CN110391415A - A kind of positive electrode active materials and the Zinc ion battery including the positive electrode active materials - Google Patents

A kind of positive electrode active materials and the Zinc ion battery including the positive electrode active materials Download PDF

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Publication number
CN110391415A
CN110391415A CN201810362531.3A CN201810362531A CN110391415A CN 110391415 A CN110391415 A CN 110391415A CN 201810362531 A CN201810362531 A CN 201810362531A CN 110391415 A CN110391415 A CN 110391415A
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China
Prior art keywords
positive electrode
electrode active
active materials
ion battery
zinc ion
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CN201810362531.3A
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Inventor
孙传福
付浴茹
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Fujian Institute of Research on the Structure of Matter of CAS
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Fujian Institute of Research on the Structure of Matter of CAS
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Priority to CN201810362531.3A priority Critical patent/CN110391415A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/42—Alloys based on zinc
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • 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 present invention provides a kind of positive electrode active materials and including the Zinc ion battery of the positive electrode active materials；The present invention uses K2‑ 2XZnXV3O8(0≤X≤1) is positive electrode active materials, is zinc ion in K using metal ion as pillar2‑2XZnXV3O8Reversible de-, the embedding offer space of (0≤X≤1) interlayer, in charge and discharge process, structure remained stable, to improve the stability of Zinc ion battery.Using K2‑2XZnXV3O8(0≤X≤1) is positive electrode active materials, and zinc is cathode, and the soluble-salt containing zinc is that the Zinc ion battery of electrolyte has the characteristics that long-life, high capacity, high stability.The experiment proved that Zinc ion battery of the invention also has excellent high rate performance, reversibility and cycle performance.It holds out broad prospects in energy storage field.

