CN114835161A - 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 PDFInfo
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- CN114835161A CN114835161A CN202210453402.1A CN202210453402A CN114835161A CN 114835161 A CN114835161 A CN 114835161A CN 202210453402 A CN202210453402 A CN 202210453402A CN 114835161 A CN114835161 A CN 114835161A
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- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000011149 active material Substances 0.000 title abstract description 6
- UDKXBPLHYDCWIG-UHFFFAOYSA-M [S-2].[S-2].[SH-].S.[V+5] Chemical compound [S-2].[S-2].[SH-].S.[V+5] UDKXBPLHYDCWIG-UHFFFAOYSA-M 0.000 claims abstract description 92
- 239000007773 negative electrode material Substances 0.000 claims abstract description 51
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 40
- 239000011593 sulfur Substances 0.000 claims abstract description 40
- 239000006183 anode active material Substances 0.000 claims abstract description 38
- 239000000463 material Substances 0.000 claims abstract description 36
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 35
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 23
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
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- CITILBVTAYEWKR-UHFFFAOYSA-L zinc trifluoromethanesulfonate Substances [Zn+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F CITILBVTAYEWKR-UHFFFAOYSA-L 0.000 description 2
- RXBXBWBHKPGHIB-UHFFFAOYSA-L zinc;diperchlorate Chemical compound [Zn+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O RXBXBWBHKPGHIB-UHFFFAOYSA-L 0.000 description 2
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- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- 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
Abstract
The application belongs to the technical field of batteries, and particularly relates to a zinc ion battery cathode, a preparation method of an active material of the zinc ion battery cathode, and a zinc ion battery. The preparation method of the zinc ion battery negative electrode 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 carrying out 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 cathode active material provides a large number of active sites for embedding and removing zinc ions, so that the migration kinetics of the zinc ions are improved, the growth of zinc dendrites is reduced, and the cycle stability of the cathode material is improved. Meanwhile, the potential of the nano vanadium tetrasulfide cathode active material is relatively low, the nano vanadium tetrasulfide cathode active material has high matching degree with a zinc ion cathode, and the low potential can better keep the structural stability of the material, so that the cycle performance of the material is further improved.
Description
Technical Field
The application belongs to the technical field of batteries, and particularly relates to a zinc ion battery negative active material, a preparation method thereof and a zinc ion battery.
Background
Most of the small and medium-sized commercialized batteries in the current market are lithium ion batteries, and since the commercialization of the lithium ion batteries is realized, 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, for example, a nickel-cobalt-manganese ternary lithium ion battery, mainly has the following disadvantages: 1. the mainstream lithium ion battery in the current market generally contains cobalt and organic electrolyte, and the lithium ion battery has toxicity and has the problem of production safety. 2. The gas is separated out and the lithium dendrite grows to cause the use safety problem during the operation of the battery. 3. The production cost caused by the scarcity and uneven distribution of resources such as lithium, cobalt and the like.
Therefore, the development of a new metal-ion battery as a substitute for a lithium-ion battery has been an important issue in the field. Among them, the water-based zinc ion battery has been widely studied because of its advantages of abundant electrode material resources, safe and environment-friendly electrolyte, simple production process, and low cost. However, most of the current research on electrode materials for zinc ion batteries has focused on the research and development of positive electrode materials, and the use of simple zinc sheets as negative electrode materials for aqueous zinc ion batteries is still the main issue. And the zinc sheet negative electrode shows relatively poor cycle performance caused by zinc dendrite growth, hydrogen evolution reaction and zinc corrosion, wherein the zinc dendrite growth is one of the main problems restricting the cycle performance of a zinc-based system. Therefore, development of a negative electrode material suitable for an aqueous zinc ion battery is a great and urgent challenge.
Disclosure of Invention
The application aims to provide a zinc ion battery cathode, a preparation method of an active material of the zinc ion battery cathode, and a zinc ion battery, and aims to solve the problem that the current zinc ion battery cathode has poor cycle performance caused by zinc dendrite growth, hydrogen evolution reaction, zinc corrosion and the like to a certain extent.
