WO2020228234A1 - Four-electrode lithium-sulfur battery and preparation method therefor, and electrode electrochemical property monitoring method - Google Patents

Four-electrode lithium-sulfur battery and preparation method therefor, and electrode electrochemical property monitoring method Download PDF

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WO2020228234A1
WO2020228234A1 PCT/CN2019/111055 CN2019111055W WO2020228234A1 WO 2020228234 A1 WO2020228234 A1 WO 2020228234A1 CN 2019111055 W CN2019111055 W CN 2019111055W WO 2020228234 A1 WO2020228234 A1 WO 2020228234A1
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Prior art keywords
material layer
electrode material
aluminum strip
positive electrode
lithium
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PCT/CN2019/111055
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French (fr)
Chinese (zh)
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申文静
方杰
尹澍
顾泽植
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深圳技术大学
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Priority to DE112019000208.2T priority Critical patent/DE112019000208T5/en
Publication of WO2020228234A1 publication Critical patent/WO2020228234A1/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
    • H01M10/42—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]
    • G01R31/385—Arrangements for measuring battery or accumulator variables
    • 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]
    • G01R31/389—Measuring internal impedance, internal conductance or related variables
    • 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
    • H01M10/052—Li-accumulators
    • 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
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • 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
    • H01M10/42—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
    • H01M4/139—Processes of manufacture
    • 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
    • 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
    • H01M50/50—Current conducting connections for cells or batteries
    • 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
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/543—Terminals
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • 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
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the invention relates to 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.
  • lithium-ion batteries use lithium iron phosphate (LiFePO4), lithium nickel cobalt manganate (NMC) and lithium nickel cobalt aluminate (NCA) as the positive electrode, graphite as the negative electrode, and the capacity is generally around 250Wh/kg.
  • LiFePO4 lithium iron phosphate
  • NMC lithium nickel cobalt manganate
  • NCA lithium nickel cobalt aluminate
  • the capacity is generally around 250Wh/kg.
  • Lithium-sulfur battery is a potential competitor of lithium-ion battery.
  • the battery system uses elemental sulfur (theoretical specific capacity of 1675mAh/g) as the positive electrode material and lithium metal as the negative electrode.
  • the average output voltage can reach 2.1V.
  • the theoretical energy density of the system is 2567Wh/kg, which is about the same as that of traditional lithium-ion batteries. 10 times.
  • elemental sulfur is widely distributed in nature, has large reserves and low cost, there are still many challenges in the large-scale commercial production of lithium-sulfur batteries. For example, the capacity loss caused by the dissolution of polysulfides, the poor conductivity of the active material leads to low output voltage, and the battery capacity is lower than the theoretical value. These are directly related to the internal resistance of the battery.
  • Electrochemical impedance spectroscopy is one of the classic methods to study the internal resistance of batteries. It can not only characterize the conductivity of ions, but also conduct the study of electrochemical reaction kinetics of electrodes. However, for an ordinary full battery, the test results are the superposition of the impedance of the positive electrode, the electrolyte and the negative electrode, and it is difficult to distinguish the respective impedances of these three parts. If you want to obtain the impedance of a single electrode, there are two commonly used methods. One is to disassemble multiple batteries, and reassemble the positive and positive electrodes (or negative and negative electrodes) into a two-electrode symmetrical battery. The second is to add a reference electrode to make a three-electrode battery.
  • the main purpose of the present invention is to provide a four-electrode lithium-sulfur battery, a preparation method thereof, and an electrode electrochemical characteristic monitoring method, which can measure accurate battery positive and negative impedance spectra without disassembling the battery.
  • a four-electrode lithium-sulfur battery comprising an outer shell and a battery assembly encapsulated in the outer shell, the outer shell including a metal bottom shell and a metal top shell buckled on the bottom shell, the top shell and the bottom shell Shell insulation, the battery assembly includes a first negative electrode material layer, a first separator layer, a first positive electrode material layer, a first aluminum tape, a second separator layer, a second aluminum tape, a second positive electrode material layer, and a first Three separator layers and a second negative electrode material layer;
  • the first negative electrode material layer is installed on the inner bottom of the bottom case and is electrically connected to the bottom case, and the second negative electrode material layer is installed with a metal gasket electrically connected to the second negative electrode material layer,
  • the metal washer is equipped with a metal spring sheet electrically connected to the metal washer, and the metal spring sheet is elastically pressed between the inner top of the top shell and the metal washer, and is connected to the top Shell electrical connection;
  • the first aluminum strip is electrically connected to the first positive electrode material layer
  • the second aluminum strip is electrically connected to the second positive electrode material layer
  • the top case is provided with openings
  • the first aluminum strip And the second aluminum strip is led out from the opening and insulated from the top case.
