CN112928388B - Iron nitride and monoatomic iron co-modified nitrogen-doped graphite composite material and preparation method and application thereof - Google Patents

Iron nitride and monoatomic iron co-modified nitrogen-doped graphite composite material and preparation method and application thereof Download PDF

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CN112928388B
CN112928388B CN202110197465.0A CN202110197465A CN112928388B CN 112928388 B CN112928388 B CN 112928388B CN 202110197465 A CN202110197465 A CN 202110197465A CN 112928388 B CN112928388 B CN 112928388B
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CN112928388A (en
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韦伟峰
马骋
张有泉
张帅
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Central South University
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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract

The invention belongs to the technical field of lithium-sulfur battery materials, and particularly relates to a nitrogen-doped graphite composite material co-modified by iron nitride and monoatomic iron, which comprises a nitrogen-doped graphite matrix and the iron nitride and the monoatomic iron loaded on the nitrogen-doped graphite matrix in situ; the chemical formula of the iron nitride is Fe2N has a polar triangular pyramid Fe-3N coordination structure; the monatomic iron has a nonpolar plane symmetry type Fe-4N coordination structure; the invention also discloses a preparation method of the material and an application of the material in a lithium-sulfur battery. After the prepared iron nitride and monoatomic iron co-modified nitrogen-doped graphite composite material is used for a lithium-sulfur battery positive electrode material or a diaphragm modification layer, the active sulfur redox reaction kinetics are remarkably improved, the dissolution shuttling of polysulfide intermediate products is effectively inhibited, and the specific capacity and the cycling stability of the lithium-sulfur battery are greatly improved.

Description

Iron nitride and monoatomic iron co-modified nitrogen-doped graphite composite material and preparation method and application thereof
Technical Field
The invention relates to the technical field of electrochemical energy storage, in particular to an iron nitride and monoatomic iron co-modified nitrogen-doped graphite composite material and a preparation method and application thereof.
Background
The lithium-sulfur battery is considered as a new generation of high-specific-energy secondary battery system with the most development potential, has high theoretical specific capacity (1675mAh/g) and energy density (2675Wh/kg), and has better application prospects in the aspects of portable electronic equipment, electric automobiles, large-scale energy storage and the like. In addition, the sulfur powder used as the positive active substance mainly comes from the petroleum processing process, and has the advantages of abundant natural reserves, low price, no toxicity and environmental friendliness.
However, the polyelectronic and heterogeneous sulfur electrochemical reaction mechanism still faces many challenges for the practical application of lithium sulfur batteries: 1)sulfur (S) of electronic insulation8) And lithium sulfide (Li)2S2/Li2S) the molecules significantly reduce the redox reaction kinetics and the conversion utilization rate of the anode active substance; 2) long-chain lithium polysulfide intermediates (Li)2SnAnd n-4-8) is easily dissolved in organic ether electrolyte, is reduced and shuttled back to the sulfur positive electrode on the negative electrode side of the lithium metal, and the serious lithium polysulfide shuttle effect causes lower coulombic efficiency, continuous loss of positive electrode active substances and rapid capacity attenuation.
In order to solve the above problems, researchers mostly use conductive carbon materials to encapsulate active sulfur inside or introduce a functional carbon coating on the separator as an epitaxial current collector. However, the nonpolar carbon material has poor chemisorption to lithium polysulfide, and the poor sulfur electrochemical reaction kinetics in the cycle process cause solid sulfur or lithium sulfide to be continuously deposited on the surface of the conductive carbon, and finally cause the interfacial failure.
Disclosure of Invention
The invention aims to provide a nitrogen-doped graphite composite material (also called composite material) co-modified by iron nitride and monatomic iron, and aims to provide a new material capable of effectively solving polysulfide shuttling of a lithium-sulfur battery and improving electrochemical performance of the lithium-sulfur battery.
The second purpose of the invention is to provide a preparation method of the iron nitride and monoatomic iron co-modified nitrogen-doped graphite composite material, and the invention aims to provide a material which can prepare the iron nitride and iron atom co-modified nitrogen-doped graphite composite material and has excellent effect in a lithium-sulfur battery.
The third purpose of the invention is to provide the application of the iron nitride and monoatomic iron co-modified nitrogen-doped graphite composite material in the aspects of lithium-sulfur battery separators and positive electrode materials.
A nitrogen-doped graphite composite material co-modified by iron nitride and monoatomic iron comprises a nitrogen-doped graphite matrix and the iron nitride and the monoatomic iron (also called as iron atoms in the invention) loaded on the nitrogen-doped graphite matrix in situ;
the chemical formula of the iron nitride is Fe2N has a polar triangular pyramid Fe-3N coordination structure;
the monatomic iron has a nonpolar plane-symmetric Fe-4N coordination structure.
According to the brand new composite material, nitrogen-doped graphite is used as a substrate, and iron nitride and monatomic iron are doubly modified on the surface of the nitrogen-doped graphite, so that researches show that the adsorption and catalytic conversion activity of polysulfide can be synergistically improved due to the coordination of the morphology, components, coordination mode and phase of the material; can effectively inhibit polysulfide shuttling and is beneficial to synergistically improving the electrochemical performance of the lithium-sulfur battery.
The research of the invention discovers that the monatomic iron and the Fe2The phase composition of N and the coordination mode are key to the synergistic improvement of polysulfide shuttling. The plane-symmetric Fe-4N coordination structure in the monatomic iron and the spatial triangular pyramid type Fe-3N coordination structure in the Fe2N respectively provide a Lewis acid adsorption site and a polar adsorption site, so that the chemical adsorption effect of polysulfide is greatly enhanced; the catalysis accelerates the reduction and oxidation reactions of polysulfides, not only of monoatomic iron and Fe2N is uniformly dispersed in the graphitized carbon matrix, which is beneficial to the rapid transfer of charges in the electrochemical process.
