CN112864365A - Nitrogen-sulfur co-doped porous carbon loaded zinc oxide negative electrode material and preparation method thereof - Google Patents
Nitrogen-sulfur co-doped porous carbon loaded zinc oxide negative electrode material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of lithium ion batteries, and discloses a nitrogen-sulfur co-doped porous carbon loaded zinc oxide negative electrode material, wherein 3-thiopheneacetic acid is used as a sulfur source, polyacrylonitrile is used as a nitrogen source and a carbon source to obtain nitrogen-sulfur co-doped porous carbon with an ultrahigh specific surface area, the nitrogen-sulfur co-doped porous carbon is used as a substrate, triethanolamine and zinc acetate are used as raw materials to obtain a nitrogen-sulfur co-doped porous carbon loaded porous ZnO hollow nanosphere which has an ultrahigh specific surface area and is beneficial to exposing electrochemical active sites, N doping improves the conductivity of the porous carbon, S doping improves the specific surface area of the porous carbon, and simultaneously cooperates with N to construct a three-dimensional conductive network to improve the conductivity of the porous carbon, the uniformly dispersed porous ZnO hollow nanosphere is coated by the nitrogen-sulfur co-doped porous carbon to buffer the volume effect of ZnO and improve, and the diffusion path of lithium ions is shortened, and the rate capability and the theoretical specific capacity of the negative electrode material are improved.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a nitrogen-sulfur co-doped porous carbon loaded zinc oxide negative electrode material and a preparation method thereof.
Background
In recent decades, lithium ion batteries have advantages of large energy density, no memory effect, high working voltage, long cycle life and the like, and are widely applied to the fields of power grids, electric automobiles, portable electronic devices and the like, and meanwhile, compared with other energy storage systems such as super capacitors and the like, the lithium ion batteries greatly meet the requirements of renewable and sustainable energy development, but the energy density and the power density of the current lithium ion batteries still cannot meet the higher use requirements of people, a negative electrode is a key component of the lithium ion batteries, the current commercial negative electrode material is graphite, but the theoretical specific capacity of the material is very low, and therefore, new electrode materials of the lithium ion batteries need to be developed.
The metal oxides such as cobaltosic oxide, zinc oxide, ferroferric oxide, nickel oxide and the like have higher theoretical specific capacity, are ideal lithium ion battery cathode materials and are greatly concerned, wherein the zinc oxide has the advantages of higher theoretical specific capacity, abundant reserve capacity, lower cost, no toxicity and the like, the zinc oxide electrode has a serious volume effect in the charging and discharging process, which causes electrode polarization, thereby reducing the cycling stability of the electrode, rapidly attenuating the capacity, shortening the service life, and having poorer conductive performance of the zinc oxide electrode, the rate capability is poor, the application range is limited, the carbon material has excellent conductivity, good chemical stability and corrosion resistance, the element-doped carbon material can be widely applied to the negative electrode material of the lithium ion battery, and the electrochemical performance of the element-doped carbon material can be further improved.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a nitrogen-sulfur co-doped porous carbon loaded zinc oxide negative electrode material and a preparation method thereof, and solves the problems of poor cycle stability and poor conductivity of zinc oxide.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: the preparation method of the nitrogen-sulfur co-doped porous carbon loaded zinc oxide negative electrode material comprises the following steps:
(1) adding deionized water solvent, catalyst piperidine, 3-hydroxy-4-methoxybenzaldehyde and 3-thiopheneacetic acid into a reaction bottle, wherein the mass ratio of the deionized water solvent to the catalyst piperidine to 3-hydroxy-4-methoxybenzaldehyde to 3-thiopheneacetic acid is 0.6-1.5: 100: 115:100, reacting for 1.5-3h at the temperature of 110-,molecular formula C13H11O2S；
(2) Adding tetrahydrofuran solvent, triethylamine as catalyst, acryloyl chloride and styryl thiophene into a reaction bottle, placing the reaction bottle in a water bath pot for uniform dispersion, carrying out reaction, filtering, washing with deionized water, and drying to obtain a terminal alkenyl thiophene compound with a molecular formula of C16H14O3S；
(3) Adding N, N-dimethylformamide solvent, azodiisobutyronitrile as an initiator, a terminal alkenyl thiophene compound and acrylonitrile into a reaction bottle, uniformly dispersing in a water bath, reacting, filtering, washing with methanol, and drying to obtain sulfur-containing polyacrylonitrile;
(4) adding a deionized water solvent, a pore-forming agent zinc chloride and sulfur-containing polyacrylonitrile into a reaction bottle, placing the reaction bottle in a water bath kettle for uniform dispersion and drying, placing a dried product in a tubular furnace for preoxidation and carbonization, removing the zinc chloride by using an ethanol aqueous solution of dilute hydrochloric acid, performing centrifugal separation, washing the product with deionized water and absolute ethanol, and drying the product to obtain nitrogen-sulfur co-doped porous carbon;
(5) adding a deionized water solvent, zinc acetate and nitrogen-sulfur co-doped porous carbon into a reaction bottle, placing the reaction bottle in a water bath pot for uniform dispersion, adding triethanolamine, placing the reaction bottle in the water bath pot for uniform dispersion, placing the reaction bottle in a microwave reactor for microwave hydrothermal reaction, cooling to room temperature, performing suction filtration, washing with deionized water and absolute ethyl alcohol, and drying to obtain the negative electrode material of the nitrogen-sulfur co-doped porous carbon loaded zinc oxide.