  • first positive electrode material layer and the second positive electrode material layer use porous carbon paper as a current collector.
  • first aluminum strip is fixedly connected to the edge of the first positive electrode material layer
  • second aluminum strip is fixedly connected to the edge of the second positive electrode material layer
  • first negative electrode material layer and the second negative electrode material layer are metal lithium sheets.
  • the casing is a casing of a button battery.
  • a method for preparing the above-mentioned four-electrode lithium-sulfur battery includes the following steps:
  • the first negative electrode material layer, the first diaphragm layer, the first positive electrode material layer, the first aluminum tape, and the second diaphragm layer in the glove box from bottom to top The second aluminum tape, the second positive electrode material layer, the third separator layer, and the second negative electrode material layer are installed after the first separator layer, the first positive electrode material layer, and the When the second separator layer, the second positive electrode material layer and the third separator layer are used, the electrolyte is injected first and then installed;
  • the opening is sealed with an insulating material to insulate the first aluminum strip and the second aluminum strip from the top case.
  • preparation methods of the first positive electrode material layer and the second positive electrode material layer both include:
  • porous carbon paper as the current collector, clean it with acetone, cut it into discs, add sulfur powder on the disc, and heat it to 120 degrees to melt the sulfur powder and be absorbed by the carbon paper.
  • the first aluminum strip is fixedly connected to the edge of the first positive electrode material layer
  • the second aluminum strip is fixedly connected At the edge of the second positive electrode material layer.
  • the insulating material is resin.
  • first aluminum strip and the second aluminum strip Connect the first aluminum strip and the second aluminum strip to the positive electrode of the charge-discharge tester and one end of the impedance spectrum tester through the first double-pole double-throw switch, and connect the top and bottom cases to the second double-pole double-throw switch.
  • the first aluminum strip and the second aluminum strip can be simultaneously connected to the positive electrode of the charge and discharge tester, or the first aluminum strip and the second aluminum strip can be connected
  • the aluminum strip is connected to one end of the impedance spectrum tester at the same time, and the top case and the bottom case can be simultaneously connected to the negative electrode of the charge and discharge tester through the second double-pole double-throw switch, or all
  • the top case and the bottom case are simultaneously connected to the other end of the impedance spectrum tester;
  • the first aluminum strip and the second aluminum strip are simultaneously connected to the positive electrode of the charge-discharge tester, and all
  • a constant current charge and discharge test can be performed, and the first aluminum strip and the second aluminum strip are simultaneously tested with the impedance spectrum After connecting one end of the instrument, and simultaneously connecting the top shell and the bottom shell to the other end of the impedance spectrum tester, impedance spectrum testing can be performed;
  • the present 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, in which the top shell and the bottom shell are two negative electrodes, two aluminum strips are two positive electrodes, and the two negative electrodes are installed on the upper and lower sides of the lithium-sulfur battery, sandwiching the two positive electrodes in the middle At the same time, the positive electrode and the negative electrode are separated by a separator, and the two positive electrodes are also separated by a separator.
  • the lithium-sulfur battery has a four-electrode structure, which can collect the electrochemical impedance of the positive and negative electrodes of the battery at the same time without damaging the structure of the battery. This solves the problem that traditional commercial two-electrode batteries and three-electrode batteries cannot accurately obtain single-electrode electrochemistry. Information problem.
  • the invention can be used for the research and development of new electrode materials.
  • FIG. 1 is a schematic diagram of the composition principle of a four-electrode lithium-sulfur battery according to an embodiment of the present invention
  • FIG. 2 is a schematic diagram of the electrochemical characteristics test connection diagram of a four-electrode lithium-sulfur battery in an embodiment of the present invention
  • Figure 3 is a voltage curve diagram of charging and discharging a four-electrode battery using a constant current method
  • Figure 4 is a graph of impedance spectra of a typical battery positive and negative electrodes
  • Fig. 5 is a graph showing changes in the internal resistance of the electrolyte, the positive electrode and the negative electrode of the battery when the battery is discharged.