Preferably, said Fe2The surface of N is evenly coated by amorphous carbon.
In the invention, the nitrogen-doped graphite is in a nano sheet shape, has a micropore and mesoporous structure, and has a specific surface area of 400-1000 square meters per gram.
Preferably, the content of the iron nitride is 1 to 30 weight percent; further preferably 5 to 15 wt.%.
Preferably, the content of the monoatomic iron is 0.1 to 5 weight percent; more preferably 1 to 3 wt%.
The invention also provides a preparation method of the iron nitride and monoatomic iron co-modified nitrogen-doped graphite composite material, which comprises the following specific steps:
the method comprises the following steps: carrying out hydrothermal reaction on a solution containing graphitized carbon-nitrogen-tetrananosheets, a carbon source and a water-soluble iron source to prepare a precursor; the molar ratio of Fe in the water-soluble iron source to graphitized carbon trinitrogen is 0.02-0.5; the temperature of the hydrothermal reaction is 120-160 ℃;
step two: and nitriding the precursor in an ammonia atmosphere at the temperature of 700-1000 ℃ to obtain the iron nitride and monoatomic iron co-modified nitrogen-doped graphite composite material.
The research of the invention discovers how to realize the iron atoms and the Fe2The double modification of N, and how to control the phase of a modifier, the coordination mode and the morphological structure of the material are the difficulties in the successful preparation of the material. Aiming at the technical difficulty, a large number of researches discover that the graphitized carbon-nitrogen-trinitrobenzene nanosheet is innovatively adopted as a precursor, and the synergistic control of a carbon source, the iron source dosage, the hydrothermal temperature and the nitriding process temperature in the hydrothermal process is matched, so that the synergistic effect can be reasonably generated, the double modification of iron and iron nitride can be reasonably realized, the coordination mode and the phase purity of iron and iron nitride can be effectively controlled, the lamellar structure morphology of the material is controlled, the adsorption and the electro-catalysis characteristics of the material to polysulfide can be synergistically improved, and the electrochemical performance of the lithium-sulfur battery can be effectively improved.
In the invention, the graphitized carbon trinitrogen tetrasheet is used as a precursor, and the key of successfully constructing the iron and iron nitride double modification is to cooperate with the cooperative control of the carbon source, the iron source and the iron source dosage in the hydrothermal process.
In the invention, the graphitized carbon tri-nitrogen four-nano sheet can be prepared by adopting the existing method.
Preferably, urea is subjected to a pyrolysis reaction in an air atmosphere to prepare the graphitized carbon-nitrogen-triazine nanosheet.
Preferably, the pyrolysis temperature is 350-550 ℃, and the reaction time is 2-4 h.
Preferably, the carbon source is at least one of glucose, sucrose, chitosan, polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, gum arabic, cellulose acetate, and dopamine.
Preferably, the molar ratio of the carbon source to the graphitized carbon trinitrogen is 0.1-5; more preferably 1-2.5: 1.
In the present invention, the water-soluble iron source may be a water-soluble salt of at least one of ferric ions and ferrous ions; for example, the material may be at least one of hydrochloride, sulfate, nitrate, acetate, and citrate.
Preferably, the molar ratio of Fe to graphitized carbon trinitrogen in the water-soluble iron source is 0.05-0.2: 1. Under the optimal conditions, the iron nitride and the monatomic iron phase can be successfully constructed, and the Fe-N coordination mode is obtained, so that the promotion effect of the material in the lithium-sulfur battery can be effectively improved.
Preferably, the temperature of the hydrothermal reaction is 140-160 ℃; more preferably 145 to 155 ℃. Researches find that under the preferable hydrothermal condition, the composite material with the nanosheet structure can be obtained, the special bonding mode between the composite component and the substrate can be constructed more conveniently, and the action mechanism of the prepared material in the lithium-sulfur battery can be further improved.
Preferably, the hydrothermal reaction time is 6-12 h; preferably 9-11 h.
In the present invention, under the above-described preferable hydrothermal conditions, the control of the nitriding temperature is further combined, so that the phase of the modified iron can be controlled in a synergistic manner, and the application effects of both in the lithium-sulfur battery can be further improved.
Preferably, the temperature of the nitridation reaction is 700-900 ℃; further preferably 840-860 ℃;
preferably, the time of the nitridation reaction is 1-3 h; further preferably 1-2 h;
the invention also provides application of the iron nitride and monoatomic iron co-modified nitrogen-doped graphite composite material in a lithium-sulfur battery.
The research of the invention finds that the synergy of the monoatomic iron and iron nitride phases and the coordination structure in the material can promote the dynamics of polysulfide redox reaction, effectively improve the shuttle problem of polysulfide, and effectively improve the electrochemical performance of the lithium-sulfur battery, such as the specific capacity and the cycling stability of the lithium-sulfur battery.
The invention discloses a preferable application method, and the composite material is used for preparing a diaphragm of a lithium-sulfur battery; further preferably, the composite is formed on the surface of the separator.
The invention also discloses a preferable application method, and the composite material is used for preparing a positive electrode material of a lithium-sulfur battery.
The invention also provides a lithium-sulfur battery composite diaphragm, which comprises a base film and a modified layer compounded on the surface of the base film; the modified layer comprises a binder and the nitrogen-doped graphite composite material co-modified by the iron nitride and the monatomic iron.
