CN111509295B - Solid electrolyte of zinc ion battery - Google Patents

Solid electrolyte of zinc ion battery Download PDF

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Publication number
CN111509295B
CN111509295B CN202010368653.0A CN202010368653A CN111509295B CN 111509295 B CN111509295 B CN 111509295B CN 202010368653 A CN202010368653 A CN 202010368653A CN 111509295 B CN111509295 B CN 111509295B
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zinc
solid electrolyte
ion battery
bromide
chloride
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CN111509295A (en
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高超
褚星远
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Hangzhou Gaoxi Technology Co Ltd
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Hangzhou Gaoxi Technology Co Ltd
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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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • 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
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Primary Cells (AREA)

Abstract

The invention discloses zincThe solid electrolyte of the ion battery is obtained by processing a zinc chloride-zinc bromide-zinc acetate ternary system at high temperature. The solid electrolyte has high ion conductivity (10)‑6S m‑1) The zinc ion solid-state battery is assembled, and the specific capacity of the positive electrode can reach 40mAh g‑1. The solid electrolyte is simple to prepare, has low cost and is expected to be applied in the field of energy storage.

Description

Solid electrolyte of zinc ion battery
Technical Field
The invention relates to a zinc ion battery solid electrolyte and a zinc ion solid battery using the electrolyte.
Background
Solid electrolytes are a class of solid materials with ionic conductivity that can be used as electrolytes in batteries. Compared with the traditional liquid electrolyte, the solid electrolyte is not easy to burn and short circuit, and has the advantage of higher safety. The solid electrolytes commonly used are inorganic salts whose conductivity results from the shuttling of smaller ions (e.g., lithium ions) into the interstitial spaces.
Zinc ion batteries are a type of battery with potential. The zinc metal has high theoretical specific capacity (820mAh g)-1) And a rich source. There is no report of using a solid electrolyte (excluding a gel electrolyte) for a zinc ion battery.
Disclosure of Invention
The invention discloses a solid electrolyte of a zinc ion battery, which is obtained by processing a zinc chloride-zinc bromide-zinc acetate ternary system at high temperature. The zinc chloride-zinc bromide-zinc acetate ternary system is prepared by the following method: adding zinc chloride, zinc bromide and zinc acetate into dispersed water, heating for dissolving, and cooling to obtain the salt with the total concentration of 60-100 mol kg-1The ternary system of zinc chloride, zinc bromide and zinc acetate. Wherein the concentration range of the zinc chloride is 20-30 mol kg-1The concentration range of the zinc bromide is 20-30 mol kg-1The concentration range of the zinc acetate is 20-40 mol kg-1. The high-temperature treatment is heating treatment at 160-180 ℃.
Furthermore, the positive electrode of the zinc ion battery is made of carbon material, and the negative electrode is made of metal zinc, zinc-containing alloy or other inert conductive substrates capable of loading zinc.
Further, the carbon material includes carbon nanotubes, natural graphite, expanded graphite, graphene assemblies, and other carbon materials having a graphite lattice structure.
The invention has the beneficial effects that the invention provides the solid electrolyte of the zinc ion battery, and the conductivity of the solid electrolyte reaches 10-6S m-1. Solves the technical bottleneck of the zinc ion solid-state battery, and leads the zinc ion to be separatedA sub-solid state battery becomes possible. Compared with other solid batteries, the zinc ion solid battery based on the electrolyte has the characteristics of low cost and simple preparation.
Drawings
FIG. 1 is a photograph of a solid electrolyte obtained by treating an aqueous gel of zinc chloride, zinc bromide and zinc acetate at a total concentration of 60mol kg-1 at 180 ℃.
Detailed Description
The invention takes zinc chloride, zinc bromide, zinc acetate and deionized water with wide sources as raw materials, firstly prepares a ternary system, and then prepares the solid electrolyte by processing the ternary system at high temperature.
The preparation of the high-concentration ternary system is the basis for obtaining the solid electrolyte, the invention inhibits the crystallization process and enables inorganic ions in the system to form three-dimensional inorganic macromolecules based on the end-capping effect, the obtained colloidal body has the property similar to hydrogel, the ternary system is placed in a strain bottle, and the ternary system can not flow after being inverted.
