Fig. 3 is an SEM picture of the negative electrode material of the wire-coil nitrogen-sulfur-oxygen co-doped sodium ion battery prepared in example 1, where the left side is high magnification and the right side is low magnification.
Fig. 4 is an XPS analysis result of the negative electrode material of the wire-coil nitrogen-sulfur-oxygen co-doped sodium ion battery prepared in example 1 of the present invention.
Fig. 5 is a comparative graph of the impedance test of the EIS electrode material of the nitrogen sulfur oxygen co-doped hard carbon material prepared in example 1 of the present invention and the non-doped hard carbon material prepared in comparative example 1.
Detailed Description
The present invention is further illustrated by the following examples, which are provided for illustrative purposes only and are not to be construed as limiting the scope of the invention.
The starting materials, reagents, methods and the like used in the examples are those conventional in the art unless otherwise specified.
The hydroquinone formaldehyde resin nano ribbon coil is prepared by the following method:
1.65g hydroquinone (0.015 mol), 2.5mL 37wt% formaldehyde and 115mL 10wt% hydrochloric acid were thoroughly mixed in a 200mL Teflon-lined autoclave. The autoclave was then sealed and heated at 180 ℃ for 12 hours. The resulting black sponge-like product was filtered and washed with water. The filter cake was dried under vacuum at 60 ℃ for 6 hours. Finally, 2.0g of a light dark brown powder was collected.
Triethylene tetramine solution was purchased from Shanghai Allantin and analyzed for pure AR (95%);
the remaining drugs were from the Michalin reagent.
Scanning Electron Microscope (SEM) adopts a field emission SU-70 microscope; elemental analysis X-ray photoelectron spectroscopy (XPS, elementar Vario MICRO CUBE, germany) was used.
Examples
Example 1
A preparation method of a coiled nitrogen-sulfur-oxygen co-doped sodium ion battery negative electrode material comprises the following steps:
(1) Preparing a precursor raw material: adding ethylenediamine and water into a polytetrafluoroethylene lining of a high-pressure reaction kettle (the structure is shown in figure 2), wherein the volume ratio of the ethylenediamine to the water is 1:1, fully stirring to prepare 80ml of mixed solvent, adding 80mg of hydroquinone formaldehyde resin nanobelt coil and 0.25mol of triethylene tetramine solution, sealing a reaction kettle, magnetically stirring the mixture under the condition of ice-water bath, reserving a feed port through the reaction kettle, slowly injecting 0.58mol of carbon disulfide solvent into the reaction kettle, heating to 25 ℃, supplementing a certain amount of carbon dioxide gas until the pressure of the reaction system reaches 1MPa after the pressure of the system reaches saturated vapor pressure, stirring at constant temperature for 2 hours under the pressure, after the reaction is finished, carrying out centrifugal separation and ethanol cleaning on the product for three times, and drying at 60 ℃ to constant weight.
(2) Carbonizing treatment: and (3) carrying out one-step carbonization treatment on the dried sample, heating to 600 ℃ at the heating rate of 5 ℃/min under the protection of inert gas, and then carrying out heat preservation for 2h. And slowly cooling to room temperature after carbonization is finished, thus obtaining the coil-shaped nitrogen-sulfur-oxygen co-doped cathode material. The SEM topography is shown in fig. 3, which shows that the negative electrode material is in a pellet shape, and in order to further determine the elemental composition of the material, XPS analysis is performed on the material, as shown in fig. 4, which shows that the material mainly includes elements such as sulfur, nitrogen, carbon, oxygen, and the like.
(3) And (3) electrochemical performance testing: a CR2032 type battery case is adopted to assemble a battery, battery slurry is prepared according to the wire-ball-shaped nitrogen-sulfur-oxygen co-doped negative electrode material, acetylene Black (AB) and a polyvinylidene fluoride adhesive according to the mass ratio of 80And (3) minutes. The cell assembly was carried out in an argon filled glove box (MBRAUN MB Labstar 1500/780) with water and oxygen levels less than 0.1ppm. The counter electrode is made of metal sodium sheet, and the electrolyte is NaClO 4 (1 mol) of propylene carbonate. Glass fibers are used as the separator material. The circulation performance and the charge-discharge efficiency of the battery are tested by using a NEWARE-BTS-4008 multi-channel battery cycler. The current of the charge and discharge test is 100mA/g, the first discharge specific capacity is 419mAh/g, the first efficiency is 89%, and the specific capacity is 352mAh/g after 100 times of circulation.
