CN110190325B - Four-electrode lithium-sulfur battery, preparation method thereof and electrode electrochemical characteristic monitoring method - Google Patents

Four-electrode lithium-sulfur battery, preparation method thereof and electrode electrochemical characteristic monitoring method Download PDF

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CN110190325B
CN110190325B CN201910388254.8A CN201910388254A CN110190325B CN 110190325 B CN110190325 B CN 110190325B CN 201910388254 A CN201910388254 A CN 201910388254A CN 110190325 B CN110190325 B CN 110190325B
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aluminum strip
material layer
shell
electrode material
electrode
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CN110190325A (en
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申文静
方杰
尹澍
顾泽植
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Shenzhen Technology University
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    • H—ELECTRICITY
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    • 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
    • H01M10/4285—Testing apparatus
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
    • G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
    • G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
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    • G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • 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
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    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
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    • 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
    • H01M10/48—Accumulators combined with arrangements for measuring, testing or indicating the condition of cells, e.g. the level or density of the 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
    • H01M50/109—Primary casings; Jackets or wrappings characterised by their shape or physical structure of button or coin shape
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/04—Processes of manufacture in general
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    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • Y02E60/10—Energy storage using batteries
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Abstract

The invention discloses a four-electrode lithium-sulfur battery, a preparation method thereof and an electrode electrochemical characteristic monitoring method. The four-electrode lithium-sulfur battery has a four-electrode structure, wherein a top shell and a bottom shell are two cathodes, two aluminum strips are led out from an opening on the top shell to serve as two anodes, the two cathodes are arranged on the upper side and the lower side of the lithium-sulfur battery, the two anodes are clamped in the middle, meanwhile, the anodes and the cathodes are separated by a diaphragm, and the two anodes are also separated by the diaphragm. The lithium-sulfur battery has a four-electrode structure, can simultaneously acquire the electrochemical impedance of the anode and the cathode of the battery on the premise of not damaging the battery structure, and solves the problem that the traditional commercial two-electrode battery and three-electrode battery can not accurately acquire the electrochemical information of a single electrode. The invention can be used for the research and development of novel electrode materials.

Description

Four-electrode lithium-sulfur battery, preparation method thereof and electrode electrochemical characteristic monitoring method
Technical Field
The invention relates to a battery preparation and detection technology, in particular to a four-electrode-based lithium-sulfur battery, a preparation method thereof and an electrode electrochemical characteristic monitoring method.
Background
In recent years, high-performance lithium batteries have become popular in electric vehicles and personal electronic devices. However, the energy density of current lithium ion batteries has approached a theoretical value. Commercial lithium ion batteries use lithium iron phosphate (LiFePO4), lithium Nickel Manganese Cobalt (NMC), lithium Nickel Cobalt Aluminate (NCA), and the like as positive electrodes and graphite as negative electrodes, and the capacity is generally about 250 Wh/kg. In order to further increase the energy density, the materials of the positive and negative electrodes need to be changed, which is the development direction of the next generation lithium battery. Lithium sulfur batteries have a great potential as lithium ion battery competitors. The battery system adopts elemental sulfur (the theoretical specific capacity is 1675mAh/g) as a positive electrode material, metal lithium as a negative electrode, the average output voltage can reach 2.1V, and the theoretical energy density of the system is 2567Wh/kg, which is about 10 times of that of the traditional lithium ion battery. Although elemental sulfur is widely distributed in nature, has a large reserve and is low in cost, the large-scale commercial production of lithium sulfur batteries has many challenges at present. Such as capacity loss due to dissolution of polysulfide, low output voltage due to poor conductivity of active material, and battery capacity lower than the theoretical value. These are directly linked to the internal resistance of the battery.
Electrochemical impedance spectroscopy is one of the classical methods for studying the internal resistance of a battery. The method can not only represent the conductivity of ions, but also carry out the research on the electrochemical reaction kinetics of the electrode. However, in a conventional full cell, the test results in the superposition of the impedances of the positive electrode, the electrolyte and the negative electrode, and it is difficult to distinguish the respective impedances of the three parts. If the impedance of a single electrode is to be obtained, two methods are currently used. One is to disassemble a plurality of batteries and reassemble the positive electrode and the positive electrode (or the negative electrode and the negative electrode) into a two-electrode symmetrical battery. And in the second method, a reference electrode is added to form a three-electrode battery.