Preferably, the mass ratio of the triethylamine, the acryloyl chloride and the styryl thiophene in the step (2) is 0.4-1:35-50: 100.
Preferably, the reaction condition in the step (2) is that the reaction is carried out for 2 to 3.5 hours at the temperature of 0 to 5 ℃.
Preferably, the mass ratio of the azobisisobutyronitrile, the terminal alkenyl thiophene compound and the acrylonitrile in the step (3) is 0.4-1:5-20: 100.
Preferably, the reaction condition in the step (3) is that the reaction is carried out for 10 to 20 hours at 85 to 100 ℃.
Preferably, the mass ratio of the zinc chloride to the sulfur-containing polyacrylonitrile in the step (4) is 45-75: 100.
Preferably, the pre-oxidation and carbonization processes in the step (4) are pre-oxidation at 300 ℃ of 270 ℃ for 1.5-3h and carbonization at 650 ℃ of 550 ℃ for 15-45min in a nitrogen atmosphere.
Preferably, the mass ratio of the zinc acetate, the nitrogen-sulfur co-doped porous carbon and the triethanolamine in the step (5) is 35-65:100: 350-650.
Preferably, the microwave hydrothermal reaction in the step (5) is carried out under the conditions of 270-330W for 3-6 min.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
according to the negative electrode material of the nitrogen-sulfur co-doped porous carbon loaded zinc oxide, under the action of a catalyst piperidine, methylene on 3-thiopheneacetic acid and aldehyde on 3-hydroxy-4-methoxybenzaldehyde are subjected to Knoevenagel reaction to obtain styryl thiophene, a hydroxy group is introduced, hydrogen atoms on the hydroxy group are further replaced by acryloyl groups of acryloyl chloride to obtain an end alkenyl thiophene compound, an end alkenyl group is introduced, the end alkenyl group is copolymerized with an acrylonitrile monomer under the action of an initiator azodiisobutyronitrile to obtain sulfur-containing polyacrylonitrile, and the nitrogen-sulfur co-doped porous carbon is obtained through zinc chloride activation, preoxidation and carbonization as a pore-making agent, has a rich pore structure and an ultrahigh specific surface area, is favorable for exposing electrochemical active sites, and takes triethanolamine and Zn as substrates2+Formation of Zn2+Metal-organic supramolecules of triethanolamine with simultaneous hydrolysis of the triethanolamine to OH-With Zn2+Complexation to Zn (OH)4 2-The complex is further decomposed under the action of microwaves to generate ZnO nano particles, in order to reduce the higher Gibbs free energy of the ZnO nano particles, the ZnO nano particles can generate directional aggregation on the nitrogen-sulfur co-doped porous carbon, ZnO nanospheres are obtained through curing self-assembly, and meanwhile, because metal-organic supermolecules have steric hindrance effect, the ZnO nano particles are dislocated and overlapped in the aggregation process to further form a pore structure, so that the nitrogen-sulfur co-doped porous carbon loaded porous ZnO nano hollow spheres are obtained, and the unique porous nano hollow spheres are uniqueThe porous membrane has the advantages of shape appearance, rich pore structure and ultrahigh specific surface area, and is beneficial to exposing more electrochemical active sites.
