CN114835161B - Zinc ion battery cathode, preparation method of active material of zinc ion battery cathode and zinc ion battery - Google Patents

Zinc ion battery cathode, preparation method of active material of zinc ion battery cathode and zinc ion battery Download PDF

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CN114835161B
CN114835161B CN202210453402.1A CN202210453402A CN114835161B CN 114835161 B CN114835161 B CN 114835161B CN 202210453402 A CN202210453402 A CN 202210453402A CN 114835161 B CN114835161 B CN 114835161B
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ion battery
active material
zinc
vanadium
zinc ion
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CN114835161A (en
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郑程
简邦权
郭祝
徐祥城
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Guangdong University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G31/00—Compounds of vanadium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
    • 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
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • 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

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Abstract

The application belongs to the technical field of batteries, and particularly relates to a preparation method of a zinc ion battery negative electrode and an active material thereof, and a zinc ion battery. The preparation method of the zinc ion battery anode active material comprises the following steps: obtaining raw material components, wherein the raw material components comprise a vanadium source and a sulfur source; and dissolving the raw material components in a solvent, and performing hydrothermal reaction to obtain the vanadium tetrasulfide anode active material. The preparation method provided by the application is simple in process, and the prepared nano vanadium tetrasulfide negative electrode active material provides a large number of active sites for zinc ions to be embedded and extracted, so that the migration dynamics of the zinc ions is improved, the growth of zinc dendrites is reduced, and the cycling stability of the negative electrode material is improved. Meanwhile, the potential of the nano vanadium tetrasulfide anode active material is relatively low, the nano vanadium tetrasulfide anode active material is used as an anode material and has higher coordination degree with a zinc ion anode, and the lower potential can better maintain the structural stability of the material, so that the cycle performance of the material is further improved.

Description

Zinc ion battery cathode, preparation method of active material of zinc ion battery cathode and zinc ion battery
Technical Field
The application belongs to the technical field of batteries, and particularly relates to a zinc ion battery anode active material and a preparation method thereof, and a zinc ion battery.
Background
The majority of medium and small commercial batteries in the current market are lithium ion batteries, and since the lithium ion batteries realize commercialization, the lithium ion batteries have the advantages of high discharge voltage, high energy density, small self-discharge, good cycle performance and the like, so that the lithium ion batteries are fully applied to a plurality of devices. However, in the application process, the lithium ion battery, taking a nickel-cobalt-manganese ternary lithium ion battery as an example, has the following main disadvantages: 1. currently, the mainstream lithium ion batteries in the market generally contain cobalt and organic electrolyte, and the toxicity of the cobalt and the organic electrolyte has production safety problems. 2. The gas is separated out in the running process of the battery, and the use safety problem is caused by the growth of lithium dendrites. 3. Lithium, cobalt and other resources are scarce and the production cost caused by uneven distribution is a problem.
Therefore, development of a novel metal ion battery that replaces a lithium ion battery has been an important subject in the field. Among them, the aqueous zinc ion battery is widely studied because of its advantages of abundant electrode material resources, safe and environment-friendly electrolyte, simple production process, low cost, etc. However, most of the current research on electrode materials of zinc ion batteries is focused on research and development of positive electrode materials, and the negative electrode materials of water-based zinc ion batteries are still mainly zinc sheets with simple use. Whereas zinc sheet cathodes exhibit relatively poor cycling performance due to zinc dendrite growth, hydrogen evolution reactions and zinc corrosion, wherein zinc dendrite growth is one of the major problems restricting cycling performance of zinc-based systems. Therefore, developing a negative electrode material suitable for aqueous zinc ion batteries is a great and urgent challenge.
Disclosure of Invention
The purpose of the application is to provide a preparation method of a zinc ion battery negative electrode and an active material thereof, and a zinc ion battery, and aims to solve the problem that the existing zinc ion battery negative electrode has poor battery cycle performance caused by zinc dendrite growth, hydrogen evolution reaction, zinc corrosion and the like to a certain extent.
In order to achieve the purposes of the application, the technical scheme adopted by the application is as follows:
in a first aspect, the present application provides a method for preparing a negative electrode active material of a zinc ion battery, including the steps of:
obtaining raw material components, wherein the raw material components comprise a vanadium source and a sulfur source;
and dissolving the raw material components in a solvent, and performing hydrothermal reaction to obtain the vanadium tetrasulfide anode active material.
Further, the raw material component also comprises at least one composite material of a conductive structural material and a metal doping material;
the step of the hydrothermal reaction comprises the following steps: and dissolving the composite material, the vanadium source and the sulfur source in a solvent to perform a hydrothermal reaction to obtain the vanadium tetrasulfide composite anode active material.