Example 2
A preparation method of a coiled nitrogen-sulfur-oxygen co-doped sodium ion battery negative electrode material comprises the following steps:
(1) Preparing a precursor raw material: adding ethylenediamine and water into a polytetrafluoroethylene lining of a high-pressure reaction kettle in a volume ratio of 1:2, fully stirring to prepare 80ml of mixed solvent, adding 60mg of hydroquinone formaldehyde resin nano ribbon coil and 0.25mol of triethylene tetramine solution, sealing the reaction kettle, magnetically stirring the mixture under the ice-water bath condition, simultaneously reserving a feed inlet in the reaction kettle, slowly injecting 0.74mol of carbon disulfide solvent into the reaction kettle, heating to 25 ℃, supplementing a certain amount of carbon dioxide gas to the pressure of the reaction system to 1MPa after the pressure of the system reaches saturated vapor pressure, stirring at constant temperature for 2 hours under the pressure, centrifugally separating and cleaning the product with ethanol for three times after the reaction is finished, and drying at 60 ℃ to constant weight.
(2) Carbonizing treatment: and (3) carrying out one-step carbonization treatment on the dried sample, heating to 800 ℃ at a heating rate of 5 ℃/min under the protection of inert gas, and then carrying out heat preservation for 2h. And slowly cooling to room temperature after the carbonization is finished, and obtaining the coil-shaped nitrogen-sulfur-oxygen co-doped negative electrode material.
(3) And (3) electrochemical performance testing: a CR2032 type battery case is adopted to assemble a battery, battery slurry is prepared according to the wire-ball-shaped nitrogen-sulfur-oxygen co-doped negative electrode material, acetylene Black (AB) and a polyvinylidene fluoride adhesive according to the mass ratio of 80. The battery assembly is in an argon filled glove box (MBRAUN MB)Labstar 1500/780), water and oxygen contents are less than 0.1ppm. The counter electrode is made of metal sodium sheet, and the electrolyte is NaClO 4 (1 mol) of propylene carbonate. Glass fibers are used as separator material. The circulation performance and the charge-discharge efficiency of the battery are tested by using a NEWARE-BTS-4008 multi-channel battery cycler. The current of the charge and discharge test is 100mA/g, the first specific discharge capacity is 452mAh/g, the first efficiency is 85%, and the specific capacity is 320mAh/g after 100 times of circulation.
Example 3
A preparation method of a coiled nitrogen-sulfur-oxygen co-doped sodium ion battery negative electrode material comprises the following steps:
(1) Preparing a precursor raw material: adding ethylenediamine and water into a polytetrafluoroethylene lining of a high-pressure reaction kettle in a volume ratio of 1: and 3, fully stirring to prepare 80ml of mixed solvent, adding 50mg of hydroquinone formaldehyde resin nanobelt coil and 0.25mol of triethylene tetramine solution, sealing the reaction kettle, magnetically stirring the mixture under the ice-water bath condition, reserving a feed port through the reaction kettle, slowly injecting 1mol of carbon disulfide solvent into the reaction kettle, heating to 25 ℃, supplementing a certain amount of carbon dioxide gas until the pressure of the reaction system reaches 1MPa after the pressure of the system reaches saturated vapor pressure, stirring at constant temperature for 2 hours under the pressure, after the reaction is finished, performing centrifugal separation and ethanol cleaning on the product for three times, and drying at 60 ℃ to constant weight.
(2) Carbonizing treatment: and (3) carrying out one-step carbonization treatment on the dried sample, heating to 600 ℃ at a heating rate of 5 ℃/min under the protection of inert gas, and then preserving heat for 2h. And slowly cooling to room temperature after carbonization is finished, thus obtaining the coil-shaped nitrogen-sulfur-oxygen co-doped cathode material.
(3) And (3) electrochemical performance testing: a CR2032 type battery case is adopted to assemble a battery, battery slurry is prepared according to the wire-ball-shaped nitrogen-sulfur-oxygen co-doped negative electrode material, acetylene Black (AB) and a polyvinylidene fluoride adhesive according to the mass ratio of 80. The cell assembly was carried out in an argon filled glove box (MBRAUN MB Labstar 1500/780) with water and oxygen contents less than0.1ppm. The counter electrode is made of metal sodium sheet, and the electrolyte is NaClO 4 (1 mol) of propylene carbonate. Glass fibers are used as the separator material. The circulation performance and the charge-discharge efficiency of the battery are tested by using a NEWARE-BTS-4008 multi-channel battery cycler. The current of the charge and discharge test is 100mA/g, the first specific discharge capacity is 441mAh/g, the first efficiency is 75%, and the specific capacity is 302mAh/g after 100 times of circulation.
