CN116605867B - Negative electrode material of sodium ion battery and preparation method and application thereof - Google Patents

Negative electrode material of sodium ion battery and preparation method and application thereof Download PDF

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CN116605867B
CN116605867B CN202310589800.0A CN202310589800A CN116605867B CN 116605867 B CN116605867 B CN 116605867B CN 202310589800 A CN202310589800 A CN 202310589800A CN 116605867 B CN116605867 B CN 116605867B
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ion battery
sodium ion
nitrogen
stirring
negative electrode
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CN116605867A (en
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何天丰
官忠明
金绍平
陈烁宇
林婵娟
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Fujian Xinsen Carbon Co ltd
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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
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    • 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
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    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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    • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
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    • H01M10/00—Secondary cells; Manufacture thereof
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    • H—ELECTRICITY
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Abstract

The invention discloses a sodium ion battery negative electrode material, a preparation method and application thereof, and belongs to the technical field of sodium ion battery negative electrode materials; coating the slurry on a copper foil, drying to obtain a loaded copper foil, rolling the loaded copper foil, punching the rolled loaded copper foil into an electrode plate, and finally assembling and forming the button cell. The invention uses 4-vinyl pyridine and polyvinylpyrrolidone containing pyridine nitrogen configuration as electrophilic auxiliary agent to assist the evolution of graphite phase carbon nitride into high nitrogen doped carbon material, and simultaneously, sulfur is doped on the graphite phase carbon nitride to finally prepare the sodium ion battery anode material with excellent electrochemical performance.

Description

Negative electrode material of sodium ion battery and preparation method and application thereof
Technical Field
The invention belongs to the technical field of sodium ion battery anode materials, and particularly relates to a sodium ion battery anode material, a preparation method and application thereof.
Background
Although the Lithium Ion Batteries (LIBs) are developed more mature, the lithium resources in China are scarce to restrict the lithium ion batteries to support two industries of electric automobiles and large-scale energy storage at the same time, so that the Sodium Ion Batteries (SIBs) become a new research hot spot and key point in the field of electrochemical energy storage by virtue of no resource limitation. Due to the slow kinetics, the sodium storage capacity of graphite and silicon anode materials commonly used in lithium ion batteries is extremely low, so that the development of anode materials matched with anode materials and having excellent performance plays a vital role in the industrial application of sodium ion batteries.
Research on Sodium Ion Battery (SIBs) anode materials has focused on carbon materials and partially non-carbon materials, including metals and their alloys, metal oxides, sulfides, nitrides, phosphides, and the like. Although the non-carbon anode material has higher capacity, the conductivity is poor, the volume change is large and the powder is easy to pulverize; the carbon material has good conductivity, and the structure is relatively stable in the charge and discharge process, and is considered as a key cathode material for promoting the practical process of SIBs. However, the carbon negative electrode material also faces the problems of low first-circle coulombic efficiency (ICE), low specific capacity and the like in practical application.
Disclosure of Invention
The invention aims to provide a sodium ion battery anode material and a preparation method and application thereof, and aims to solve the problems of low initial coulomb efficiency and low specific capacity of a carbon anode material.
The aim of the invention can be achieved by the following technical scheme:
The invention provides a preparation method of a negative electrode material of a sodium ion battery, which comprises the following specific steps: adding a nitrogen-rich material and a conductive additive into absolute ethyl alcohol, stirring for 10-15min, adding an adhesive, continuously stirring for 10-15min to obtain slurry, and performing spray drying on the slurry to obtain a sodium ion battery anode material;
the nitrogen-rich material is prepared by denitrification doping modification of graphite phase carbon nitride;
the conductive additive is three-dimensional graphene.
Further, the mass ratio of the nitrogen-rich material to the conductive additive to the adhesive is 8:1:1.
Further, the preparation process of the nitrogen-rich material comprises the following steps:
Step A1, stirring and adding 4-vinylpyridine, N-methylenebisacrylamide, polyvinylpyrrolidone, azodiisobutyronitrile and sodium dodecyl sulfate into styrene, mixing, introducing nitrogen, deoxidizing, continuing to mix and stir for 30min, heating to 65-85 ℃, stirring and reacting for 12-24h, and obtaining porous microspheres after decompression and suction filtration, water washing and drying;
step A2, adding graphite-phase carbon nitride and porous microspheres into absolute ethyl alcohol, stirring for 3 hours, and drying at 60 ℃ to remove the absolute ethyl alcohol to obtain a pale yellow precursor;
and A3, placing the precursor into a crucible, placing the crucible into a tube furnace, vacuumizing reciprocally, introducing pure argon for 3 times, heating to 650-700 ℃ at the speed of 10 ℃/min, preserving heat for 2 hours, and naturally cooling to room temperature to obtain the nitrogen-rich material.