Further, the ratio of the sulfur source, the vanadium source, and the composite material is (4 to 7) mol:1mol: (20-60) g.
Further, the hydrothermal reaction conditions include: the reaction is carried out for 4 to 24 hours under the conditions that the temperature is 120 to 200 ℃ and the pressure is 0.5 to 0.9 MPa.
Further, the vanadium source is selected from NH 4 VO 3 、NaVO 3 、Na 3 VO 4 At least one of them.
Further, the sulfur source is selected from CH 3 CSNH 2 、CH 4 N 2 At least one of the S is selected from the group consisting of,
further, the solvent is selected from water or a mixed solvent of water and an alcohol solvent.
Further, the metal doping material is at least one selected from ferric salt, cobalt salt, nickel salt, manganese salt and molybdenum salt.
Further, the conductive structural material is at least one selected from activated carbon, graphene oxide, carbon nanotubes and conductive polymers.
Further, the particle size of the vanadium tetrasulfide anode active material is 0.5-3 μm.
Further, in the vanadium tetrasulfide composite anode active material, the particle size of the vanadium tetrasulfide is 50-80 nm.
Further, in the vanadium tetrasulfide composite anode active material, the mass percentage of the vanadium tetrasulfide is 20-90%.
In a second aspect, the application provides a zinc ion battery anode, which comprises the zinc ion battery anode active material prepared by the method.
Further, the zinc ion battery negative electrode further comprises a conductive agent and a binder, wherein the mass ratio of the conductive agent to the binder to the zinc ion battery negative electrode active material is (5-15): (5-15): (70-90).
In a third aspect, the present application provides a zinc-ion battery, where the zinc-ion battery includes the negative electrode of the zinc-ion battery.
According to the preparation method of the zinc ion battery anode active material, provided by the first aspect, after raw material components comprising a vanadium source and a sulfur source are obtained, the raw material components are fully dissolved in a solvent, and the nano vanadium tetrasulfide anode active material can be prepared through hydrothermal reaction. The preparation process is simple and easy to operate, and the prepared nano vanadium tetrasulfide negative electrode active material is of a layered structure, has a larger interlayer spacing, provides a large number of active sites for zinc ions to be inserted and extracted, is beneficial to zinc ion insertion and extraction in the charge and discharge process, improves the uniformity of zinc ion diffusion, distribution and deposition, improves the migration dynamics of zinc ions, reduces the growth of zinc dendrites, and further improves the cycling stability of the negative electrode material. Meanwhile, the potential of the nano vanadium tetrasulfide anode active material is relatively low, the nano vanadium tetrasulfide anode active material is used as an anode material and has higher coordination degree with a zinc ion anode, and the lower potential can better maintain the structural stability of the material, so that the cycle performance of the material is further improved.
The zinc ion battery anode provided by the second aspect of the application comprises the zinc ion battery anode active material prepared by the method, wherein the zinc ion battery anode active material comprises a vanadium tetrasulfide anode active material or a vanadium tetrasulfide composite anode active material combined with a conductive structure material and a metal doping element, a large number of active sites can be provided for zinc ion intercalation and deintercalation, the migration dynamics of zinc ions is improved, the growth of zinc dendrites is reduced, and the material has good cycling stability. And the cathode active material has low potential, so that the matching degree of the cathode and the zinc ion anode can be improved. Therefore, the zinc ion battery cathode provided by the application has the advantages of good cycling stability, high safety and higher coordination degree with the zinc ion anode.
The zinc ion battery provided by the third aspect of the application has the advantages that due to the fact that the zinc ion battery cathode is included, the cathode is good in circulation stability and high in safety, and has higher matching degree with a zinc ion anode, so that the circulation stability and the service life of the zinc ion battery are improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the following description will briefly introduce the drawings that are needed in the embodiments or the description of the prior art, it is obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic flow chart of a preparation method of a negative electrode active material of a zinc ion battery according to an embodiment of the present application;
FIG. 2 is a schematic illustration of vanadium tetrasulfide (VS) provided in example 1 of the present application 4 ) Scanning electron microscope SEM morphology graph of the cathode active material;
fig. 3 is a SEM morphology diagram of the vanadium tetrasulfide @ graphene (3D-VG) composite anode active material provided in example 2 of the present application;
fig. 4 is a macro-morphology diagram of the vanadium tetrasulfide @ graphene (3D-VG) composite anode active material provided in example 3 of the present application.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved by the present application more clear, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the present application.