Description

A kind of positive electrode active materials and the Zinc ion battery including the positive electrode active materials
Technical field
The invention belongs to battery technology fields, and in particular to a kind of positive electrode active materials and including the positive electrode active materials Zinc ion battery.
Background technique
Rechargeable battery is widely used in various electronic equipments, currently, commercialized lithium ion battery accounts on the market Leading position, still, limited lithium resource and the shortage that will lead to lithium resource to the wilderness demand of lithium ion battery are compeled to be essential Develop rechargeable battery of new generation.Zinc ion battery has the advantages that cheap, capacity is high, and environmental pollution is small and is considered It is one of most promising rechargeable battery of new generation.
Zinc ion battery zinc ion in charging is deviate from from anode, deposits in negative terminal surface；When electric discharge, cathode zinc is lost Electronics becomes zinc ion, is embedded into anode.In existing Zinc ion battery, negative electrode material is usually the material that main body is Zn-ef ficiency Material, the theoretical specific capacity of zinc are 819.8mAh/g；And presently, there are positive electrode its specific capacity be far smaller than the theoretical ratio of zinc Capacity.
A kind of oxide based on trivalent or tetravalent manganese is disclosed in Chinese invention patent application CN101783419A is Anode, using zinc as cathode, using the solution containing zinc ion as the Rechargeable zinc ion battery of electrolyte, when with manganese dioxide be anode When, battery specific capacity is close to 190mAh/g.
Disclosed in Chinese invention patent application CN102110858A it is a kind of with the oxide of vanadium or its hyrate for anode, Using zinc as cathode, using the aqueous solution of the soluble-salt of zinc as the Rechargeable zinc ion battery of electrolyte, it is positive when with vanadium dioxide When pole, charge and discharge under 250mA/g constant current, battery specific capacity is 300mAh/g.
It can thus be seen that the performance of Zinc ion battery is influenced by positive electrode, the positive material of function admirable is found Material can be effectively improved the performance of Zinc ion battery, provide solution for extensive energy storage.
Summary of the invention
In order to improve the deficiencies in the prior art, just the object of the present invention is to provide a kind of positive electrode active materials and including this The Zinc ion battery of pole active material；The present invention uses K2-2XZnXV3O8(0≤X≤1) is positive electrode active materials, metal therein Ion can be used as pillar, in charge and discharge process, structure remained stable, to improve the stability of Zinc ion battery.And Potassium, vanadium and zinc resource are abundant, can reduce the cost of material.The present invention uses K2-2XZnXV3O8(0≤X≤1) is positive-active material Material, zinc is cathode, the soluble-salt containing zinc be electrolyte Zinc ion battery during long-time charge and discharge cycles battery hold Amount keeps stablizing, and has the characteristics that long-life, high capacity, high stability.
Object of the present invention is to what is be achieved through the following technical solutions:
A kind of positive electrode active materials, chemical formula K2-2XZnXV3O8；Wherein, 0≤X≤1.
The present invention also provides a kind of anodes comprising above-mentioned positive electrode active materials.
Wherein, the anode includes that positive membrane carrier and cathode film, the cathode film are overlying on cathode film carrier surface, institute Stating cathode film includes above-mentioned positive electrode active materials.
Wherein, the cathode film further includes conductive agent carbon material.
Wherein, the cathode film further includes binder.
Wherein, the conductive agent carbon material is selected from graphite, carbon black, unformed charcoal, active carbon, acetylene black, graphene, carbon and receives One of mitron is a variety of.
Wherein, the binder is the conventional binders being used in electrode as known to those skilled in the art, illustratively, The binder is selected from one of Kynoar, hydroxymethyl cellulose, polyacrylic acid, Sodium Polyacrylate or a variety of.
Wherein, the positive membrane carrier is selected from filter paper or common Zinc ion battery plus plate current-collecting body.
Wherein, it is more than or equal to 50wt% that the positive electrode active materials, which account for the mass percent of the cathode film,.
Wherein, it is less than 50wt% that the conductive agent carbon material, which accounts for the mass percent of the cathode film,.
Preferably, the positive electrode active materials account for the cathode film mass percent be more than or equal to 70wt%, it is described The mass percent that conductive agent carbon material accounts for the cathode film is less than 30wt%, and surplus is binder.
The present invention also provides a kind of Zinc ion batteries comprising above-mentioned anode.
Wherein, the Zinc ion battery further includes the cathode containing Zn element, the diaphragm between positive and negative anodes and leaching Moisten the electrolyte of the positive electrode, the negative electrode and the separator.
Wherein, the cathode containing Zn element is selected from metallic zinc, or apply selected from kirsite or zinc powder/it is deposited on conduction Metallic zinc in substrate.
Wherein, the conductive substrates are the conventional use of conduction suitable for Zinc ion battery of those skilled in the art Substrate, illustratively, the conductive substrates are selected from titanium foil, molybdenum foil, carbon cloth, at least one of graphite.
Wherein, the solute of the electrolyte is ZnSO4、Zn(NO3)2、ZnCl2、Zn(CF3SO3)2、Zn(TFSI)2Etc. solvable One of property zinc salt is a variety of.
Wherein, the solvent of the electrolyte is the conventional nonaqueous solvents of water or this field for Zinc ion battery, such as second Nitrile.
Wherein, the concentration of zinc ion is 0.1-5mol/L in the electrolyte.
Wherein, the diaphragm is the conventional separator for being used to prepare Zinc ion battery as known to those skilled in the art.
Wherein, the Zinc ion battery can be made button, column type or square structure.
Beneficial effects of the present invention:
The present invention provides a kind of positive electrode active materials and including the Zinc ion battery of the positive electrode active materials；The present invention Using K2-2XZnXV3O8(0≤X≤1) is positive electrode active materials, is zinc ion in K using metal ion as pillar2-2XZnXV3O8 Reversible de-, the embedding offer space of (0≤X≤1) interlayer, in charge and discharge process, structure remained stable, to improve Zinc ion battery Stability.Using K2-2XZnXV3O8(0≤X≤1) is positive electrode active materials, and zinc is cathode, and the soluble-salt containing zinc is electrolysis The Zinc ion battery of liquid has the characteristics that long-life, high capacity, high stability.The experiment proved that Zinc ion battery of the invention Also there is excellent high rate performance, reversibility and cycle performance.It holds out broad prospects in energy storage field.