Example 4
A preparation method of a coiled nitrogen-sulfur-oxygen co-doped sodium ion battery negative electrode material comprises the following steps:
(1) Preparing a precursor raw material: adding ethylenediamine and water into a polytetrafluoroethylene lining of a high-pressure reaction kettle in a volume ratio of 1:4, fully stirring to prepare 80ml of mixed solvent, adding 100mg of hydroquinone formaldehyde resin nanobelt coil and 0.25mol of triethylene tetramine solution, sealing the reaction kettle, magnetically stirring the mixture under the condition of ice-water bath, reserving a feed port through the reaction kettle, slowly injecting 1.25mol of carbon disulfide solvent into the reaction kettle, heating to 25 ℃, supplementing a certain amount of carbon dioxide gas until the pressure of the reaction system reaches 1MPa after the pressure of the system reaches saturated vapor pressure, stirring at constant temperature for 2 hours under the pressure, after the reaction is finished, carrying out centrifugal separation and ethanol cleaning on the product for three times, and drying at 60 ℃ to constant weight.
(2) Carbonizing treatment: and (3) carrying out one-step carbonization treatment on the dried sample, heating to 900 ℃ at the heating rate of 5 ℃/min under the protection of inert gas, and then carrying out heat preservation for 2h. And slowly cooling to room temperature after the carbonization is finished, and obtaining the coil-shaped nitrogen-sulfur-oxygen co-doped negative electrode material.
(3) And (3) electrochemical performance testing: a CR2032 type battery case is adopted to assemble a battery, battery slurry is prepared according to the wire-ball-shaped nitrogen-sulfur-oxygen co-doped negative electrode material, acetylene Black (AB) and a polyvinylidene fluoride adhesive according to the mass ratio of 80. The cell assembly was carried out in an argon filled glove box (MBRAUN MB Labstar 1500/780) with water and oxygen levels less than 0.1ppm. The counter electrode is made of metal sodium sheet and the electrolyte isWith addition of NaClO 4 (1 mol) of propylene carbonate. Glass fibers are used as the separator material. The circulation performance and the charge-discharge efficiency of the battery are tested by using a NEWARE-BTS-4008 multi-channel battery cycler. The current of the charge and discharge test is 100mA/g, the first discharge specific capacity is 500mAh/g, the first efficiency is 71%, and the specific capacity is 314mAh/g after 100 times of circulation.
Comparative example 1
The difference between the comparative example and the example 1 is that only hydroquinone formaldehyde resin nanobelt coil is adopted as a carbon precursor, a nitrogen/sulfur-containing high molecular material is not polymerized on the surface of the carbon precursor, and the material is a hard carbon material without nitrogen/sulfur elements after carbonization, and the specific steps are as follows: carbonizing 80mg of hydroquinone formaldehyde resin nanobelt coil, heating to 600 ℃ at a heating rate of 5 ℃/min under the protection of inert gas, and then preserving heat for 2 hours. And slowly cooling to room temperature after carbonization is finished to obtain the hydroquinone formaldehyde resin nanobelt coil derived hard carbon cathode, and testing the electrochemical performance of the hydroquinone formaldehyde resin nanobelt coil derived hard carbon cathode according to the method in the embodiment 1. The current of the charge and discharge test is 100mA/g, the first discharge specific capacity is 728mAh/g, the first efficiency is 52%, the specific capacity is 211mAh/g after 100 times of circulation, and comparison shows that the first charge and discharge efficiency can be improved by doping the heteroatom, and the circulation performance of the cathode material is improved.
In addition, the negative electrode materials of example 1 and comparative example 1 were subjected to the EIS electrode material resistance test by the method of: the electrode potential is perturbed by adopting alternating voltage (sine wave), so that the electrode potential can oscillate near the equilibrium potential, the amplitude of a current (or voltage) signal can be recorded in the process of returning the electrode potential to a stable state, and therefore, the alternating current impedance (EIS) information of the electrode can be calculated, and an alternating current impedance spectrogram can be drawn. The different cells were all 10 in this experiment -2 ～10 5 EIS was recorded in the frequency range of Hz.