This negative electrode material of nitrogen-sulphur codope porous carbon load-carrying zinc oxide, during the doping of N atom advances the crystal lattice of porous carbon, the electrochemical property of porous carbon has been improved, the electric conductivity of porous carbon has been improved, S atomic radius is great, during the doping advances the crystal lattice of porous carbon, make the porous carbon defect increase, the specific surface area of porous carbon has been improved, thereby expose more electrochemical activity sites, construct three-dimensional porous network structure with the N atom is cooperative simultaneously, electron transfer accelerates, thereby the electric conductivity of porous carbon has been improved.
This negative electrode material of nitrogen-sulphur codope porous carbon load zinc oxide, ZnO homodisperse is in the basement of nitrogen-sulphur codope porous carbon, make ZnO by nitrogen-sulphur codope porous carbon cladding, thereby make the volume effect that ZnO produced at the charge-discharge in-process obtain the buffering, the reunion of ZnO has been reduced simultaneously, thereby negative electrode material's cyclic stability has been improved, and the cladding of nitrogen-sulphur codope porous carbon, the transfer of electron has been accelerated, thereby negative electrode material's electric conductivity has been improved, in the charge-discharge in-process, ZnO gets electron and Li+Reversible reaction to generate Zn and Li2O, further Zn to obtain electrons and Li+The LiZn is generated through reversible reaction, so that ZnO has excellent electrochemical reversibility, the lithium storage performance of the negative electrode material is improved, meanwhile, the size of the porous ZnO nano hollow sphere is small, the diffusion path of lithium ions is shortened, the rate capability and the theoretical specific capacity of the negative electrode material are improved, and the nitrogen-sulfur co-doped porous carbon loaded zinc oxide negative electrode material has excellent conductivity, cycling stability, rate capability and theoretical specific capacity.
Drawings
FIG. 1 is a structural formula of styryl thiophene;
FIG. 2 shows the structural formula of a terminal alkenyl thiophene compound.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: a preparation method of a nitrogen-sulfur co-doped porous carbon loaded zinc oxide negative electrode material comprises the following steps:
(1) adding deionized water solvent, catalyst piperidine, 3-hydroxy-4-methoxybenzaldehyde and 3-thiopheneacetic acid into a reaction bottle, wherein the mass ratio of the deionized water solvent to the catalyst piperidine to 3-hydroxy-4-methoxybenzaldehyde to 3-thiopheneacetic acid is 0.6-1.5: 100: 115:100, and reacting for 1.5-3h at the temperature of 110-13H11O2S；
(2) Adding tetrahydrofuran solvent, catalyst triethylamine, acryloyl chloride and styryl thiophene into a reaction bottle, wherein the mass ratio of the tetrahydrofuran solvent to the catalyst triethylamine to the acryloyl chloride to the styryl thiophene is 0.4-1:35-50:100, placing the mixture into a water bath kettle for uniform dispersion, reacting for 2-3.5h at 0-5 ℃, filtering, washing with deionized water, and drying to obtain the end-alkenyl thiophene compound with the molecular formula C16H14O3S；
(3) Adding N, N-dimethylformamide solvent, initiator azodiisobutyronitrile, terminal alkenyl thiophene compound and acrylonitrile into a reaction bottle, wherein the mass ratio of the N, N-dimethylformamide solvent to the initiator azodiisobutyronitrile to the terminal alkenyl thiophene compound to the acrylonitrile is 0.4-1:5-20:100, placing the mixture into a water bath pot for uniform dispersion, reacting for 10-20h at 85-100 ℃, filtering, washing with methanol, and drying to obtain sulfur-containing polyacrylonitrile;
(4) adding a deionized water solvent, a pore-making agent zinc chloride and sulfur-containing polyacrylonitrile into a reaction bottle, wherein the mass ratio of the deionized water solvent to the pore-making agent zinc chloride to the sulfur-containing polyacrylonitrile is 45-75:100, placing the reaction bottle in a water bath kettle for uniform dispersion and drying, placing a dried product in a tubular furnace, pre-oxidizing the dried product at the temperature of 270-;
(5) adding a deionized water solvent, zinc acetate and nitrogen-sulfur co-doped porous carbon into a reaction bottle, placing the reaction bottle in a water bath pot for uniform dispersion, adding triethanolamine, placing the reaction bottle in a microwave reactor for uniform dispersion, reacting for 3-6min at the mass ratio of the zinc acetate to the nitrogen-sulfur co-doped porous carbon to the triethanolamine of 35-65:100:350, cooling to room temperature, performing suction filtration, washing with deionized water and absolute ethyl alcohol, and drying to obtain the negative electrode material of the nitrogen-sulfur co-doped porous carbon loaded zinc oxide.
