CN107221716B - Rechargeable aqueous zinc ion battery - Google Patents

Rechargeable aqueous zinc ion battery Download PDF

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Publication number
CN107221716B
CN107221716B CN201710369663.4A CN201710369663A CN107221716B CN 107221716 B CN107221716 B CN 107221716B CN 201710369663 A CN201710369663 A CN 201710369663A CN 107221716 B CN107221716 B CN 107221716B
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zinc
ion battery
electrolyte
positive electrode
diaphragm
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CN107221716A (en
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麦立强
何攀
张国彬
陈丽能
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Wuhan University of Technology WUT
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Wuhan University of Technology WUT
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/36Accumulators not provided for in groups H01M10/05-H01M10/34
    • H01M10/38Construction or manufacture
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/38Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/42Alloys based on zinc
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00Electrolytes
    • H01M2300/0002Aqueous electrolytes
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention belongs to the field of novel chemical power sources and new energy materials, and particularly relates to a novel rechargeable water-based zinc ion battery with vanadate as an electrode active material, which consists of a positive electrode, a negative electrode, a diaphragm between the positive electrode and the negative electrode, and electrolyte containing anions and cations and having ionic conductivity, wherein the active material of the positive electrode is mainly vanadate for de-intercalation of zinc ions, the electrolyte is soluble salt of zinc as a solute, water as a solvent and has the concentration of 0.1-5 mol/L, and a liquid or gel-state material with ionic conductivity is assembled into the water-based zinc ion battery.