According to the invention, the modification layer containing the composite material is modified on the surface of the base film, so that polysulfide can be effectively adsorbed, the electrochemical conversion of the polysulfide can be catalyzed and accelerated, the shuttle problem of the polysulfide can be effectively solved, and the specific capacity and the cycling stability of the lithium-sulfur battery can be improved.
In the present invention, the base film may be a separator applicable to a lithium sulfur battery, which is well known in the industry.
In the invention, the modified layer can be compounded on one surface of the base film or both surfaces of the base film.
In the invention, the amount of the composite material in the modified layer can be adjusted based on the use requirement.
Preferably, in the modified layer, the mass percentage of the iron nitride and monoatomic iron co-modified nitrogen-doped graphite composite material is 50-95 wt%.
As an inventive concept, the invention also provides a lithium-sulfur battery composite positive electrode material, which comprises amorphous sulfur, a binder and the nitrogen-doped graphite composite material co-modified by the iron nitride and the monatomic iron.
According to the invention, the composite material is applied to the sulfur anode, and the effects of reducing polysulfide shuttling and improving the specific capacity and the cycling stability of the lithium-sulfur battery can be achieved.
Preferably, the weight percentage content of the iron nitride and monoatomic iron co-modified nitrogen-doped graphite composite material is 5wt% -30 wt%.
The design idea of the invention is to simultaneously convert an iron salt into two components, namely iron nitride and monatomic iron supported on nitrogen-doped graphite through a hydrothermal reaction and heat treatment control process. The nitrogen-doped graphite has a high specific area, an electron conduction network structure is constructed, and the iron nitride and the monatomic iron are effectively communicated. The synergistic polar iron nitride matter site and the monoatomic iron active site can fix polysulfide intermediate products in the electrochemical reaction process, can realize the oxidation-reduction bidirectional electrocatalysis of polysulfide, and obviously improves the polysulfide conversion reaction kinetics.
Compared with the prior art, the invention has the following advantages:
1) the invention provides a brand-new material, which takes nitrogen-doped graphite as a substrate and innovatively modifies iron nitride and monatomic iron in situ; researches find that the novel composite material can effectively improve shuttling of polysulfide and improve specific capacity and cycling stability of the lithium-sulfur battery.
2) The invention also innovatively provides a preparation method of the composite material, which takes graphitized carbon-nitrogen-IV as a precursor, further cooperates with the combined control of a carbon source, the iron source dosage and the temperature in the nitriding process in the hydrothermal process, can controllably realize the double modification of monatomic iron and iron nitride, and controls the morphology structure of the composite material, the phase composition of modified components and the Fe-N coordination form.
3) The reactant raw materials and instruments used in the preparation process are simple and easily available, the price is low, the possibility of large-scale production is realized, and the modified lithium-sulfur battery cathode material or the modified diaphragm layer has a great promoting effect on large-scale commercial application of the lithium-sulfur battery.
Drawings
FIG. 1X-ray diffraction pattern of nitrogen-doped graphite composite material co-modified by iron nitride and monoatomic iron in example 1
FIG. 2 scanning electron microscope image of nitrogen-doped graphite composite material co-modified with iron nitride and monoatomic iron in example 1
FIG. 3 SEM image of nitrogen-doped graphite composite material co-modified with iron nitride and monatomic iron in example 1
FIG. 4X-ray diffraction pattern of iron nitride and monoatomic iron co-modified nitrogen-doped graphite composite material in example 2
FIG. 5X-ray diffraction pattern of iron nitride and monoatomic iron co-modified nitrogen-doped graphite composite material in example 3
FIG. 6 test results of electrochemical properties of lithium-sulfur battery corresponding to modified separator in example 10
FIG. 7 electrochemical performance test results of modified sulfur positive electrode in example 11
FIG. 8 scanning electron micrograph of nitrogen-doped graphite material of comparative example 1
FIG. 9 is a scanning electron microscope image of a nitrogen-doped graphite material modified with monatomic iron in comparative example 2
FIG. 10 is an X-ray diffraction pattern of a nitrogen-doped graphite material modified with monoatomic iron in comparative example 2
FIG. 11 projection electron microscope image of nitrogen-doped graphite material modified with monatomic iron in comparative example 2
FIG. 12 is a graph showing the X-ray absorption spectrum and the fine spectrum of the nitrogen-doped graphite composite material co-modified with iron nitride and monoatomic iron in example 1 and the nitrogen-doped graphite material co-modified with monoatomic iron in comparative example 2, and the fitting results thereof
FIG. 13 test results of electrochemical performance of lithium-sulfur battery corresponding to modified diaphragm of comparative example 3
FIG. 14 scanning electron microscope image of nitrogen-doped graphite composite material co-modified with iron nitride and monoatomic iron in comparative example 4
FIG. 15 is an X-ray diffraction pattern of the nitrogen-doped graphite composite material co-modified by iron nitride and monoatomic iron in comparative example 5
Detailed Description
Example 1
Weighing a certain amount of urea, putting the urea into a crucible, and putting the crucible into a muffle furnace to heat to 550 ℃ and keep the temperature for 4 hours to obtain the graphitized carbon trinitrogen IV.
Weighing a certain amount of the prepared graphitized carbon trinitrogen IV, glucose and ferrous chloride tetrahydrate (the molar ratio of the glucose to the graphitized carbon trinitrogen is 2.21, and the molar ratio of the ferrous chloride tetrahydrate to the graphitized carbon trinitrogen is 0.09), adding 40mL of deionized water for ultrasonic treatment for 4h, then placing the solution in a hydrothermal reaction kettle, heating to 150 ℃, preserving heat for 10h, and after the reaction is finished, performing the processes of centrifugation, water washing, ethanol washing, drying and the like on the product to obtain precursor powder for later use.
