CN110581273B - Zinc-position sodium-copper co-doped synergetic nitrogen-sulfur doped carbon-coated modified zinc titanate negative electrode material and preparation method and application thereof - Google Patents

Zinc-position sodium-copper co-doped synergetic nitrogen-sulfur doped carbon-coated modified zinc titanate negative electrode material and preparation method and application thereof Download PDF

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CN110581273B
CN110581273B CN201910882225.7A CN201910882225A CN110581273B CN 110581273 B CN110581273 B CN 110581273B CN 201910882225 A CN201910882225 A CN 201910882225A CN 110581273 B CN110581273 B CN 110581273B
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zinc
nitrogen
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copper
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CN110581273A (en
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伊廷锋
齐思雨
仇立英
韩梦成
罗绍华
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Northeastern University Qinhuangdao Branch
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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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M4/624—Electric conductive fillers
    • H01M4/626—Metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to a zinc-position sodium-copper co-doped synergetic nitrogen-sulfur doped carbon-coated modified zinc titanate negative electrode material, and a preparation method and application thereof. The preparation method comprises the following steps: (1) preparing a nitrogen-doped carbon material; (2) dissolving a zinc source, a sodium source and a copper source to obtain a solution A; dissolving a titanium source to obtain a solution B; mixing the two to obtain a solution C; (3) adding a nitrogen-doped carbon material into a solvent to obtain a solution D; (4) and mixing the solution C and the solution D, stirring, centrifugally drying, mixing the obtained solid powder with a sulfur source, and sintering to obtain the cathode material. The negative electrode material prepared by the invention has the advantages of uniform particle size, stable and compact structure, high conductivity and good cycling stability, and the negative electrode plate and the lithium ion battery prepared by the negative electrode material have good cycling performance and longer service life and meet the requirements in practical application.

Description

Zinc-position sodium-copper co-doped synergetic nitrogen-sulfur doped carbon-coated modified zinc titanate negative electrode material and preparation method and application thereof
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a zinc-position sodium-copper co-doped synergetic nitrogen-sulfur doped carbon-coated modified zinc titanate negative electrode material and a preparation method and application thereof.
Background
With the development of various electronic devices, electric vehicles and hybrid vehicles, higher requirements are put on lithium ion batteries for supplying energy to the electronic devices. Lithium ion batteries have high capacity density and energy density and are recognized as the most promising power batteries. At present, various lithium-intercalated carbon/graphite materials are mostly adopted as the negative electrode material of the lithium ion battery, but the lithium-intercalated potential (0-0.26V) of the carbon material is very close to the deposition potential of metallic lithium, when the battery is overcharged, the metallic lithium may be separated out on the surface of a carbon electrode to form lithium dendrite, and the lithium dendrite may pierce a diaphragm along with the further growth of the dendrite to cause the connection of a positive electrode and a negative electrode, thereby causing short circuit; in addition, the carbon material has the defects of low first charge-discharge efficiency, obvious voltage hysteresis phenomenon and complex preparation method and the like when acting with electrolyte. The titanate-based material has higher lithium intercalation potential, can effectively avoid the precipitation of metal lithium, has a certain oxygen absorption function at high temperature, has obvious safety characteristic, and is considered as an ideal choice for replacing a carbon material as a lithium ion battery cathode material.
However, when a simple titanate-based material is used as a negative electrode material, the electronic conductivity and the ionic conductivity are poor, the performance of the electrochemical performance of titanate is seriously influenced, particularly, the capacity attenuation is fast during large-current charging and discharging, the rate performance is poor, and rapid charging and discharging are difficult to perform in practical application, so that effective measures are urgently needed to modify the titanate-based material to improve the electrochemical performance of the titanate-based material.
At present, the modification of titanate-based materials is researched more, and mainly methods of ion doping, carbon coating and compounding with other materials are adopted. CN106816592A discloses a preparation method of a potassium chloride modified lithium zinc titanate negative electrode material, which adopts the technical scheme that: the method comprises the following steps: and uniformly mixing lithium zinc titanate and potassium chloride in water according to a ratio, and then drying, sintering and grinding to obtain the lithium zinc titanate. The method solves the problem that the electron conductivity and the ion conductivity of the lithium zinc titanate negative electrode material are poor in the prior art, effectively solves the problem that the electron conductivity and the ion conductivity of the lithium zinc titanate negative electrode material are poor by doping potassium ions and chloride ions into the lithium zinc titanate, and remarkably improves the electrochemical performance, especially the rate capability, of the lithium zinc titanate negative electrode material.
CN109244415A discloses a preparation method of a spherical carbon-coated titanate composite negative electrode material, which comprises the following steps: preparing a chloride solution, and then completely stirring and mixing the chloride solution and ethanol to obtain a mixed solution; adding tetrabutyl titanate into the mixed solution, fully hydrolyzing and precipitating, filtering and washing the generated white precipitate, drying and grinding to obtain a spherical titanium dioxide precursor; adding a carbon source, a sodium source and a spherical titanium dioxide precursor into deionized water, and heating and stirring until the carbon source, the sodium source and the spherical titanium dioxide precursor are completely dissolved; or adding a carbon source, a lithium source and the spherical titanium dioxide precursor into deionized water, and heating and stirring until the carbon source, the lithium source and the spherical titanium dioxide precursor are completely dissolved; continuously heating and stirring until the mixture is dried by distillation, drying and grinding to obtain a titanate precursor; heating the titanate precursor at constant temperature under inert atmosphere, cooling and grinding to obtain pre-sintered powder; and calcining the pre-sintered powder at constant temperature in an inert atmosphere, cooling, grinding and sieving to obtain the spherical carbon-coated titanate composite negative electrode material. The spherical carbon-coated sodium titanate or lithium titanate composite battery material prepared by the invention has good sphericity and narrow particle size distribution, and the carbon-coated layer is beneficial to improving the electronic conductivity of the material.
CN107768635A discloses a preparation method of a barium sodium titanate composite negative electrode material for a lithium ion battery, belonging to the technical field of lithium ion batteries. The method comprises the following specific steps: dissolving sodium nitrate and barium nitrate in an aqueous solution of alcohol, and adding an organic acid, and marking as a solution A; mixing TiCl4Dissolving in alcohol solution, and marking as solution B; mixing A and B, stirring, and evaporating to dryness; then placing the mixture into a muffle furnace for pre-sintering, cooling to room temperature, and ball-milling to obtain BaNa2Ti6O14A material; putting the mixture into a beaker, adding a surfactant and deionized water, performing ultrasonic treatment, and stirring; then adding pyrrole and acid solution, adding oxidant, stirring in ice water bath, and washing to obtain BaNa2Ti6O14@ PPy composite anode material. The negative electrode material has uniform particle size, stable and compact structure, considerable reversible capacity of a wide potential window, excellent rate capability and stable cycle life.
In the prior art, modification researches on titanate-based materials such as lithium titanate, sodium titanate, barium lithium titanate and barium sodium titanate are more, but the modification researches on zinc titanate materials are still blank, so that the important point of the researches is how to prepare the zinc titanate materials with uniform particle size, stable and compact structure and high electronic conductivity and ionic conductivity, and how to improve the cycle stability of the zinc titanate materials so as to meet the requirements of practical application of high-power and long-life lithium ion batteries.