Description

Rechargeable aqueous zinc ion battery
Technical Field
The invention belongs to the field of novel chemical power sources and new energy materials, and particularly relates to a novel rechargeable aqueous zinc ion battery taking vanadate as an electrode active material.
Background
The development and utilization of green clean energy have important significance for solving the energy crisis faced by the current human society. New energy sources such as solar energy, wind energy and the like are gradually accepted and popularized in the world due to the advantages of regeneration, no pollution and the like. However, after these energy sources are converted into electric energy, efficient and recyclable electric energy storage devices are required to meet the requirements of consumers for portable electronic products. Under such circumstances, the development of batteries is receiving attention. The application of primary batteries, such as nickel-cadmium batteries, nickel-hydrogen batteries, lead-acid batteries and the like, is limited due to the defects of low specific capacity, short cycle life, long charging time, environmental pollution and the like. The lithium ion secondary battery has high working voltage, large specific energy, long cycle life, no memory effect, environmental friendliness and other performances, so that the lithium ion secondary battery becomes a key research object of scientific researchers and is more and more widely applied. However, the application of the lithium battery in the large-scale energy storage field is limited by the problems of limited lithium resources, increasing production cost, potential safety hazards in the use process and the like.
As another important green energy storage device in the new century, zinc ion batteries are widely developed and researched due to their unique advantages of low cost, safety, environmental protection and the like. However, the development space of zinc ion batteries is limited by their lower energy density, longer charge time and shorter cycle life. The development of the zinc ion battery based on the nano material, which has high performance, compounding, low cost and greening, is the intersection and frontier of new energy technology and nano technology, and has important scientific significance and potential application value. The performance of the zinc ion battery depends on the electrode material to a great extent, so that the research and development of the electrode material with low cost, high capacity and long service life is the key to promote the rapid development and wide application of the zinc ion battery.
Disclosure of Invention
The invention aims to provide a rechargeable aqueous zinc ion battery which is safe, environment-friendly, low in cost, high in energy density and long in cycle life.
The technical scheme adopted by the invention for solving the technical problems is that the rechargeable water system zinc ion battery consists of a positive electrode, a negative electrode, a diaphragm between the positive electrode and the negative electrode and an electrolyte containing anions and cations and having ionic conductivity, wherein the active material of the positive electrode is mainly vanadate for de-intercalation of zinc ions, and the electrolyte is a liquid or gel material with ionic conductivity, wherein soluble salt of zinc is a solute, water is a solvent, and the concentration of the electrolyte is 0.1-5 mol/L.
According to the scheme, the molecular formula of the vanadate is AxVyOzWherein A is L i, Na, K or Rb 0<x<20,0<y<20,0<z<20。
According to the scheme, x is 0.33, y is 2, and z is 5.
According to the scheme, the diaphragm is a glass fiber diaphragm, filter paper or polytetrafluoroethylene diaphragm with excellent wettability.
According to the scheme, the active material of the negative electrode adopts a metal zinc sheet, zinc powder or a zinc-carbon compound.
According to the scheme, the soluble salt of zinc is zinc trifluoromethanesulfonate, zinc perchlorate or zinc sulfate.
According to the scheme, the additive in the electrolyte is vanadium-containing soluble salt.
The invention discovers that zinc ions can be reversible in the vanadate material A in the aqueous electrolyte for the first timexVyOzThe preparation method of the zinc ion battery comprises the following steps of dissolving a binder in a corresponding reagent, adding a certain amount of vanadate material and a conductive agent into the solution after grinding uniformly, performing ultrasonic dispersion to prepare slurry, uniformly coating the slurry on a current collector, wherein the thickness of the coating layer is 50-250 mu m, and performing vacuum drying to obtain the positive plate, wherein the current collector comprises carbon cloth, foamed nickel, stainless steel foil, copper foil, aluminum foil, molybdenum foil and titanium foil, the conductive agent comprises activated carbon, carbon fiber, acetylene black, Ketjen black and graphite carbon nanotubes, the binder is polyvinylidene fluoride (PVDF), Polytetrafluoroethylene (PTFE) or sodium carboxymethylcellulose (CMC), the negative plate can be prepared by the following preparation scheme, wherein a metal zinc plate is ground by using sand paper, washed by using alcohol and acetone for several times and directly used as a negative plate, when zinc powder is adopted, the slurry is uniformly ground by using the conductive agent, is uniformly mixed with the binder to prepare slurry, is coated on a current collector, the thickness of the zinc ion battery is 0.01-1.0 mm, the coated on the current collector, the zinc sulfate is prepared by adding a soluble zinc chlorate, the zinc sulfate electrolyte, the zinc sulfate buffer solution, the zinc sulfate buffer is prepared by adding a high-zinc sulfate ion battery, and the zinc sulfate buffer solution, wherein the zinc sulfate buffer solution is prepared by adding zinc sulfate buffer solution, and the zinc sulfate buffer solution, the zinc sulfate buffer solution is prepared by the zinc sulfate buffer solution, and the zinc sulfate buffer.
The invention has the beneficial effects that: vanadate material A capable of being reversible in aqueous electrolyte by utilizing zinc ionsxVyOz(wherein A is L i, Na, K, Rb; 0<x<20,0<y<20,0<z<20) The negative electrode mainly containing zinc has a stable energy storage mechanism of oxidation-reduction reaction in aqueous solution, and the electricity is generatedThe pool has the characteristics of good circulation and high capacity. The vanadate electrode material has low requirement on equipment, simple and feasible process, short operation period and easy expanded production; the electrolyte adopts water system zinc trifluoromethanesulfonate, bis-trifluoromethanesulfonimide, zinc perchlorate and zinc sulfate electrolyte, and has the advantages of low price, safety and environmental protection; meanwhile, the cathode is made of zinc material with abundant resources and low price. The material is assembled into a water system zinc ion battery, has excellent high rate performance, excellent cycle stability and excellent long service life, is a potential application material of a high-power and long-service-life zinc ion battery, and has wide application prospect in the aspect of large-scale energy storage.
Drawings
FIG. 1 shows Na in example 1 of the present invention0.33V2O5XRD pattern of nanowire material;
FIG. 2 shows Na in example 1 of the present invention0.33V2O5At 0.2Ag-1Battery cycle performance curve under current density;
FIG. 3 shows a button cell assembled in accordance with example 2 of the present invention;