The two-electrode symmetrical battery is complex to manufacture, and the battery needs to be disassembled and reassembled, so that the battery cannot be charged and discharged continuously. And the electrode is damaged inevitably in the process of disassembling, and the electrolyte is lost, which all cause inaccurate measuring results. Although the three-electrode battery is often used for testing the impedance of a single electrode, the inherent electrochemical asymmetry of the three-electrode battery is proved to influence the testing precision by early research.
There is no report on a method for accurately measuring the impedance of the positive electrode and the negative electrode of a battery without damaging the battery.
Disclosure of Invention
The invention mainly aims to provide a four-electrode lithium-sulfur battery, a preparation method thereof and an electrode electrochemical characteristic monitoring method, which can be used for measuring accurate impedance spectrums of a positive electrode and a negative electrode of the battery under the condition of not disassembling the battery.
The invention is realized by the following technical scheme:
a four-electrode lithium-sulfur battery comprises a shell and a battery assembly packaged in the shell, wherein the shell comprises a metal bottom shell and a metal top shell buckled on the bottom shell, the top shell is insulated from the bottom shell, and the battery assembly comprises a first negative electrode material layer, a first diaphragm layer, a first positive electrode material layer, a first aluminum tape, a second diaphragm layer, a second aluminum tape, a second positive electrode material layer, a third diaphragm layer and a second negative electrode material layer from bottom to top;
the first negative electrode material layer is arranged at the bottom of the inner side of the bottom shell and is electrically connected with the bottom shell, the second negative electrode material layer is provided with a metal gasket which is electrically connected with the second negative electrode material layer, the metal gasket is provided with a metal spring piece which is electrically connected with the metal gasket, and the metal spring piece is elastically pressed between the top of the inner side of the top shell and the metal gasket and is electrically connected with the top shell;
the first aluminum strip is electrically connected with the first anode material layer, the second aluminum strip is electrically connected with the second anode material layer, the first aluminum strip is insulated from the second aluminum strip, a hole is formed in the top shell, the first aluminum strip and the second aluminum strip are led out from the hole, and the first aluminum strip, the second aluminum strip and the top shell are mutually insulated.
Further, the first positive electrode material layer and the second positive electrode material layer adopt porous carbon paper as current collectors.
Further, the first aluminum strip is fixedly connected to the edge of the first positive electrode material layer, and the second aluminum strip is fixedly connected to the edge of the second positive electrode material layer.
Further, the first negative electrode material layer and the second negative electrode material layer are metal lithium sheets.
Further, the shell is a shell of a button cell battery.
A method of making a four-electrode lithium-sulfur battery as described above, comprising the steps of:
preparing a top shell and a bottom shell, and forming an opening on the top shell;
preparing the first negative electrode material layer, the first separator layer, the first positive electrode material layer, the first aluminum tape, the second separator layer, the second aluminum tape, the second positive electrode material layer, the third separator layer, and the second negative electrode material layer;
sequentially installing the bottom shell, the first cathode material layer, the first diaphragm layer, the first anode material layer, the first aluminum tape, the second diaphragm layer, the second aluminum tape, the second anode material layer, the third diaphragm layer and the second cathode material layer from bottom to top in a glove box, and injecting electrolyte and then installing when installing the first diaphragm layer, the first anode material layer, the second diaphragm layer, the second anode material layer and the third diaphragm layer;
leading the first aluminum strip and the second aluminum strip out of the open hole;
mounting a metal gasket on the second negative electrode material layer, and mounting a metal spring piece on the metal gasket;
the top shell is buckled on the bottom shell, so that the metal spring piece is elastically pressed between the top of the inner side of the top shell and the metal gasket and is electrically connected with the top shell;
and sealing the opening by using an insulating material, and insulating the first aluminum strip, the second aluminum strip and the top shell when sealing.
Further, the preparation method of the first cathode material layer and the second cathode material layer comprises the following steps:
porous carbon paper is used as a current collector, the current collector is cleaned by acetone, then cut into round pieces, sulfur powder is added on the round pieces, and the round pieces are heated to 120 ℃ so that the sulfur powder is dissolved and absorbed by the carbon paper.