Disclosure of Invention
In view of the problems in the prior art, the invention provides a zinc-position sodium-copper co-doped synergetic nitrogen-sulfur-doped carbon-coated modified zinc titanate negative electrode material, and a preparation method and application thereof. The preparation method provided by the invention solves the problems of high energy consumption, easy powder agglomeration and large particle size of the traditional high-temperature solid phase method for synthesizing the zinc titanate, solves the problems of low electronic conductivity and ionic conductivity of the pure zinc titanate by the method of co-doping modification of the zinc site sodium and copper of the zinc titanate and coating and modifying the zinc titanate by the nitrogen-sulfur doped carbon material, improves the electrochemical performance of the zinc titanate, and the lithium ion battery assembled by the zinc titanate has excellent cycle stability.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a preparation method of a zinc-position sodium-copper co-doped synergetic nitrogen-sulfur-doped carbon-coated modified zinc titanate negative electrode material, which comprises the following steps:
(1) adding a carbon material into an organic solvent I to prepare a nitrogen-doped carbon material;
(2) dissolving a zinc source, a sodium source and a copper source in an organic solvent II to obtain a solution A; dissolving a titanium source in an organic solvent III to obtain a solution B; mixing the solution A and the solution B to obtain a solution C;
(3) adding the nitrogen-doped carbon material obtained in the step (1) into an organic solvent containing a non-ionic high polymer to obtain a solution D;
(4) and adding the solution C into the solution D, stirring, centrifugally drying, mixing the obtained solid powder with a sulfur source, and sintering to obtain the zinc-site sodium-copper co-doped synergetic nitrogen-sulfur-doped carbon-coated modified zinc titanate negative electrode material.
According to the invention, the zinc-position sodium-copper co-doping and nitrogen-sulfur-doped carbon material coating modified zinc titanate is prepared by modifying the zinc-position sodium-copper co-doping of zinc titanate and coating the modified zinc titanate with the nitrogen-sulfur-doped carbon material, so that the zinc titanate negative electrode material has uniform particle size, stable structure and compactness, and the problems of high energy consumption, easy powder agglomeration and large particle size of the traditional high-temperature solid phase method for synthesizing zinc titanate are solved; the nitrogen-sulfur-doped carbon material can uniformly coat the zinc titanate material, so that the electronic conductivity of the zinc titanate is obviously improved, the ionic conductivity of the zinc titanate is greatly improved by co-doping the zinc site with sodium and copper, the problems of low electronic conductivity and ionic conductivity of the pure zinc titanate are solved, the zinc titanate negative electrode material has excellent electrochemical performance, especially circulation stability, and the requirements of high-power and long-service-life lithium ion battery practical application are met.
In the present invention, the specific type of the carbon material is not particularly limited, and the carbon material may be a multi-walled carbon nanotube, a single-walled carbon nanotube, or a carbon fiber, and any type commonly used by those skilled in the art is applicable to the present invention.
Preferably, the preparation of the nitrogen-doped carbon material in step (1) comprises the following steps:
and adding the carbon material into an organic solvent I, heating and refluxing, then centrifuging, washing a centrifugal product, and drying to prepare the nitrogen-doped carbon material.
Preferably, the organic solvent I is a mixed solution of diethylenetriamine, ethanolamine, and ethanol, which enables uniform dispersion of the carbon material while providing a nitrogen source.
Preferably, the volume ratio of diethylenetriamine, ethanolamine and ethanol is (1-3): (1-3): (10-16), and may be, for example, 1:1:10, 1:2:12, 1:2:15, 1:3:10, 1:3:16, 2:1:10, 2:2:12, 2:2:16, 2:3:10, 2:3:12, 2:3:16, 3:1:10, 3:1:12, 3:1:16, 3:2:10, 3:2:13, 3:2:16, 3:3:10, 3:3:12 and 3:3:16, preferably 3:1: 16.
Preferably, the temperature of the heating reflux is 70 to 100 ℃, for example, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃ and 100 ℃, preferably 80 to 90 ℃.
Preferably, the heating reflux time is 3 to 10 hours, and for example, may be 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours and 10 hours, preferably 5 to 7 hours.
Preferably, the centrifuged product is washed with absolute ethanol.
Preferably, the washing is 3 or more times, preferably 3 to 4 times.
Preferably, the drying is vacuum drying.
Preferably, the temperature of the vacuum drying is 50 to 80 ℃, and may be, for example, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃ and 80 ℃, preferably 60 to 70 ℃.
Preferably, the vacuum drying time is 6-15h, for example, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h and 10h, preferably 10-15 h.
Preferably, the zinc source in step (2) is selected from any one of zinc nitrate, zinc acetate or zinc citrate or a combination of at least two thereof.
Preferably, the sodium source is selected from any one of sodium acetate, sodium citrate or sodium nitrate or a combination of at least two thereof.
Preferably, the copper source is selected from copper acetate and/or copper nitrate, preferably copper acetate.
Preferably, the titanium source is selected from any one of tetrabutyl titanate, isopropyl titanate or titanium tetrachloride or a combination of at least two of them.
Preferably, the organic solvent II is a mixed solution of ethylene glycol, N-dimethylformamide and glycerol, which enables the zinc source, the sodium source and the copper source to be rapidly dissolved and prevents the copper ions from being hydrolyzed, so that the metal ions in the solution a are uniformly distributed.
Preferably, the volume ratio of the ethylene glycol, the N, N-dimethylformamide and the glycerol is (6-10): (1-3): (0.1-0.5), and may be, for example, 6:1:0.1, 6:1:0.2, 6:1:0.5, 6:2:0.1, 6:2:0.3, 6:2:0.5, 6:3:0.1, 6:3:0.2, 6:3:0.5, 7:2:0.1, 7:2:0.5, 8:2:0.1, 8:3:0.3, 8:3:0.5, 9:2:0.1, 9:2:0.2, 9:2:0.5, 10:1:0.1, 10:1:0.3, 10:1:0.5, 10:2:0.1, 10:3:0.5, 10:1:0.1, 10: 0.5, 10:3:0.5, 10: 0.5, and preferably 10: 0.5.
Preferably, the organic solvent III is a mixed solution of ethylene glycol and acetone, which can prevent the titanium source from hydrolyzing and accelerate the dissolution rate of the titanium source.
Preferably, the volume ratio of ethylene glycol to acetone is (4-8): 1-3, and may be, for example, 4:1, 4:2, 4:3, 5:1, 5:2, 5:3, 6:1, 6:2, 6:3, 7:1, 7:3, 8:1, 8:2 and 8:3, preferably 8: 1.
Preferably, the non-ionic polymer in step (3) is a mixture of polyvinylpyrrolidone and polyacrylamide, which facilitates the formation of material morphology and particle size.
Preferably, the mass ratio of polyvinylpyrrolidone to polyacrylamide is (4-10): (1-5), and may be, for example, 4:1, 4:3, 4:5, 5:1, 5:2, 5:5, 6:1, 6:4, 6:5, 7:1, 7:3, 7:5, 8:1, 8:3, 8:5, 9:1, 9:3, 9:5, 10:1, 10:3 and 10:5, preferably 9: 1.
Preferably, the organic solvent is ethylene glycol.
Preferably, the temperature of the stirring in step (4) is 35 to 55 ℃, and may be, for example, 35 ℃, 40 ℃, 45 ℃, 50 ℃ and 55 ℃, preferably 45 to 55 ℃.