In this application, the term "and/or" describes an association relationship of an association object, which means that there may be three relationships, for example, a and/or B may mean: a alone, a and B together, and B alone. Wherein A, B may be singular or plural. The character "/" generally indicates that the context-dependent object is an "or" relationship.
In the present application, "at least one" means one or more, and "a plurality" means two or more. "at least one of" or the like means any combination of these items, including any combination of single item(s) or plural items(s). For example, "at least one (individual) of a, b, or c," or "at least one (individual) of a, b, and c" may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, c may be single or multiple, respectively.
It should be understood that, in various embodiments of the present application, the sequence number of each process does not mean that the sequence of execution is sequential, and some or all of the steps may be executed in parallel or sequentially, where the execution sequence of each process should be determined by its functions and internal logic, and should not constitute any limitation on the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in this application in the examples and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weights of the relevant components mentioned in the embodiments of the present application may refer not only to specific contents of the components, but also to the proportional relationship between the weights of the components, and thus, any ratio of the contents of the relevant components according to the embodiments of the present application may be enlarged or reduced within the scope disclosed in the embodiments of the present application. Specifically, the mass in the specification of the embodiment of the present application may be a mass unit well known in the chemical industry field such as μ g, mg, g, kg.
The terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated for distinguishing between objects such as substances from each other. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of embodiments of the present application. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature.
As shown in fig. 1, a first aspect of the embodiment of the present application provides a method for preparing a negative electrode active material of a zinc ion battery, including the following steps:
s10, obtaining raw material components, wherein the raw material components comprise a vanadium source and a sulfur source;
s20, dissolving the raw material components in a solvent, and performing hydrothermal reaction to obtain the vanadium tetrasulfide anode active material.
According to the preparation method of the zinc ion battery anode active material, provided by the embodiment of the application, after raw material components comprising a vanadium source and a sulfur source are obtained, the raw material components are fully dissolved in a solvent, and the nano vanadium tetrasulfide anode active material can be prepared through hydrothermal reaction. The preparation process is simple and easy to operate, and the prepared nano vanadium tetrasulfide negative electrode active material is of a layered structure, has a larger interlayer spacing, provides a large number of active sites for zinc ions to be inserted and extracted, is beneficial to zinc ion insertion and extraction in the charge and discharge process, improves the uniformity of zinc ion diffusion, distribution and deposition, improves the migration dynamics of zinc ions, reduces the growth of zinc dendrites, and further improves the cycling stability of the negative electrode material. Meanwhile, the potential of the nano vanadium tetrasulfide anode active material is relatively low, the nano vanadium tetrasulfide anode active material is used as an anode material and has higher coordination degree with a zinc ion anode, and the lower potential can better maintain the structural stability of the material, so that the cycle performance of the material is further improved.
In some embodiments, in step S10, the raw material component further includes at least one composite material of a conductive structural material and a metal doped material; by adding the composite materials, not only the electrochemical performance such as conductivity and the like of the vanadium tetrasulfide anode active material can be optimized, but also the structure of the anode material can be optimized, the structural support is provided for the vanadium tetrasulfide anode active material, the active sites of the anode material are further enriched, and zinc ions are more favorably embedded and extracted.
In some embodiments, the vanadium source is selected from NH 4 VO 3 、NaVO 3 、Na 3 VO 4 At least one of (a) and (b); the pentavalent vanadium salts are good in stability, easy to dissolve in water, and oxidative, and easy to react with sulfur sources to generate vanadium tetrasulfide anode active materials.
In some embodiments, the sulfur source is selected from CH 3 CSNH 2 、CH 4 N 2 At least one of S; the sulfur sources are not only easy to dissolve in water, but also have reducibility, and have high reaction efficiency with the vanadium sources with oxidability, so that the preparation efficiency of the vanadium tetrasulfide anode active material can be improved.
In some embodiments, the metal-doped material is selected from at least one of an iron salt, a cobalt salt, a nickel salt, a manganese salt, a molybdenum salt; the metal doping materials can provide Fe, co, ni, mn, mo and other metal doping elements for the vanadium tetrasulfide anode active material, and doping the metal elements is beneficial to improving the electrochemistry of the vanadium tetrasulfide anode active material. In some embodiments, the metal doping material of iron salt, cobalt salt, nickel salt, manganese salt, molybdenum salt, etc. may be nitrate, sulfate, chloride salt, etc.
In some embodiments, the conductive structural material is at least one selected from activated carbon, graphene oxide, carbon nanotubes and conductive polymers, and the materials have conductive performance, so that the conductive performance of the composite material can be improved, pores are rich, vanadium tetrasulfide can be attached to the pore surfaces of the materials to be generated in situ, so that the vanadium tetrasulfide is uniformly and stably distributed in the materials with small particle size, the space structure of the anode material is enriched, the structure of the composite material is optimized, and the anode material has more active sites.