As a result, as shown in fig. 5, it can be seen that the impedance of the heteroatom-doped anode material is significantly lower than that of the undoped sample, which further confirms that the heteroatom doping can effectively improve the conductivity of the anode material.
Comparative example 2
The difference between the comparative example and the example 1 is that the nitrogen-oxygen co-doped nanobelt is obtained by adopting the method of the patent CN 108666570A, the nanobelt is taken as a substrate to further load elemental sulfur to obtain the nitrogen-oxygen-sulfur co-doped electrode material, the performance of the sodium ion battery of the cathode material is tested according to the method of the example 1, the current of the charge and discharge test is 100mA/g, the first discharge specific capacity of the cathode material is 815mAh/g, the first efficiency is 41%, and the specific capacity is 151mAh/g after 100 cycles.
Through comparison, the nitrogen doping is different from the method for directly pyrolyzing the nitrogen-rich precursor, the nitrogen-containing functional group is introduced into the obtained carbon material through the method of ammonia water activation post-treatment, the nitrogen doping amount is extremely low, and meanwhile, the nitrogen-sulfur-oxygen co-doped carbon nanoribbon can be obtained by further mixing with elemental sulfur and heating. The carbon material obtained by the method has overlarge specific surface area, the overlarge specific surface area increases the irreversible capacity of initial charge and discharge, the initial charge and discharge efficiency is reduced, and meanwhile, elemental sulfur is further doped, so that sulfur is not beneficial to entering the interlayer spacing of the carbon material, and the carbon material is easy to fall off in the charge and discharge process, and the cycle performance of the cathode material is poor.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (9)
1. A preparation method of a coiled nitrogen-sulfur-oxygen co-doped sodium ion battery negative electrode material is characterized by comprising the following steps:
(1) Mixing hydroquinone formaldehyde resin nanobelt coils, ethylene amine and a solvent in an ice water bath, adding carbon disulfide, heating to 25-30 ℃, supplementing carbon dioxide to 1-2 MPa after the system pressure reaches saturated vapor pressure, carrying out constant temperature reaction, and separating, cleaning and drying the product;
(2) And carbonizing the dried product in an inert atmosphere to obtain the coil-shaped nitrogen-sulfur-oxygen co-doped sodium ion battery negative electrode material.
2. The method according to claim 1, wherein in step (1), the ethyleneamine is one or more selected from diethylenetriamine, triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine.
3. The method according to claim 1, wherein in the step (1), the solvent is a mixed solvent of water and ethylenediamine, and the volume ratio of water to ethylenediamine is 1.
4. The preparation method according to claim 1, wherein in the step (1), the ratio of the mass of the hydroquinone formaldehyde resin nanobelt coil to the molar amount of the ethylene amine is 30 to 100mg.
5. The method of claim 1, wherein the concentration of the hydroquinone formaldehyde resin nanoribbon coils in the solvent is 0.375 to 1.25g/L.
6. The preparation method according to claim 1, wherein the molar ratio of the ethylene amine to the carbon disulfide is 1.
7. The production method according to any one of claims 1 to 6, wherein in the step (2), the carbonization treatment has the following process parameters: heating to 500-900 ℃ at the speed of 5 ℃/min, and then preserving heat for 1.5-3 h.
8. A coiled nitrogen-sulfur-oxygen co-doped sodium ion battery cathode material is characterized by being prepared by the preparation method of any one of claims 1 to 7;
the negative electrode material of the coil-shaped nitrogen-sulfur-oxygen co-doped sodium ion battery is hard carbon with a ribbon coil structure, the hard carbon is of a core-shell structure, the inner core is a carbon skeleton derived from hydroquinone formaldehyde resin, and the surface of the inner core is coated with a nitrogen-sulfur-oxygen doped carbon shell layer.
9. A sodium ion battery, which is characterized by comprising the coil-shaped nitrogen-sulfur-oxygen co-doped sodium ion battery negative electrode material of claim 8.
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| KR20160126857A (en) * | 2015-04-24 | 2016-11-02 | 삼성전자주식회사 | Complex for anode active material, anode including the complex, lithium secondary battery including the anode, and method of preparing the complex |
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