Preferably, the stirring time is 8 to 18 hours, and for example, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours and 18 hours, preferably 10 to 15 hours, may be used.
Preferably, the product obtained after the centrifugal drying is washed by absolute ethyl alcohol.
Preferably, the washing is 3 or more times, preferably 3 to 4 times.
Preferably, the drying is vacuum drying.
Preferably, the temperature of the vacuum drying is 50 to 80 ℃, and may be, for example, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃ and 80 ℃, preferably 60 to 70 ℃.
Preferably, the vacuum drying time is 8-16h, for example, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h and 16h, preferably 12-15 h.
Preferably, the sulfur source is elemental sulfur and/or thiourea.
Preferably, the sintering in step (4) comprises: sintering the obtained solid powder and a sulfur source in a mixed gas atmosphere, preferably heating to 300-400 ℃ in the mixed gas atmosphere at the heating rate of 2-4 ℃/min, cooling to room temperature, ball-milling in an organic solvent IV, finally heating to 500-700 ℃ in an inert gas atmosphere at the heating rate of 2-4 ℃/min, and keeping the temperature.
Preferably, the mixed gas is N2And NH3The mixed gas of (1).
Preferably, said N is2And NH3The volume ratio of (2-5) to (1-3) may be, for example, 2:1, 2:2, 2:3, 3:1, 3:2, 3:3, 4:1, 4:2, 4:3, 5:1, 5:2 and 5:3, preferably 2: 1.
Preferably, the organic solvent IV is an ethanol solution of polyacrylic acid.
Preferably, the ball milling time is 2 to 4 hours, and may be, for example, 2 hours, 2.5 hours, 3 hours, 3.5 hours and 4 hours, preferably 2.5 to 3 hours.
Preferably, the incubation time is 2-5h, and may be, for example, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h and 5h, preferably 2.5-4 h.
In the present invention, the specific type of the inert gas is not particularly limited, and the inert gas may be nitrogen, helium or argon, and any type commonly used by those skilled in the art is suitable for the present invention.
Preferably, the preparation method of the zinc titanate negative electrode material comprises the following steps:
(1) adding a carbon material into a mixed solution of diethylenetriamine, ethanolamine and ethanol, heating and refluxing for 3-10h at 70-100 ℃, and then centrifuging; washing the centrifugal product with absolute ethyl alcohol for more than 3 times, and drying in vacuum at 50-80 ℃ for 6-15h to obtain a nitrogen-doped carbon material;
(2) dissolving a zinc source, a sodium source and a copper source in a mixed solution of ethylene glycol, N-dimethylformamide and glycerol under the condition of mechanical stirring to obtain a solution A; dissolving tetrabutyl titanate in a mixed solution of ethylene glycol and acetone under a stirring condition to obtain a solution B; then, slowly dripping the solution A into the solution B under the stirring condition to obtain a solution C;
(3) dissolving a mixture of polyvinylpyrrolidone and polyacrylamide in ethylene glycol, adding concentrated ammonia water, uniformly stirring, and then adding the nitrogen-doped carbon material prepared in the step (1) to obtain a solution D;
(4) slowly adding the solution C into the solution D at 35-55 ℃, and violently stirring for 8-18 h; centrifuging with high speed centrifuge, washing the centrifuged product with anhydrous ethanol for more than 3 times, drying in vacuum drying oven at 50-80 deg.C for 8-16h, mixing the obtained solid powder with sulfur source, heating at N at a rate of 2-4 deg.C/min2And NH3Raising the temperature to 300-400 ℃ in the mixed gas atmosphere, cooling to room temperature, and ball-milling in an ethanol solution of polyacrylic acid for 2-4 h; and finally, heating to 500-700 ℃ in the inert gas atmosphere at the heating rate of 2-4 ℃/min, preserving the heat for 2-5h, and cooling to room temperature to obtain the zinc-site sodium-copper co-doped synergetic nitrogen-sulfur doped carbon-coated modified zinc titanate negative electrode material.
In a second aspect, the invention provides the zinc-site sodium-copper co-doped synergetic nitrogen-sulfur-doped carbon-coated modified zinc titanate negative electrode material prepared by the preparation method of the first aspect.
According to the invention, the zinc titanate particles can be homogenized by adding the carbon material, the ionic conductivity of the zinc titanate can be greatly improved by co-doping the zinc site with sodium and copper, the electronic conductivity of the zinc titanate can be obviously improved by coating the nitrogen and sulfur doped carbon material, so that the zinc titanate negative electrode material has good electronic conductivity and ionic conductivity, the cycle stability is greatly improved, and the electrochemical performance is excellent.
In a third aspect, the invention provides a lithium ion battery negative electrode plate, which contains the zinc-position sodium-copper co-doped synergetic nitrogen-sulfur-doped carbon-coated modified zinc titanate negative electrode material described in the second aspect.
According to the lithium ion battery cathode pole piece provided by the invention, the zinc-position sodium-copper co-doping and nitrogen-sulfur-doped carbon-coated modified zinc titanate is used as a cathode active material, so that the resistance of the cathode is reduced, the cycle stability of the cathode is improved, and the service life of the cathode is prolonged.
In a fourth aspect, the present invention further provides a lithium ion battery, where the lithium ion battery includes the negative electrode sheet described in the third aspect.
According to the lithium ion battery provided by the invention, the negative pole piece containing zinc-position sodium-copper co-doping synergistic nitrogen-sulfur-doped carbon-coated modified zinc titanate is used, so that the internal resistance of the battery is reduced, the cycle performance of the battery is improved, and the requirements of high power and long service life in the practical application of the lithium ion battery are met.
Compared with the prior art, the invention has the following beneficial effects:
(1) the zinc-position sodium-copper co-doped synergetic nitrogen-sulfur-doped carbon-coated modified zinc titanate negative electrode material provided by the invention has the advantages of uniform particle size, stable structure and compactness. The addition of the carbon material can make zinc titanate particles uniform, the co-doping of sodium and copper at a zinc position can greatly improve the ionic conductivity of the zinc titanate, and the nitrogen-sulfur doped carbon coating can obviously improve the electronic conductivity of the zinc titanate, so that the zinc titanate negative electrode material has excellent electrochemical performance.
(2) The preparation method provided by the invention has the advantages of less energy consumption and simple and convenient process operation, the nitrogen-sulfur doped carbon material can uniformly wind the zinc titanate material, the discharge capacity after 90 weeks of circulation is 1.4 times of the capacity of the pure zinc titanate material under the condition of not reducing the reversible capacity of the zinc titanate negative electrode material, and the circulation stability is improved.
(3) According to the lithium ion battery negative pole piece provided by the invention, the zinc-position sodium-copper co-doped and nitrogen-sulfur-doped carbon-coated modified zinc titanate negative pole material is used as an electrode active material, so that the negative pole piece has good cycle stability and long service life.
(4) According to the lithium ion battery provided by the invention, the negative pole piece containing zinc-position sodium-copper co-doping synergistic nitrogen-sulfur-doped carbon-coated modified zinc titanate is used, so that the cycle performance of the lithium ion battery is improved, and the requirements of high power and long service life in the practical application of the lithium ion battery are met.
Drawings
Fig. 1 is an SEM image of the zinc-site sodium-copper co-doped synergistic nitrogen-sulfur doped carbon-coated modified zinc titanate negative electrode material prepared in example 1 of the present invention.