In order to achieve the purpose 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 active material of a zinc ion battery, comprising 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 carrying out 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 structure material and a metal doped material;
the hydrothermal reaction comprises the following steps: and dissolving the composite material, the vanadium source and the sulfur source in a solvent, and carrying out hydrothermal reaction to obtain the vanadium tetrasulfide composite negative active material.
Further, the ratio of the sulfur source, the vanadium source and the composite material is (4-7) mol: 1mol: (20-60) g.
Further, the hydrothermal reaction conditions include: reacting for 4-24 hours at the temperature of 120-200 ℃ and the pressure of 0.5-0.9 MPa.
Further, the vanadium source is selected from NH 4 VO 3 、NaVO 3 、Na 3 VO 4 At least one of (1).
Further, the sulfur source is selected from CH 3 CSNH 2 、CH 4 N 2 At least one of the S-component (S),
further, the solvent is selected from water or a mixed solvent of water and an alcohol solvent.
Further, the metal doping material is selected from at least one of iron salt, cobalt salt, nickel salt, manganese salt and molybdenum salt.
Further, the conductive structure material is selected from at least one of 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 negative active material, the particle size of the vanadium tetrasulfide is 50-80 nm.
Further, in the vanadium tetrasulfide composite negative active material, the mass percentage of the vanadium tetrasulfide is 20-90%.
In a second aspect, the present application provides a zinc ion battery anode comprising the zinc ion battery anode active material prepared by the above method.
Further, the zinc ion battery negative electrode also 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 comprising the zinc ion battery negative electrode described above.
According to the preparation method of the zinc ion battery cathode active material provided by the first aspect of the application, after raw material components including a vanadium source and a sulfur source are obtained, the raw material components are fully dissolved in a solvent, and the nano vanadium tetrasulfide cathode active material can be prepared through a hydrothermal reaction. The preparation process is simple and easy to operate, and the prepared nano vanadium tetrasulfide cathode active material is of a layered structure and has larger interlayer spacing, provides a large number of active sites for embedding and removing zinc ions, is beneficial to embedding and removing the zinc ions in the charging and discharging process, improves the uniformity of zinc ion diffusion, distribution and deposition, improves the migration kinetics of the zinc ions, reduces the growth of zinc dendrites, and thus improves the cycle stability of the cathode material. Meanwhile, the potential of the nano vanadium tetrasulfide cathode active material is relatively low, the nano vanadium tetrasulfide cathode active material has high matching degree with a zinc ion cathode, and the low potential can better keep the structural stability of the material, so that the cycle performance of the material is further improved.
The zinc ion battery cathode provided by the second aspect of the application comprises the zinc ion battery cathode active material prepared by the method, and the zinc ion battery cathode active material comprises a vanadium tetrasulfide cathode active material or a vanadium tetrasulfide composite cathode active material combined with a conductive structure material and metal doping elements, so that a large number of active sites can be provided for zinc ion embedding and separation, the zinc ion migration dynamics is improved, the growth of zinc dendrites is reduced, and the material circulation stability is good. And the matching degree of the negative electrode and the zinc ion positive electrode can be improved by the low potential of the negative electrode active material. Therefore, the zinc ion battery cathode provided by the application has the advantages of good cycling stability, high safety and higher matching degree with a zinc ion cathode.
The zinc ion battery provided by the third aspect of the application has the advantages that the zinc ion battery cathode is included, the cathode is good in cycling stability and high in safety, and has high matching degree with the zinc ion anode, so that the cycling stability and the service life of the zinc ion battery are improved.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
Fig. 1 is a schematic flow chart of a method for preparing a negative active material of a zinc-ion battery provided in an embodiment of the present application;
FIG. 2 shows vanadium tetrasulfide (VS) provided in example 1 of the present application 4 ) Scanning electron microscope SEM topography of the negative active material;
fig. 3 is a scanning electron microscope SEM topography of the vanadium tetrasulfide @ graphene (3D-VG) composite anode active material provided in embodiment 2 of the present application;
fig. 4 is a macro topography 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 solutions and advantageous effects to be solved by the present application more clearly apparent, 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 merely illustrative of the present application and are not intended to limit the present application.