FIG. 4 shows L i in example 2 of the present invention0.33V2O5A rate performance graph of the material;
fig. 5 is an assembled flexible packaged battery of example 3 of the present invention;
FIG. 6 shows Na in example 3 of the present invention0.33V2O51.0Ag of the material-1Battery cycling performance plots at current density.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
Example 1:
a long-life high-energy-density rechargeable zinc ion battery has a positive electrode made of Na as active material0.33V2O5The nanowire material (XRD is shown in figure 1), the negative electrode is made of zinc sheet, the diaphragm is made of glass fiber diaphragm, and the electrolyte is 3 mol/L zinc trifluoromethanesulfonateThe preparation method comprises the following steps:
(1)Na0.33V2O5preparation of positive plate
Dissolving binder polyvinylidene fluoride (PVDF) or Polytetrafluoroethylene (PTFE) in N-methylpyrrolidone (NMP) to obtain clear solution, adding a certain amount of Na0.33V2O5And grinding the nanowire positive electrode material uniformly, adding the ground nanowire positive electrode material into the solution (according to the active substance, acetylene black and adhesive, the ratio of 7:2:1), dispersing by ultrasonic to prepare slurry, uniformly coating the slurry on a titanium foil with the thickness of 0.05mm, wherein the thickness of the coating layer is 150 mu m, and drying in vacuum to obtain the positive electrode plate.
(2) Preparation of the electrolyte
Dissolving a certain amount of zinc Trifluoromethanesulfonate (TFMA) in deionized water to prepare electrolyte with the concentration of 3 mol/L;
(3) preparation of negative plate
And (3) polishing the metal zinc sheet by using sand paper, washing the metal zinc sheet for several times by using alcohol and acetone, and blanking to obtain a circular sheet with the diameter of 12mm as a negative plate.
(4) Assembly of aqueous zinc ion battery
And (3) separating the positive plate prepared in the step (1) and the negative plate prepared in the step (3) by using a glass fiber membrane with the thickness of 0.2mm, placing the positive plate and the negative plate into a battery shell, respectively injecting zinc sulfate salt with the concentration of 3 mol/L, and finally packaging the battery.
The nanowire material prepared in example 1 showed pure phase Na by X-ray diffraction analysis0.33V2O5As shown in fig. 1. The zinc ion battery positive electrode active material has excellent electrochemical performance. As shown in FIG. 2, the current density was 0.2Ag-1Constant current charge and discharge tests are carried out, and the discharge capacity is 276.6mAh g-1After 100 cycles, the capacity retention rate was 91.3%. The water system zinc ion battery not only has high specific capacity and long cycle life, but also has the advantages of simple process, safety, environmental protection and low cost, and has wide application prospect in the aspect of large-scale energy storage.
Example 2:
rechargeable battery with long service life and high energy densityThe positive active material of the zinc ion battery adopts L i0.33V2O5The nanowire material has a negative electrode made of zinc sheets, a diaphragm made of glass fiber, and electrolyte of 3 mol/L zinc sulfate, and the preparation method comprises the following steps:
(1)Li0.33V2O5preparation of positive plate
Dissolving binder polyvinylidene fluoride (PVDF) or Polytetrafluoroethylene (PTFE) in N-methylpyrrolidone (NMP) to obtain clear solution, and adding L i0.33V2O5The materials are uniformly ground and added into the solution (according to the active substance, acetylene black and adhesive, the ratio is 7:2:1), ultrasonic dispersion is carried out, slurry is prepared, the slurry is uniformly coated on a titanium foil with the thickness of 0.05mm, the thickness of the coating layer is 150 mu m, and the positive plate is prepared by vacuum drying.
(2) Preparation of the electrolyte
A certain amount of zinc sulfate salt is dissolved in deionized water to prepare electrolyte with the concentration of 3 mol/L.
(3) Preparation of negative plate
And (3) polishing the metal zinc sheet by using sand paper, washing the metal zinc sheet for several times by using alcohol and acetone, and blanking to obtain a circular sheet with the diameter of 12mm as a negative plate.
(4) Assembly of aqueous zinc ion battery
And (3) separating the positive plate prepared in the step (1) and the negative plate prepared in the step (3) by using a glass fiber membrane with the thickness of 0.2mm, placing the separated positive plate and the negative plate into a battery case, then respectively injecting zinc sulfate salt with the concentration of 3 mol/L, and finally packaging the obtained product into a button battery, as shown in figure 3.
L i prepared in example 20.33V2O5The nanowire material is used as a positive electrode active material of a zinc ion battery and shows excellent electrochemical performance. As shown in FIG. 4, at current densities of 0.1, 0.2, 0.5, 0.8, 1.0 and 2.0Ag-1Constant current charge and discharge tests are carried out, and the discharge capacities are 362.2, 254.6, 172.5, 141.7, 138.2 and 100.4mA h g-1And excellent rate performance is shown.
Example 3:
long-life high energy densityThe positive active material of the rechargeable zinc ion battery adopts Na0.33V2O5The nanowire material has a negative electrode made of zinc sheets, a diaphragm made of glass fiber, and electrolyte of 3 mol/L zinc sulfate, and the preparation method comprises the following steps:
(1)Na0.33V2O5preparation of positive plate
Dissolving binder polyvinylidene fluoride (PVDF) or Polytetrafluoroethylene (PTFE) in N-methylpyrrolidone (NMP) to obtain clear solution, adding a certain amount of Na0.33V2O5The materials are uniformly ground and added into the solution (according to the active substance, acetylene black and adhesive, the ratio is 7:2:1), ultrasonic dispersion is carried out, slurry is prepared, the slurry is uniformly coated on a titanium foil with the thickness of 0.05mm, the thickness of the coating layer is 150 mu m, and the positive plate is prepared by vacuum drying.
(2) Preparation of the electrolyte
A certain amount of zinc sulfate salt is dissolved in deionized water to prepare electrolyte with the concentration of 3 mol/L, and 0.01 mol/L vanadyl sulfate solution is also added.
(3) Preparation of negative plate
And (3) polishing the metal zinc sheet by using sand paper, washing the metal zinc sheet for several times by using alcohol and acetone, and blanking to obtain a circular sheet with the diameter of 12mm as a negative plate.
(4) Assembly of aqueous zinc ion battery
And (3) separating the positive plate prepared in the step (1) and the negative plate prepared in the step (3) by using a glass fiber membrane with the thickness of 0.2mm, placing the separated positive plate and the negative plate into a battery shell, then respectively injecting zinc sulfate salt with the concentration of 3 mol/L, and finally packaging the zinc sulfate salt and the zinc sulfate salt into a flexible package battery, wherein the components are shown in figure 5.
Na prepared in example 30.33V2O5The nanowire material is used as a positive electrode active material of a zinc ion battery and shows excellent electrochemical performance. As shown in FIG. 6, at 1.0Ag-1The discharge specific capacity can reach 212.4mAh g after the test is carried out for 1000 times of circulation-1The capacity retention rate is higher than 92%, and excellent cycle performance is shown.