FIG. 2 shows that the zinc-site sodium-copper co-doped synergistic nitrogen-sulfur-doped carbon-coated modified zinc titanate negative electrode material prepared in example 1 of the inventionAt 100mA · g-1Current density of (a).
Detailed Description
The following further describes the technical means of the present invention to achieve the predetermined technical effects by means of embodiments with reference to the accompanying drawings, and the embodiments of the present invention are described in detail as follows.
Example 1
The embodiment provides a zinc-position sodium-copper co-doped synergetic nitrogen-sulfur doped carbon-coated modified zinc titanate negative electrode material and a preparation method thereof, and the zinc-position sodium-copper co-doped synergetic nitrogen-sulfur doped carbon-coated modified zinc titanate negative electrode material comprises the following steps:
(1) adding 0.3g of multi-walled carbon nano-tube into 100mL of a mixed solution of diethylenetriamine, ethanolamine and ethanol, wherein the volume ratio of the diethylenetriamine to the ethanolamine to the ethanol in the mixed solution is 3:1:16, heating and refluxing for 6h at 80 ℃, and then centrifuging; washing the centrifugal product with absolute ethyl alcohol for 3 times, and drying in vacuum at 70 ℃ for 12h to obtain the nitrogen-doped multi-walled carbon nanotube;
(2) dissolving 0.0098mol of zinc nitrate, 0.0001mol of sodium acetate and 0.0001mol of copper acetate in 20mL of mixed solution of ethylene glycol, N-dimethylformamide and glycerol under the condition of mechanical stirring, wherein the volume ratio of the ethylene glycol to the N, N-dimethylformamide to the glycerol in the mixed solution is 10:1:0.5, so as to obtain a solution A; dissolving 0.01mol of tetrabutyl titanate in 20mL of mixed solution of ethylene glycol and acetone under the stirring condition, wherein the volume ratio of the ethylene glycol to the acetone in the mixed solution is 8:1, so as to obtain solution B; then, slowly dripping the solution A into the solution B under the stirring condition to obtain a solution C;
(3) dissolving 1.0g of a mixture of polyvinylpyrrolidone and polyacrylamide in 60ml of ethylene glycol, wherein the mass ratio of the polyvinylpyrrolidone to the polyacrylamide in the mixture is 9:1, adding 300 mu L of concentrated ammonia water, uniformly stirring, and then adding the nitrogen-doped multi-walled carbon nanotube prepared in the step (1) to obtain a solution D;
(4) slowly adding the solution C into the solution D at 45 ℃, and violently stirring for 12 hours; centrifuging with high speed centrifuge, washing the centrifuged product with anhydrous ethanol for 3 times, and vacuum drying at 70 deg.C for 13 hr to obtain the final productMixing the obtained solid powder with sulfur simple substance at a temperature rise rate of 2 ℃/min in N2And NH3Raising the temperature to 350 ℃ in the mixed gas atmosphere with the volume ratio of 2:1, cooling to room temperature, and ball-milling in an ethanol solution of polyacrylic acid for 3 hours; and finally, heating to 600 ℃ in a nitrogen atmosphere at a heating rate of 4 ℃/min, preserving the heat for 3h, and cooling to room temperature to obtain the zinc titanate negative electrode material modified by the zinc-site sodium-copper co-doping and nitrogen-sulfur-doped carbon coating.
The zinc-position sodium-copper co-doped and nitrogen-sulfur-doped carbon-coated modified zinc titanate negative electrode material prepared in the embodiment is characterized by SEM, and the characterization result is shown in FIG. 1, which shows that the negative electrode material has uniform particle size, stable and compact structure, and the nitrogen-sulfur-doped multi-walled carbon nanotube is uniformly wound around the zinc titanate material.
Example 2
The embodiment provides a zinc-position sodium-copper co-doped synergetic nitrogen-sulfur doped carbon-coated modified zinc titanate negative electrode material and a preparation method thereof, and the zinc-position sodium-copper co-doped synergetic nitrogen-sulfur doped carbon-coated modified zinc titanate negative electrode material comprises the following steps:
(1) adding 0.3g of multi-walled carbon nano-tube into 100mL of a mixed solution of diethylenetriamine, ethanolamine and ethanol, wherein the volume ratio of the diethylenetriamine to the ethanolamine to the ethanol in the mixed solution is 3:1:16, heating and refluxing for 5h at 80 ℃, and then centrifuging; washing the centrifugal product with absolute ethyl alcohol for 4 times, and drying in vacuum at 70 ℃ for 10h to obtain the nitrogen-doped multi-walled carbon nanotube;
(2) dissolving 0.0098mol of zinc nitrate, 0.0001mol of sodium acetate and 0.0001mol of copper acetate in 20mL of mixed solution of ethylene glycol, N-dimethylformamide and glycerol under the condition of mechanical stirring, wherein the volume ratio of the ethylene glycol to the N, N-dimethylformamide to the glycerol in the mixed solution is 10:1:0.5, so as to obtain a solution A; dissolving 0.01mol of tetrabutyl titanate in 20mL of mixed solution of ethylene glycol and acetone under the stirring condition, wherein the volume ratio of the ethylene glycol to the acetone in the mixed solution is 8:1, so as to obtain solution B; then, slowly dripping the solution A into the solution B under the stirring condition to obtain a solution C;
(3) dissolving 1.0g of a mixture of polyvinylpyrrolidone and polyacrylamide in 60ml of ethylene glycol, wherein the mass ratio of the polyvinylpyrrolidone to the polyacrylamide in the mixture is 9:1, adding 300 mu L of concentrated ammonia water, uniformly stirring, and then adding the nitrogen-doped multi-walled carbon nanotube prepared in the step (1) to obtain turbid liquid D;
(4) slowly adding the solution C into the turbid solution D at 45 ℃, and vigorously stirring for 12 hours; centrifuging with high speed centrifuge, washing the centrifuged product with anhydrous ethanol for 3 times, vacuum drying at 70 deg.C for 12 hr, mixing the obtained solid powder with sulfur simple substance, heating at 2 deg.C/min under N2And NH3Raising the temperature to 350 ℃ in the mixed gas atmosphere with the volume ratio of 2:1, cooling to room temperature, and ball-milling in an ethanol solution of polyacrylic acid for 2.5 h; and finally, heating to 600 ℃ in a nitrogen atmosphere at a heating rate of 4 ℃/min, preserving the heat for 3h, and cooling to room temperature to obtain the zinc titanate negative electrode material modified by the zinc-site sodium-copper co-doping and nitrogen-sulfur-doped carbon coating.