Further, when the first aluminum strip and the second aluminum strip are installed, the first aluminum strip is fixedly connected to the edge of the first positive electrode material layer, and the second aluminum strip is fixedly connected to the edge of the second positive electrode material layer.
Further, the insulating material is resin.
The electrode electrochemical characteristic monitoring method based on the four-electrode lithium-sulfur battery comprises the following steps:
connecting a first aluminum strip and a second aluminum strip to the positive electrode of a charge and discharge tester and one end of an impedance spectrum tester through a first double-pole double-throw switch, and connecting a top shell and a bottom shell to the negative electrode of the charge and discharge tester and the other end of the impedance spectrum tester through a second double-pole double-throw switch;
the first aluminum strip and the second aluminum strip can be simultaneously connected with the anode of the charge and discharge tester through the first double-pole double-throw switch, or the first aluminum strip and the second aluminum strip can be simultaneously connected with one end of the impedance spectrum tester, and the top shell and the bottom shell can be simultaneously connected with the cathode of the charge and discharge tester through the second double-pole double-throw switch, or the top shell and the bottom shell are simultaneously connected with the other end of the impedance spectrum tester; simultaneously connecting the first aluminum strip and the second aluminum strip with the anode of the charge-discharge tester, simultaneously connecting the top shell and the bottom shell with the cathode of the charge-discharge tester, performing constant-current charge-discharge test, simultaneously connecting the first aluminum strip and the second aluminum strip with one end of the impedance spectrum tester, simultaneously connecting the top shell and the bottom shell with the other end of the impedance spectrum tester, and performing impedance spectrum test;
and carrying out constant current charge-discharge test and impedance spectrum test on the four-electrode lithium-sulfur battery according to a preset program, and recording a corresponding voltage curve and an impedance spectrum curve.
Compared with the prior art, the invention provides a four-electrode lithium-sulfur battery, a preparation method thereof and an electrode electrochemical characteristic monitoring method. The four-electrode lithium-sulfur battery has a four-electrode structure, wherein the top shell and the bottom shell are two cathodes, the two aluminum strips are two anodes, the two cathodes are arranged on the upper side and the lower side of the lithium-sulfur battery, the two anodes are clamped in the middle, meanwhile, the anodes and the cathodes are separated by a diaphragm, and the two anodes are also separated by the diaphragm. The lithium-sulfur battery has a four-electrode structure, can simultaneously acquire the electrochemical impedance of the anode and the cathode of the battery on the premise of not damaging the battery structure, and solves the problem that the traditional commercial two-electrode battery and three-electrode battery can not accurately acquire the electrochemical information of a single electrode. The invention can be used for the research and development of novel electrode materials.
Drawings
FIG. 1 is a schematic diagram of the composition of a four-electrode lithium sulfur battery according to an embodiment of the present invention;
FIG. 2 is a schematic diagram of an electrochemical property test connection of a four-electrode lithium sulfur battery according to an embodiment of the present invention;
FIG. 3 is a graph of voltage curves for charging and discharging a four electrode battery using a constant current method;
FIG. 4 is a graph of impedance spectra of a typical battery positive and negative electrode;
fig. 5 is a graph showing changes in internal resistances of the electrolyte, the positive electrode, and the negative electrode of the battery when the battery is discharged.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be further described in detail with reference to the following embodiments and the accompanying drawings.
As shown in fig. 1, a four-electrode lithium sulfur battery provided in an embodiment of the present invention includes a housing and a battery assembly packaged in the housing, where the housing includes a metal bottom case 1 and a metal top case 2 fastened on the bottom case 1, the top case 2 is insulated from the bottom case 1, and the battery assembly includes, from bottom to top, a first negative electrode material layer 3, a first separator layer 4, a first positive electrode material layer 5, a first aluminum tape 6, a second separator layer 7, a second aluminum tape 8, a second positive electrode material layer 9, a third separator layer 10, and a second negative electrode material layer 11.
