CN111934003A - Method for inducing AgBr super-ionic state - Google Patents

Method for inducing AgBr super-ionic state Download PDF

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Publication number
CN111934003A
CN111934003A CN202010816208.6A CN202010816208A CN111934003A CN 111934003 A CN111934003 A CN 111934003A CN 202010816208 A CN202010816208 A CN 202010816208A CN 111934003 A CN111934003 A CN 111934003A
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agbr
sample
super
temperature
sample cavity
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王佳
闫雅兰
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Jilin Teachers Institute of Engineering and Technology
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Jilin Teachers Institute of Engineering and Technology
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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
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B12/00—Superconductive or hyperconductive conductors, cables, or transmission lines
    • 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
    • Y02E40/00—Technologies for an efficient electrical power generation, transmission or distribution
    • Y02E40/60—Superconducting electric elements or equipment; Power systems integrating superconducting elements or equipment
    • 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)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)

Abstract

The invention discloses a method for inducing an AgBr super ionic state, which belongs to the technical field of ionic conductors and is carried out in a diamond anvil cell, wherein an AgBr sample is mechanically ground for 1 hour by using an agate mortar, so that the grains of the powder sample are refined, the powder sample is placed into a sample cavity, the pressure of 0.6GPa is applied to the interior of the sample cavity, then the sample cavity is placed into a muffle furnace, and the muffle furnace is heated to 473K-503K to induce the AgBr super ionic state. The invention simultaneously applies pressure and temperature to the material, so that the super-ionic state transition temperature of the material is reduced by 82K compared with the traditional method, and the invention also has the advantages of simple operation, controllable experimental conditions and the like.