Example 1
(1) Adding deionized water solvent, catalyst piperidine, 3-hydroxy-4-methoxybenzaldehyde and 3-thiopheneacetic acid into a reaction bottle at a mass ratio of 0.6:100:100, and reacting at 110 deg.C for 1.5h to obtain styryl thiophene with molecular formula C13H11O2S；
(2) Adding tetrahydrofuran solvent, catalyst triethylamine, acryloyl chloride and styryl thiophene into a reaction bottle, wherein the mass ratio of the tetrahydrofuran solvent to the catalyst triethylamine to the acryloyl chloride to the styryl thiophene is 0.4:35:100, placing the mixture into a water bath pot for uniform dispersion, reacting for 2 hours at 0 ℃, filtering, washing with deionized water, and drying to obtain a terminal alkenyl thiophene compound with the molecular formula C16H14O3S；
(3) Adding an N, N-dimethylformamide solvent, an initiator azodiisobutyronitrile, a terminal alkenyl thiophene compound and acrylonitrile into a reaction bottle, wherein the mass ratio of the N, N-dimethylformamide solvent to the initiator azodiisobutyronitrile to the terminal alkenyl thiophene compound to the acrylonitrile is 0.4:5:100, uniformly dispersing in a water bath, reacting for 10 hours at 85 ℃, filtering, washing with methanol, and drying to obtain sulfur-containing polyacrylonitrile;
(4) adding a deionized water solvent, a pore-forming agent zinc chloride and sulfur-containing polyacrylonitrile into a reaction bottle, wherein the mass ratio of the deionized water solvent to the pore-forming agent zinc chloride to the sulfur-containing polyacrylonitrile is 45:100, placing the reaction bottle in a water bath kettle for uniform dispersion and drying, placing a dried product in a tubular furnace, pre-oxidizing the dried product for 1.5h at 270 ℃, carbonizing the dried product for 15min at 550 ℃ in a nitrogen atmosphere, removing zinc chloride by using an ethanol aqueous solution of dilute hydrochloric acid, performing centrifugal separation, washing the product with deionized water and absolute ethanol, and drying the product to obtain nitrogen-sulfur co-doped porous carbon;
(5) adding a deionized water solvent, zinc acetate and nitrogen-sulfur co-doped porous carbon into a reaction bottle, placing the reaction bottle in a water bath pot for uniform dispersion, adding triethanolamine, placing the reaction bottle in a microwave reactor for reaction for 3min at 270W, cooling to room temperature, performing suction filtration, washing with deionized water and absolute ethyl alcohol, and drying to obtain the negative electrode material of the nitrogen-sulfur co-doped porous carbon loaded zinc oxide.
Example 2
(1)Adding deionized water solvent, catalyst piperidine, 3-hydroxy-4-methoxybenzaldehyde and 3-thiopheneacetic acid into a reaction bottle at a mass ratio of 0.9:105:100, and reacting at 120 ℃ for 2h to obtain styryl thiophene with a molecular formula of C13H11O2S；
(2) Adding tetrahydrofuran solvent, catalyst triethylamine, acryloyl chloride and styryl thiophene into a reaction bottle, wherein the mass ratio of the tetrahydrofuran solvent to the catalyst triethylamine to the acryloyl chloride to the styryl thiophene is 0.6:40:100, placing the mixture into a water bath pot for uniform dispersion, reacting for 2.5h at the temperature of 2 ℃, filtering, washing with deionized water, and drying to obtain a terminal alkenyl thiophene compound with the molecular formula of C16H14O3S；
(3) Adding an N, N-dimethylformamide solvent, an initiator azodiisobutyronitrile, a terminal alkenyl thiophene compound and acrylonitrile into a reaction bottle, wherein the mass ratio of the N, N-dimethylformamide solvent to the initiator azodiisobutyronitrile to the terminal alkenyl thiophene compound to the acrylonitrile is 0.6:10:100, uniformly dispersing in a water bath, reacting for 13 hours at 90 ℃, filtering, washing with methanol, and drying to obtain sulfur-containing polyacrylonitrile;