Claims (3)

1.A rechargeable aqueous zinc ion battery comprises a positive electrode, a negative electrode, a diaphragm between the positive electrode and the negative electrode, and an electrolyte containing anions and cations and having ion conductivity, wherein the active material of the positive electrode is Na0.33V2O5The electrolyte is a liquid or gel material with ionic conductivity and the concentration of 3 mol/L, wherein zinc sulfate salt is used as a solute, water is used as a solvent, and an additive in the electrolyte is 0.01 mol/L vanadyl sulfate solution.
2. The rechargeable aqueous zinc-ion battery of claim 1, wherein: the diaphragm is a glass fiber diaphragm, filter paper or polytetrafluoroethylene diaphragm with excellent wettability.
3. The rechargeable aqueous zinc-ion battery of claim 1, wherein: the active material of the negative electrode adopts a metal zinc sheet, zinc powder or a zinc-carbon compound.
CN201710369663.4A 2017-05-23 2017-05-23 Rechargeable aqueous zinc ion battery Active CN107221716B (en)

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CN108448168B (en) * 2018-03-14 2021-01-15 华中科技大学 Electrolyte for water-based zinc ion secondary battery and preparation method and application thereof
CN110364771A (en) * 2018-04-10 2019-10-22 中国科学院上海硅酸盐研究所 A kind of water system zinc ion soft-package battery and preparation method thereof
CN110391415A (en) * 2018-04-20 2019-10-29 中国科学院福建物质结构研究所 A kind of positive electrode active materials and the Zinc ion battery including the positive electrode active materials
CN108767215B (en) * 2018-05-15 2021-03-26 华中科技大学 Material for inhibiting zinc dendrite and preparation method and application thereof
CN108832062A (en) * 2018-06-13 2018-11-16 深圳市寒暑科技新能源有限公司 A kind of Zinc ion battery diaphragm and preparation method thereof
CN108878877B (en) * 2018-07-03 2021-01-05 中国科学院宁波材料技术与工程研究所 Positive electrode active material for aqueous zinc ion secondary battery and aqueous zinc ion secondary battery
CN110707268A (en) * 2019-04-24 2020-01-17 中南大学 SiO (silicon dioxide)2-polymer composite water-based battery diaphragm material and preparation method and application thereof
CN110474044A (en) * 2019-09-05 2019-11-19 山东大学 A kind of high-performance water system Zinc ion battery positive electrode and the preparation method and application thereof
CN111659407A (en) * 2020-05-30 2020-09-15 河南省计量科学研究院 Zinc ion doped transition metal vanadate nanowire photocatalyst and preparation method thereof

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