In this application, the term "and/or" describes an association relationship of associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
In the present application, "at least one" means one or more, "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one (one) of a, b, or c," or "at least one (one) 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, and c may be single or plural, respectively.
It should be understood that, in various embodiments of the present application, the sequence numbers of the above-mentioned processes do not mean the execution sequence, some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its function and inherent logic, and should not constitute any limitation to the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the examples of this application 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 weight of the related components mentioned in the description of the embodiments of the present application may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present application as long as it is scaled up or down according to the description of the embodiments of the present application. Specifically, the mass in the description of the embodiments of the present application may be in units of mass known in the chemical industry, such as μ g, mg, g, and kg.
The terms "first" and "second" are used for descriptive purposes only and are used for distinguishing purposes such as substances from one another, and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. 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 defined as "first" or "second" may explicitly or implicitly include one or more of that feature.
As shown in fig. 1, a first aspect of the embodiments of the present application provides a method for preparing a negative 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 carrying out hydrothermal reaction to obtain the vanadium tetrasulfide anode active material.
According to the preparation method of the zinc ion battery cathode active material provided by the first aspect of the embodiment of the application, after raw material components including a vanadium source and a sulfur source are obtained, the raw material components are fully dissolved in a solvent, and the nano vanadium tetrasulfide cathode active material can be prepared through a hydrothermal reaction. The preparation process is simple and easy to operate, and the prepared nano vanadium tetrasulfide cathode active material is of a layered structure and has larger interlayer spacing, provides a large number of active sites for embedding and removing zinc ions, is beneficial to embedding and removing the zinc ions in the charging and discharging process, improves the uniformity of zinc ion diffusion, distribution and deposition, improves the migration kinetics of the zinc ions, reduces the growth of zinc dendrites, and thus improves the cycle stability of the cathode material. Meanwhile, the potential of the nano vanadium tetrasulfide cathode active material is relatively low, the nano vanadium tetrasulfide cathode active material has high matching degree with a zinc ion cathode, and the low potential can better keep 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 composition further includes at least one composite material of a conductive structure material and a metal-doped material; by adding the composite materials, the electrochemical properties such as the conductivity and the like of the vanadium tetrasulfide cathode active material can be optimized, the structure of the cathode material can be optimized, structural support is provided for the vanadium tetrasulfide cathode active material, the active sites of the cathode material are further enriched, and the zinc ions can be embedded and removed more favorably.
In some embodiments, the source of vanadium is selected from NH 4 VO 3 、NaVO 3 、Na 3 VO 4 At least one of; the pentavalent vanadium salt has good stability, is easy to dissolve in water, has oxidability and is easy to react with a sulfur source to generate the vanadium tetrasulfide cathode active material.
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, have high reaction efficiency with vanadium sources with oxidability, and can improve the preparation efficiency of vanadium tetrasulfide cathode active materials.
In some embodiments, the metal doping material is selected from at least one of iron, cobalt, nickel, manganese, molybdenum salts; the metal doping materials can provide metal doping elements such as Fe, Co, Ni, Mn, Mo and the like for the vanadium tetrasulfide anode active material, and the metal doping elements are beneficial to improving the electrochemistry of the vanadium tetrasulfide anode active material. In some embodiments, the metal doping material such as iron salt, cobalt salt, nickel salt, manganese salt, molybdenum salt, etc. may be nitrate, sulfate, chloride, etc.
In some embodiments, the conductive structure material is selected from at least one of activated carbon, graphene oxide, carbon nanotubes and conductive polymers, the conductive structure material has conductive performance, the conductive performance of the composite material can be improved, pores are rich, vanadium tetrasulfide can be generated in situ by attaching to the surfaces of the pores of the conductive structure material, the vanadium tetrasulfide is uniformly and stably distributed in the conductive structure material with small particle size, the spatial structure of the negative electrode material is enriched, and the structure of the composite material is optimized, so that the negative electrode material has more active sites.