(4) adding a deionized water solvent, a pore-forming agent zinc chloride and sulfur-containing polyacrylonitrile into a reaction bottle, wherein the mass ratio of the deionized water solvent to the pore-forming agent zinc chloride to the sulfur-containing polyacrylonitrile is 55:100, placing the reaction bottle in a water bath kettle for uniform dispersion and drying, placing a dried product in a tubular furnace, pre-oxidizing the dried product at 280 ℃ for 2h, carbonizing the dried product at 580 ℃ for 25min in a nitrogen atmosphere, removing the zinc chloride by using an ethanol aqueous solution of dilute hydrochloric acid, performing centrifugal separation, washing the product with deionized water and absolute ethanol, and drying the product to obtain nitrogen-sulfur co-doped porous carbon;
(5) adding a deionized water solvent, zinc acetate and nitrogen-sulfur co-doped porous carbon into a reaction bottle, placing the reaction bottle in a water bath pot for uniform dispersion, adding triethanolamine, placing the reaction bottle in a microwave reactor for reaction for 4min at 290W, cooling to room temperature, performing suction filtration, washing with deionized water and absolute ethyl alcohol, and drying to obtain the negative electrode material of the nitrogen-sulfur co-doped porous carbon loaded zinc oxide.
Example 3
(1) Adding deionized water solvent, catalyst piperidine and 3-hydroxy-4-methoxybenzaldehyde into a reaction bottleAnd 3-thiopheneacetic acid with the mass ratio of 1.2:110:100, reacting for 2.5 hours at 130 ℃ to obtain styryl thiophene with the molecular formula of C13H11O2S；
(2) Adding tetrahydrofuran solvent, catalyst triethylamine, acryloyl chloride and styryl thiophene into a reaction bottle, wherein the mass ratio of the tetrahydrofuran solvent to the catalyst triethylamine to the acryloyl chloride to the styryl thiophene is 0.8:45:100, placing the mixture into a water bath pot for uniform dispersion, reacting for 3 hours at the temperature of 3 ℃, filtering, washing with deionized water, and drying to obtain a terminal alkenyl thiophene compound with the molecular formula of C16H14O3S；
(3) Adding an N, N-dimethylformamide solvent, an initiator azodiisobutyronitrile, a terminal alkenyl thiophene compound and acrylonitrile into a reaction bottle, wherein the mass ratio of the N, N-dimethylformamide solvent to the initiator azodiisobutyronitrile to the terminal alkenyl thiophene compound to the acrylonitrile is 0.8:15:100, uniformly dispersing in a water bath, reacting for 16 hours at 95 ℃, filtering, washing with methanol, and drying to obtain sulfur-containing polyacrylonitrile;
(4) adding a deionized water solvent, a pore-forming agent zinc chloride and sulfur-containing polyacrylonitrile into a reaction bottle, wherein the mass ratio of the deionized water solvent to the pore-forming agent zinc chloride to the sulfur-containing polyacrylonitrile is 65:100, placing the reaction bottle in a water bath kettle for uniform dispersion and drying, placing a dried product in a tubular furnace, pre-oxidizing the dried product at 290 ℃ for 2.5h, carbonizing the dried product at 610 ℃ for 35min in a nitrogen atmosphere, removing zinc chloride by using an ethanol aqueous solution of dilute hydrochloric acid, performing centrifugal separation, washing the product with deionized water and absolute ethanol, and drying the product to obtain nitrogen-sulfur co-doped porous carbon;
(5) adding a deionized water solvent, zinc acetate and nitrogen-sulfur co-doped porous carbon into a reaction bottle, placing the reaction bottle in a water bath pot for uniform dispersion, adding triethanolamine, placing the reaction bottle in a microwave reactor for reaction for 5min under 310W, cooling to room temperature, carrying out suction filtration, washing with deionized water and absolute ethyl alcohol, and drying to obtain the negative electrode material of the nitrogen-sulfur co-doped porous carbon loaded zinc oxide.