Further, the dosage ratio of the styrene, the 4-vinylpyridine, the N, N-methylene bisacrylamide, the polyvinylpyrrolidone, the azodiisobutyronitrile and the sodium dodecyl sulfate in the step A1 is 100mL to 15g to 1g to 15g to 0.1-0.3g to 5-7g.
Further, in the step A2, the mass ratio of the graphite phase carbon nitride to the porous microspheres is 20:1.
Further, the preparation process of the graphite phase carbon nitride (g-C 3N4) comprises the following steps:
Uniformly mixing ammonium chloride (NH 4 Cl) and guanidine hydrochloride (CH 5N3 HCl) according to a mass ratio of 1:1, grinding fully, then placing into a semi-closed alumina crucible, reacting in a muffle furnace, heating from room temperature to 580-620 ℃ at a heating rate of 4-6 ℃/min under an air atmosphere, preserving heat for 3 hours, and naturally cooling to room temperature to obtain graphite-phase carbon nitride of light yellow solid.
Further, the preparation process of the adhesive comprises the following steps:
Adding 4-allylcatechol and trimethoxy silane into toluene, stirring uniformly, heating to 70 ℃ under nitrogen atmosphere, stirring and reacting for 2-4h, removing toluene by rotary evaporation after the reaction is finished, adding polytetrafluoroethylene emulsion with the solid content of 60%, and stirring for 30-50min at the rotating speed of 10-20r/min to obtain the adhesive.
Further, the dosage ratio of the 4-allylcatechol, trimethoxysilane, toluene and polytetrafluoroethylene emulsion is 15g to 12g to 150-200mL to 25-27mL.
Further, the molecular weight of the polytetrafluoroethylene is 8000-10000.
The second part, the invention provides a negative electrode material of a sodium ion battery, which is prepared by the preparation method.
The third part, the invention provides an application of the negative electrode material of the sodium ion battery, which is prepared by the preparation method, in button cells, and the specific application process comprises the following steps:
Coating the slurry on a copper foil, drying at 70 ℃ for 6 hours, and then vacuum drying at 120 ℃ for 12 hours to obtain a loaded copper foil, rolling the loaded copper foil, punching the loaded copper foil into an electrode sheet, then using a sodium sheet as a counter electrode, using a polypropylene film as a diaphragm, using dimethyl ether containing 1M NaPF 6 as an electrolyte, and assembling and forming the button cell in a glove box.
The invention has the beneficial effects that:
the graphite phase carbon nitride prepared by the invention is a graphite structure compound with extremely high nitrogen content, but the graphite phase carbon nitride has a bridge head nitrogen structure, the bridge head nitrogen structure can influence the stability of a sodium ion battery anode material constructed by graphene silicon nitride in Na + storage (the graphite nitrogen and amino nitrogen in the graphene carbon nitride can inhibit Na + storage, and pyridine nitrogen and pyrrole nitrogen can improve Na + migration rate), so that firstly, the graphite phase carbon nitride is subjected to selective reduction and denitrification, and in the conventional denitrification process, if metal (Al, mg and the like) is used for thermal reduction and denitrification, the nitrogen content in the graphite phase carbon nitride is excessively reduced, and the 4-vinyl pyridine and polyvinylpyrrolidone containing pyridine nitrogen structures are used as electrophilic auxiliary agents to assist the evolution of the graphite phase carbon nitride into a high-nitrogen (pyridine nitrogen) doped carbon material, and the specific reaction process is as follows: under the high-temperature heat treatment condition, 4-vinyl pyridine and polyvinylpyrrolidone are grafted to the surface of graphite-phase carbon nitride, then thermal decomposition and volatilization are carried out under the high-temperature condition, grafting sites remain at the grafting sites, the grafting sites are rearranged and carbonized at high temperature to form sp 2 carbon structures with higher thermal stability, then the rearrangement and carbonization of the integral graphite-phase carbon nitride are promoted, and finally the high-nitrogen doped carbon material, namely the nitrogen-rich material with excellent electrochemical performance, is formed.