Example 3
The embodiment provides a zinc-position sodium-copper co-doped synergetic nitrogen-sulfur doped carbon-coated modified zinc titanate negative electrode material and a preparation method thereof, and the zinc-position sodium-copper co-doped synergetic nitrogen-sulfur doped carbon-coated modified zinc titanate negative electrode material comprises the following steps:
(1) adding 0.3g of multi-walled carbon nano-tube into 100mL of a mixed solution of diethylenetriamine, ethanolamine and ethanol, wherein the volume ratio of the diethylenetriamine to the ethanolamine to the ethanol in the mixed solution is 3:1:16, heating and refluxing for 7h at 80 ℃, and then centrifuging; washing the centrifugal product with absolute ethyl alcohol for 4 times, and drying in vacuum at 70 ℃ for 15h to obtain the nitrogen-doped multi-walled carbon nanotube;
(2) dissolving 0.0098mol of zinc nitrate, 0.0001mol of sodium acetate and 0.0001mol of copper acetate in 20mL of mixed solution of ethylene glycol, N-dimethylformamide and glycerol under the condition of mechanical stirring, wherein the volume ratio of the ethylene glycol to the N, N-dimethylformamide to the glycerol in the mixed solution is 10:1:0.5, so as to obtain a solution A; dissolving 0.01mol of tetrabutyl titanate in 20mL of mixed solution of ethylene glycol and acetone under the stirring condition, wherein the volume ratio of the ethylene glycol to the acetone in the mixed solution is 8:1, so as to obtain solution B; then, slowly dripping the solution A into the solution B under the stirring condition to obtain a solution C;
(3) dissolving 1.0g of a mixture of polyvinylpyrrolidone and polyacrylamide in 60ml of ethylene glycol, wherein the mass ratio of the polyvinylpyrrolidone to the polyacrylamide in the mixture is 9:1, adding 300 mu L of concentrated ammonia water, uniformly stirring, and then adding the nitrogen-doped multi-walled carbon nanotube prepared in the step (1) to obtain turbid liquid D;
(4) slowly adding the solution C into the turbid solution D at 45 ℃, and vigorously stirring for 12 hours; centrifuging with high speed centrifuge, washing the centrifuged product with anhydrous ethanol for 4 times, vacuum drying at 70 deg.C for 15 hr, mixing the obtained solid powder with sulfur simple substance, heating at 2 deg.C/min under N2And NH3Raising the temperature to 350 ℃ in the mixed gas atmosphere with the volume ratio of 2:1, cooling to room temperature, and ball-milling in an ethanol solution of polyacrylic acid for 2.5 h; and finally, heating to 600 ℃ in a nitrogen atmosphere at a heating rate of 4 ℃/min, preserving the heat for 4h, and cooling to room temperature to obtain the zinc-site sodium-copper co-doped synergetic nitrogen-doped carbon-coated modified zinc titanate negative electrode material.
Example 4
The embodiment provides a zinc-position sodium-copper co-doped synergetic nitrogen-sulfur doped carbon-coated modified zinc titanate negative electrode material and a preparation method thereof, and the zinc-position sodium-copper co-doped synergetic nitrogen-sulfur doped carbon-coated modified zinc titanate negative electrode material comprises the following steps:
(1) adding 0.5g of carbon fiber into 100mL of a mixed solution of diethylenetriamine, ethanolamine and ethanol, wherein the volume ratio of the diethylenetriamine to the ethanolamine to the ethanol in the mixed solution is 1:2:10, heating and refluxing for 3h at 100 ℃, and then centrifuging; washing the centrifugal product with absolute ethyl alcohol for 4 times, and drying in vacuum at 55 ℃ for 10 hours to obtain nitrogen-doped carbon fiber;
(2) dissolving 0.0098mol of zinc nitrate, 0.0001mol of sodium acetate and 0.0001mol of copper acetate in 20mL of mixed solution of ethylene glycol, N-dimethylformamide and glycerol under the condition of mechanical stirring, wherein the volume ratio of the ethylene glycol to the N, N-dimethylformamide to the glycerol in the mixed solution is 6:3:0.5, so as to obtain a solution A; dissolving 0.01mol of tetrabutyl titanate in 20mL of mixed solution of ethylene glycol and acetone under the stirring condition, wherein the volume ratio of the ethylene glycol to the acetone in the mixed solution is 4:3, so as to obtain solution B; then, slowly dripping the solution A into the solution B under the stirring condition to obtain a solution C;
(3) dissolving 1.0g of a mixture of polyvinylpyrrolidone and polyacrylamide in 60ml of ethylene glycol, wherein the mass ratio of the polyvinylpyrrolidone to the polyacrylamide in the mixture is 5:1, adding 300 mu L of concentrated ammonia water, uniformly stirring, and then adding the nitrogen-doped carbon fiber prepared in the step (1) to obtain a solution D;
(4) slowly adding the solution C into the solution D at 40 ℃, and violently stirring for 8 hours; centrifuging with high speed centrifuge, washing the centrifuged product with anhydrous ethanol for 3 times, vacuum drying at 60 deg.C for 15 hr, mixing the obtained solid powder with sulfur simple substance, heating at 2 deg.C/min under N2And NH3Raising the temperature to 400 ℃ in the mixed gas atmosphere with the volume ratio of 3:1, cooling to room temperature, and ball-milling for 4 hours in an ethanol solution of polyacrylic acid; and finally, heating to 500 ℃ in a nitrogen atmosphere at a heating rate of 3 ℃/min, preserving the heat for 5h, and cooling to room temperature to obtain the zinc titanate negative electrode material modified by the zinc-site sodium-copper co-doping and nitrogen-sulfur-doped carbon coating.
Example 5
The embodiment provides a zinc-position sodium-copper co-doped synergetic nitrogen-sulfur doped carbon-coated modified zinc titanate negative electrode material and a preparation method thereof, and the zinc-position sodium-copper co-doped synergetic nitrogen-sulfur doped carbon-coated modified zinc titanate negative electrode material comprises the following steps:
(1) adding 0.3g of multi-walled carbon nano-tube into 100mL of a mixed solution of diethylenetriamine, ethanolamine and ethanol, wherein the volume ratio of the diethylenetriamine to the ethanolamine to the ethanol in the mixed solution is 2:2:11, heating and refluxing for 8h at 72 ℃, and then centrifuging; washing the centrifugal product with absolute ethyl alcohol for 3 times, and drying in vacuum at 80 ℃ for 7h to obtain the nitrogen-doped multi-walled carbon nanotube;
(2) dissolving 0.0098mol of zinc nitrate, 0.0001mol of sodium acetate and 0.0001mol of copper acetate in 20mL of mixed solution of ethylene glycol, N-dimethylformamide and glycerol under the condition of mechanical stirring, wherein the volume ratio of the ethylene glycol to the N, N-dimethylformamide to the glycerol in the mixed solution is 10:2:0.3, so as to obtain a solution A; dissolving 0.01mol of tetrabutyl titanate in 20mL of mixed solution of ethylene glycol and acetone under the stirring condition, wherein the volume ratio of the ethylene glycol to the acetone in the mixed solution is 7:1, so as to obtain solution B; then, slowly dripping the solution A into the solution B under the stirring condition to obtain a solution C;
(3) dissolving 1.0g of a mixture of polyvinylpyrrolidone and polyacrylamide in 60ml of ethylene glycol, wherein the mass ratio of the polyvinylpyrrolidone to the polyacrylamide in the mixture is 5:3, adding 300 mu L of concentrated ammonia water, uniformly stirring, and then adding the nitrogen-doped multi-walled carbon nanotube prepared in the step (1) to obtain a solution D;
(4) slowly adding the solution C into the solution D at 55 ℃, and violently stirring for 10 hours; centrifuging with high speed centrifuge, washing the centrifuged product with anhydrous ethanol for 4 times, vacuum drying at 80 deg.C for 15 hr, mixing the obtained solid powder with sulfur simple substance, heating at 4 deg.C/min under N2And NH3Raising the temperature to 400 ℃ in the atmosphere of mixed gas with the volume ratio of 5:3, cooling to room temperature, and ball-milling for 5 hours in an ethanol solution of polyacrylic acid; and finally, heating to 700 ℃ in a nitrogen atmosphere at a heating rate of 2 ℃/min, preserving the heat for 5h, and cooling to room temperature to obtain the zinc titanate negative electrode material modified by co-doping the zinc-site sodium and copper with the nitrogen-sulfur doped carbon.