Example 4
(1) Adding deionized water solvent, catalyst piperidine, 3-hydroxy-4-methoxybenzaldehyde and 3-thiopheneacetic acid into a reaction bottle at a mass ratio of 1.5:115:100, and reacting at 140 ℃ for 3h to obtain benzeneVinyl thiophene of the formula C13H11O2S；
(2) Adding tetrahydrofuran solvent, catalyst triethylamine, acryloyl chloride and styryl thiophene into a reaction bottle, wherein the mass ratio of the tetrahydrofuran solvent to the catalyst triethylamine to the acryloyl chloride to the styryl thiophene is 1:50:100, placing the mixture into a water bath pot to be uniformly dispersed, reacting for 3.5h at the temperature of 5 ℃, filtering, washing with deionized water, and drying to obtain a terminal alkenyl thiophene compound with the molecular formula of C16H14O3S；
(3) Adding an N, N-dimethylformamide solvent, an initiator azodiisobutyronitrile, a terminal alkenyl thiophene compound and acrylonitrile into a reaction bottle, wherein the mass ratio of the N, N-dimethylformamide solvent to the initiator azodiisobutyronitrile to the terminal alkenyl thiophene compound to the acrylonitrile is 1:20:100, uniformly dispersing in a water bath, reacting for 20 hours at 100 ℃, filtering, washing with methanol, and drying to obtain sulfur-containing polyacrylonitrile;
(4) adding a deionized water solvent, a pore-forming agent zinc chloride and sulfur-containing polyacrylonitrile into a reaction bottle, wherein the mass ratio of the deionized water solvent to the pore-forming agent zinc chloride to the sulfur-containing polyacrylonitrile is 75:100, placing the reaction bottle in a water bath kettle for uniform dispersion and drying, placing a dried product in a tubular furnace, pre-oxidizing the dried product for 3 hours at 300 ℃, carbonizing the dried product for 45 minutes at 650 ℃ in a nitrogen atmosphere, removing the zinc chloride by using an ethanol aqueous solution of dilute hydrochloric acid, performing centrifugal separation, washing the product with deionized water and absolute ethanol, and drying the product to obtain nitrogen-sulfur co-doped porous carbon;
(5) adding a deionized water solvent, zinc acetate and nitrogen-sulfur co-doped porous carbon into a reaction bottle, placing the reaction bottle in a water bath pot for uniform dispersion, adding triethanolamine, placing the reaction bottle in a microwave reactor for reaction for 6min at 330W, cooling to room temperature, carrying out suction filtration, washing with deionized water and absolute ethyl alcohol, and drying to obtain the negative electrode material of the nitrogen-sulfur co-doped porous carbon loaded zinc oxide.
Comparative example 1
(1) Adding deionized water solvent, catalyst piperidine, 3-hydroxy-4-methoxybenzaldehyde and 3-thiopheneacetic acid into a reaction bottle at a mass ratio of 0.3:50:100, and reacting at 110 ℃ for 1.5h to obtain styryl thiophene with molecular formula C13H11O2S；
(2) Adding tetrahydrofuran solvent, catalyst triethylamine, acryloyl chloride and styryl thiophene into a reaction bottle, wherein the mass ratio of the tetrahydrofuran solvent to the catalyst triethylamine to the acryloyl chloride to the styryl thiophene is 0.2:17:100, placing the mixture into a water bath pot for uniform dispersion, reacting for 2 hours at 0 ℃, filtering, washing with deionized water, and drying to obtain a terminal alkenyl thiophene compound with the molecular formula of C16H14O3S；
(3) Adding an N, N-dimethylformamide solvent, an initiator azodiisobutyronitrile, a terminal alkenyl thiophene compound and acrylonitrile into a reaction bottle, wherein the mass ratio of the N, N-dimethylformamide solvent to the initiator azodiisobutyronitrile to the terminal alkenyl thiophene compound to the acrylonitrile is 0.2:2.5:100, uniformly dispersing in a water bath, reacting for 10 hours at 85 ℃, filtering, washing with methanol, and drying to obtain sulfur-containing polyacrylonitrile;
(4) adding a deionized water solvent, a pore-forming agent zinc chloride and sulfur-containing polyacrylonitrile into a reaction bottle, wherein the mass ratio of the deionized water solvent to the pore-forming agent zinc chloride to the sulfur-containing polyacrylonitrile is 22:100, placing the reaction bottle in a water bath kettle for uniform dispersion and drying, placing a dried product in a tubular furnace, pre-oxidizing the dried product for 1.5h at 270 ℃, carbonizing the dried product for 15min at 550 ℃ in a nitrogen atmosphere, removing zinc chloride by using an ethanol aqueous solution of dilute hydrochloric acid, performing centrifugal separation, washing the product with deionized water and absolute ethanol, and drying the product to obtain nitrogen-sulfur co-doped porous carbon;
(5) adding a deionized water solvent, zinc acetate and nitrogen-sulfur co-doped porous carbon into a reaction bottle, placing the reaction bottle in a water bath pot for uniform dispersion, adding triethanolamine, placing the reaction bottle in a microwave reactor for reaction for 3min at 270W, cooling to room temperature, performing suction filtration, washing with deionized water and absolute ethyl alcohol, and drying to obtain the negative electrode material of the nitrogen-sulfur co-doped porous carbon loaded zinc oxide.