In some embodiments, in step S20, the raw material components including the vanadium source and the sulfur source are dissolved in a solvent, and a hydrothermal reaction is performed to react the vanadium source and the sulfur source to generate vanadium tetrasulfide, so as to obtain the vanadium tetrasulfide negative electrode active material.
In some embodiments, the molar ratio of sulfur source to vanadium source is (4-7) mol:1mol, the proportion is favorable for the reaction of a vanadium source and a sulfur source to generate vanadium tetrasulfide, and if the proportion of the vanadium source is too high, the negative electrode material S has more defects; if the proportion of the vanadium source is too low, pure vanadium tetrasulfide is not obtained through synthesis, and S simple substance and other vanadium compounds can be produced to influence the electrochemical performance of the cathode material. In some embodiments, the molar ratio of sulfur source to vanadium source includes, but is not limited to, 4:1, 5:1, 6:1, 7:1, and the like.
In other embodiments, the composite material is dissolved in a solvent with a vanadium source and a sulfur source, and a hydrothermal reaction is performed to react the vanadium source and the sulfur source to generate a vanadium tetrasulfide negative electrode active material, and the vanadium tetrasulfide negative electrode active material is combined with the composite material to form the vanadium tetrasulfide composite negative electrode active material. By combining the composite material, the structure and performance of the negative electrode material are further optimized.
In some embodiments, the ratio of sulfur source, vanadium source, and composite is (4-7) mol:1mol: (20-60) g, wherein the ratio ensures the electrochemical performance and the structural performance of the vanadium tetrasulfide composite anode active material, and if the composite material is excessively high, the content of the vanadium tetrasulfide active material in the vanadium tetrasulfide composite anode active material is reduced, so that the high-efficiency energy storage of the material is not facilitated; if the addition amount of the composite material is too low, the growth of vanadium tetrasulfide is not regulated and controlled, and the conductivity of the composite anode material is not improved. In some embodiments, the ratio of sulfur source, vanadium source, and composite material includes, but is not limited to (4-7) mol:1mol:20g, (4-7) mol:1mol:30g, (4-7) mol:1mol:40g, (4-7) mol:1mol:50g, (4-7) mol:1mol:60g, etc.
In some embodiments, in step S20, the conditions of the hydrothermal reaction include: the reaction is carried out for 4 to 24 hours under the conditions of the temperature of 120 to 200 ℃ and the pressure of 0.5 to 0.9MPa, so that the raw material components are fully contacted and reacted to generate the vanadium tetrasulfide anode active material. In some embodiments, the hydrothermal reaction can be performed in a hydrothermal reaction kettle, the reaction pressure can be regulated and controlled by a loading amount, and in particular, the loading amount can be 30-80% of the volume of the reaction kettle, and under the loading condition, not only is enough pressure provided for the reaction, but also the reaction safety is ensured. The higher the reaction temperature is, the longer the time is, the larger the size of the obtained vanadium tetrasulfide anode active material is, the intercalation/deintercalation path of zinc ions in the anode material with large size is increased, and the migration efficiency of the zinc ions is reduced. In some embodiments, the temperature of the hydrothermal reaction includes, but is not limited to, 120-140 ℃, 140-160 ℃, 160-180 ℃, 180-200 ℃, etc., and the pressure includes, but is not limited to, 0.5MPa, 0.6MPa, 0.7MPa, 0.8MPa, 0.9MPa, the reaction time includes, but is not limited to, 5-24 hours, further 10-24 hours, further 12-20 hours, etc.
In some embodiments, the solvent is selected from water or a mixed solvent of water and an alcohol solvent, and the solvent has better dissolving/dispersing effect on raw material components such as a vanadium source, a sulfur source, a composite material and the like, so that the raw material components can be fully contacted and reacted.
In some embodiments, the step of preparing the vanadium tetrasulfide negative electrode active material includes:
s11, weighing 1mmol of vanadium source, adding distilled water, heating and stirring to completely dissolve the vanadium source, and obtaining vanadium source solution; and weighing (4-7) mmol of sulfur source, adding distilled water, stirring to dissolve completely, and obtaining sulfur source solution.
S21, slowly adding a vanadium source solution into a sulfur source solution, slowly adding a mixed solution favorable for obtaining homogeneous phase, stirring to uniformly mix the mixed solution, pouring the mixed solution into a high-pressure reaction kettle, preserving heat for 4-24 hours at 120-200 ℃ for hydrothermal reaction, and purifying a product through a series of procedures such as washing, filtering, drying and the like to obtain vanadium tetrasulfide (VS) 4 ) A nano negative electrode active material.