Meanwhile, in the process of preparing the nitrogen-rich material, firstly, porous microspheres are prepared, and the formation mechanism is as follows: the method comprises the steps of performing emulsion polymerization on monomers such as 4-vinylpyridine, N-methylene bisacrylamide, polyvinylpyrrolidone and the like in oil-phase styrene under the action of an initiator azodiisobutyronitrile to form microspheres, performing high-temperature heat treatment on the microspheres under the action of sodium dodecyl sulfate to obtain a complex compound by pyridine nitrogen and sodium ions (sodium dodecyl sulfate) contained in the 4-vinylpyridine, ensuring the content of sodium dodecyl sulfate in the porous microspheres (preventing excessive loss of sodium dodecyl sulfate in suction filtration and water washing), and uniformly carrying the porous microspheres on graphite-phase carbon nitride by utilizing the excellent adsorption performance of the porous microspheres, and finally obtaining the nitrogen-rich material. The sodium dodecyl sulfate is used as a solid sulfur source, the solid sulfur source is uniformly carried on graphite-phase carbon nitride by taking microspheres as a medium, and under the high-temperature condition, the sodium dodecyl sulfate is carbonized to prepare the sulfur-doped graphite-phase carbon nitride material, and the sulfur doping is beneficial to improving the specific capacity of the negative electrode material of the sodium ion battery.
Finally, in the process of preparing the negative electrode material of the sodium ion battery, three-dimensional graphene is selected to replace conventional carbon black to be used as a conductive additive, and the three-dimensional graphene is embedded in gaps of the three-dimensional graphene by utilizing the porous structure of the three-dimensional graphene, so that the nitrogen-rich material and the three-dimensional graphene are tightly combined and uniformly distributed, and are connected with an adhesive in the following modes of hydrogen bonding, coordination, condensation reaction and the like, so that the raw material distribution is more uniform, and a compact continuous conductive network is formed. Meanwhile, the invention adopts a hybridized adhesive, in particular to a hybridized solution composed of 4-allylcatechol, trimethoxy silane and polytetrafluoroethylene emulsion, which form a cross-linked network in a negative electrode material, wherein polytetrafluoroethylene has strong hydrophobicity, electrolyte has poor wettability to the polytetrafluoroethylene, plays a channel role in the negative electrode material, forms stronger coordination chelating capability between catechol groups and copper foil, and improves the adhesiveness between slurry and the copper foil through chemical linking and coordination. The electrochemical performance of the negative electrode material of the sodium ion battery is promoted.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Preparing graphite phase carbon nitride:
Uniformly mixing ammonium chloride (NH 4 Cl) and guanidine hydrochloride (CH 5N3 HCl) according to a mass ratio of 1:1, grinding fully, then placing into a semi-closed alumina crucible, reacting in a muffle furnace, heating from room temperature to 580 ℃ at a heating rate of 4 ℃/min under an air atmosphere, preserving heat for 3 hours, and naturally cooling to room temperature to obtain light yellow solid graphite phase carbon nitride.
Example 2
Preparing graphite phase carbon nitride:
Uniformly mixing ammonium chloride (NH 4 Cl) and guanidine hydrochloride (CH 5N3 HCl) according to a mass ratio of 1:1, grinding fully, then placing into a semi-closed alumina crucible, reacting in a muffle furnace, heating from room temperature to 610 ℃ at a heating rate of 5 ℃/min under an air atmosphere, preserving heat for 3 hours, and naturally cooling to room temperature to obtain light yellow solid graphite phase carbon nitride.
Example 3
Preparing graphite phase carbon nitride:
Uniformly mixing ammonium chloride (NH 4 Cl) and guanidine hydrochloride (CH 5N3 HCl) according to the mass ratio of 1:1, grinding fully, then placing into a semi-closed alumina crucible, reacting in a muffle furnace, heating from room temperature to 620 ℃ at the heating rate of 6 ℃/min under the air atmosphere, preserving heat for 3 hours, and naturally cooling to room temperature to obtain the graphite-phase carbon nitride of light yellow solid.