  • the four-electrode lithium-sulfur battery provided in the first embodiment of the present invention includes a shell and a battery assembly enclosed in the shell.
  • the shell includes a metal bottom shell 1 and a metal top shell 2 fastened to the bottom shell 1.
  • the top case 2 is insulated from the bottom case 1, and the battery assembly includes a first negative electrode material layer 3, a first separator layer 4, a first positive electrode material layer 5, a first aluminum strip 6, a second separator layer 7, and a second aluminum from bottom to top.
  • Belt 8 second positive electrode material layer 9, third separator layer 10, and second negative electrode material layer 11.
  • the first negative electrode material layer 3 is installed on the inner bottom of the bottom case 1 and is electrically connected to the bottom case 1.
  • the second negative electrode material layer 11 is equipped with a metal gasket 12 electrically connected to the second negative electrode material layer 11, and the metal gasket 12
  • a metal spring sheet 13 electrically connected to the metal washer 12 is installed on it.
  • the metal spring sheet 13 is elastically pressed between the inner top of the top shell 2 and the metal washer 12 and is electrically connected to the top shell 2.
  • the first aluminum strip 6 is electrically connected to the first positive electrode material layer 5
  • the second aluminum strip 8 is electrically connected to the second positive electrode material layer 9
  • the top case 2 is provided with an opening 14, the first aluminum strip 6 and the second aluminum strip 8 leads from the opening 14 and is insulated from the top case 2.
  • the four-electrode lithium-sulfur battery can directly use the shell of the button cell as its shell.
  • the shell of CR2032 button-type stainless steel battery can be directly used to encapsulate the battery assembly, and the negative electrode of the shell (ie, the top shell 2) needs to be adjusted slightly, and a small hole is cut to lead out the first aluminum strip 6 and the second aluminum Opening 14 with 8
  • the first positive electrode material layer 5 and the second positive electrode material layer 9 use porous carbon paper as the current collector with a thickness of 0.28 mm. After the porous carbon paper is cleaned with acetone, it is cut into 14 mm diameter discs, and a certain amount is added.
  • the amount of sulfur powder is heated to 120 degrees on the wafer, so that the sulfur powder is dissolved and absorbed by the carbon paper.
  • the first diaphragm layer 4, the second diaphragm layer 7 and the third diaphragm layer 10 can all be commercial lithium-ion battery diaphragms with a thickness of 25 microns and cut into discs with a diameter of 15 mm.
  • the first aluminum strip 6 and the second aluminum strip 8 can be made by cutting aluminum foil 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 second The edge of the positive electrode material layer 9.
  • the first negative electrode material layer 3 and the second negative electrode material layer 11 are both metal lithium sheets, with a thickness of 0.5 mm and a diameter of 14 mm.
  • the electrolyte injected into each cathode material layer and each separator layer is a mixed solvent of 1,3-dioxolane (DOL) and 1,2-dimethoxyethane (DME) in equal proportions, containing 1M bis( Trifluoromethane)sulfonimide (LiTFSI).
  • the prepared four-electrode lithium-sulfur battery has two positive electrodes and two negative electrodes, a total of four electrodes, in which the top shell 2 and the bottom shell 1 are two negative electrodes, the two aluminum strips are two positive electrodes, and the two negative electrodes are installed on the lithium sulfur
  • the upper and lower sides of the battery are sandwiched between the two positive electrodes.
  • the positive electrode and the negative electrode are separated by a separator, and the two positive electrodes are also separated by a separator.
  • the electrochemical impedance of the positive and negative electrodes of the battery can be collected at the same time without destroying the battery structure, which solves the problem that the current traditional commercial two-electrode batteries and three-electrode batteries cannot accurately obtain a single electrode.
  • the question of chemical information is that the current traditional commercial two-electrode batteries and three-electrode batteries cannot accurately obtain a single electrode.
  • the second embodiment of the present invention provides a method for preparing the above four-electrode lithium-sulfur battery, which includes the following steps:
  • a metal gasket 12 is installed on the second negative electrode material layer 11, and a metal spring sheet 13 is installed on the metal gasket 12;
  • the opening 14 is sealed with an insulating material 15 to insulate the first aluminum strip 6 and the second aluminum strip 8 from the top case 2.
  • the insulating material 15 is made of resin, and the opening 14 is sealed by a hydraulic sealer.