In some embodiments, the vanadium tetrasulfide anode active material is a two-dimensional layered structure, the sheet diameter/particle size of the vanadium tetrasulfide anode active material is 0.5-3 μm, the particle size anode material provides a large number of active sites for zinc ions to intercalate and deintercalate; the negative electrode material has excellent cycling stability in a water-based zinc ion battery system.
In other embodiments, the step of preparing the vanadium tetrasulfide composite anode active material includes:
s12, weighing 1mmol of vanadium source, adding distilled water, heating and stirring to completely dissolve the vanadium source, and obtaining vanadium source solution; weighing (4-7) mmol of sulfur source, adding distilled water, and stirring to completely dissolve the sulfur source to obtain a sulfur source solution; the composite material is measured according to the proportion of the vanadium source and the composite material of 1mol (20-60 g), deionized water is added for dilution, and ultrasonic dispersion is carried out, so as to prepare the composite material solution.
S22, adding the vanadium source solution into the composite material solution, stirring and mixing uniformly, adding the sulfur source solution, stirring and mixing uniformly, pouring the mixed solution into a high-pressure reaction kettle, preserving heat for 4-24 hours at 120-200 ℃ for hydrothermal reaction, and purifying the product through a series of procedures such as washing, filtering, drying and the like to obtain vanadium tetrasulfide (VS) 4 ) Nanocomposite anode active material.
In some embodiments, the vanadium tetrasulfide composite negative electrode active material has a particle size of 50-80 nm. The vanadium tetrasulfide composite anode active material is combined with the conductive structural material and the metal doping material, so that the composite material can be in a three-dimensional net-shaped structure and the like, and the structure of the anode active material is further optimized through the combination of the composite material. In addition, due to the addition of the composite material, the particle size of the vanadium tetrasulfide can be optimized, and the effect of embedding and removing zinc ions can be improved. In some embodiments, the particle size of the vanadium tetrasulfide in the vanadium tetrasulfide composite negative electrode active material includes, but is not limited to, 50 to 60nm, 60 to 70nm, 70 to 80nm, etc.
In some embodiments, in the vanadium tetrasulfide composite anode active material, the mass percentage of the vanadium tetrasulfide is 20-90%, the proportion effectively ensures the energy storage efficiency of the composite anode material, if the content of the vanadium tetrasulfide is too low, the energy storage efficiency is low, and if the content of the vanadium tetrasulfide is too high, the optimization of the structure is not obvious. In some embodiments, the mass percent of the vanadium tetrasulfide in the vanadium tetrasulfide composite negative electrode active material includes, but is not limited to, 20-30%, 30-40%, 40-50%, 50-60%, 60-70%, 70-80%, 80-90% and the like.
The second aspect of the embodiment of the application provides a zinc ion battery anode, which comprises the zinc ion battery anode active material prepared by the method.
The zinc ion battery anode provided by the second aspect of the embodiment of the application comprises the zinc ion battery anode active material prepared by the method, wherein the zinc ion battery anode active material comprises a vanadium tetrasulfide anode active material or a vanadium tetrasulfide composite anode active material combined with a conductive structure material and a metal doping element, a large number of active sites can be provided for zinc ion intercalation and deintercalation, the zinc ion migration dynamics is improved, the growth of zinc dendrites is reduced, and the material has good cycling stability. And the cathode active material has low potential, so that the matching degree of the cathode and the zinc ion anode can be improved. Therefore, the zinc ion battery cathode provided by the embodiment of the application has good cycling stability, high safety and higher coordination degree with the zinc ion anode.
In some embodiments, the zinc ion battery anode further comprises a conductive agent and a binder, wherein the mass ratio of the conductive agent to the binder to the zinc ion battery anode active material is (5-15): (5-15): (70-90), wherein the conductive agent can improve the conductivity of the negative electrode of the zinc ion battery, and the adhesive can improve the stability of the negative electrode plate of the zinc ion battery, and prevent the situations of powder falling, cracking and the like of the electrode plate in the manufacturing process.
In some embodiments, the conductive agent includes one or more of acetylene black, carbon nanotubes, graphene.
In some embodiments, the binder comprises one or more of polyvinylidene fluoride, sodium alginate, sodium carboxymethyl cellulose.
A third aspect of the embodiments of the present application provides a zinc ion battery, where the zinc ion battery includes the negative electrode of the zinc ion battery.
According to the zinc ion battery provided by the third aspect of the embodiment of the application, due to the fact that the zinc ion battery cathode is included, the cathode is good in circulation stability and high in safety, and has higher matching degree with the zinc ion cathode, so that the circulation stability and the service life of the zinc ion battery are improved.