Example 4
Preparing a nitrogen-rich material:
Step A1, stirring and adding 15g of 4-vinylpyridine, 1g of N, N-methylenebisacrylamide, 15g of polyvinylpyrrolidone, 0.1g of azodiisobutyronitrile and 5g of sodium dodecyl sulfate into 100mL of styrene, mixing, introducing nitrogen, deoxidizing, continuing mixing and stirring for 30min, heating to 65 ℃, stirring and reacting for 12h, and obtaining porous microspheres after decompression, suction filtration, water washing and drying;
step A2, adding graphite-phase carbon nitride and porous microspheres prepared in the embodiment 1 into absolute ethyl alcohol, wherein the mass ratio of the graphite-phase carbon nitride to the porous microspheres is 20:1, stirring for 3 hours, and drying at 60 ℃ to remove the absolute ethyl alcohol to obtain a pale yellow precursor;
And A3, placing the precursor into a crucible, placing the crucible into a tube furnace, vacuumizing reciprocally, introducing pure argon for 3 times, heating to 650 ℃ at the speed of 10 ℃/min, preserving heat for 2 hours, and naturally cooling to room temperature to obtain the nitrogen-rich material.
Example 5
Preparing a nitrogen-rich material:
Step A1, stirring and adding 15g of 4-vinyl pyridine, 1g of N, N-methylene bisacrylamide, 15g of polyvinylpyrrolidone, 0.2g of azodiisobutyronitrile and 6g of sodium dodecyl sulfate into 100mL of styrene, mixing, introducing nitrogen, deoxidizing, continuing mixing and stirring for 30min, heating to 65-85 ℃, stirring and reacting for 20h, decompressing, filtering, washing and drying to obtain porous microspheres;
step A2, adding graphite-phase carbon nitride and porous microspheres prepared in the example 2 into absolute ethyl alcohol, wherein the mass ratio of the graphite-phase carbon nitride to the porous microspheres is 20:1, stirring for 3h, and drying at 60 ℃ to remove absolute ethyl alcohol to obtain a pale yellow precursor;
And A3, placing the precursor into a crucible, placing the crucible into a tube furnace, vacuumizing reciprocally, introducing pure argon for 3 times, heating to 680 ℃ at the speed of 10 ℃/min, preserving heat for 2 hours, and naturally cooling to room temperature to obtain the nitrogen-rich material.
Example 6
Preparing a nitrogen-rich material:
Step A1, stirring and adding 15g of 4-vinylpyridine, 1g of N, N-methylenebisacrylamide, 15g of polyvinylpyrrolidone, 0.3g of azobisisobutyronitrile and 7g of sodium dodecyl sulfate into 100mL of styrene, mixing, introducing nitrogen, deoxidizing, continuing mixing and stirring for 30min, heating to 85 ℃, stirring and reacting for 24h, decompressing, filtering, washing and drying to obtain porous microspheres;
step A2, adding graphite-phase carbon nitride and porous microspheres prepared in the example 3 into absolute ethyl alcohol, wherein the mass ratio of the graphite-phase carbon nitride to the porous microspheres is 20:1, stirring for 3h, and drying at 60 ℃ to remove absolute ethyl alcohol to obtain a pale yellow precursor;
and A3, placing the precursor into a crucible, placing the crucible into a tube furnace, vacuumizing reciprocally, introducing pure argon for 3 times, heating to 700 ℃ at the speed of 10 ℃/min, preserving heat for 2 hours, and naturally cooling to room temperature to obtain the nitrogen-rich material.
Example 7
Preparing an adhesive:
15g of 4-allyl catechol and 12g of trimethoxy silane are added into 150mL of toluene, after being uniformly stirred, the temperature is raised to 70 ℃ under the nitrogen atmosphere, the mixture is stirred and reacts for 2 hours, after the reaction is finished, toluene is removed by rotary evaporation, 25mL of polytetrafluoroethylene emulsion with the solid content of 60% is added, and the mixture is stirred for 30 minutes under the condition of the rotating speed of 10r/min, so that the adhesive is obtained.
Example 8
Preparing an adhesive:
15g of 4-allyl catechol and 12g of trimethoxy silane are added into 180mL of toluene, after being uniformly stirred, the temperature is raised to 70 ℃ under the nitrogen atmosphere, the mixture is stirred and reacts for 3 hours, after the reaction is finished, toluene is removed by rotary evaporation, 26mL of polytetrafluoroethylene emulsion with the solid content of 60% is added, and the mixture is stirred for 40 minutes under the condition of the rotating speed of 18r/min, so that the adhesive is obtained.