  • the moisture content of the glove box should not be higher than 1 ppm.
  • Some steps do not conflict with each other. They can be executed synchronously, or they can be executed one after the other or the order of execution can be changed. The specific whether they can be executed synchronously or the order of execution depends on the actual situation. .
  • the four-electrode lithium-sulfur battery is assembled. After the four-electrode lithium-sulfur battery is assembled, it needs to stand for 8 hours to allow the resin to completely cure before taking it out of the glove box.
  • the assembled four-electrode lithium-sulfur battery has a four-electrode symmetrical structure as shown in Figure 1.
  • the preparation methods of the first positive electrode material layer 5 and the second positive electrode material layer 9 are:
  • porous carbon paper as the current collector, clean it with acetone, cut it into discs, add sulfur powder on the disc, and heat it to 120 degrees to melt the sulfur powder and be absorbed by the carbon paper.
  • the first aluminum strip 6 is fixedly connected to the edge of the first positive electrode material layer 5
  • the second aluminum strip 8 is fixedly connected to the edge of the second positive electrode material layer 9 .
  • the third embodiment of the present invention provides an electrode electrochemical characteristic monitoring method based on the above four-electrode lithium-sulfur battery, which includes the following steps:
  • the double pole double throw switch 17 is connected to the negative electrode of the charge and discharge tester 19 and the other end of the impedance spectrum tester 18;
  • the first aluminum strip 6 and the second aluminum strip 8 can be connected to the positive electrode of the charge and discharge tester 19 at the same time, or the first aluminum strip 6 and the second aluminum strip 8 can be connected to the impedance spectrum at the same time.
  • One end of the tester 18 is connected, and the top case 2 and the bottom case 1 can be connected to the negative electrode of the charge and discharge tester 19 at the same time through the second double-pole double-throw switch 17, or the top case 2 and the bottom case 1 can be simultaneously tested with the impedance spectrum
  • the other end of the meter 18 is connected; the first aluminum strip 6 and the second aluminum strip 8 are simultaneously connected to the positive electrode of the charge and discharge tester 19, and the top case 2 and the bottom case 1 are simultaneously connected to the negative electrode of the charge and discharge tester 19 , Can perform constant current charge and discharge test, connect the first aluminum strip 6 and the second aluminum strip 8 to one end of the impedance spectrum tester 18 at the same time, and simultaneously connect the top shell 2 and the bottom shell 1 to the other end of the impedance spectrum tester 18 After one end is connected, impedance spectrum test can be performed;
  • the charge and discharge tester 19 uses Arbin BT2000, and the impedance spectrum tester 18 uses Zahner IM6 electrochemical workstation. Connect according to Figure 2.
  • the four-electrode lithium-sulfur battery is connected to the charge and discharge tester 19.
  • the 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 was connected to Arbin BT2000, and the constant current charge and discharge test was performed to check the usability of the battery.
  • the discharge and charge current is 177mA (0.1mA/cm2)
  • the discharge cut-off voltage is 1.7V
  • the charge cut-off voltage is 2.8V.
  • the charge and discharge voltage was recorded at the same time of charging and discharging.
  • the recorded voltage curve is shown in Figure 3. Among them, the high-potential discharge platform at 2.3V and the low-potential discharge platform at 2.1V are typical dual-discharge platforms. Consistent. It shows that the newly assembled four-electrode lithium-sulfur battery can work normally and is effective.
  • the impedance spectrum test of the four-electrode lithium-sulfur battery can obtain the online impedance spectrum of the battery. First, fully charge the battery, then set the single discharge capacity in Arbin BT2000, start constant current discharge, and record the battery voltage during the discharge process. At this time, the first double-pole double-throw switch 16 and the second double-pole double-throw switch 17 in FIG. 2 are in the left position. When the discharge reaches the set capacity, pause the discharge, switch the first double-pole double-throw switch 16 and the second double-pole double-throw switch 17 to the right position, and connect the battery to the Zahner IM6 electrochemical workstation for impedance spectroscopy test.