In some embodiments, in step S20, raw material components including a vanadium source and a 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, that is, to obtain a vanadium tetrasulfide anode active material.
In some embodiments, the molar ratio of the sulfur source to the vanadium source is (4-7) mol: 1mol, the proportion is beneficial to 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 defects of the cathode material S are more; if the vanadium source proportion is too low, pure vanadium tetrasulfide cannot be obtained through synthesis, S simple substance and other vanadium compounds can be produced, and the electrochemical performance of the cathode material is affected. In some embodiments, the molar ratio of the sulfur source to the 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, a vanadium source and a sulfur source are dissolved in a solvent to perform a hydrothermal reaction, and the vanadium source and the sulfur source react to generate the vanadium tetrasulfide anode active material and simultaneously combine with the composite material to form the vanadium tetrasulfide composite anode active material. By combining the composite material, the structure and the performance of the anode material are further optimized.
In some embodiments, the ratio of the sulfur source, the vanadium source, and the composite material is (4-7) mol: 1mol: (20-60) g, the proportion simultaneously ensures the electrochemical performance and the structural performance of the vanadium tetrasulfide composite negative active material, and if the composite material is added too high, the content of the vanadium tetrasulfide active material in the vanadium tetrasulfide composite negative 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 favorably regulated and controlled, and the conductivity of the composite cathode material is not favorably improved. In some embodiments, the ratio of the 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, and the like.
In some embodiments, in the step S20, the hydrothermal reaction conditions include: reacting for 4-24 hours at the temperature of 120-200 ℃ and the pressure of 0.5-0.9 MPa, 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, and the reaction pressure can be controlled by the loading amount, specifically, the loading amount can be 30-80% of the volume of the reaction kettle, so that sufficient pressure is provided for the reaction under the loading condition, and the reaction safety is ensured. The higher the reaction temperature is, the longer the reaction time is, the larger the size of the obtained vanadium tetrasulfide anode active material is, the larger the insertion/extraction path of zinc ions in the anode material with large size is, and the zinc ion migration efficiency is reduced. In some embodiments, the hydrothermal reaction is performed at a temperature of 120-140 ℃, 140-160 ℃, 160-180 ℃, 180-200 ℃ and the like, at a pressure of 0.5MPa, 0.6MPa, 0.7MPa, 0.8MPa and 0.9MPa, and for a reaction time of 5-24 hours, further 10-24 hours, further 12-20 hours and the like.
In some embodiments, the solvent is selected from water or a mixed solvent of water and an alcohol solvent, and the solvents have good dissolving/dispersing effects on raw material components such as a vanadium source, a sulfur source and a composite material, so that sufficient contact reaction among the raw material components is facilitated.
In some embodiments, the step of preparing the vanadium tetrasulfide anode active material comprises:
s11, weighing 1mmol of vanadium source, adding distilled water, heating and stirring to completely dissolve the vanadium source to obtain a vanadium source solution; and weighing (4-7) mmol of sulfur source, adding distilled water, and stirring to completely dissolve the sulfur source to obtain a sulfur source solution.
S21, slowly adding a vanadium source solution into a sulfur source solution, slowly adding a mixed solution which is beneficial to obtaining a homogeneous phase, stirring to uniformly mix the mixed solution, pouring the mixed solution into a high-pressure reaction kettle, carrying out hydrothermal reaction at the temperature of 120-200 ℃ for 4-24 hours, purifying the product through a series of procedures of washing, filtering, drying and the like to obtain vanadium tetrasulfide (VS) 4 ) A nano anode 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, and the anode material with the particle size provides a large amount of active sites for embedding and removing zinc ions; so that the negative electrode material shows excellent cycle stability in an aqueous zinc ion battery system.
In other embodiments, the step of preparing the vanadium tetrasulfide composite anode active material comprises:
s12, weighing 1mmol of vanadium source, adding distilled water, heating and stirring to completely dissolve the vanadium source to obtain a 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; measuring the composite material according to the proportion of the vanadium source to the composite material of 1mol (20-60), adding deionized water for dilution, and performing ultrasonic dispersion 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, carrying out hydrothermal reaction at the temperature of 120-200 ℃ for 4-24 hours, purifying the product through a series of procedures of washing, filtering, drying and the like to obtain vanadium tetrasulfide (VS) 4 ) A nanocomposite negative active material.