Description

Method for inducing AgBr super-ionic state
Technical Field
The invention belongs to the technical field of ionic conductors, and particularly relates to a method for inducing an AgBr super-ionic state.
Background
Conventional ion batteries use liquid electrolyte as a medium for the intercalation and deintercalation of ions between positive and negative electrodes. The stability of the liquid electrolyte is very sensitive to factors such as the use environment, the charging voltage, the charging time and the like, and once the safety use conditions are exceeded, a series of safety problems such as spontaneous combustion and even explosion can be caused. The solid electrolyte is adopted to replace the traditional liquid electrolyte to prepare a new generation of solid ion battery, and the potential safety hazard problem can be effectively solved.
The super ionic conductor is an ideal solid electrolyte material, and the ionic conductivity can reach the range of liquid electrolyte (more than or equal to 0.01S/cm) under certain conditions. Only the super ionic conductor with high ionic conductivity can provide rapid migration of ions, and the cycle performance of the solid-state ion battery is improved. However, high ionic conductivity is generally obtained under high temperature conditions. The solid-state ion battery under high-temperature operation needs special design, and the components such as the battery anode, the battery cathode, the battery diaphragm and the like need to be made of high-temperature resistant materials, so that the preparation cost is high. In addition, there is a great safety risk in operating the solid-state ion battery in a higher temperature environment. Therefore, it is of great significance to lower the transition temperature of the super-ionic state of the solid electrolyte.
AgBr is a typical super-ion conductor material, and the super-ion state transition temperature under the high-temperature condition is 555K. The traditional method for reducing the transition temperature of the AgBr super-ionic state is chemical doping, but the chemical doping method needs to accurately control the chemical proportion and reaction conditions of reactants, and has high experimental operation difficulty and low result controllability.
Disclosure of Invention
In view of this, the technical problem to be solved by the present invention is to provide a novel method for inducing AgBr super-ionic state, which overcomes the shortcomings of the background art.
The specific technical scheme of the invention is as follows:
a method for inducing the super-ionic state of AgBr is carried out in a diamond anvil cell, the diameter of the anvil surface of the diamond anvil cell device is 300um, a T301 steel sheet with the initial thickness of 200um is selected as a pressure packaging gasket, after pre-pressing to 50um, a round hole with the diameter of 150um is punched in the center of an indentation as a sample cavity, an AgBr sample is mechanically ground for 1 hour by an agate mortar, so that the crystal grains of the powder sample are refined, the powder sample is placed in the sample cavity, a quasi-parallel plate electrode configuration is selected for high-pressure high-temperature in-situ alternating current impedance spectroscopy measurement, wherein Pt is used as one electrode, the inner wall of the T301 metal gasket sample cavity is used as the other electrode, the powder formed by mixing cubic boron nitride and epoxy resin is used as insulating powder, the Pt electrode and the metal gasket are insulated, the internal pressure of the sample cavity is calibrated by utilizing the R1 line fluorescence peak displacement of ruby, in order to avoid introducing additional effect, and (3) applying pressure of 0.6GPa on the interior of the sample cavity of the anvil cell device by the diamond, placing the sample cavity in a muffle furnace, heating to 473K-503K, and inducing the super-ionic state of AgBr.
In the present invention, the heating temperature is preferably 473K.
Has the advantages that:
AgBr is taken as a typical super-ion conductor material, and the transition temperature of a super-ion state is 555K under normal pressure. According to the invention, the material is subjected to alternating current impedance spectrum measurement by applying pressure and temperature at the same time, and the super-ionic state phenomenon of AgBr is induced under the conditions of 0.6GPa and 473K, so that the super-ionic state transition temperature is reduced by 82K. Meanwhile, the invention also has the advantages of simple operation, controllable experimental conditions and the like.
Description of the drawings:
FIG. 1 is a sectional view of an inventive sample assembly
FIG. 2 is an AgBr high pressure normal temperature in situ impedance spectrum under the conditions of example 2.
FIG. 3 is an AgBr high pressure high temperature in situ impedance spectrum under the conditions of example 3.
FIG. 4 is an AgBr high pressure high temperature in situ impedance spectrum under the conditions of example 4.
FIG. 5 is an AgBr high pressure high temperature in situ impedance spectrum under the conditions of example 5.
FIG. 6 is a graph of the conductivity of AgBr at 0.6GPa as a function of temperature under the conditions of example 6.
Detailed Description
Example 1
The experimental set-up and measurements are described with reference to figure 1. The AgBr sample was mechanically ground with an agate mortar for 1 hour to refine the grains of the powder sample. As shown in figure 1, 1 is a diamond anvil cell, 2 is a T301 steel sheet, 3 is a Pt metal electrode, 4 is a T301 electrode, 5 is an insulating layer, and 6 is a ruby. The anvil surface diameter of the diamond anvil cell device is 300 um. Prepressing a T301 steel sheet with the initial thickness of 200um to 50um to be used as a pressure packaging gasket, and punching a hole with the diameter of 150um in the center of the indentation of the prepressed T301 gasket to be used as a sample cavity. A quasi-parallel plate electrode configuration is selected for high-voltage high-temperature in-situ alternating-current impedance spectroscopy measurement, wherein Pt above a sample cavity serves as one electrode, and the inner wall of the sample cavity of a T301 metal gasket serves as the other electrode. The powder obtained by mixing cubic boron nitride and epoxy resin is used as insulating powder to insulate the electrode and the metal gasket. An AgBr sample and a ruby were filled into the sample chamber and the sample was encapsulated. The internal pressure of the sample cavity is calibrated by using the R1 line fluorescence peak displacement of the ruby. In order to avoid introducing additional effects, no pressure-transmitting medium is placed inside the sample chamber.
Selecting an integrated muffle furnace to provide experimental high-temperature conditions, model: KSL-1200X, providing a temperature range of 293 and 503K. Selecting a parallel Solartron 1260/1296 impedance analyzer for high-pressure high-temperature in-situ AC impedance spectrum measurement, wherein the AC voltage is 1V, and the frequency range is 10-3-107Hz. And selecting Zview software to analyze the alternating current impedance spectrum measurement result.
Example 2:
the internal pressure of the sample chamber of the diamond anvil cell device of example 1 was applied from 0GPa to 0.6GPa, and the pressure was calibrated using the R1 line fluorescence peak shift of ruby. The AgBr sample high-pressure normal-temperature in-situ AC impedance spectroscopy measurement is carried out by utilizing a parallel Solartron 1260/1296 impedance analyzer, and the result is shown in figure 2. Under the condition, AgBr shows typical ion transport characteristics, an impedance spectrum consists of a semicircular arc of a high-frequency part and a straight line of a low-frequency part which inclines upwards, and the semicircular arc represents Ag under the disturbance of a high-frequency signal+Ion around Br-The front and back oscillation process of the crystal lattice, the straight line represents Ag under the disturbance of low-frequency signal+Long-range diffusion of ions. The intersection point of the semicircular arc of the high-frequency part and the real axis of the impedance is about the resistance value, and the resistance of AgBr under the condition is about 4 multiplied by 107Ω。
Example 3
The diamond anvil device of example 2 was placed in an integral muffle furnace with a constant applied pressure of 0.6 GPa. Slowly increasing the application temperature from room temperature 293K to 323K and keeping the temperature for 20 minutes to enable the internal temperature of the sample cavity to reach 323K, and carrying out high-pressure high-temperature in-situ alternating-current impedance spectroscopy measurement; the temperature of the sample chamber is slowly increased from 323K to 353K and kept for 20 minutes, so that the temperature inside the sample chamber can reach 353K, and high-pressure high-temperature in-situ AC impedance spectroscopy measurement is carried out, and the result is shown in FIG. 3. Under the condition, AgBr still maintains the typical ion transport characteristics, and the impedance spectrum is composed of a semicircular arc of a high-frequency part and a straight line of a low-frequency part inclined upwards. Along with the temperature rise, the intersection point of the semi-circular arc of the high-frequency part and the real axis moves to a low resistance state, and the resistance is reduced along with the temperature rise.
Example 4
The diamond of example 3 was placed in an integral muffle furnace with constant pressure and temperature 443K, and high-pressure high-temperature in-situ ac impedance spectroscopy measurements were performed at 383K, 413K and 443K temperature points in this temperature range, with the results shown in fig. 4. And keeping the temperature of each selected temperature point constant for more than 20 minutes, and then carrying out impedance spectrum measurement to ensure that the internal temperature of the sample cavity meets the requirement. Under the condition, the intersection point of the half-circular arc of the high-frequency part of the AgBr impedance spectrum and the real axis continuously moves towards a low resistance state, and the resistance continuously decreases along with the temperature rise.
Example 5
The temperature in the muffle furnace of example 4 is further increased to 503K, the applied pressure is unchanged, and two temperature points 473K and 503K in the temperature range are taken to perform high-pressure high-temperature in-situ AC impedance spectroscopy measurement, and the result is shown in FIG. 5. Under the condition, the impedance spectrogram changes obviously, the intersection point of the semicircular arc and the solid axis of the high-frequency part becomes smaller obviously, the inclined upward straight line of the low-frequency part is vertical to the solid axis, and a large amount of Ag+After long-range diffusion, the ions are gathered between the sample and the electrode, and the AgBr super-ionic state phenomenon is generated.
Example 6
The results of the AC impedance spectra measured in examples 2-5 were fitted by Zview software to obtain the relationship between the change of ionic conductivity of 0.6GPa and the temperature, as shown in FIG. 6. At 0.6GPa, the ionic conductivity of AgBr gradually increases with the increase of temperature, and at 473K, the ionic conductivity reaches the value of a super-ionic state (0.01S/cm), and the ionic conductivity continues to increase with the increase of temperature to 503K. The temperature of the AgBr super-ionic state induced at high pressure and high temperature is reduced by 82K compared with the temperature of the super-ionic state in the traditional method.
The above embodiment shows that the super-ionic state phenomenon is induced under the conditions of 0.6GPa and 473K by simply applying a certain pressure and temperature to the AgBr material, so that the super-ionic state temperature of the AgBr is reduced by 82K, the preparation cost of the solid-state ion battery is greatly reduced by reducing the transition temperature, and the safety is greatly improved. The invention greatly expands the application condition of AgBr material in solid-state ion battery.