And (3) placing the obtained precursor powder in a tubular furnace, introducing ammonia gas atmosphere, heating to 850 ℃, and preserving heat for 1.5h to obtain black powder, namely the iron nitride and monoatomic iron co-modified nitrogen-doped graphite composite material.
FIG. 1 is an X-ray diffraction pattern of the iron nitride and monatomic iron co-modified nitrogen-doped graphite composite material obtained in example 1, in which peaks at 24 degrees and 44.1 degrees correspond to the crystal faces of graphitized carbon (002) and (001), and peaks at 37.5 degrees, 40.8 degrees, 42.9 degrees, 56.6 degrees, 67.7 degrees and 75.7 degrees correspond to hexagonal crystal form iron nitride (Fe)2N, space group is P-31m) (110), (002),
Figure BDA0002947579880000061
(300) And
Figure BDA0002947579880000062
crystal face showing that the composite material contains Fe2N, and Fe2N itself has a Fe-3N coordination structure. Fig. 12 is an X-ray absorption spectrum and a fine spectrum of the iron nitride and monoatomic iron co-modified nitrogen-doped graphite composite material in example 1 and the monoatomic iron-modified nitrogen-doped graphite material in comparative example 2, and a fitting result thereof, and the coordination number of Fe and N in monoatomic Fe obtained by fitting is 4.3, which proves that monoatomic Fe is an Fe-4N coordination structure. The content of iron nitride is 7.44 wt% through measurement; the content of monoatomic iron was 1.33 wt%.
Fig. 2 is a scanning electron microscope image of the iron nitride and monoatomic iron co-modified nitrogen-doped graphite composite material obtained in example 1, which proves that the composite material has a porous sheet structure.
FIG. 3 is a transmission electron micrograph of the iron nitride and monoatomic iron co-modified nitrogen-doped graphite composite material obtained in example 1, and it can be seen that Fe2The average particle size of N is about 20nm, and the uniformly distributed bright spots around it are monatomic iron.
Example 2
The difference compared to example 1 is only that the amount of iron is increased, specifically:
a certain amount of urea is weighed and placed in a crucible, and the crucible is placed in a muffle furnace to be heated to 550 ℃ and kept for 4 hours to obtain graphitized carbon trinitrogen IV (the same as the example 1).
Weighing a certain amount of the prepared graphitized carbon trinitrogen IV, glucose and ferrous chloride tetrahydrate (the molar ratio of the glucose to the graphitized carbon trinitrogen IV is 2.21, and the molar ratio of the ferrous chloride tetrahydrate to the graphitized carbon trinitrogen IV is 0.05), adding 40mL of deionized water for ultrasonic treatment for 4h, then placing the solution in a hydrothermal reaction kettle, heating to 150 ℃, preserving heat for 10h, and after the reaction is finished, performing the processes of centrifugation, water washing, ethanol washing, drying and the like on the product to obtain precursor powder for later use.
And (3) placing the obtained precursor powder in a tubular furnace, introducing ammonia gas atmosphere, heating to 850 ℃, and preserving heat for 1.5h to obtain black powder, namely the iron nitride and monoatomic iron co-modified nitrogen-doped graphite composite material.
FIG. 4 is an X-ray diffraction pattern of the iron nitride and monoatomic iron co-modified nitrogen-doped graphite composite material obtained in example 2, which demonstrates that graphitized carbon and Fe2The presence of N.
Example 3
The difference compared to example 1 is only that the amount of iron is increased, specifically:
a certain amount of urea is weighed and placed in a crucible, and the crucible is placed in a muffle furnace to be heated to 550 ℃ and kept for 4 hours to obtain graphitized carbon trinitrogen IV (the same as the example 1).
Weighing a certain amount of the prepared graphitized carbon trinitrogen IV, glucose and ferrous chloride tetrahydrate (the molar ratio of the glucose to the graphitized carbon trinitrogen is 2.21, and the molar ratio of the ferrous chloride tetrahydrate to the graphitized carbon trinitrogen is 0.18), adding 40mL of deionized water for ultrasonic treatment for 4h, then placing the solution in a hydrothermal reaction kettle, heating to 150 ℃, preserving heat for 10h, and after the reaction is finished, performing the processes of centrifugation, water washing, ethanol washing, drying and the like on the product to obtain precursor powder for later use.
And (3) placing the obtained precursor powder in a tubular furnace, introducing ammonia gas atmosphere, heating to 850 ℃, and preserving heat for 1.5h to obtain black powder, namely the iron nitride and monoatomic iron co-modified nitrogen-doped graphite composite material.
FIG. 5 is an X-ray diffraction pattern of the iron nitride and monoatomic iron co-modified nitrogen-doped graphite composite material obtained in example 3, and also shows that graphitized carbon and Fe2The presence of N.
Example 4
Compared with the embodiment 1, the difference is mainly that the dosage of the carbon source is regulated and controlled, and the specific steps are as follows:
weighing a certain amount of urea, putting the urea into a crucible, and putting the crucible into a muffle furnace to heat to 550 ℃ and keep the temperature for 4 hours to obtain the graphitized carbon trinitrogen IV.
Weighing a certain amount of the prepared graphitized carbon trinitrogen-tetrakisglucose and ferrous chloride tetrahydrate (the molar ratio of the glucose to the graphitized carbon trinitrogen-tetrakisis 1.10, and the molar ratio of the ferrous chloride tetrahydrate to the graphitized carbon trinitrogen-tetrakisis 0.09), adding 40mL of deionized water for ultrasonic treatment for 4h, then placing the solution in a hydrothermal reaction kettle, heating to 150 ℃, preserving heat for 10h, and after the reaction is finished, performing the processes of centrifugation, water washing, ethanol washing, drying and the like on the product to obtain precursor powder for later use.