In some embodiments, the vanadium tetrasulfide composite anode active material has a particle size of 50 to 80 nm. The vanadium tetrasulfide composite negative active material is combined with the conductive structure material and the metal doping material, so that the composite material can present a three-dimensional net-like structure, and the structure of the negative 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 vanadium tetrasulfide can be optimized, and the embedding and removing effects of zinc ions are improved. In some embodiments, the particle size of the vanadium tetrasulfide in the vanadium tetrasulfide composite anode active material includes, but is not limited to, 50 to 60nm, 60 to 70nm, 70 to 80nm, and the like.
In some embodiments, in the vanadium tetrasulfide composite negative active material, the mass percentage of vanadium tetrasulfide is 20-90%, the proportion effectively ensures the energy storage efficiency of the composite negative material, if the content of vanadium tetrasulfide is too low, the energy storage efficiency is low, and if the content of vanadium tetrasulfide is too high, the optimization of the structure is not significant. In some embodiments, the vanadium tetrasulfide composite negative active material includes, but is not limited to, 20 to 30% by mass, 30 to 40% by mass, 40 to 50% by mass, 50 to 60% by mass, 60 to 70% by mass, 70 to 80% by mass, 80 to 90% by mass, and the like.
In a second aspect, the present embodiments provide a zinc ion battery negative electrode including the zinc ion battery negative electrode active material prepared by the above method.
The zinc ion battery cathode provided by the second aspect of the embodiment of the application comprises the zinc ion battery cathode active material prepared by the method, and the zinc ion battery cathode active material comprises a vanadium tetrasulfide cathode active material or a vanadium tetrasulfide composite cathode active material combined with a conductive structure material and metal doping elements, so that a large number of active sites can be provided for zinc ion embedding and separation, the zinc ion migration dynamics is improved, the growth of zinc dendrites is reduced, and the material circulation stability is good. And the matching degree of the negative electrode and the zinc ion positive electrode can be improved by the low potential of the negative electrode active material. Therefore, the zinc ion battery cathode provided by the embodiment of the application has the advantages of good cycling stability, high safety and high matching degree with a zinc ion cathode.
In some embodiments, the zinc ion battery negative electrode further comprises a conductive agent and a binder, and 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), wherein the conductive agent can improve the conductivity of the zinc ion battery cathode, and the adhesive can improve the stability of the zinc ion battery cathode plate and prevent the cathode plate from falling powder, cracking and the like in the manufacturing process.
In some embodiments, the conductive agent comprises one or more of acetylene black, carbon nanotubes, graphene.
In some embodiments, the binder comprises one or more of polyvinylidene fluoride, sodium alginate, sodium carboxymethylcellulose.
In a third aspect of the embodiments of the present application, there is provided a zinc ion battery, including the zinc ion battery negative electrode described above.
The zinc ion battery provided by the third aspect of the embodiment of the application has the advantages that the zinc ion battery negative electrode is included, the negative electrode is good in cycling stability and high in safety, and has high matching degree with the zinc ion positive electrode, so that the cycling stability and the service life of the zinc ion battery are improved.
In some embodiments, the positive electrode in a zinc-ion battery can employ a zinc sheet.
The embodiment of the application does not specifically limit the electrolyte, the diaphragm and the like in the zinc ion battery, and only needs to meet the application requirements.
In some embodiments, the electrolyte in a zinc ion battery includes, but is not limited to, an aqueous solution of zinc trifluoromethanesulfonate, zinc sulfate, or zinc perchlorate.
In some embodiments, the separator in a zinc-ion battery includes, but is not limited to, glass fibers.
In order to make the details and operations of the above-mentioned embodiments of the present application clearly understood by those skilled in the art, and to make the preparation method of the negative electrode of the zinc ion battery and its active material, and the improvement performance of the zinc ion battery obviously appear in the embodiments of the present application, the above-mentioned technical solutions are exemplified by a plurality of examples below.