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Abstract

A four-electrode lithium-sulfur battery and a preparation method therefor, and an electrode electrochemical property monitoring method. The four-electrode lithium-sulfur battery has a four-electrode structure, wherein a top housing (2) and a bottom housing (1) are two negative electrodes, two aluminum strips (6, 8) are two positive electrodes, and the two negative electrodes (3, 11) are mounted at the upper and lower sides of the lithium-sulfur battery and clamp two positive electrodes (5, 9) in the middle; moreover, the positive electrodes (5, 9) and the negative electrodes (3, 11) are separated by diaphragms (4, 10), and the two positive electrodes (5, 9) are also separated by a diaphragm (7). The lithium-sulfur battery has the four-electrode structure, and the electrochemical impedance of the positive electrodes and the negative electrodes can be simultaneously collected without damaging the battery structure, thereby solving a problem that conventional commercial two-electrode batteries and three-electrode batteries at present cannot accurately obtain electrochemical information of a single electrode.

Description

四电极锂硫电池、其制备方法及电极电化学特性监测方法Four-electrode lithium-sulfur battery, its preparation method and electrode electrochemical characteristics monitoring method 技术领域Technical field
本发明涉及电池制备及检测技术，尤其涉及一种基于四电极锂硫电池、其制备方法及电极电化学特性监测方法。The invention relates to 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.
背景技术Background technique
近年来的电动车和个人电子设备的普及，离不开高性能的锂电池。然而，目前的锂离子电池能量密度已经接近理论值。商业化的锂离子电池以磷酸铁锂(LiFePO4)，镍钴锰酸锂(NMC)和镍钴铝酸锂(NCA)等为正极，石墨为负极，容量一般在250Wh/kg左右。想要进一步提高能量密度，则需要改变正负极的材料，这是下一代锂电池的发展方向。锂硫电池极具潜力的锂离子电池竞争者。该电池体系采用单质硫(理论比容量为1675mAh/g)为正极材料，以金属锂做负极，平均输出电压可达2.1V，体系的理论能量密度为2567Wh/kg，大约是传统锂离子电池的10倍。虽然单质硫在自然界分布广泛，储量大，成本低，然而目前锂硫电池大规模的商业化生产还有很多挑战。比如多硫化物的溶解导致的容量损失，活性物质的导电性差导致输出电压低，电池容量低于理论值。这些都和电池的内阻有着直接的联系。In recent years, the popularization of electric vehicles and personal electronic equipment is inseparable from high-performance lithium batteries. However, the current energy density of lithium-ion batteries is close to the theoretical value. Commercial lithium-ion batteries use lithium iron phosphate (LiFePO4), lithium nickel cobalt manganate (NMC) and lithium nickel cobalt aluminate (NCA) as the positive electrode, graphite as the negative electrode, and the capacity is generally around 250Wh/kg. To further increase the energy density, it is necessary to change the materials of the positive and negative electrodes, which is the development direction of the next generation of lithium batteries. Lithium-sulfur battery is a potential competitor of lithium-ion battery. The battery system uses elemental sulfur (theoretical specific capacity of 1675mAh/g) as the positive electrode material and lithium metal as the negative electrode. The average output voltage can reach 2.1V. The theoretical energy density of the system is 2567Wh/kg, which is about the same as that of traditional lithium-ion batteries. 10 times. Although elemental sulfur is widely distributed in nature, has large reserves and low cost, there are still many challenges in the large-scale commercial production of lithium-sulfur batteries. For example, the capacity loss caused by the dissolution of polysulfides, the poor conductivity of the active material leads to low output voltage, and the battery capacity is lower than the theoretical value. These are directly related to the internal resistance of the battery.
电化学阻抗谱是研究电池内阻的经典方法之一。它不仅能表征离子的电导率，还能进行电极的电化学反应动力学研究。但是，普通的全电池，测试所得到的是正极，电解液和负极阻抗的叠加，并且很难将这三部分各自的阻抗区分出来。如果要得到单个电极的阻抗，目前常用的方法有两种。一种是将多个电池拆解，正极和正极(或者负极和负极)重新组装成二电极对称电池。第二种是加入一个参比电极，做成三电极电池。Electrochemical impedance spectroscopy is one of the classic methods to study the internal resistance of batteries. It can not only characterize the conductivity of ions, but also conduct the study of electrochemical reaction kinetics of electrodes. However, for an ordinary full battery, the test results are the superposition of the impedance of the positive electrode, the electrolyte and the negative electrode, and it is difficult to distinguish the respective impedances of these three parts. If you want to obtain the impedance of a single electrode, there are two commonly used methods. One is to disassemble multiple batteries, and reassemble the positive and positive electrodes (or negative and negative electrodes) into a two-electrode symmetrical battery. The second is to add a reference electrode to make a three-electrode battery.