Example 9
Preparing an adhesive:
15g of 4-allyl catechol and 12g of trimethoxy silane are added into 200mL of toluene, after being uniformly stirred, the temperature is raised to 70 ℃ under the nitrogen atmosphere, the mixture is stirred and reacts for 4 hours, after the reaction is finished, the toluene is removed by rotary evaporation, 27mL of polytetrafluoroethylene emulsion with the solid content of 60% is added, and the mixture is stirred for 50 minutes under the condition of the rotating speed of 20r/min, so that the adhesive is obtained.
Example 10
Preparing a negative electrode material of a sodium ion battery:
Adding the nitrogen-rich material prepared in the example 4 and the three-dimensional graphene into absolute ethyl alcohol, stirring for 10min, adding the adhesive prepared in the example 7, continuously stirring for 10min to obtain slurry, and performing spray drying on the slurry to obtain the negative electrode material of the sodium ion battery.
Example 11
Preparing a negative electrode material of a sodium ion battery:
adding the nitrogen-rich material and the three-dimensional graphene prepared in the example 5 into absolute ethyl alcohol, stirring for 12min, adding the adhesive prepared in the example 8, continuing stirring for 12min to obtain slurry, and performing spray drying on the slurry to obtain the negative electrode material of the sodium ion battery.
Example 12
Preparing a negative electrode material of a sodium ion battery:
Adding the nitrogen-rich material prepared in the example 6 and the three-dimensional graphene into absolute ethyl alcohol, stirring for 15min, adding the adhesive prepared in the example 9, continuing stirring for 15min to obtain slurry, and performing spray drying on the slurry to obtain the negative electrode material of the sodium ion battery.
Example 13
Application of sodium ion battery anode material:
The slurry prepared in example 10 was coated on a copper foil, dried at 70℃for 6 hours and then dried at 120℃for 12 hours in vacuo to obtain a supported copper foil, which was rolled and punched into an electrode sheet having a diameter of 12mm for use, wherein the mass of the active material was about 1.3mg/cm. Then, a CR2032 type coin cell was assembled in a glove box with sodium foil as a counter electrode and a polypropylene film (glass microfiber film) as a separator. The first circle coulombic efficiency and the cycle performance of the button cell are tested by taking dimethyl ether (DME) containing NaPF 6 of 1M as electrolyte and taking metal sodium sheets as electricity, and under the current density of 50mA/g, the test result is that: the specific capacity of the negative electrode material of the sodium ion battery prepared in example 10 is 312.8mAh/g, the initial coulombic efficiency reaches 91.2%, and the capacity retention rate is 97.0% after the battery circulates 1000 circles.
Example 14
Application of sodium ion battery anode material:
The slurry prepared in example 11 was coated on a copper foil, dried at 70℃for 6 hours and then dried at 120℃for 12 hours in vacuo to obtain a supported copper foil, which was rolled and punched into an electrode sheet having a diameter of 12mm for use, wherein the mass of the active material was about 1.3mg/cm. Then, a CR2032 type coin cell was assembled in a glove box with sodium foil as a counter electrode and a polypropylene film (glass microfiber film) as a separator. The first circle coulombic efficiency and the cycle performance of the button cell are tested by taking dimethyl ether (DME) containing NaPF 6 of 1M as electrolyte and taking metal sodium sheets as electricity, and under the current density of 50mA/g, the test result is that: the specific capacity of the negative electrode material of the sodium ion battery prepared in example 11 is 328.6mAh/g, the initial coulombic efficiency reaches 92.1%, and the capacity retention rate is 91.8% after 1000 cycles of the battery.
Example 15
Application of sodium ion battery anode material:
The slurry prepared in example 12 was coated on a copper foil, dried at 70 ℃ for 6 hours, and vacuum-dried at 120 ℃ for 12 hours to obtain a loaded copper foil, which was rolled and punched into an electrode sheet having a diameter of 12mm for use, wherein the mass of the active material was about 1.3mg/cm. Then, a CR2032 type coin cell was assembled in a glove box with sodium foil as a counter electrode and a polypropylene film (glass microfiber film) as a separator. The first circle coulombic efficiency and the cycle performance of the button cell are tested by taking dimethyl ether (DME) containing NaPF 6 of 1M as electrolyte and taking metal sodium sheets as electricity, and under the current density of 50mA/g, the test result is that: the specific capacity of the negative electrode material of the sodium ion battery prepared in example 12 is 312.5mAh/g, the initial coulombic efficiency reaches 91.4%, and the capacity retention rate is 91.3% after 1000 cycles of the battery.