Example 1
Vanadium tetrasulfide (VS) 4 ) An anode active material, the preparation of which comprises the steps of:
4mmol of NH are weighed 4 VO 3 Adding 75ml of distilled water, heating and stirring for half an hour to completely dissolve the NH to obtain 4 VO 3 A solution; weigh 24mmol of C 2 H 5 NS, adding 65ml of distilled water, stirring to completely dissolve to obtain C 2 H 5 And (3) NS solution.
② dissolved NH 4 VO 3 Slowly adding C into the solution 2 H 5 And stirring the NS solution for half an hour to uniformly mix the NS solution and the NS solution to obtain a mixed solution.
Thirdly, pouring the mixed solution into a stainless steel high-pressure kettle, and preserving heat for 20 hours at 180 ℃. Purifying the product by a series of procedures such as washing, filtering, drying and the like to obtain vanadium tetrasulfide (VS) 4 ) And a negative electrode active material.
Example 2
Vanadium tetrasulfide (VS) 4 ) A negative electrode active material, which is different from example 1 inIn the following steps: NH (NH) 4 VO 3 And C 2 H 5 The molar ratio of NS is 1:6 mol.
Example 3
A vanadium tetrasulfide @ graphene (3D-VG) composite anode active material is prepared by the following steps:
firstly, according to NH 4 VO 3 And weighing a GO solution (the solvent is water, and the concentration is 2mg/mL) according to the proportion that GO is 1mol:40g, adding 75mL of deionized water for dilution, and performing ultrasonic dispersion for 2h to prepare a Graphene Oxide (GO) colloidal solution 1.
Is according to NH 4 VO 3 :NH 3 ·H 2 O1 mol to 1L ratio 4mmol NH 4 VO 3 And 4ml of NH 3 ·H 2 O was dissolved in 65ml of deionized water and stirred continuously until completely dissolved to prepare solution 2.
③ using a peristaltic pump to inject the solution 2 into the colloidal solution 1 at the speed of 80r/min, stirring simultaneously, and continuing to stir for 0.5h after the injection is finished to form a uniform mixture 3.
Fourthly according to NH 4 VO 3 :C 2 H 5 NS 1mol:5mol ratio 2 H 5 NS was added to mixture 3 and stirred for 1h to give mixture 4.
Fifthly, transferring the mixture 4 into a stainless steel autoclave, and then preserving the heat for 20 hours at the temperature of 180 ℃ to obtain the 3D-VG composite material of the three-dimensional columnar macroscopic body shown in the figure 4.
Sixthly, cleaning the 3D-VG composite material obtained in the step (4) with deionized water, freeze-drying for 24 hours, mechanically crushing a dried sample, and sieving with a 100-200-mesh sieve to obtain the vanadium tetrasulfide @ graphene (3D-VG) composite anode active material.
Example 4
A vanadium tetrasulfide @ graphene (3D-VG) composite anode active material, which is different from example 3 in that: NH (NH) 4 VO 3 :GO＝1mol:20g。
Example 5
A vanadium tetrasulfide @ graphene (3D-VG) composite anode active material, which is different from example 3 in that: NH (NH) 4 VO 3 :GO＝1mol:60g。
Example 6
Sulfur composite vanadium tetrasulfide (VS) 4 @ S) nano-anode active material, the preparation of which includes the steps of:
4mmol of NH are weighed 4 VO 3 75ml of distilled water was added thereto, the mixture was stirred under heating for half an hour to completely dissolve the C, and 16mmol of C was weighed 2 H 5 NS, and 65ml of distilled water was added thereto and stirred to completely dissolve the NS.
② dissolved NH 4 VO 3 Slowly adding C into the solution 2 H 5 And adding 2mmol of sulfur powder into the NS solution, and stirring for half an hour to uniformly mix.