Comparative example 2
(1) Adding deionized water solvent, catalyst piperidine, 3-hydroxy-4-methoxybenzaldehyde and 3-thiopheneacetic acid into a reaction bottle at a mass ratio of 2.1:173:100, and reacting at 140 deg.C for 3h to obtain styryl thiophene with molecular formula C13H11O2S；
(2) Adding tetrahydrofuran solvent and catalyst triethylamine into a reaction bottle,The mass ratio of acryloyl chloride to styryl thiophene is 1.5:75:100, the three are placed in a water bath pot to be dispersed evenly, reacted for 3.5 hours at the temperature of 5 ℃, filtered, washed clean by deionized water and dried to obtain the end-alkenyl thiophene compound with the molecular formula of C16H14O3S；
(3) Adding an N, N-dimethylformamide solvent, an initiator azodiisobutyronitrile, a terminal alkenyl thiophene compound and acrylonitrile into a reaction bottle, wherein the mass ratio of the N, N-dimethylformamide solvent to the initiator azodiisobutyronitrile to the terminal alkenyl thiophene compound to the acrylonitrile is 1.5:30:100, uniformly dispersing in a water bath, reacting for 20 hours at 100 ℃, filtering, washing with methanol, and drying to obtain sulfur-containing polyacrylonitrile;
(4) adding a deionized water solvent, a pore-forming agent zinc chloride and sulfur-containing polyacrylonitrile into a reaction bottle, wherein the mass ratio of the deionized water solvent to the pore-forming agent zinc chloride to the sulfur-containing polyacrylonitrile is 102:100, placing the reaction bottle in a water bath kettle for uniform dispersion and drying, placing a dried product in a tubular furnace, pre-oxidizing the dried product for 3 hours at 300 ℃, carbonizing the dried product for 45 minutes at 650 ℃ in a nitrogen atmosphere, removing the zinc chloride by using an ethanol aqueous solution of dilute hydrochloric acid, performing centrifugal separation, washing the product with deionized water and absolute ethanol, and drying the product to obtain nitrogen-sulfur co-doped porous carbon;
(5) adding a deionized water solvent, zinc acetate and nitrogen-sulfur co-doped porous carbon into a reaction bottle, placing the reaction bottle in a water bath pot for uniform dispersion, adding triethanolamine, wherein the mass ratio of the zinc acetate to the nitrogen-sulfur co-doped porous carbon to the triethanolamine is 97:100:970, placing the reaction bottle in a microwave reactor for uniform dispersion, placing the reaction bottle in the microwave reactor for reaction for 6min under 330W, cooling to room temperature, carrying out suction filtration, washing with deionized water and absolute ethyl alcohol, and drying to obtain the negative electrode material of the nitrogen-sulfur co-doped porous carbon loaded zinc oxide.
Uniformly dispersing the nitrogen-sulfur co-doped porous carbon loaded zinc oxide negative electrode material, polyvinylidene fluoride and acetylene black obtained in the examples and the comparative examples in N-methylpyrrolidone according to the mass ratio of 7:1:2, uniformly stirring to obtain a colloidal mixture, uniformly coating the colloidal mixture on copper foil, drying, pressing the colloidal mixture on copper foil into an electrode plate by using a tablet press, using the electrode plate as a working electrode, using a lithium sheet as a counter electrode, using a 1mol/L mixed solution of ethylene carbonate and dimethyl carbonate as an electrolyte, using Celgard 2400 as a diaphragm, assembling the button cell in a glove box filled with argon, and performing charge and discharge tests on the button cell by using a CS350H type electrochemical workstation, wherein the test standard is GB/T36276-2018.