Claims (2)

1. A method for inducing the super-ionic state of AgBr is carried out in a diamond anvil cell, the diameter of the anvil surface of the diamond anvil cell device is 300um, a T301 steel sheet with the initial thickness of 200um is selected as a pressure packaging gasket, after pre-pressing to 50um, a round hole with the diameter of 150um is punched in the center of an indentation as a sample cavity, an AgBr sample is mechanically ground for 1 hour by an agate mortar, so that the crystal grains of the powder sample are refined, the powder sample is placed in the sample cavity, a quasi-parallel plate electrode configuration is selected for high-pressure high-temperature in-situ alternating current impedance spectroscopy measurement, wherein Pt is used as one electrode, the inner wall of the T301 metal gasket sample cavity is used as the other electrode, the powder formed by mixing cubic boron nitride and epoxy resin is used as insulating powder, the Pt electrode and the metal gasket are insulated, the internal pressure of the sample cavity is calibrated by utilizing the R1 line fluorescence peak displacement of ruby, in order to avoid introducing additional effect, and (3) applying pressure of 0.6GPa on the interior of the sample cavity of the anvil cell device by the diamond, placing the sample cavity in a muffle furnace, heating to 473K-503K, and inducing the super-ionic state of AgBr.
2. The method of claim 1, wherein the AgBr super ionic state is induced by heating to a temperature of 473K in a muffle furnace.
CN202010816208.6A 2020-08-14 2020-08-14 Method for inducing AgBr super-ionic state Pending CN111934003A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115201241A (en) * 2022-07-18 2022-10-18 吉林大学 SnBi regulated and controlled by high-voltage technology 2 Te 4 Method for detecting Sn atom defect

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103076501A (en) * 2013-01-05 2013-05-01 吉林大学 Method for measuring dielectric properties of diamond anvil cells in situ

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103076501A (en) * 2013-01-05 2013-05-01 吉林大学 Method for measuring dielectric properties of diamond anvil cells in situ

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
王佳: "高压下超离子导体AgX（X=Cl,Br）及YF<sub>3</sub>（Y=La,Lu）的电输运性质研究", 《中国优秀博士论文全文数据库，《工程科技Ⅰ辑》》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115201241A (en) * 2022-07-18 2022-10-18 吉林大学 SnBi regulated and controlled by high-voltage technology 2 Te 4 Method for detecting Sn atom defect

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Application publication date: 20201113