Example 6
In comparison with example 1, the volume ratio of diethylenetriamine, ethanolamine and ethanol in the mixed solution used in step (1) was replaced with 1:3: 16.
Example 7
In comparison with example 1, the volume ratio of diethylenetriamine, ethanolamine and ethanol in the mixed solution used in step (1) was replaced with 3:3: 16.
Example 8
Compared with example 1, the mixed solution used in step (1) was replaced with a mixed solution of ethanolamine and ethanol, and the volume ratio of ethanolamine to ethanol was 4: 16.
Example 9
Compared with the embodiment 1, the mixed solution of the ethylene glycol, the N, N-dimethylformamide and the glycerol used in the step (2) is replaced by the mixed solution of the ethylene glycol and the glycerol, and the volume ratio is 10: 1.5.
Example 10
Compared with example 1, the mixed solution of ethylene glycol and acetone used in step (2) was replaced with ethylene glycol alone, and the acetone component was omitted.
Example 11
In comparison with example 1, the mixture of polyvinylpyrrolidone and polyacrylamide used in step (3) was replaced with polyvinylpyrrolidone only, omitting the polyacrylamide component.
Comparative example 1
Compared with example 1, the present comparative example provides a method for preparing pure zinc titanate, comprising the steps of:
(1) dissolving 0.0098mol of zinc nitrate in 20mL of mixed solution of glycol, N-dimethylformamide and glycerol under the condition of mechanical stirring, wherein the volume ratio of the glycol, the N, N-dimethylformamide and the glycerol in the mixed solution is 10:1:0.5, so as to obtain solution A; dissolving 0.01mol of tetrabutyl titanate in 20mL of mixed solution of ethylene glycol and acetone under the stirring condition, wherein the volume ratio of the ethylene glycol to the acetone in the mixed solution is 8:1, so as to obtain solution B; then, slowly dripping the solution A into the solution B under the stirring condition to obtain a solution C;
(2) dissolving 1.0g of a mixture of polyvinylpyrrolidone and polyacrylamide in 60ml of ethylene glycol, wherein the mass ratio of the polyvinylpyrrolidone to the polyacrylamide in the mixture is 9:1, adding 300 mu L of concentrated ammonia water, and uniformly stirring to obtain a solution D;
(3) slowly adding the solution C into the solution D at 45 ℃, and violently stirring for 12 hours; centrifuging with a high-speed centrifuge, washing the centrifuged product with anhydrous ethanol for 3 times, drying in a vacuum drying oven at 70 deg.C for 13h to obtain solid powder, and heating the solid powder at a temperature rise rate of 2 deg.C/min in N2And NH3Raising the temperature to 350 ℃ in the mixed gas atmosphere with the volume ratio of 2:1, cooling to room temperature, and ball-milling in an ethanol solution of polyacrylic acid for 3 hours; and finally, heating to 600 ℃ in a nitrogen atmosphere at the heating rate of 4 ℃/min, preserving the heat for 3h, and cooling to room temperature to obtain the zinc titanate negative electrode material.
Comparative example 2
Compared with example 1, the comparative example provides a nitrogen-sulfur doped carbon-coated zinc titanate negative electrode material, which comprises the following steps:
(1) adding 0.3g of multi-walled carbon nano-tube into 100mL of a mixed solution of diethylenetriamine, ethanolamine and ethanol, wherein the volume ratio of the diethylenetriamine to the ethanolamine to the ethanol in the mixed solution is 3:1:16, heating and refluxing for 6h at 80 ℃, and then centrifuging; washing the centrifugal product with absolute ethyl alcohol for 3 times, and drying in vacuum at 70 ℃ for 12h to obtain the nitrogen-doped multi-walled carbon nanotube;
(2) dissolving 0.0098mol of zinc nitrate in 20mL of mixed solution of glycol, N-dimethylformamide and glycerol under the condition of mechanical stirring, wherein the volume ratio of the glycol, the N, N-dimethylformamide and the glycerol in the mixed solution is 10:1:0.5, so as to obtain solution A; dissolving 0.01mol of tetrabutyl titanate in 20mL of mixed solution of ethylene glycol and acetone under the stirring condition, wherein the volume ratio of the ethylene glycol to the acetone in the mixed solution is 8:1, so as to obtain solution B; then, slowly dripping the solution A into the solution B under the stirring condition to obtain a solution C;
(3) dissolving 1.0g of a mixture of polyvinylpyrrolidone and polyacrylamide in 60ml of ethylene glycol, wherein the mass ratio of the polyvinylpyrrolidone to the polyacrylamide in the mixture is 9:1, adding 300 mu L of concentrated ammonia water, uniformly stirring, and then adding the nitrogen-doped multi-walled carbon nanotube prepared in the step (1) to obtain a solution D;
(4) slowly adding the solution C into the solution D at 45 ℃, and violently stirring for 12 hours; centrifuging with high speed centrifuge, washing the centrifuged product with anhydrous ethanol for 3 times, vacuum drying at 70 deg.C for 13 hr, mixing the obtained solid powder with sulfur simple substance, heating at 2 deg.C/min under N2And NH3Raising the temperature to 350 ℃ in the mixed gas atmosphere with the volume ratio of 2:1, cooling to room temperature, and ball-milling in an ethanol solution of polyacrylic acid for 3 hours; and finally, heating to 600 ℃ in a nitrogen atmosphere at a heating rate of 4 ℃/min, preserving the heat for 3h, and cooling to room temperature to obtain the nitrogen-sulfur doped carbon-coated zinc titanate negative electrode material.
Comparative example 3
Compared with the embodiment 1, the invention provides a preparation method of a zinc-position sodium-copper co-doped zinc titanate negative electrode material, which comprises the following steps:
(1) dissolving 0.0098mol of zinc nitrate, 0.0001mol of sodium acetate and 0.0001mol of copper acetate in 20mL of mixed solution of ethylene glycol, N-dimethylformamide and glycerol under the condition of mechanical stirring, wherein the volume ratio of the ethylene glycol to the N, N-dimethylformamide to the glycerol in the mixed solution is 10:1:0.5, so as to obtain a solution A; dissolving 0.01mol of tetrabutyl titanate in 20mL of mixed solution of ethylene glycol and acetone under the stirring condition, wherein the volume ratio of the ethylene glycol to the acetone in the mixed solution is 8:1, so as to obtain solution B; then, slowly dripping the solution A into the solution B under the stirring condition to obtain a solution C;
(2) dissolving 1.0g of a mixture of polyvinylpyrrolidone and polyacrylamide in 60ml of ethylene glycol, wherein the mass ratio of the polyvinylpyrrolidone to the polyacrylamide in the mixture is 9:1, adding 300 mu L of concentrated ammonia water, and uniformly stirring to obtain a solution D;
(3) slowly adding the solution C into the solution D at 45 ℃, and violently stirring for 12 hours; centrifuging with a high-speed centrifuge, washing the centrifuged product with anhydrous ethanol for 3 times, drying in a vacuum drying oven at 70 deg.C for 13h to obtain solid powder, and heating the solid powder at a temperature rise rate of 2 deg.C/min in N2And NH3Raising the temperature to 350 ℃ in the mixed gas atmosphere with the volume ratio of 2:1, cooling to room temperature, and ball-milling for 4 hours in an ethanol solution of polyacrylic acid; and finally, heating to 600 ℃ in a nitrogen atmosphere at a heating rate of 4 ℃/min, preserving the heat for 3h, and cooling to room temperature to obtain the zinc-site sodium-copper co-doped zinc titanate negative electrode material.