The first negative electrode material layer 3 is arranged at the bottom of the inner side of the bottom shell 1 and is electrically connected with the bottom shell 1, the second negative electrode material layer 11 is provided with a metal gasket 12 which is electrically connected with the second negative electrode material layer 11, the metal gasket 12 is provided with a metal spring piece 13 which is electrically connected with the metal gasket 12, and the metal spring piece 13 is elastically pressed between the top of the inner side of the top shell 2 and the metal gasket 12 and is electrically connected with the top shell 2.
First aluminium strip 6 is connected with first anodal material layer 5 electricity, and second aluminium strip 8 is connected with second anodal material layer 9 electricity, has seted up trompil 14 on the top shell 2, and first aluminium strip 6 and second aluminium strip 8 are drawn out from trompil 14, and first aluminium strip 6, second aluminium strip 8, top shell 2 three are insulating each other. Carbon paper can be respectively connected to the first aluminum strip 6 and the second aluminum strip 8, the first aluminum strip 6 and the second aluminum strip 8 are led out from the open hole 14 through the carbon paper, and the carbon paper connected to the first aluminum strip 6 and the second aluminum strip 8 serves as two anodes.
The four-electrode lithium-sulfur battery is taken as a four-electrode symmetric battery, and the shell of a button cell can be directly taken as the shell of the four-electrode symmetric battery. For example, the housing of a CR2032 button stainless steel battery can be used directly to enclose the battery assembly, with only a slight adjustment to the negative electrode of the housing (i.e., the top housing 2) and a small hole cut as the opening 14 for the first aluminum strip 6 and the second aluminum strip 8 to exit. The first positive electrode material layer 5 and the second positive electrode material layer 9 adopt porous carbon paper as a current collector, the thickness of the porous carbon paper is 0.28 mm, the porous carbon paper is cleaned by acetone and then cut into round pieces with the diameter of 14 mm, a certain amount of sulfur powder is added on the round pieces, and the round pieces are heated to 120 ℃ so that the sulfur powder is dissolved and absorbed by the carbon paper. The first separator layer 4, the second separator layer 7 and the third separator layer 10 can all adopt commercial lithium ion battery separators, have the thickness of 25 micrometers, and are cut into round pieces with the diameter of 15 millimeters. The first aluminum strip 6 and the second aluminum strip 8 can be made of aluminum foil cut into elongated strips, the first aluminum strip 6 is fixedly connected to the edge of the first positive electrode material layer 5, and the second aluminum strip 8 is fixedly connected to the edge of the second positive electrode material layer 9. The first negative electrode material layer 3 and the second negative electrode material layer 11 are both metallic lithium sheets, and have a thickness of 0.5 mm and a diameter of 14 mm. The electrolyte injected into each positive electrode material layer and each separator layer is a mixed solvent of 1, 3-Dioxolane (DOL) and 1, 2-Dimethoxyethane (DME) in equal proportion, and contains 1M bis (trifluoromethane) sulfimide (LiTFSI). The prepared four-electrode lithium-sulfur battery has four electrodes including two anodes and two cathodes, wherein the top shell 2 and the bottom shell 1 are two cathodes, the two aluminum strips are two anodes, the two cathodes are arranged on the upper side and the lower side of the lithium-sulfur battery, the two anodes are clamped between the two cathodes, and meanwhile, the anodes and the cathodes are separated by a diaphragm, and the two anodes are also separated by the diaphragm. The lithium-sulfur battery has a four-electrode structure, so that the electrochemical impedance of the anode and the cathode of the battery can be acquired simultaneously on the premise of not damaging the battery structure, and the problem that the conventional commercial two-electrode battery and the conventional three-electrode battery cannot accurately acquire single-electrode electrochemical information is solved.