And (3) placing the obtained precursor powder in a tubular furnace, introducing ammonia gas atmosphere, heating to 850 ℃, and preserving heat for 1.5h to obtain black powder, namely the iron nitride and monoatomic iron co-modified nitrogen-doped graphite composite material.
Example 5
Compared with the example 1, the difference is mainly that the type of the carbon source is regulated and controlled, and the specific steps are as follows:
weighing a certain amount of urea, putting the urea into a crucible, and putting the crucible into a muffle furnace to heat to 550 ℃ and keep the temperature for 4 hours to obtain the graphitized carbon trinitrogen IV.
Weighing a certain amount of the prepared graphitized carbon trinitrogen IV, sucrose and ferrous chloride tetrahydrate (the molar ratio of sucrose to graphitized carbon trinitrogen is 2.21, and the molar ratio of ferrous chloride tetrahydrate to graphitized carbon trinitrogen is 0.09), adding 40mL of deionized water, carrying out ultrasonic treatment for 4h, then placing the solution in a hydrothermal reaction kettle, heating to 150 ℃, carrying out heat preservation for 10h, and after the reaction is finished, carrying out centrifugation-washing-ethanol washing-drying on the product to obtain precursor powder for later use.
And (3) putting the obtained precursor powder into a tubular furnace, introducing ammonia gas, heating for 850h, and keeping the temperature for 1.5h to obtain black powder, namely the iron nitride and monoatomic iron co-modified nitrogen-doped graphite composite material.
Example 6
Compared with the embodiment 1, the difference is mainly that the hydrothermal range temperature is regulated and controlled, specifically:
weighing a certain amount of urea, putting the urea into a crucible, and putting the crucible into a muffle furnace to heat to 550 ℃ and keep the temperature for 4 hours to obtain the graphitized carbon trinitrogen IV.
Weighing a certain amount of the prepared graphitized carbon trinitrogen IV, glucose and ferrous chloride tetrahydrate (the molar ratio of the glucose to the graphitized carbon trinitrogen is 2.21, and the molar ratio of the ferrous chloride tetrahydrate to the graphitized carbon trinitrogen is 0.09), adding 40mL of deionized water for ultrasonic treatment for 4h, then placing the solution in a hydrothermal reaction kettle, heating to 120 ℃, preserving heat for 10h, and after the reaction is finished, performing the processes of centrifugation, water washing, ethanol washing, drying and the like on the product to obtain precursor powder for later use.
And (3) placing the obtained precursor powder in a tubular furnace, introducing ammonia gas atmosphere, heating to 850 ℃, and preserving heat for 1.5h to obtain black powder, namely the iron nitride and monoatomic iron co-modified nitrogen-doped graphite composite material.
Example 7)
Compared with the embodiment 1, the difference is mainly that the preparation method of the graphitized carbon III-N is different, specifically:
weighing a certain amount of melamine, putting the melamine into a crucible, and putting the crucible into a muffle furnace to heat to 550 ℃ and keep the temperature for 4 hours to obtain the graphitized carbon trinitrogen IV.
Weighing a certain amount of the prepared graphitized carbon trinitrogen IV, glucose and ferrous chloride tetrahydrate (the molar ratio of the glucose to the graphitized carbon trinitrogen is 2.21, and the molar ratio of the ferrous chloride tetrahydrate to the graphitized carbon trinitrogen is 0.09), adding 40mL of deionized water for ultrasonic treatment for 4h, then placing the solution in a hydrothermal reaction kettle, heating to 150 ℃, preserving heat for 10h, and after the reaction is finished, performing the processes of centrifugation, water washing, ethanol washing, drying and the like on the product to obtain precursor powder for later use.
And (3) placing the obtained precursor powder in a tubular furnace, introducing ammonia gas atmosphere, heating to 850 ℃, and preserving heat for 1.5h to obtain black powder, namely the iron nitride and monoatomic iron co-modified nitrogen-doped graphite composite material.
Example 8
Compared with the embodiment 1, the difference is mainly that the temperature of the nitridation process is regulated and controlled, specifically:
weighing a certain amount of urea, putting the urea into a crucible, and putting the crucible into a muffle furnace to heat to 550 ℃ and keep the temperature for 4 hours to obtain the graphitized carbon trinitrogen IV.
Weighing a certain amount of the prepared graphitized carbon trinitrogen IV, glucose and ferrous chloride tetrahydrate (the molar ratio of the glucose to the graphitized carbon trinitrogen is 2.21, and the molar ratio of the ferrous chloride tetrahydrate to the graphitized carbon trinitrogen is 0.09), adding 40mL of deionized water for ultrasonic treatment for 4h, then placing the solution in a hydrothermal reaction kettle, heating to 150 ℃, preserving heat for 10h, and after the reaction is finished, performing the processes of centrifugation, water washing, ethanol washing, drying and the like on the product to obtain precursor powder for later use.
And (3) placing the obtained precursor powder in a tubular furnace, introducing ammonia gas atmosphere, heating to 750 ℃, and preserving heat for 2h to obtain black powder, namely the iron nitride and monoatomic iron co-modified nitrogen-doped graphite composite material.
Example 9
Compared with the embodiment 1, the difference is mainly that the temperature of the nitridation process is regulated and controlled, specifically:
weighing a certain amount of urea, putting the urea into a crucible, and putting the crucible into a muffle furnace to heat to 550 ℃ and keep the temperature for 4 hours to obtain the graphitized carbon trinitrogen IV.