Thirdly, pouring the mixed solution into a stainless steel high-pressure kettle, and preserving heat for 20 hours at 180 ℃. And processing the product through a series of procedures such as washing, filtering, drying and the like to obtain the sulfur composite vanadium tetrasulfide precursor material. Then putting the sulfur composite vanadium tetrasulfide precursor material into a tube furnace to be heated for 2h under vacuum at 200 ℃ to obtain sulfur composite vanadium tetrasulfide (VS) 4 @ S) nano-anode active material.
Example 7
Sulfur composite vanadium tetrasulfide (VS) 4 @ S) 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 is 4:24: 3.
Example 8
Sulfur composite vanadium tetrasulfide (VS) 4 @ S) 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 is 4:16: 3.
Example 9
Sulfur composite vanadium tetrasulfide (VS) 4 @ S) 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 is 5:25: 2.
Example 10
Copper-doped vanadium tetrasulfide (Cu-VS) 4 ) The preparation method of the nanometer negative active material comprises the following steps:
4mmol of NH are weighed 4 VO 3 75ml of distilled water was added thereto, the mixture was stirred under heating for half an hour to completely dissolve the C, and 16mmol of C was weighed 2 H 5 NS, adding 65ml of distilled water, stirring to completely dissolve, and weighing 0.04mmol of CuSO 4 2ml of distilled water was added thereto to dissolve the resulting solution.
② dissolved NH 4 VO 3 Slowly adding C into the solution 2 H 5 Adding the NS solution into the solution, and then slowly dropwise adding CuSO 4 The solution was stirred simultaneously for half an hour to mix it evenly.
Thirdly, pouring the mixed solution into a stainless steel high-pressure kettle, and preserving heat for 20 hours at 180 ℃. And processing the product through a series of procedures such as washing, filtering, drying and the like to obtain the copper-doped vanadium tetrasulfide precursor material. Then placing the copper-doped vanadium tetrasulfide precursor material in a tube furnace to be heated for 2h under vacuum at 200 ℃ to obtain copper-doped vanadium tetrasulfide (Cu-VS) 4 ) A nano anode active material.
Example 11
Copper-doped vanadium tetrasulfide (Cu-VS) 4 ) A nano anode 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: 0.01.
Example 12
Copper-doped vanadium tetrasulfide (Cu-VS) 4 ) A nano anode 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: 0.03.
Example 13
Copper-doped vanadium tetrasulfide (Cu-VS) 4 ) A nano anode 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: 0.05.
Example 14
Copper-doped vanadium tetrasulfide (Cu-VS) 4 ) A nano anode active material, which is different from example 10 in that: NH (NH) 4 VO 3 、C 2 H 5 NS and CuSO 4 Molar ratio ofIs 1:4: 0.07.
Further, in order to verify the advancement of the examples of the present application, the following performance tests were performed on the negative electrode active materials prepared in examples 1 to 14:
1. grinding 10 parts of conductive agent, 10 parts of adhesive and 80 parts of negative active material according to the components, rolling into a sheet, coating the sheet on a current collector with a required size, and compacting to obtain the negative electrode. And selecting an aqueous solution of zinc trifluoromethanesulfonate, zinc sulfate or zinc perchlorate with the concentration of 0.8-5 mol/L as the electrolyte. And (3) assembling a CR2302 button type half cell by taking a zinc sheet as a counter electrode and glass fiber as a diaphragm, and carrying out electrochemical performance test, wherein the voltage range is 0.1-1.0V. The test results are shown in the following tables 1 to 3:
TABLE 1
TABLE 2
TABLE 3
As can be seen from the test results in Table 1, the vanadium tetrasulfide (VS) prepared in examples 1-2 of the present application 4 ) Negative electrode active material, vanadium tetrasulfide @ graphene (3D-VG) composite negative electrode active material prepared in examples 3 to 5, and sulfur-composite vanadium tetrasulfide (VS) prepared in examples 6 to 9 4 @ S) nano-negative electrode active materialMaterial, and copper-doped vanadium tetrasulfide (Cu-VS) prepared in examples 10 to 13 4 ) After the nano cathode active material is assembled into the zinc ion battery, the battery has higher capacity and cycling stability.