Claims (9)
1. The utility model provides a nitrogen-sulphur codope porous carbon load zinc oxide's negative electrode material which characterized in that: the preparation method of the nitrogen-sulfur co-doped porous carbon loaded zinc oxide negative electrode material comprises the following steps:
(1) adding catalyst piperidine, 3-hydroxy-4-methoxybenzaldehyde and 3-thiopheneacetic acid into deionized water solvent, wherein the mass ratio of the piperidine to the 3-hydroxy-4-methoxybenzaldehyde to the 3-thiopheneacetic acid is 0.6-1.5: 100: 115:100, and reacting for 1.5-3h at the temperature of 110-13H11O2S；
(2) Adding catalyst triethylamine, acryloyl chloride and styryl thiophene into tetrahydrofuran solvent, placing the mixture into a water bath pot for uniform dispersion, reacting, filtering, washing and drying to obtain a terminal alkenyl thiophene compound with a molecular formula of C16H14O3S；
(3) Adding initiator azobisisobutyronitrile, terminal alkenyl thiophene compound and acrylonitrile into N, N-dimethylformamide solvent, placing in a water bath pot for uniform dispersion, reacting, filtering, washing and drying to obtain sulfur-containing polyacrylonitrile;
(4) adding pore-forming agents zinc chloride and sulfur-containing polyacrylonitrile into a deionized water solvent, placing the mixture into a water bath kettle for uniform dispersion and drying, placing a dried product into a tubular furnace for preoxidation and carbonization, removing the zinc chloride by using an ethanol aqueous solution of dilute hydrochloric acid, performing centrifugal separation, washing and drying to obtain nitrogen-sulfur co-doped porous carbon;
(5) adding zinc acetate and nitrogen-sulfur co-doped porous carbon into a deionized water solvent, placing the mixture in a water bath pot for uniform dispersion, adding triethanolamine, placing the mixture in a water bath pot for uniform dispersion, placing the mixture in a microwave reactor for microwave hydrothermal reaction, cooling, suction filtering, washing and drying to obtain the negative electrode material of the nitrogen-sulfur co-doped porous carbon loaded zinc oxide.
2. The nitrogen-sulfur co-doped porous carbon zinc oxide-loaded negative electrode material of claim 1, which is characterized in that: the mass ratio of the triethylamine, the acryloyl chloride and the styryl thiophene in the step (2) is 0.4-1:35-50: 100.
3. The nitrogen-sulfur co-doped porous carbon zinc oxide-loaded negative electrode material of claim 1, which is characterized in that: the reaction condition in the step (2) is that the reaction is carried out for 2 to 3.5 hours at the temperature of between 0 and 5 ℃.
4. The nitrogen-sulfur co-doped porous carbon zinc oxide-loaded negative electrode material of claim 1, which is characterized in that: in the step (3), the mass ratio of the azodiisobutyronitrile to the alkenyl thiophene compound to the acrylonitrile is 0.4-1:5-20: 100.
5. The nitrogen-sulfur co-doped porous carbon zinc oxide-loaded negative electrode material of claim 1, which is characterized in that: the reaction condition in the step (3) is that the reaction is carried out for 10 to 20 hours at the temperature of between 85 and 100 ℃.
6. The nitrogen-sulfur co-doped porous carbon zinc oxide-loaded negative electrode material of claim 1, which is characterized in that: the mass ratio of the zinc chloride to the sulfur-containing polyacrylonitrile in the step (4) is 45-75: 100.
7. The nitrogen-sulfur co-doped porous carbon zinc oxide-loaded negative electrode material of claim 1, which is characterized in that: the pre-oxidation and carbonization processes in the step (4) are pre-oxidation at 300 ℃ of 270 ℃ for 1.5-3h, and carbonization at 650 ℃ of 550 ℃ for 15-45min in a nitrogen atmosphere.
8. The nitrogen-sulfur co-doped porous carbon zinc oxide-loaded negative electrode material of claim 1, which is characterized in that: the mass ratio of the zinc acetate, the nitrogen-sulfur co-doped porous carbon and the triethanolamine in the step (5) is 35-65:100: 350-650.
9. The nitrogen-sulfur co-doped porous carbon zinc oxide-loaded negative electrode material of claim 1, which is characterized in that: the microwave hydrothermal reaction in the step (5) is carried out for 3-6min under the conditions of 270-330W.
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