In the present invention, unless otherwise specified, the concentration is expressed by solute-solvent ratio, and is 60 to 100mol kg-1The amount of solute dissolved in water is 60-100 mol per kilogram.
The present invention is described in detail by the following embodiments, which are only used for further illustration of the present invention and should not be construed as limiting the scope of the present invention, and the non-essential changes and modifications made by the person skilled in the art according to the above disclosure are all within the scope of the present invention.
Example 1:
(1) sequentially adding 0.2mol of zinc chloride, 0.2mol of zinc bromide and 0.2mol of zinc acetate into 10g of deionized water, heating to 120 ℃ for dissolution, and naturally cooling to room temperature to obtain 60mol kg of total concentration-1The zinc chloride-zinc bromide-zinc acetate aqueous colloid.
(2) The colloidal body obtained in step 1 was heated at 180 ℃ for 5 minutes and cooled to obtain a solid electrolyte, as shown in FIG. 1.
(3) And (3) heating the colloidal body obtained in the step (1) at 180 ℃ for 5 minutes, pouring the colloidal body on a polytetrafluoroethylene film, covering a second polytetrafluoroethylene film on the polytetrafluoroethylene film, pressing an iron block, and cooling to obtain a sheet with the thickness of 0.1 mm.
(4) The sheet conductivity was found to be 10-6S m-1. The test method comprises the following steps: the titanium foil, the solid electrolyte sheet and the titanium foil were sequentially stacked in a Swaglok cell mold and heat-sealed under pressure. The resistance is measured by using an alternating current impedance method, and the conductivity is calculated.
(5) And (3) sequentially overlapping the zinc cathode, the solid electrolyte sheet and the graphene film anode into a battery mould for pressurization and heat sealing. The obtained battery cell is 0.1A g-1The specific mass capacity is 40mAh g at the current density of (2)-1(calculated based on the positive electrode active material).
In step 3 of this embodiment, the solid obtained in step 2 may be reheated to 160-200 ℃, and poured and molded after melting.
Example 2:
(1) sequentially adding 0.3mol of zinc chloride, 0.3mol of zinc bromide and 0.4mol of zinc acetate into 10g of deionized water, heating to 130 ℃ for dissolution, and naturally cooling to room temperature to obtain 100mol kg of total concentration-1The zinc chloride-zinc bromide-zinc acetate aqueous colloid.
(2) And (3) heating the colloidal body obtained in the step (1) at 180 ℃ for 5 minutes, pouring the colloidal body on a polytetrafluoroethylene film, covering a second polytetrafluoroethylene film on the polytetrafluoroethylene film, pressing an iron block, and cooling to obtain a sheet with the thickness of 0.1 mm.
(3) The conductivity was found to be 8X 10-7S m-1。
(4) And sequentially overlapping the zinc cathode, the solid electrolyte sheet and the expanded graphite anode into a battery mould for pressurization and heat sealing. The obtained battery cell is 0.1A g-1The specific mass capacity is 30mAh g at the current density of (2)-1(calculated based on the positive electrode active material).
Example 3:
(1) sequentially adding 0.2mol of zinc chloride, 0.2mol of zinc bromide and 0.2mol of zinc acetate into 10g of deionized water, heating to 120 ℃ for dissolution, and naturally cooling to room temperature to obtain 60mol kg of total concentration-1Zinc chloride-bromine ofZinc oxide-zinc acetate aqueous colloid.
(2) And (3) heating the colloidal body obtained in the step (1) at 160 ℃ for 10 minutes, pouring the colloidal body on a polytetrafluoroethylene film, covering a second polytetrafluoroethylene film on the polytetrafluoroethylene film, pressing an iron block, and cooling to obtain a sheet with the thickness of 0.1 mm.
(3) Measured to have a conductivity of 10-6S m-1。
(4) And (3) sequentially overlapping the zinc cathode, the solid electrolyte sheet and the graphene film anode into a battery mould for pressurization and heat sealing. The obtained battery cell is 0.1A g-1The specific mass capacity is 38mAh g at the current density of (2)-1(calculated based on the positive electrode active material).
Example 4:
(1) sequentially adding 0.3mol of zinc chloride, 0.3mol of zinc bromide and 0.4mol of zinc acetate into 10g of deionized water, heating to 120 ℃ for dissolution, and naturally cooling to room temperature to obtain 100mol kg of total concentration-1The zinc chloride-zinc bromide-zinc acetate aqueous colloid.
(2) Heating the colloidal body obtained in the step 1 at 200 ℃ for 1 minute, pouring the colloidal body on a polytetrafluoroethylene film, covering a second layer of the polytetrafluoroethylene film on the colloidal body, pressing an iron block, and cooling to obtain a sheet with the thickness of 0.1 mm.
(3) The conductivity was measured to be 6X 10-7S m-1。
(4) And sequentially overlapping the zinc cathode, the solid electrolyte sheet and the natural graphite anode into a battery mould for pressurization and heat sealing. The obtained battery cell is 0.1A g-1The specific mass capacity is 2mAh g at the current density of (2)-1。