Comparative example 1
Application of sodium ion battery anode material:
first, a nitrogen-rich material (control group with example 4):
Step A1, stirring and adding 15g of 4-vinyl pyridine, 1g of N, N-methylene bisacrylamide, 15g of polyvinylpyrrolidone and 0.1g of azodiisobutyronitrile into 100mL of styrene, mixing, introducing nitrogen, deoxidizing, continuing mixing and stirring for 30min, heating to 65 ℃, stirring and reacting for 12h, decompressing and filtering, washing with water and drying to obtain porous microspheres;
step A2, adding graphite-phase carbon nitride and porous microspheres prepared in the embodiment 1 into absolute ethyl alcohol, wherein the mass ratio of the graphite-phase carbon nitride to the porous microspheres is 20:1, stirring for 3 hours, and drying at 60 ℃ to remove the absolute ethyl alcohol to obtain a pale yellow precursor;
And A3, placing the precursor into a crucible, placing the crucible into a tube furnace, vacuumizing reciprocally, introducing pure argon for 3 times, heating to 650 ℃ at the speed of 10 ℃/min, preserving heat for 2 hours, and naturally cooling to room temperature to obtain the nitrogen-rich material.
Then, a negative electrode material for sodium ion battery (comparative group to example 10):
adding the prepared nitrogen-rich material and the three-dimensional graphene into absolute ethyl alcohol, stirring for 10min, adding the adhesive prepared in the example 7, and continuing stirring for 10min to obtain slurry; coating the slurry on a copper foil, drying at 70 ℃ for 6 hours, and then drying at 120 ℃ for 12 hours in vacuum to obtain a loaded copper foil, rolling the loaded copper foil, and punching the rolled loaded copper foil into an electrode sheet with the diameter of 12mm for standby, wherein the mass of an active substance is about 1.3mg/cm. Then, a CR2032 type coin cell was assembled in a glove box with sodium foil as a counter electrode and a polypropylene film (glass microfiber film) as a separator. The first circle coulombic efficiency and the cycle performance of the button cell are tested by taking dimethyl ether (DME) containing NaPF 6 of 1M as electrolyte and taking metal sodium sheets as electricity, and under the current density of 50mA/g, the test result is that: the specific capacity of the prepared sodium ion battery cathode material is 278.9mAh/g, the first-circle coulomb efficiency reaches 85.7%, and the capacity retention rate is 89.2% after the battery circulates 1000 circles.
Comparative example 2
Application of sodium ion battery anode material:
first, a sodium ion battery anode material (comparative to example 11) was prepared:
Adding graphite-phase carbon nitride and three-dimensional graphene prepared in example 2 into absolute ethyl alcohol, stirring for 12min, adding the adhesive prepared in example 8, and continuing stirring for 12min to obtain slurry; coating the prepared slurry on a copper foil, drying at 70 ℃ for 6 hours, and then drying at 120 ℃ for 12 hours in vacuum to obtain a loaded copper foil, rolling the loaded copper foil, and punching the rolled loaded copper foil into an electrode sheet with the diameter of 12mm for standby, wherein the mass of an active substance is about 1.3mg/cm. Then, a CR2032 type coin cell was assembled in a glove box with sodium foil as a counter electrode and a polypropylene film (glass microfiber film) as a separator. The first circle coulombic efficiency and the cycle performance of the button cell are tested by taking dimethyl ether (DME) containing NaPF 6 of 1M as electrolyte and taking metal sodium sheets as electricity, and under the current density of 50mA/g, the test result is that: the specific capacity of the prepared sodium ion battery cathode material is 231.3mAh/g, the initial coulomb efficiency reaches 78.3%, and the capacity retention rate is 84.8% after the battery circulates 1000 circles.