Weighing a certain amount of the prepared graphitized carbon trinitrogen IV, glucose and ferrous chloride tetrahydrate (the molar ratio of the glucose to the graphitized carbon trinitrogen is 2.21, and the molar ratio of the ferrous chloride tetrahydrate to the graphitized carbon trinitrogen is 0.09), adding 40mL of deionized water for ultrasonic treatment for 4h, then placing the solution in a hydrothermal reaction kettle, heating to 150 ℃, preserving heat for 10h, and after the reaction is finished, performing the processes of centrifugation, water washing, ethanol washing, drying and the like on the product to obtain precursor powder for later use.
And (3) placing the obtained precursor powder in a tubular furnace, introducing ammonia gas atmosphere, heating to 900 ℃, and preserving heat for 1h to obtain black powder, namely the iron nitride and monoatomic iron co-modified nitrogen-doped graphite composite material.
Example 10
The iron nitride and monoatomic iron co-modified nitrogen-doped graphite composite materials prepared in the embodiments 1, 2 and 3 and the PVDF binder are mixed according to the mass ratio of 4:1, then are coated on the surface of the polypropylene diaphragm in a blade mode, and then are dried in vacuum to obtain the modified diaphragm. The modified separator prepared above was transferred to an argon-protected glove box and assembled into a button cell, where the positive electrode was a sulfur positive electrode (sulfur/carbon black/PVDF ═ 7/2/1), the negative electrode was lithium metal, and the electrolyte was LiTFSI (concentration 1mol/L) dissolved in DOL/DME solvent. The assembled battery is kept stand for 6h at room temperature, and then a constant current charge and discharge test (the current density is 0.2C, and 1C is 1675mAh/g) is carried out on a blue test system, and the voltage range is 1.8-2.8V.
Fig. 6 is a result of the electrochemical performance test in example 10, and the result shows that the three modified separators all improve the specific capacity and the cycling stability of the battery compared with the common polypropylene separator, however, the electrochemical performance of the lithium-sulfur battery is improved by the modified separators prepared by using the composite materials in examples 1 and 3 more than that of the composite material in example 2.
Example 11
Uniformly mixing the iron nitride and monoatomic iron co-modified nitrogen-doped graphite composite material prepared in the example 1 with sulfur powder according to the mass ratio of 1:4, heating the mixture in a tubular furnace to 155 ℃, and preserving heat for 6 hours to obtain the modified sulfur cathode material. And then mixing the modified sulfur positive electrode material with carbon black and PVDF according to a mass ratio of 8/1/1, blade-coating the mixture on an aluminum foil, and then carrying out vacuum drying to obtain the modified sulfur positive electrode piece. And finally transferring the modified sulfur positive pole piece to an argon-protected glove box to be assembled into a button cell, wherein the negative pole is lithium metal, the diaphragm is a polypropylene diaphragm, and the electrolyte is LiTFSI (the concentration is 1mol/L) dissolved in DOL/DME solvent. The assembled battery is kept still for 6 hours at room temperature, and then a constant current charge and discharge test (the current density is 0.2C, and 1C is 1675mAh/g) is carried out on a blue test system, and the voltage range is 1.8-2.8V.
FIG. 7 is a result of electrochemical performance testing in example 11, which shows that the specific capacity and the cycling stability of the lithium-sulfur battery are greatly improved by the composite modified sulfur positive electrode, and the first-cycle specific capacity of the lithium-sulfur battery is 1218.2mAh g under the current density of 0.2C-1The capacity retention after 100 cycles was 86.57%.
Comparative example 1
Compared with the example 1, the difference is that no ferrous chloride tetrahydrate is added in the hydrothermal process, and the specific process is as follows:
weighing a certain amount of urea, putting the urea into a crucible, and putting the crucible into a muffle furnace to heat to 550 ℃ and keep the temperature for 4 hours to obtain the graphitized carbon trinitrogen IV.
Weighing a certain amount of the prepared graphitized carbon trinitrogen IV, glucose (the molar ratio of the glucose to the graphitized carbon trinitrogen IV is 2.21), adding 40mL of deionized water for ultrasonic treatment for 4h, then placing the solution in a hydrothermal reaction kettle, heating to 150 ℃, preserving heat for 10h, and after the reaction is finished, performing centrifugation-water washing-ethanol washing on the product to obtain precursor powder for later use.
And (3) placing the obtained precursor powder in a tubular furnace, introducing ammonia gas atmosphere, heating to 850 ℃, and keeping the temperature for 1.5h to obtain the nitrogen-doped graphite composite material.
FIG. 8 is a scanning electron microscope image of the nitrogen-doped graphite material in comparative example 1, wherein the micro-morphology of the nitrogen-doped graphite material is a porous sheet structure. The result shows that the introduction of the iron source does not change the microscopic morphology of the nitrogen-doped graphite material.
Comparative example 2
Compared with the embodiment 1, the difference lies in that the molar ratio of the ferrous chloride tetrahydrate and the graphitized carbon trinitrogen added in the hydrothermal process is 0.01, and the specific process is as follows:
weighing a certain amount of urea, putting the urea into a crucible, and putting the crucible into a muffle furnace to heat to 550 ℃ and keep the temperature for 4 hours to obtain the graphitized carbon trinitrogen IV.
Weighing a certain amount of the prepared graphitized carbon trinitrogen tetranitrate, glucose and ferrous chloride tetrahydrate (the molar ratio of the glucose to the graphitized carbon trinitrogen tetranitrate is 2.21, and the molar ratio of the ferrous chloride tetrahydrate to the graphitized carbon trinitrogen tetranitrate is 0.01), adding 40mL of deionized water for ultrasonic treatment for 4h, then placing the solution in a hydrothermal reaction kettle, heating to 150 ℃, and preserving heat for 10h
And after the reaction is finished, performing the processes of centrifugation, water washing, ethanol washing and the like on the product to obtain precursor powder for later use.