The second embodiment of the invention provides a method for preparing the four-electrode lithium-sulfur battery, which comprises the following steps:
preparing a top shell 2 and a bottom shell 1, and forming an opening 14 on the top shell 2;
preparing a first cathode material layer 3, a first separator layer 4, a first anode material layer 5, a first aluminum strip 6, a second separator layer 7, a second aluminum strip 8, a second anode material layer 9, a third separator layer 10 and a second cathode material layer 11;
a bottom shell 1, a first cathode material layer 3, a first diaphragm layer 4, a first anode material layer 5, a first aluminum strip 6, a second diaphragm layer 7, a second aluminum strip 8, a second anode material layer 9, a third diaphragm layer 10 and a second cathode material layer 11 are sequentially arranged in the glove box from bottom to top, and when the first diaphragm layer 4, the first anode material layer 5, the second diaphragm layer 7, the second anode material layer 9 and the third diaphragm layer 10 are arranged, electrolyte is injected firstly and then the glove box is arranged;
leading the first aluminium strip 6 and the second aluminium strip 8 out of the opening 14;
mounting a metal gasket 12 on the second negative electrode material layer 11, and mounting a metal spring piece 13 on the metal gasket 12;
the top shell 2 is buckled on the bottom shell 1, so that the metal spring piece 13 is elastically pressed between the top of the inner side of the top shell 2 and the metal gasket 12 and is electrically connected with the top shell 2;
the opening 14 is sealed by an insulating material 15, and the first aluminum strip 6, the second aluminum strip 8 and the top case 2 are insulated from each other during sealing. In this embodiment, the insulating material 15 is made of resin, and the opening 14 is sealed by a hydraulic sealing machine.
When the first aluminum strip 6 and the second aluminum strip 8 are led out from the opening 14, carbon paper can be respectively connected to the first aluminum strip 6 and the second aluminum strip 8, the first aluminum strip 6 and the second aluminum strip 8 are led out from the opening 14 through the carbon paper, the opening 14 is sealed after the first aluminum strip 6 and the second aluminum strip 8 are led out, and the carbon paper connected to the first aluminum strip 6 and the second aluminum strip 8 serves as two anodes.
It is to be noted that the water content of the glove box is not required to be higher than 1 ppm. Meanwhile, the steps do not have an absolute sequence, and some steps are not conflicted in execution, so that the steps can be executed synchronously, or the execution sequence can be executed sequentially or exchanged, and whether the execution sequence can be executed synchronously or exchanged is determined according to actual conditions. And (3) the four-electrode lithium-sulfur battery is assembled after the opening 14 is sealed, and the four-electrode lithium-sulfur battery needs to stand for 8 hours after being assembled, so that the resin is completely cured and then taken out of the glove box. The four-electrode symmetric structure of the assembled four-electrode lithium-sulfur battery is shown in figure 1.
In this embodiment, the preparation method of the first cathode material layer 5 and the second cathode material layer 9 is as follows:
porous carbon paper is used as a current collector, the current collector is cleaned by acetone, then cut into round pieces, sulfur powder is added on the round pieces, and the round pieces are heated to 120 ℃ so that the sulfur powder is dissolved and absorbed by the carbon paper.
When the first aluminum strip 6 and the second aluminum strip 8 are mounted, the first aluminum strip 6 is fixedly connected to the edge of the first positive electrode material layer 5, and the second aluminum strip 8 is fixedly connected to the edge of the second positive electrode material layer 9.
The third embodiment of the invention provides an electrode electrochemical characteristic monitoring method based on the four-electrode lithium-sulfur battery, which comprises the following steps:
connecting the first aluminum strip 6 and the second aluminum strip 8 to the positive electrode of a charge and discharge tester 19 and one end of an impedance spectrum tester 18 through a first double-pole double-throw switch 16, and connecting the top shell 2 and the bottom shell 1 to the negative electrode of the charge and discharge tester 19 and the other end of the impedance spectrum tester 18 through a second double-pole double-throw switch 17;
the first aluminum strip 6 and the second aluminum strip 8 can be simultaneously connected with the positive electrode of the charge and discharge tester 19 through the first double-pole double-throw switch 16, or the first aluminum strip 6 and the second aluminum strip 8 can be simultaneously connected with one end of the impedance spectrum tester 18, the top shell 2 and the bottom shell 1 can be simultaneously connected with the negative electrode of the charge and discharge tester 19 through the second double-pole double-throw switch 17, or the top shell 2 and the bottom shell 1 can be simultaneously connected with the other end of the impedance spectrum tester 18; simultaneously connecting the first aluminum strip 6 and the second aluminum strip 8 with the positive electrode of a charge-discharge tester 19, simultaneously connecting the top shell 2 and the bottom shell 1 with the negative electrode of the charge-discharge tester 19, performing constant-current charge-discharge testing, simultaneously connecting the first aluminum strip 6 and the second aluminum strip 8 with one end of an impedance spectrum tester 18, and simultaneously connecting the top shell 2 and the bottom shell 1 with the other end of the impedance spectrum tester 18, and performing impedance spectrum testing;
and carrying out constant current charge-discharge test and impedance spectrum test on the four-electrode lithium-sulfur battery according to a preset program, and recording a corresponding voltage curve and an impedance spectrum curve.