2. Vanadium tetrasulfide (VS) prepared in example 1 4 ) The negative electrode active material and the vanadium tetrasulfide @ graphene (3D-VG) composite negative electrode active material prepared in example 4 were observed in morphology by a scanning electron microscope, and the test results are shown in fig. 2 and 3. Wherein, the attached drawing 2 is an SEM image of a vanadium tetrasulfide (VS4) cathode active material, and as can be seen from the attached drawing 2, the vanadium tetrasulfide (VS4) cathode active material is of a two-dimensional layered structure, the sheet diameter is 0.5-3 μm, the gaps are rich, and the insertion and the extraction of zinc ions are facilitated. Fig. 3 is an SEM image of vanadium tetrasulfide @ graphene (3D-VG) composite negative active material, and it can be seen from fig. 3 that the microstructure of the composite negative active material is three-dimensional network, and the pore structure of the negative active material is further increased by compounding with graphene oxide, which is more beneficial to the insertion and extraction of zinc ions.
3. In addition, the macroscopic morphology of the vanadium tetrasulfide @ graphene (3D-VG) composite anode active material prepared in example 3 is columnar as shown in fig. 4, and the macroscopic morphology formed in a certain shape indicates that the material has a good three-dimensional composite structure, and the composite graphene provides a good structural support effect.
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. A preparation method of a zinc ion battery negative electrode active material is characterized by comprising 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 carrying out hydrothermal reaction to obtain the vanadium tetrasulfide anode active material.
2. The method for preparing the negative active material of the zinc-ion battery according to claim 1, wherein the raw material components further comprise at least one composite material selected from a conductive structure material and a metal-doped material;
the hydrothermal reaction comprises the following steps: and dissolving the composite material, the vanadium source and the sulfur source in a solvent, and carrying out hydrothermal reaction to obtain the vanadium tetrasulfide composite negative active material.
3. The method for preparing the negative active material of the zinc-ion battery according to claim 2, wherein the ratio of the sulfur source, the vanadium source and the composite material is (4-7) mol: 1mol: (20-60) g.
4. The preparation method of the negative active material of the zinc ion battery as claimed in any one of claims 1 to 3, wherein the hydrothermal reaction conditions include: reacting for 4-24 hours at the temperature of 120-200 ℃ and the pressure of 0.5-0.9 MPa.
5. The method of preparing the negative active material of the zinc-ion battery 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;
and/or the sulfur source is selected from CH 3 CSNH 2 、CH 4 N 2 At least one of S;
and/or the solvent is selected from water or a mixed solvent of water and an alcohol solvent.
6. The method for preparing the negative active material of the zinc-ion battery of claim 2 or 3, wherein the metal doping material is at least one selected from iron salt, cobalt salt, nickel salt, manganese salt and molybdenum salt;
and/or the conductive structure material is selected from at least one of activated carbon, graphene oxide, carbon nanotubes and conductive polymers.
7. The method for preparing the negative active material of the zinc-ion battery according to claim 6, wherein the particle size of the vanadium tetrasulfide negative active material is 0.5 to 3 μm;
and/or in the vanadium tetrasulfide composite negative active material, the particle size of the vanadium tetrasulfide is 50-80 nm;
and/or the vanadium tetrasulfide composite negative active material contains 20-90% of vanadium tetrasulfide by mass.
8. A zinc ion battery negative electrode, which is characterized by comprising the zinc ion battery negative electrode active material prepared by the method of any one of claims 1 to 7.
9. The zinc ion battery negative electrode according to claim 8, further comprising 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).
10. A zinc ion battery, characterized in that the zinc ion battery comprises the zinc ion battery negative electrode according to any one of claims 8 to 9.
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| WO2021227594A1 (en) * | 2020-05-11 | 2021-11-18 | 中国科学院过程工程研究所 | Composite positive electrode material, preparation method therefor, and application in zinc ion battery |
| AU2020101299A4 (en) * | 2020-06-08 | 2020-08-20 | Qilu University Of Technology | Vanadium tetrasulfide-nitrogen-doped carbon tube composite and preparation method and use thereof |
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