Detailed description of the invention
Fig. 1 is for Rechargeable zinc ion battery made from embodiment 1 (with positive electrode active materials quality under different current densities Calculate) energy density-power density diagram.
Fig. 2 is Rechargeable zinc ion battery made from embodiment 1 in 10mA/g (with positive electrode active materials Mass Calculation) electricity Voltage-specific capacity curve graph under current density.
Fig. 3 is Rechargeable zinc ion battery made from embodiment 1 in 1500mA/g (with positive electrode active materials Mass Calculation) Charge and discharge cycles curve graph under current density.
Fig. 4 is Rechargeable zinc ion battery made from embodiment 2 in 300mA/g (with positive electrode active materials Mass Calculation) electricity Charge and discharge cycles curve graph under current density.
Fig. 5 is Rechargeable zinc ion battery made from embodiment 3 in 300mA/g (with positive electrode active materials Mass Calculation) electricity Charge and discharge cycles curve graph under current density.
Specific embodiment
Further detailed description is done to preparation method of the invention below in conjunction with specific embodiment.It should be appreciated that The following example is merely illustrative the ground description and interpretation present invention, and is not necessarily to be construed as limiting the scope of the invention. In the range of all technologies realized based on above content of the present invention are encompassed by the present invention is directed to protect.
Experimental method used in following embodiments is conventional method unless otherwise specified；Institute in following embodiments Reagent, material etc., are commercially available unless otherwise specified.
The positive active material K occurred in following embodiments2V3O8(X=0) and positive active material K2-2XZnXV3O8(0<X ≤ 1) prepare bibliography: Journal of Crystal Growth 260 (2004) 447-450.
Illustratively, the positive active material K2-2XZnXV3O8Preparing for (0 < X≤1) is as described below:
KOH, ZnO, V of corresponding mol ratio are taken by the molar ratio of K, Zn, V in chemical formula2O5It is placed in autoclave, adds Enter the dehydrated alcohol of 60% reaction kettle volume, 200 DEG C of reaction 48h can by product centrifugation, washing after reaction kettle natural cooling Obtain the positive active material.
Embodiment 1
By positive active material K2V3O8, the conductive agent carbon material graphene and carbon nanotube of 1:1 (mass ratio be) is with 70: 30 mass ratio after mixing, filters film forming, and vacuum drying is simultaneously cut into a certain size, and it is conventional filter that anode membrane carrier, which is made, Paper, cathode film are the electrode slice of positive active material and conductive agent carbon material.
It is anode with above-mentioned electrode slice, zinc metal is cathode, the Zn (CF of 3mol/L3SO3)2Aqueous solution is electrolyte group Dress up Rechargeable zinc ion battery.
After tested, energy density-power density of the obtained Rechargeable zinc ion battery under different current densities be such as Shown in Fig. 1；In Fig. 1 the representative current density of each point test be followed successively by 10 from right to left, 30,50,100,300,500,1500, 3000,4000mA/g (with positive electrode active materials Mass Calculation)；As seen from Figure 1, energy density is in 96-273Wh/Kg model It encloses, power density is in 8.5-2600W/Kg.
Electricity of the Rechargeable zinc ion battery obtained under 10mA/g (with positive electrode active materials Mass Calculation) current density Pressure-specific capacity curve is as shown in Figure 2；As seen from Figure 2, under the current density, specific discharge capacity is put down up to 323mAh/g Equal discharge voltage plateau is 0.75V；
Rechargeable zinc ion battery obtained is under 1500mA/g (with positive electrode active materials Mass Calculation) current density Charge and discharge cycles curve is as shown in Figure 3；As seen from Figure 3, under the current density, specific discharge capacity is reached as high as 201mAh/g, after 10000 circle of circulation, specific discharge capacity 100.4mAh/g, coulombic efficiency is close to 100%.Show the anode material Material good reversibility in charge and discharge process, has extended cycle life.
Embodiment 2
By positive active material K2V3O8, conductive agent carbon material (acetylene black), binder (Kynoar) is with 80:10:10 Mass ratio after mixing, be coated on collector (titanium foil) on, vacuum drying is simultaneously cut into a certain size, be made anode membrane carrier For titanium foil, cathode film is that positive active material is K2V3O8, conductive agent carbon material is acetylene black and binder is Kynoar Electrode slice.
It is anode with above-mentioned electrode slice, zinc metal is cathode, the Zn (CF of 3mol/L3SO3)2Aqueous solution is electrolyte group Dress up Rechargeable zinc ion battery.
After tested, obtained Rechargeable zinc ion battery is in 300mA/g (with positive electrode active materials Mass Calculation) electric current Multiple charge and discharge cycles curve is as shown in Figure 4 under density；As seen from Figure 4, under the current density, specific discharge capacity highest Up to 139mAh/g, charging and discharging curve is overlapped, coulombic efficiency 100%, and after 100 circle of circulation, protecting capacity rate is 94.8%.Show this Positive electrode good reversibility in charge and discharge process.
Embodiment 3
By positive active material K2-2XZnXV3O8(X=0.5), (mass ratio is the graphene and carbon of 1:1 to conductive agent carbon material Nanotube) with the mass ratio of 70:30 after mixing, filter film forming, vacuum drying is simultaneously cut into a certain size, and cathode film is made and carries Body is conventional filter paper, and cathode film is positive active material K2-2XZnXV3O8(X=0.5) and the electrode slice of conductive agent carbon material.
It is anode with above-mentioned electrode slice, zinc metal is cathode, the Zn (CF of 3mol/L3SO3)2Aqueous solution is electrolyte group Dress up Rechargeable zinc ion battery.
After tested, obtained Rechargeable zinc ion battery is in 300mA/g (with positive electrode active materials Mass Calculation) electric current Multiple charge and discharge cycles curve is as shown in Figure 5 under density；As seen from Figure 5, under the current density, specific discharge capacity highest Up to 230.6mAh/g, after 1000 circle of circulation, specific discharge capacity 192.4mAh/g, coulombic efficiency is close to 100%.Show this just Pole material good reversibility in charge and discharge process, has extended cycle life.
More than, embodiments of the present invention are illustrated.But the present invention is not limited to above embodiment.It is all Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in guarantor of the invention Within the scope of shield.