The specific test can be carried out according to the following method:
the charging and discharging tester 19 uses Arbin BT2000, and the impedance spectroscopy tester 18 uses Zahner IM6 electrochemical workstation. According to fig. 2, when the first double-pole double-throw switch 16 and the second double-pole double-throw switch 17 are switched to the left position, the four-electrode lithium-sulfur battery is connected to the charge and discharge tester 19, and when the first double-pole double-throw switch 16 and the second double-pole double-throw switch 17 are switched to the right position, the four-electrode lithium-sulfur battery is connected to the impedance spectrum tester 18.
The four-electrode lithium-sulfur battery is connected into Arbin BT2000 to perform constant-current charge-discharge test, and the availability of the battery is detected. The discharge and charge currents were 177mA (0.1mA/cm2), the discharge cut-off voltage was 1.7V, and the charge cut-off voltage was 2.8V. The charging and discharging voltage is recorded while charging and discharging, and the recorded voltage curve is shown in fig. 3, wherein a high-potential discharging platform at 2.3V and a low-potential discharging platform at 2.1V are typical double discharging platforms, and are consistent with related research reports. The newly assembled four-electrode lithium-sulfur battery can work normally and is effective.
And (3) carrying out impedance spectrum test on the four-electrode lithium-sulfur battery to obtain an online impedance spectrum of the battery. The battery was first fully charged, then a single discharge capacity was set at Arbin BT2000, a constant current discharge was started, and the battery voltage was recorded during the discharge. The first double pole double throw switch 16 and the second double pole double throw switch 17 are now in the left position in figure 2. When the discharge reaches the set capacity, the discharge is suspended, the first double-pole double-throw switch 16 and the second double-pole double-throw switch 17 are switched to the right position, and the battery is connected with a Zahner IM6 electrochemical workstation for impedance spectrum test. And setting the open-circuit voltage as the voltage of the test signal, wherein the amplitude is 10mV, and the frequency is from 1MHz to 0.1Hz, and obtaining the impedance spectrums of the anode and the cathode. The impedance spectra of the obtained positive and negative electrodes are shown in fig. 4. After the test is completed, the first double-pole double-throw switch 16 and the second double-pole double-throw switch 17 are switched to the left position again, the discharge is continued, and the battery voltage is recorded. The above steps are repeated until the discharge voltage of the battery is reduced to 1.7V. The black curve in fig. 5 is a voltage plot of a single 50mAh/g discharge capacity. The three filling diagrams from top to bottom in fig. 5 are respectively the impedance changes of the positive electrode, the negative electrode and the electrolyte during the discharging process of the battery.
The above-described embodiments are merely preferred embodiments, which are not intended to limit the scope of the present invention, and any modifications, equivalents, improvements, etc. made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (10)

1. A four-electrode lithium-sulfur battery comprises a shell and a battery assembly packaged in the shell, wherein the shell comprises a metal bottom shell and a metal top shell buckled on the bottom shell, and the top shell is insulated from the bottom shell;
the first negative electrode material layer is arranged at the bottom of the inner side of the bottom shell and is electrically connected with the bottom shell, the second negative electrode material layer is provided with a metal gasket which is electrically connected with the second negative electrode material layer, the metal gasket is provided with a metal spring piece which is electrically connected with the metal gasket, and the metal spring piece is elastically pressed between the top of the inner side of the top shell and the metal gasket and is electrically connected with the top shell;
the first aluminum strip is electrically connected with the first anode material layer, the second aluminum strip is electrically connected with the second anode material layer, the first aluminum strip is insulated from the second aluminum strip, a hole is formed in the top shell, the first aluminum strip and the second aluminum strip are led out from the hole, and the first aluminum strip, the second aluminum strip and the top shell are mutually insulated.