The zinc titanate negative electrode materials prepared in examples 1 to 11 and comparative examples 1 to 3 were subjected to electrochemical performance evaluation:
the zinc titanate negative electrode materials prepared in the above examples 1 to 11 and comparative examples 1 to 3 were used as electrode materials, and assembled into an experimental lithium ion button cell in a glove box filled with argon gas at a rate of 100mA · g-1The current density of (A) was measured in a charge-discharge cycle at 0 to 2.5V, and the results are shown in tables 1 to 2.
TABLE 1
Figure BDA0002206238520000181
TABLE 2
Figure BDA0002206238520000191
The zinc-site sodium-copper co-doped synergetic nitrogen-sulfur doped carbon-coated modified zinc titanate negative electrode material prepared in the embodiment 1 is used for preparing a button lithium ion battery with the voltage of between 0 and 2.5V and the voltage of 100 mAh.g-1The current density of the discharge capacitor was subjected to a charge-discharge cycle test, and the result is shown in FIG. 2, which shows that the first discharge capacity can reach 533.7mAh g-1And the reversible discharge capacity after 90 weeks of circulation was 224.4mAh g-1And the material shows excellent discharge performance with a wide potential window and good cycle stability.
It can be seen from tables 1 and 2 that the first discharge capacity of the lithium ion battery assembled from the zinc-site sodium-copper co-doped synergetic nitrogen-sulfur doped carbon-coated modified zinc titanate negative electrode materials prepared in examples 1 to 11 is 497.3 to 533.7mAh g-1In contrast, the lithium ion batteries assembled with the zinc titanate negative electrode materials prepared in comparative examples 1 to 3 had first discharge capacities of 480.0mAh · g, respectively-1、510.0mAh·g-1482.0mAh g-1. The first capacity of the lithium ion battery assembled by the negative electrode material prepared in the embodiment 1 is increased by 11.2% compared with the first capacity of the lithium ion battery assembled by the negative electrode material prepared in the comparative example 1; the first capacity of the lithium ion battery assembled by the negative electrode material prepared in the embodiment 1 is improved by 4.6% compared with the capacity of the lithium ion battery assembled by the negative electrode material prepared in the comparative example 2; the first capacity of the lithium ion battery assembled by the negative electrode material prepared in example 1 is 10.7% higher than that of the lithium ion battery assembled by the negative electrode material prepared in comparative example 3.
It can be seen from tables 1 and 2 that the discharge capacity of the lithium ion battery assembled from the zinc-site sodium-copper co-doped synergetic nitrogen-sulfur doped carbon-coated modified zinc titanate negative electrode materials prepared in examples 1 to 11 after 90 weeks of cycle is 189.6 to 224.4mAh g-1In contrast, the lithium ion batteries assembled with the zinc titanate negative electrode materials prepared in comparative examples 1 to 3 had discharge capacities of 160.0mAh · g, respectively, after 90 weeks of cycle-1、190mAh·g-1And 180 mAh. g-1. Wherein, the cycle capacity of the lithium ion battery assembled by the negative electrode material prepared in the example 1 is 1.4 times of that of the lithium ion battery assembled by the negative electrode material prepared in the comparative example 1, and the cycle capacity of the lithium ion battery assembled by the negative electrode material prepared in the example 1 is improved by 18.1 percent compared with that of the lithium ion battery assembled by the negative electrode material prepared in the comparative example 2; the cycle capacity of the lithium ion battery assembled by the negative electrode material prepared in the embodiment 1 is improved by 24.7 percent compared with the cycle capacity of the lithium ion battery assembled by the negative electrode material prepared in the comparative example 3; data analysis shows that the zinc-position sodium-copper co-doped synergetic nitrogen-sulfur-doped carbon-coated modified zinc titanate negative electrode material prepared by the method has good cycle stability, and the lithium ion battery prepared by the zinc-position sodium-copper co-doped synergetic nitrogen-sulfur-doped carbon-coated modified zinc titanate negative electrode material has long cycle life.
The lithium ion batteries assembled with the negative electrode materials prepared in examples 6 to 8 were all lower in capacity than the lithium ion batteries assembled with the negative electrode material prepared in example 1, indicating that the optimum volume ratio of diethylenetriamine, ethanolamine and ethanol was present in the mixed solution of diethylenetriamine, ethanolamine and ethanol and that diethylenetriamine plays an important role in dispersing the carbon material; compared with the capacity of the lithium ion battery assembled by the negative electrode material prepared in example 1, the capacity of the lithium ion battery assembled by the negative electrode material prepared in example 9 is 1.12 times, which shows that the N, N-dimethylformamide can adjust the distribution of metal ions in the solution, and plays an important role in the process of preparing the zinc titanate negative electrode material modified by co-doping of sodium and copper at the zinc position and coating of nitrogen and sulfur doped carbon.
The applicant declares that the present invention illustrates the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (58)

1. A preparation method of a zinc-position sodium-copper co-doped synergetic nitrogen-sulfur doped carbon-coated modified zinc titanate negative electrode material is characterized by comprising the following steps:
(1) adding a carbon material into an organic solvent I, wherein the organic solvent I is a mixed solution of diethylenetriamine, ethanolamine and ethanol, and preparing to obtain a nitrogen-doped carbon material;
(2) dissolving a zinc source, a sodium source and a copper source in an organic solvent II to obtain a solution A; dissolving a titanium source in an organic solvent III to obtain a solution B; mixing the solution A and the solution B to obtain a solution C;
(3) adding the nitrogen-doped carbon material obtained in the step (1) into an organic solvent containing a non-ionic high polymer to obtain a solution D;
(4) and adding the solution C into the solution D, stirring, centrifugally drying, mixing the obtained solid powder with a sulfur source, and sintering to obtain the zinc-site sodium-copper co-doped synergetic nitrogen-sulfur-doped carbon-coated modified zinc titanate negative electrode material.
2. The production method according to claim 1, wherein the production of the nitrogen-doped carbon material in step (1) comprises the steps of:
and adding the carbon material into an organic solvent I, heating and refluxing, then centrifuging, washing a centrifugal product, and drying to prepare the nitrogen-doped carbon material.
3. The method of claim 1, wherein the volume ratio of diethylenetriamine, ethanolamine and ethanol is (1-3): (10-16).
4. The method according to claim 3, wherein the volume ratio of diethylenetriamine to ethanolamine to ethanol is 3:1: 16.