And (3) placing the obtained precursor powder in a tubular furnace, introducing ammonia gas atmosphere, heating to 850 ℃, and keeping the temperature for 1.5h to obtain black powder, namely the monatomic iron-modified nitrogen-doped graphite material.
Fig. 9 is a scanning electron microscope image of the nitrogen-doped graphite material modified by monoatomic iron in comparative example 2, and the microscopic morphology of the material is a porous sheet structure.
FIG. 10 is an X-ray diffraction pattern of the monatomic iron-modified nitrogen-doped graphite material in comparative example 2, which shows that no extra crystallization peak appears in the monatomic iron-modified nitrogen-doped graphite material, and proves that the Fe source content is reduced to cause Fe2The N diffraction peak signal disappeared.
Fig. 11 is a projection electron microscope image of the nitrogen-doped graphite material modified by monatomic iron in comparative example 2, and it can be seen that the uniformly distributed bright spots in the image are monatomic iron.
The results show that the selection of the content of the iron source plays a key role in obtaining the iron nitride and monoatomic iron co-modified nitrogen-doped graphite composite material.
Comparative example 3
The composite material, the nitrogen-doped graphite material and the monatomic iron modified nitrogen-doped graphite material prepared in the example 1, the comparative example 1 and the comparative example 2 are mixed with the PVDF binder according to the mass ratio of 4:1, then are coated on the surface of the polypropylene diaphragm in a scraping mode, and then are dried in vacuum to obtain the modified diaphragm. The modified separator prepared above was transferred to an argon-protected glove box and assembled into a button cell, where the positive electrode was a sulfur positive electrode (sulfur/carbon black/PVDF ═ 7/2/1), the negative electrode was lithium metal, and the electrolyte was LiTFSI (concentration 1mol/L) dissolved in DOL/DME solvent. After the assembled battery is kept stand for 6 hours at room temperature, a constant current charge and discharge test (the current density is 0.2C, and 1C is 1675mAh/g) and a rate performance test are carried out on a blue test system, and the voltage range is 1.8-2.8V.
Fig. 13 is a result of the electrochemical performance test in comparative example 3, and compared with the common separator, the modified separators corresponding to the three samples can improve the electrochemical performance of the lithium-sulfur battery, and the battery assembled by the modified separators corresponding to the iron nitride and monatomic iron co-modified nitrogen-doped graphite composite material has the best cycling stability and rate performance.
Comparative example 4
Compared with the example 1, the difference is mainly that the temperature of the hydrothermal process is regulated and controlled by the following steps: the temperature of the hydrothermal process is increased from 150 ℃ to 180 DEG C
The comparative example provides a preparation method of a nitrogen-doped graphite composite material co-modified by iron nitride and monoatomic iron, which comprises the following specific steps:
weighing a certain amount of urea, putting the urea into a crucible, and putting the crucible into a muffle furnace to heat to 550 ℃ and keep the temperature for 4 hours to obtain the graphitized carbon trinitrogen IV.
Weighing a certain amount of the prepared graphitized carbon trinitrogen IV, glucose and ferrous chloride tetrahydrate (the molar ratio of the glucose to the graphitized carbon trinitrogen is 2.21, and the molar ratio of the ferrous chloride tetrahydrate to the graphitized carbon trinitrogen is 0.09), adding 40mL of deionized water for ultrasonic treatment for 4h, then placing the solution in a hydrothermal reaction kettle for heating to 180 ℃, preserving heat for 10h, and after the reaction is finished, performing centrifugation-water washing-ethanol washing on the product to obtain precursor powder for later use.
And (3) placing the obtained precursor powder in a tubular furnace, introducing ammonia gas atmosphere, heating to 850 ℃, and preserving heat for 1.5h to obtain black powder, namely the iron nitride and monoatomic iron co-modified nitrogen-doped graphite composite material.
Fig. 14 is a scanning electron microscope image of the nitrogen-doped graphite composite material co-modified with iron nitride and monoatomic iron in comparative example 4, in which a spherical structure appears in addition to a sheet structure, due to the fact that the hydrothermal temperature is too high, resulting in the evolution of glucose into carbon spheres. The result shows that the hydrothermal reaction temperature has a key effect on the sheet structure of the nitrogen-doped graphite composite material co-modified by the iron nitride and the monoatomic iron.
Comparative example 5
Compared with the embodiment 1, the difference is only that the sintering temperature is regulated and controlled as follows:
compared with example 1, the difference is that the heat treatment temperature is reduced from 850 ℃ to 650 ℃ under the ammonia atmosphere.
The comparative example provides a preparation method of a nitrogen-doped graphite composite material co-modified by iron nitride and monoatomic iron, which comprises the following specific steps:
weighing a certain amount of urea, putting the urea into a crucible, and putting the crucible into a muffle furnace to heat to 550 ℃ and keep the temperature for 4 hours to obtain the graphitized carbon trinitrogen IV.
Weighing a certain amount of the prepared graphitized carbon trinitrogen IV, glucose and ferrous chloride tetrahydrate (the molar ratio of the glucose to the graphitized carbon trinitrogen IV is 2.21, and the molar ratio of the ferrous chloride tetrahydrate to the graphitized carbon trinitrogen IV is 0.18), adding 40mL of deionized water for ultrasonic treatment for 4h, then placing the solution in a hydrothermal reaction kettle, heating to 150 ℃, preserving heat for 10h, and after the reaction is finished, performing centrifugation-water washing-ethanol washing on the product to obtain precursor powder for later use.