2. The four-electrode lithium sulfur battery as defined in claim 1 wherein said first positive electrode material layer and said second positive electrode material layer employ porous carbon paper as current collectors.
3. The four-electrode lithium sulfur battery of claim 2 wherein the first aluminum strip is fixedly attached to an edge of the first positive electrode material layer and the second aluminum strip is fixedly attached to an edge of the second positive electrode material layer.
4. The four-electrode lithium sulfur battery of claim 1 wherein the first negative electrode material layer and the second negative electrode material layer are metallic lithium sheets.
5. The four-electrode lithium sulfur battery of claim 3 wherein the housing is a housing of a button cell battery.
6. A method of making a four-electrode lithium sulfur battery as defined in any one of claims 1 to 5, comprising the steps of:
preparing a top shell and a bottom shell, and forming an opening on the top shell;
preparing the first negative electrode material layer, the first separator layer, the first positive electrode material layer, the first aluminum tape, the second separator layer, the second aluminum tape, the second positive electrode material layer, the third separator layer, and the second negative electrode material layer;
sequentially installing the bottom shell, the first cathode material layer, the first diaphragm layer, the first anode material layer, the first aluminum tape, the second diaphragm layer, the second aluminum tape, the second anode material layer, the third diaphragm layer and the second cathode material layer from bottom to top in a glove box, and injecting electrolyte and then installing when installing the first diaphragm layer, the first anode material layer, the second diaphragm layer, the second anode material layer and the third diaphragm layer;
leading the first aluminum strip and the second aluminum strip out of the open hole;
mounting a metal gasket on the second negative electrode material layer, and mounting a metal spring piece on the metal gasket;
the top shell is buckled on the bottom shell, so that the metal spring piece is elastically pressed between the top of the inner side of the top shell and the metal gasket and is electrically connected with the top shell;
and sealing the opening by using an insulating material, and insulating the first aluminum strip, the second aluminum strip and the top shell when sealing.
7. The method of claim 6, wherein the first positive electrode material layer and the second positive electrode material layer are each prepared by a method comprising:
porous carbon paper is used as a current collector, acetone is used for cleaning, then the porous carbon paper is cut into round pieces, sulfur powder is added on the round pieces, and the temperature is heated to 120 ℃, so that the sulfur powder is melted and absorbed by the carbon paper.
8. The method of claim 6, wherein the first aluminum strip is fixedly attached to an edge of the first layer of positive electrode material and the second aluminum strip is fixedly attached to an edge of the second layer of positive electrode material when the first aluminum strip and the second aluminum strip are installed.
9. The method of claim 6, wherein the insulating material is a resin.
10. The method for monitoring the electrochemical characteristics of an electrode of a four-electrode lithium-sulfur battery according to any one of claims 1 to 5, comprising the steps of:
connecting a first aluminum strip and a second aluminum strip to the positive electrode of a charge and discharge tester and one end of an impedance spectrum tester through a first double-pole double-throw switch, and connecting a top shell and a bottom shell to the negative electrode of the charge and discharge tester and the other end of the impedance spectrum tester through a second double-pole double-throw switch;
the first aluminum strip and the second aluminum strip can be simultaneously connected with the anode of the charge and discharge tester through the first double-pole double-throw switch, or the first aluminum strip and the second aluminum strip can be simultaneously connected with one end of the impedance spectrum tester, and the top shell and the bottom shell can be simultaneously connected with the cathode of the charge and discharge tester through the second double-pole double-throw switch, or the top shell and the bottom shell are simultaneously connected with the other end of the impedance spectrum tester; simultaneously connecting the first aluminum strip and the second aluminum strip with the anode of the charge-discharge tester, simultaneously connecting the top shell and the bottom shell with the cathode of the charge-discharge tester, performing constant-current charge-discharge test, simultaneously connecting the first aluminum strip and the second aluminum strip with one end of the impedance spectrum tester, simultaneously connecting the top shell and the bottom shell with the other end of the impedance spectrum tester, and performing impedance spectrum test;
and carrying out constant current charge-discharge test and impedance spectrum test on the four-electrode lithium-sulfur battery according to a preset program, and recording a corresponding voltage curve and an impedance spectrum curve.
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