5. The method according to claim 2, wherein the temperature of the heating reflux is 70 to 100 ℃.
6. The method according to claim 5, wherein the temperature of the heating reflux is 80 to 90 ℃.
7. The method according to claim 2, wherein the heating reflux time is 3 to 10 hours.
8. The method according to claim 7, wherein the heating and refluxing time is 5 to 7 hours.
9. The method of claim 2, wherein the centrifuged product is washed with absolute ethanol.
10. The method according to claim 9, wherein the washing is performed 3 or more times.
11. The method of claim 10, wherein the washing is performed 3 to 4 times.
12. The method of claim 2, wherein the drying is vacuum drying.
13. The method of claim 12, wherein the vacuum drying temperature is 50-80 ℃.
14. The method of claim 13, wherein the vacuum drying temperature is 60-70 ℃.
15. The method of claim 12, wherein the vacuum drying time is 6-15 hours.
16. The method of claim 15, wherein the vacuum drying time is 10-15 hours.
17. The method according to claim 1, wherein the zinc source in step (2) is selected from any one of zinc nitrate, zinc acetate or zinc citrate or a combination of at least two thereof.
18. The method of claim 1, wherein the sodium source is selected from any one of sodium acetate, sodium citrate, or sodium nitrate, or a combination of at least two thereof.
19. The method of claim 1, wherein the copper source is selected from copper acetate and/or copper nitrate.
20. The method of claim 19, wherein the copper source is copper acetate.
21. The method according to claim 1, wherein the titanium source is selected from the group consisting of tetrabutyl titanate, isopropyl titanate, and titanium tetrachloride.
22. The method according to claim 1, wherein the organic solvent II is a mixed solution of ethylene glycol, N-dimethylformamide and glycerol.
23. The method of claim 22, wherein the volume ratio of the ethylene glycol, the N, N-dimethylformamide and the glycerol is (6-10): 1-3): 0.1-0.5.
24. The method according to claim 23, wherein the volume ratio of the ethylene glycol, the N, N-dimethylformamide and the glycerol is 10:1: 0.5.
25. The production method according to claim 1, wherein the organic solvent III is a mixed solution of ethylene glycol and acetone.
26. The method of claim 25, wherein the volume ratio of the ethylene glycol to the acetone is (4-8): 1-3.
27. The method of claim 26, wherein the volume ratio of the ethylene glycol to the acetone is 8: 1.
28. The method according to claim 1, wherein the nonionic polymer in the step (3) is a mixture of polyvinylpyrrolidone and polyacrylamide.
29. The method of claim 28, wherein the mass ratio of polyvinylpyrrolidone to polyacrylamide is (4-10): 1-5.
30. The method according to claim 29, wherein the mass ratio of polyvinylpyrrolidone to polyacrylamide is 9: 1.
31. The method according to claim 1, wherein the organic solvent is ethylene glycol.
32. The method according to claim 1, wherein the stirring temperature in the step (4) is 35 to 55 ℃.
33. The method according to claim 32, wherein the stirring temperature in the step (4) is 45 to 55 ℃.
34. The method according to claim 1, wherein the stirring time in the step (4) is 8 to 18 hours.
35. The method according to claim 1, wherein the stirring time in the step (4) is 10 to 15 hours.
36. The method according to claim 1, wherein the product obtained after the centrifugal drying in step (4) is washed with absolute ethanol.
37. The method of claim 36, wherein the washing is performed 3 or more times.
38. The method of claim 37, wherein the washing is performed 3 to 4 times.
39. The method according to claim 1, wherein the drying in step (4) is vacuum drying.
40. The method of claim 39, wherein the vacuum drying temperature is 50-80 ℃.
41. The method of claim 40, wherein the vacuum drying temperature is 60-70 ℃.
42. The method of claim 39, wherein the vacuum drying time is 8-16 h.
43. The method of claim 42, wherein the vacuum drying time is 12-15 hours.
44. The method according to claim 1, wherein the sulfur source in the step (4) is elemental sulfur and/or thiourea.
45. The production method according to claim 1, wherein the obtained solid powder and the sulfur source are sintered in a mixed gas atmosphere.
46. The method according to claim 45, wherein the sintering in the step (4) comprises: heating to 400 ℃ in the mixed gas atmosphere at the heating rate of 2-4 ℃/min, cooling to room temperature, ball milling in the organic solvent IV, finally heating to 700 ℃ in the inert gas atmosphere at the heating rate of 2-4 ℃/min, and preserving heat.
47. The method as claimed in claim 46, wherein the mixed gas is N2And NH3The mixed gas of (1).
48. The method of claim 47, wherein N is2And NH3The volume ratio of (2-5) to (1-3).
49. The method of claim 48, wherein N is2And NH3Is 2: 1.
50. The method as claimed in claim 46, wherein the organic solvent IV is an ethanol solution of polyacrylic acid.
51. The method of claim 46, wherein the ball milling time is 2-4 hours.
52. The method of claim 51, wherein the ball milling time is 2.5 to 3 hours.
53. The method of claim 46, wherein the incubation time is 2-5 hours.
54. The method of claim 53, wherein the incubation time is 2.5-4 hours.
55. The method for preparing according to claim 1, characterized in that it comprises the following steps:
(1) adding a carbon material into a mixed solution of diethylenetriamine, ethanolamine and ethanol, heating and refluxing for 3-10h at 70-100 ℃, and then centrifuging; washing the centrifugal product with absolute ethyl alcohol for more than 3 times, and drying in vacuum at 50-80 ℃ for 6-15h to obtain a nitrogen-doped carbon material;
(2) dissolving a zinc source, a sodium source and a copper source in a mixed solution of ethylene glycol, N-dimethylformamide and glycerol under the condition of mechanical stirring to obtain a solution A; dissolving a titanium source in a mixed solution of ethylene glycol and acetone under the stirring condition to obtain a solution B; then, slowly dripping the solution A into the solution B under the stirring condition to obtain a solution C;
(3) dissolving a mixture of polyvinylpyrrolidone and polyacrylamide in ethylene glycol, adding concentrated ammonia water, uniformly stirring, and then adding the nitrogen-doped carbon material prepared in the step (1) to obtain a solution D;
(4) slowly adding the solution C into the solution D at 35-55 ℃, and violently stirring for 8-18 h; centrifuging with high speed centrifuge, washing the centrifuged product with anhydrous ethanol for more than 3 times, drying in vacuum drying oven at 50-80 deg.C for 8-16h, mixing the obtained solid powder with sulfur source, heating at N at a rate of 2-4 deg.C/min2And NH3Raising the temperature to 300-400 ℃ in the mixed gas atmosphere, cooling to room temperature, and ball-milling in an ethanol solution of polyacrylic acid for 2-4 h; and finally, heating to 500-700 ℃ in the inert gas atmosphere at the heating rate of 2-4 ℃/min, preserving the heat for 2-5h, and cooling to room temperature to obtain the zinc-site sodium-copper co-doped synergetic nitrogen-sulfur doped carbon-coated modified zinc titanate negative electrode material.
56. The zinc-site sodium-copper co-doped synergetic nitrogen-sulfur-doped carbon-coated modified zinc titanate negative electrode material prepared by the preparation method according to any one of claims 1 to 55.
57. A lithium ion battery negative electrode plate is characterized by comprising the zinc-position sodium-copper co-doped synergetic nitrogen-sulfur-doped carbon-coated modified zinc titanate negative electrode material of claim 56.
58. A lithium ion battery, characterized in that the lithium ion battery comprises the negative electrode sheet of claim 57.
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