Claims (3)

1. A zinc ion battery solid electrolyte is characterized in that the electrolyte is obtained by processing a zinc chloride-zinc bromide-zinc acetate ternary system at high temperature; the zinc chloride-zinc bromide-zinc acetate ternary system is prepared by the following method: adding zinc chloride, zinc bromide and zinc acetate into dispersed water, heating for dissolving, and cooling to obtain the salt with the total concentration of 60-100 mol kg-1The ternary system of zinc chloride, zinc bromide and zinc acetate; wherein the concentration range of the zinc chloride is 20-30 mol kg-1The concentration range of the zinc bromide is 20-30 mol kg-1The concentration range of the zinc acetate is 20-40 mol kg-1(ii) a The high-temperature treatment is heating at 160-200 ℃ for 1-10 min.
2. A zinc ion battery comprising the solid electrolyte of claim 1, wherein the positive electrode of the zinc ion battery is a carbon material and the negative electrode is metallic zinc, a zinc-containing alloy or an inert conductive substrate capable of supporting zinc.
3. The zinc-ion battery of claim 2, wherein the carbon material comprises carbon nanotubes, natural graphite, expanded graphite, graphene, and other carbon materials having a graphite lattice structure.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105336952A (en) * 2015-10-15 2016-02-17 中国科学院青岛生物能源与过程研究所 Sodium zinc double-ion chargeable cell
CN108172833A (en) * 2017-12-26 2018-06-15 深圳先进技术研究院 Zinc-base Dual-ion cell and preparation method thereof
CN110190344A (en) * 2019-06-13 2019-08-30 深圳市寒暑科技新能源有限公司 A kind of flexibility water system Zinc ion battery
WO2020076985A1 (en) * 2018-10-10 2020-04-16 Oregon State University Aqueous zinc-metal batteries comprising "water-in-salt" electrolyte

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8950862B2 (en) * 2011-02-28 2015-02-10 Johnson & Johnson Vision Care, Inc. Methods and apparatus for an ophthalmic lens with functional insert layers

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105336952A (en) * 2015-10-15 2016-02-17 中国科学院青岛生物能源与过程研究所 Sodium zinc double-ion chargeable cell
CN108172833A (en) * 2017-12-26 2018-06-15 深圳先进技术研究院 Zinc-base Dual-ion cell and preparation method thereof
WO2020076985A1 (en) * 2018-10-10 2020-04-16 Oregon State University Aqueous zinc-metal batteries comprising "water-in-salt" electrolyte
CN110190344A (en) * 2019-06-13 2019-08-30 深圳市寒暑科技新能源有限公司 A kind of flexibility water system Zinc ion battery

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