In some embodiments, a zinc sheet may be used as the positive electrode in a zinc ion battery.
The embodiment of the application does not limit electrolyte, diaphragm and the like in the zinc ion battery specifically, so long as the application requirement can be met.
In some embodiments, the electrolyte in the zinc-ion battery includes, but is not limited to, an aqueous solution of zinc triflate, zinc sulfate, or zinc perchlorate.
In some embodiments, the separator of the zinc ion battery includes, but is not limited to, fiberglass.
In order to make the implementation details and operation of the present application clearly understood by those skilled in the art, and the preparation method of the negative electrode of the zinc ion battery and the active material thereof and the obvious embodiment of the advanced performance of the zinc ion battery in the embodiments of the present application, the technical solutions described above are exemplified by the following multiple embodiments.
Example 1
Vanadium tetrasulfide (VS) 4 ) A negative electrode active material, the preparation of which comprises the steps of:
(1) weigh 4mmol of NH 4 VO 3 Adding 75ml of distilled water, heating and stirring for half an hour to dissolve completely to obtain NH 4 VO 3 A solution; weigh 24mmol of C 2 H 5 NS, 65ml of distilled water is added and stirred to be completely dissolved to obtain C 2 H 5 NS solution.
(2) To dissolve NH 4 VO 3 Slowly adding the solution into the C 2 H 5 The NS solution was stirred for half an hour to be uniformly mixed, thereby obtaining a mixed solution.
(3) The mixed solution was poured into a stainless steel autoclave and incubated at 180℃for 20h. The product is purified by a series of procedures such as washing, filtering, drying and the like to obtain vanadium tetrasulfide (VS 4 ) Negative electrode active material.
Example 2
Vanadium tetrasulfide (VS) 4 ) A negative electrode active material, which is different from example 1 in that: NH (NH) 4 VO 3 And C 2 H 5 The molar ratio of NS is 1:6mol.
Example 3
The preparation method of the vanadium tetrasulfide@graphene (3D-VG) composite anode active material comprises the following steps:
(1) according to NH 4 VO 3 GO=1 mol:40g ratio, measuring GO solution (solvent is water, concentration is 2 mg/mL), adding 75mL deionized water for dilution, and performing ultrasonic dispersion for 2h to obtain the productGraphene Oxide (GO) colloid solution 1.
(2) According to NH 4 VO 3 :NH 3 ·H 2 O=1 mol:1L ratio 4mmol NH 4 VO 3 And 4ml NH 3 ·H 2 O was dissolved in 65ml deionized water and continuously stirred until completely dissolved, to prepare solution 2.
(3) Solution 2 was introduced into colloidal solution 1 at a rate of 80r/min using a peristaltic pump while stirring, and after the introduction was completed, stirring was continued for 0.5h to form a homogeneous mixture 3.
(4) According to NH 4 VO 3 :C 2 H 5 Ns=1 mol:5mol ratio C 2 H 5 NS was added to mixture 3 and stirred for 1h to give mixture 4.
(5) The mixture 4 was transferred to a stainless steel autoclave and then incubated at 180℃for 20 hours, resulting in a 3D-VG composite material of the three-dimensional columnar macrostructure shown in FIG. 4.
(6) And (3) cleaning the 3D-VG composite material in the step (4) by deionized water, freeze-drying for 24 hours, mechanically crushing a dried sample, and sieving the crushed sample with a 100-200-mesh sieve to obtain the vanadium tetrasulfide@graphene (3D-VG) composite anode active material.
Example 4
The vanadium tetrasulfide @ graphene (3D-VG) composite anode active material differs from example 3 in that: NH (NH) 4 VO 3 :GO＝1mol:20g。
Example 5
The vanadium tetrasulfide @ graphene (3D-VG) composite anode active material differs from example 3 in that: NH (NH) 4 VO 3 :GO＝1mol:60g。
Example 6
Sulfur composite vanadium tetrasulfide (VS) 4 @s) nano negative electrode active material, the preparation of which comprises the steps of:
(1) weigh 4mmol of NH 4 VO 3 75ml of distilled water was added thereto, heated and stirred for half an hour to dissolve completely, and 16mmol of C was weighed 2 H 5 NS, 65ml of distilled water was added and stirred to dissolve completely.
(2) Will beDissolved NH 4 VO 3 Slowly adding the solution into the C 2 H 5 To the NS solution, 2mmol of sulfur powder was added and stirred for half an hour to mix homogeneously.