And (3) placing the obtained precursor powder in a tubular furnace, introducing ammonia gas atmosphere, heating to 650 ℃, and preserving heat for 1.5h to obtain black powder, namely the iron nitride and monoatomic iron co-modified nitrogen-doped graphite composite material.
FIG. 15 is an X-ray diffraction pattern of the nitrogen-doped graphite composite material co-modified with iron nitride and monoatomic iron in comparative example 5, in which diffraction peak signals of the iron nitride include iron di (Fe) nitride2N), iron tetranitride (Fe)4N) and elemental iron (Fe). The result shows that the heat treatment temperature in the ammonia atmosphere plays a key role in co-modifying the iron nitride and the monoatomic iron with the iron nitride in the nitrogen-doped graphite composite material.

Claims (18)

1. The nitrogen-doped graphite composite material co-modified by iron nitride and monoatomic iron is characterized by comprising a nitrogen-doped graphite matrix and the iron nitride and the monoatomic iron loaded on the nitrogen-doped graphite matrix in situ;
the chemical formula of the iron nitride is Fe2N has a polar triangular pyramid Fe-3N coordination structure;
the monatomic iron has a nonpolar plane symmetry type Fe-4N coordination structure;
the nitrogen-doped graphite is in a nano sheet shape, has a micropore and mesoporous structure, and has a specific surface area of 400-1000m2/g。
2. The iron nitride and monoatomic iron co-modified nitrogen-doped graphite composite material according to claim 1, wherein the iron nitride content is 1wt% to 30 wt%.
3. The iron nitride and monatomic iron co-modified nitrogen-doped graphite composite material of claim 1, wherein the monatomic iron content is 0.1wt% to 5 wt%.
4. The preparation method of the iron nitride and monoatomic iron co-modified nitrogen-doped graphite composite material according to any one of claims 1 to 3, which is characterized by comprising the following specific steps:
the method comprises the following steps: carrying out hydrothermal reaction on a solution containing graphitized carbon-nitrogen-tetrananosheets, a carbon source and a water-soluble iron source to prepare a precursor; the molar ratio of Fe in the water-soluble iron source to graphitized carbon trinitrogen is 0.02-0.5; the temperature of the hydrothermal reaction is 120-160 ℃;
step two: and nitriding the precursor in an ammonia atmosphere at the temperature of 700-1000 ℃ to obtain the iron nitride and monoatomic iron co-modified nitrogen-doped graphite composite material.
5. The preparation method of the iron nitride and monatomic iron co-modified nitrogen-doped graphite composite material according to claim 4, wherein the graphitized carbon tri-nitrogen nanosheet is prepared by subjecting urea to a pyrolysis reaction in an air atmosphere.
6. The method for preparing the iron nitride and monatomic iron co-modified nitrogen-doped graphite composite material of claim 5, wherein the pyrolysis temperature is 350-550 ℃, and the reaction time is 2-4 h.
7. The method for preparing the iron nitride and monatomic iron co-modified nitrogen-doped graphite composite material of claim 4, wherein the carbon source is at least one of glucose, sucrose, chitosan, polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, gum arabic, cellulose acetate, and dopamine.
8. The preparation method of the iron nitride and monatomic iron co-modified nitrogen-doped graphite composite material according to claim 4, wherein the molar ratio of the carbon source to the graphitized carbon, trinitrogen, is 0.1-5.
9. The method for preparing the iron nitride and monatomic iron co-modified nitrogen-doped graphite composite material as claimed in claim 4, wherein the temperature of the hydrothermal reaction is 140-160 ℃; the hydrothermal reaction time is 6-12 h.
10. The preparation method of the iron nitride and monoatomic iron co-modified nitrogen-doped graphite composite material according to claim 4, wherein the temperature of the nitriding reaction is 700-900 ℃.
11. The preparation method of the iron nitride and monoatomic iron co-modified nitrogen-doped graphite composite material according to claim 4, wherein the nitriding reaction time is 1-3 h.
12. The application of the iron nitride and monoatomic iron co-modified nitrogen-doped graphite composite material according to any one of claims 1 to 3 or the iron nitride and monoatomic iron co-modified nitrogen-doped graphite composite material prepared by the preparation method according to any one of claims 4 to 11 in a lithium-sulfur battery.
13. The use according to claim 12 for producing a separator for a lithium-sulfur battery or for producing a positive electrode material for a lithium-sulfur battery.
14. Use according to claim 13, characterized in that it is compounded on the surface of the membrane.
15. The composite diaphragm of the lithium-sulfur battery is characterized by comprising a base film and a modified layer compounded on the surface of the base film; the modified layer is compounded with a binder, and the iron nitride and monoatomic iron co-modified nitrogen-doped graphite composite material according to any one of claims 1 to 3 or the iron nitride and monoatomic iron co-modified nitrogen-doped graphite composite material prepared by the preparation method according to any one of claims 4 to 11.
16. The composite separator membrane for a lithium-sulfur battery as claimed in claim 15, wherein the weight percentage of the iron nitride and monoatomic iron co-modified nitrogen-doped graphite composite material in the modified layer is 50 to 95 wt%.
17. A composite positive electrode material of a lithium-sulfur battery is characterized by comprising amorphous sulfur, a binder and the iron nitride and monoatomic iron co-modified nitrogen-doped graphite composite material according to any one of claims 1 to 3 or the iron nitride and monoatomic iron co-modified nitrogen-doped graphite composite material prepared by the preparation method according to any one of claims 4 to 11.
18. The composite positive electrode material for a lithium-sulfur battery as defined in claim 17, wherein the iron nitride and the monoatomic iron co-modified nitrogen-doped graphite composite material is present in an amount of 5wt% to 30 wt%.
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