The test results in examples 13-15 and comparative examples 1-2 are summarized in Table 1 below;
table 1 shows the test results in examples 13-15 and comparative examples 1-2
As can be seen from Table 1, the final sodium ion battery anode material prepared by the composite process of denitrification and doping of graphite phase carbon nitride has excellent initial coulombic efficiency and cycle performance.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (7)

1. The preparation method of the negative electrode material of the sodium ion battery is characterized by comprising the following specific steps: adding a nitrogen-rich material and a conductive additive into absolute ethyl alcohol, stirring for 10-15min, adding an adhesive, continuously stirring for 10-15min to obtain slurry, and performing spray drying on the slurry to obtain a sodium ion battery anode material;
the nitrogen-rich material is prepared by denitrification doping modification of graphite phase carbon nitride, and the preparation process of the nitrogen-rich material comprises the following steps:
Step A1, stirring and adding 4-vinylpyridine, N-methylenebisacrylamide, polyvinylpyrrolidone, azodiisobutyronitrile and sodium dodecyl sulfate into styrene, mixing, introducing nitrogen, deoxidizing, continuing to mix and stir for 30min, heating to 65-85 ℃, stirring and reacting for 12-24h, and obtaining porous microspheres after decompression and suction filtration, water washing and drying;
step A2, adding graphite-phase carbon nitride and porous microspheres into absolute ethyl alcohol, stirring for 3 hours, and drying at 60 ℃ to remove the absolute ethyl alcohol to obtain a pale yellow precursor;
step A3, placing the precursor into a crucible, placing the crucible into a tube furnace, vacuumizing reciprocally, introducing pure argon for 3 times, heating to 650-700 ℃ at the speed of 10 ℃/min, preserving heat for 2 hours, and naturally cooling to room temperature to obtain a nitrogen-rich material;
the preparation process of the graphite phase carbon nitride comprises the following steps: ammonium chloride and guanidine hydrochloride are mixed according to the mass ratio of 1:1, uniformly mixing and fully grinding, then placing into a semi-closed alumina crucible, reacting in a muffle furnace, heating from room temperature to 580-620 ℃ at a heating rate of 4-6 ℃/min under an air atmosphere, preserving heat for 3 hours, and naturally cooling to room temperature to generate graphite-phase carbon nitride as a light yellow solid;
the preparation process of the adhesive comprises the following steps: adding 4-allylcatechol and trimethoxy silane into toluene, stirring uniformly, heating to 70 ℃ under nitrogen atmosphere, stirring and reacting for 2-4h, after the reaction is finished, removing toluene by rotary evaporation, adding polytetrafluoroethylene emulsion with the solid content of 60%, and stirring for 30-50min at the rotating speed of 10-20r/min to obtain an adhesive;
the conductive additive is three-dimensional graphene.
2. The preparation method of the negative electrode material of the sodium ion battery according to claim 1, wherein the mass ratio of the nitrogen-rich material to the conductive additive to the adhesive is 8:1:1.
3. The method for preparing the negative electrode material of the sodium ion battery according to claim 1, wherein the dosage ratio of the styrene, the 4-vinylpyridine, the N, N-methylenebisacrylamide, the polyvinylpyrrolidone, the azodiisobutyronitrile and the sodium dodecyl sulfate in the step A1 is 100mL:15g:1g:15g:0.1-0.3g:5-7g.
4. The method for preparing a negative electrode material of a sodium ion battery according to claim 1, wherein in the step A2, the mass ratio of the graphite phase carbon nitride to the porous microspheres is 20:1.
5. The preparation method of the negative electrode material of the sodium ion battery according to claim 1, wherein the dosage ratio of the 4-allylcatechol, trimethoxysilane, toluene and polytetrafluoroethylene emulsion is 15g:12g:150-200mL:25-27mL.
6. A negative electrode material for sodium ion batteries, characterized by being prepared by the preparation method of any one of claims 1-5.
7. The application of the sodium ion battery anode material is characterized in that the application of the sodium ion battery anode material in the button battery is as follows:
Coating the slurry on a copper foil, drying at 70 ℃ for 6 hours, and then vacuum drying at 120 ℃ for 12 hours to obtain a loaded copper foil, rolling the loaded copper foil, punching the loaded copper foil into an electrode sheet, then using a sodium sheet as a counter electrode, using a polypropylene film as a diaphragm, using dimethyl ether containing 1M NaPF 6 as an electrolyte, and assembling and forming the button cell in a glove box.
CN202310589800.0A 2023-05-24 2023-05-24 Negative electrode material of sodium ion battery and preparation method and application thereof Active CN116605867B (en)

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