(3) The mixed solution was poured into a stainless steel autoclave and incubated at 180℃for 20h. The product is treated by a series of procedures such as washing, filtering, drying and the like to obtain the sulfur composite vanadium tetrasulfide precursor material. Then placing the sulfur compound vanadium tetrasulfide precursor material into a tube furnace, and heating at 200 ℃ in vacuum for 2 hours to obtain sulfur compound vanadium tetrasulfide (VS) 4 @ S) nano-anode active material.
Example 7
Sulfur composite vanadium tetrasulfide (VS) 4 @ S) a nano-anode active material, which is different from example 6 in that: NH (NH) 4 VO 3 、C 2 H 5 The molar ratio of NS to sulfur powder was 4:24:3.
Example 8
Sulfur composite vanadium tetrasulfide (VS) 4 @ S) a nano-anode active material, which is different from example 6 in that: NH (NH) 4 VO 3 、C 2 H 5 The molar ratio of NS to sulfur powder was 4:16:3.
Example 9
Sulfur composite vanadium tetrasulfide (VS) 4 @ S) a nano-anode active material, which is different from example 6 in that: NH (NH) 4 VO 3 、C 2 H 5 The molar ratio of NS to sulfur powder was 5:25:2.
Example 10
Copper doped vanadium tetrasulfide (Cu-VS 4 ) The preparation method of the nano negative electrode active material comprises the following steps:
(1) weigh 4mmol of NH 4 VO 3 75ml of distilled water was added thereto, heated and stirred for half an hour to dissolve completely, and 16mmol of C was weighed 2 H 5 NS, 65ml of distilled water was added thereto and stirred to dissolve completely, and 0.04mmol of CuSO was weighed 4 2ml of distilled water was added for dissolution.
(2) To dissolve NH 4 VO 3 Slowly adding the solution into the C 2 H 5 To NS solution, then slowly drop CuSO 4 Solution simultaneousStirring was carried out for half an hour to allow uniform mixing.
(3) The mixed solution was poured into a stainless steel autoclave and incubated at 180℃for 20h. The copper doped vanadium tetrasulfide precursor material is obtained by treating the product through a series of procedures such as washing, filtering, drying and the like. Then placing the copper-doped vanadium tetrasulfide precursor material in a tube furnace, and heating at 200 ℃ in vacuum for 2 hours to obtain copper-doped vanadium tetrasulfide (Cu-VS) 4 ) A nano negative electrode active material.
Example 11
Copper doped vanadium tetrasulfide (Cu-VS 4 ) A nano negative active material, which is different from example 10 in that: NH (NH) 4 VO 3 、C 2 H 5 NS and CuSO 4 The molar ratio is 1:4:0.01.
Example 12
Copper doped vanadium tetrasulfide (Cu-VS 4 ) A nano negative active material, which is different from example 10 in that: NH (NH) 4 VO 3 、C 2 H 5 NS and CuSO 4 The molar ratio is 1:4:0.03.
Example 13
Copper doped vanadium tetrasulfide (Cu-VS 4 ) A nano negative active material, which is different from example 10 in that: NH (NH) 4 VO 3 、C 2 H 5 NS and CuSO 4 The molar ratio is 1:4:0.05.
Example 14
Copper doped vanadium tetrasulfide (Cu-VS 4 ) A nano negative active material, which is different from example 10 in that: NH (NH) 4 VO 3 、C 2 H 5 NS and CuSO 4 The molar ratio was 1:4:0.07.
Further, in order to verify the progress of the examples of the present application, the following performance tests were performed on the anode active materials prepared in examples 1 to 14:
1. 10 parts of a conductive agent, 10 parts of a binder and 80 parts of a negative electrode active material are ground according to components, and then rolled into a sheet and coated on a current collector of a desired size, and compacted to obtain a negative electrode. The electrolyte is aqueous solution of zinc trifluoromethane sulfonate, zinc sulfate or zinc perchlorate with concentration of 0.8-5 mol/L. The electrochemical performance test is carried out by assembling CR2302 button half-cell with zinc sheet as counter electrode and glass fiber as diaphragm, and the voltage range is 0.1-1.0V. The test results are shown in tables 1 to 3 below:
TABLE 1
TABLE 2
TABLE 3 Table 3
As can be seen from the test results in Table 1, the vanadium tetrasulfide produced by examples 1-2 of the present application (VS 4 ) Negative electrode active material, vanadium tetrasulfide @ graphene (3D-VG) composite negative electrode active material prepared in examples 3-5, sulfur composite vanadium tetrasulfide (VS) prepared in examples 6-9 4 @S) nano negative active material, copper-doped vanadium tetrasulfide (Cu-VS) prepared in examples 10 to 13 4 ) After the nano negative electrode active material is assembled into the zinc ion battery, the battery has higher capacity and cycle stability.