Claims (10)

1. a kind of positive electrode active materials, which is characterized in that the chemical formula of the positive electrode active materials is K2-2XZnXV3O8；Wherein, 0 ≤X≤1。
2. a kind of anode, which is characterized in that the anode includes positive electrode active materials described in claim 1.
3. anode according to claim 2, which is characterized in that the anode includes positive membrane carrier and cathode film, described Cathode film is overlying on cathode film carrier surface, and the cathode film includes positive electrode active materials described in claim 1.
4. anode according to claim 3, which is characterized in that the cathode film further includes conductive agent carbon material.
Preferably, the conductive agent carbon material is selected from graphite, carbon black, unformed charcoal, active carbon, acetylene black, graphene, carbon nanometer One of pipe is a variety of.
5. anode according to claim 3 or 4, which is characterized in that the cathode film further includes binder.
Preferably, the binder is selected from one of Kynoar, hydroxymethyl cellulose, polyacrylic acid, Sodium Polyacrylate Or it is a variety of.
Preferably, the positive membrane carrier is selected from filter paper or Zinc ion battery plus plate current-collecting body.
6. according to the described in any item anodes of claim 3-5, which is characterized in that the positive electrode active materials account for the cathode film Mass percent be more than or equal to 50wt%.
Preferably, it is less than 50wt% that the conductive agent carbon material, which accounts for the mass percent of the cathode film,.
Preferably, it is more than or equal to 70wt%, the conduction that the positive electrode active materials, which account for the mass percent of the cathode film, The mass percent that agent carbon material accounts for the cathode film is less than 30wt%, and surplus is binder.
7. a kind of Zinc ion battery comprising the described in any item anodes of claim 2-6.
8. Zinc ion battery according to claim 7, which is characterized in that the Zinc ion battery further includes containing Zn-ef ficiency Cathode, the diaphragm between positive and negative anodes and infiltrate the positive electrode, the negative electrode and the separator electrolyte.
9. Zinc ion battery according to claim 8, which is characterized in that the cathode containing Zn-ef ficiency is selected from metal Zinc, or the metallic zinc in conductive substrates is applied/is deposited on selected from kirsite or zinc powder.
Preferably, the conductive substrates are selected from least one of titanium foil, molybdenum foil, carbon cloth, graphite.
10. Zinc ion battery according to claim 8 or claim 9, which is characterized in that the solute of the electrolyte is ZnSO4、Zn (NO3)2、ZnCl2、Zn(CF3SO3)2、Zn(TFSI)2One of or it is a variety of.
Preferably, the concentration of zinc ion is 0.1-5mol/L in the electrolyte.
CN201810362531.3A 2018-04-20 2018-04-20 A kind of positive electrode active materials and the Zinc ion battery including the positive electrode active materials Pending CN110391415A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
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CN112952047A (en) * 2019-12-10 2021-06-11 中国科学院大连化学物理研究所 Preparation method of carbon-loaded potassium vanadate and application of carbon-loaded potassium vanadate in potassium ion battery
CN113437368A (en) * 2021-06-16 2021-09-24 江苏大学 Method for improving capacity of anode material of water-based zinc ion battery based on static activation reaction
CN113839031A (en) * 2020-06-24 2021-12-24 中国科学院福建物质结构研究所 Positive active material and application thereof in zinc ion battery

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CN107311230A (en) * 2017-06-30 2017-11-03 武汉理工大学 Nano wire nano material containing the crystallization water and its preparation method and application

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Cited By (6)

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Publication number Priority date Publication date Assignee Title
CN112952047A (en) * 2019-12-10 2021-06-11 中国科学院大连化学物理研究所 Preparation method of carbon-loaded potassium vanadate and application of carbon-loaded potassium vanadate in potassium ion battery
CN112952047B (en) * 2019-12-10 2022-11-08 中国科学院大连化学物理研究所 Preparation method of carbon-loaded potassium vanadate and application of carbon-loaded potassium vanadate in potassium ion battery
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CN113437368A (en) * 2021-06-16 2021-09-24 江苏大学 Method for improving capacity of anode material of water-based zinc ion battery based on static activation reaction
CN113437368B (en) * 2021-06-16 2022-08-23 江苏大学 Method for improving capacity of anode material of water-based zinc ion battery based on static activation reaction

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