2. For the vanadium tetrasulfide prepared in example 1 (VS 4 ) The morphology of the anode active material and the vanadium tetrasulfide@graphene (3D-VG) composite anode active material prepared in example 4 is observed through a scanning electron microscope, and the test results are shown in figures 2 and 3. Wherein the method comprises the steps ofFig. 2 is an SEM image of a vanadium tetrasulfide (VS 4) anode active material, and it can be seen from fig. 2 that the vanadium tetrasulfide (VS 4) anode active material has a two-dimensional layered structure, a sheet diameter of 0.5-3 μm, and abundant gaps, which are beneficial to zinc ion intercalation and deintercalation. Fig. 3 is an SEM image of a vanadium tetrasulfide @ graphene (3D-VG) composite anode active material, and as can be seen from fig. 3, the microstructure of the composite anode active material is in a three-dimensional network shape, and by compounding with graphene oxide, the pore structure of the anode active material is further increased, so that zinc ions are more favorably embedded and extracted.
3. In addition, the macro morphology of the vanadium tetrasulfide@graphene (3D-VG) composite anode active material prepared in the embodiment 3 is columnar as shown in fig. 4, and the formed macro morphology with a certain shape shows that the material has a good three-dimensional composite structure, and the composite graphene provides a good structural support effect.
The foregoing description of the preferred embodiments of the present application is not intended to be limiting, but is intended to cover any and all modifications, equivalents, and alternatives falling within the spirit and principles of the present application.

Claims (9)

1. A zinc ion battery negative electrode, characterized in that the zinc ion battery negative electrode comprises a zinc ion battery negative electrode active material;
the preparation method of the zinc ion battery anode active material comprises the following steps:
obtaining raw material components, wherein the raw material components comprise a vanadium source and a sulfur source;
the raw material components are dissolved in a solvent to carry out hydrothermal reaction, so as to obtain a vanadium tetrasulfide anode active material;
the solvent is selected from water or a mixed solvent of water and an alcohol solvent;
the prepared vanadium tetrasulfide anode active material has a two-dimensional lamellar structure, and the sheet diameter of the vanadium tetrasulfide anode active material is 0.5-3 mu m.
2. The negative electrode of zinc-ion battery according to claim 1, wherein the raw material composition further comprises at least one composite material of a conductive structural material and a metal-doped material;
the step of the hydrothermal reaction comprises the following steps: and dissolving the composite material, the vanadium source and the sulfur source in a solvent to perform a hydrothermal reaction to obtain the vanadium tetrasulfide composite anode active material.
3. The zinc-ion battery anode according to claim 2, wherein the ratio of the sulfur source, the vanadium source and the composite material is (4 to 7) mol:1mol: (20-60) g.
4. A zinc-ion battery anode according to any one of claims 1 to 3, wherein the conditions of the hydrothermal reaction include: the reaction is carried out for 4 to 24 hours under the conditions that the temperature is 120 to 200 ℃ and the pressure is 0.5 to 0.9 MPa.
5. The zinc-ion battery anode of claim 4, wherein the vanadium source is selected from the group consisting of NH 4 VO 3 、NaVO 3 、Na 3 VO 4 At least one of (a) and (b);
and/or the sulfur source is selected from CH 3 CSNH 2 、CH 4 N 2 At least one of S.
6. The negative electrode of zinc-ion battery according to claim 2 or 3, wherein the metal doping material is at least one selected from the group consisting of iron salt, cobalt salt, nickel salt, manganese salt, and molybdenum salt;
and/or the conductive structural material is at least one selected from activated carbon, graphene oxide, carbon nanotubes and conductive polymers.
7. The negative electrode of zinc ion battery according to claim 6, wherein in the vanadium tetrasulfide composite negative electrode active material, the particle size of vanadium tetrasulfide is 50-80 nm;
and/or, in the vanadium tetrasulfide composite anode active material, the mass percentage of the vanadium tetrasulfide is 20-90%.
8. The zinc-ion battery anode according to any one of claims 1 to 3, 5 or 7, further comprising a conductive agent and a binder, wherein the mass ratio of the conductive agent, the binder and the zinc-ion battery anode active material is (5 to 15): (5-15): (70-90).
9. A zinc ion battery, characterized in that the zinc ion battery comprises the zinc ion battery cathode according to any one of claims 1 to 8.
CN202210453402.1A 2022-04-27 2022-04-27 Zinc ion battery cathode, preparation method of active material of zinc ion battery cathode and zinc ion battery Active CN114835161B (en)

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