二电极对称电池制作繁琐，需要将电池拆开重新组装，这种电池将不能继续充放电。并且拆开的过程不可避免的会对电极有所破坏，电解液也会有损失，这些因素都会导致测量结果不准确。三电极电池虽然常常被用来测试单一电极的 阻抗，但是早有研究证明其内在的电化学不对称，会影响测试精度。The production of a two-electrode symmetrical battery is complicated, and the battery needs to be disassembled and reassembled. This kind of battery cannot continue to charge and discharge. In addition, the disassembly process will inevitably damage the electrodes and the electrolyte will also be lost. These factors will lead to inaccurate measurement results. Although the three-electrode battery is often used to test the impedance of a single electrode, long ago studies have shown that its inherent electrochemical asymmetry will affect the test accuracy.
在不破坏电池的情况下，又能精确的测定电池正极和负极阻抗的方法，还未见报道。The method of accurately measuring the impedance of the positive and negative electrodes of the battery without damaging the battery has not been reported yet.
发明概述Summary of the invention
技术问题technical problem
问题的解决方案The solution to the problem
技术解决方案Technical solutions
本发明主要目的在于，提供一种四电极锂硫电池、其制备方法及电极电化学特性监测方法，可在不拆解电池的情况下，测得精确的电池正极和负极阻抗谱。The main purpose of the present invention is to provide a four-electrode lithium-sulfur battery, a preparation method thereof, and an electrode electrochemical characteristic monitoring method, which can measure accurate battery positive and negative impedance spectra without disassembling the battery.
本发明是通过如下技术方案实现的：The present invention is realized through the following technical solutions:
一种四电极锂硫电池，包括外壳和封装在所述外壳内的电池组件，所述外壳包括金属底壳和扣合在所述底壳上的金属顶壳，所述顶壳与所述底壳绝缘，所述电池组件由下至上包括第一负极材料层、第一隔膜层、第一正极材料层、第一铝带、第二隔膜层、第二铝带、第二正极材料层、第三隔膜层和第二负极材料层；A four-electrode lithium-sulfur battery, comprising an outer shell and a battery assembly encapsulated in the outer shell, the outer shell including a metal bottom shell and a metal top shell buckled on the bottom shell, the top shell and the bottom shell Shell insulation, the battery assembly includes a first negative electrode material layer, a first separator layer, a first positive electrode material layer, a first aluminum tape, a second separator layer, a second aluminum tape, a second positive electrode material layer, and a first Three separator layers and a second negative electrode material layer;
所述第一负极材料层安装在所述底壳内侧底部，并与所述底壳电连接，所述第二负极材料层上安装有与所述第二负极材料层电连接的金属垫片，所述金属垫片上安装有与所述金属垫片电连接的金属弹簧片，所述金属弹簧片弹性抵压在所述顶壳内侧顶部与所述金属垫片之间，并与所述顶壳电连接；The first negative electrode material layer is installed on the inner bottom of the bottom case and is electrically connected to the bottom case, and the second negative electrode material layer is installed with a metal gasket electrically connected to the second negative electrode material layer, The metal washer is equipped with a metal spring sheet electrically connected to the metal washer, and the metal spring sheet is elastically pressed between the inner top of the top shell and the metal washer, and is connected to the top Shell electrical connection;
所述第一铝带与所述第一正极材料层电连接，所述第二铝带与所述第二正极材料层电连接，所述顶壳上开设有开孔，所述第一铝带和所述第二铝带从所述开孔引出，并与所述顶壳绝缘。The first aluminum strip is electrically connected to the first positive electrode material layer, the second aluminum strip is electrically connected to the second positive electrode material layer, the top case is provided with openings, and the first aluminum strip And the second aluminum strip is led out from the opening and insulated from the top case.
进一步地，所述第一正极材料层和所述第二正极材料层采用多孔碳纸作为集流体。Further, the first positive electrode material layer and the second positive electrode material layer use porous carbon paper as a current collector.
进一步地，所述第一铝带固定连接在所述第一正极材料层的边缘，所述第二铝带固定连接在所述第二正极材料层的边缘。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.
进一步地，所述第一负极材料层和所述第二负极材料层为金属锂片。Further, the first negative electrode material layer and the second negative electrode material layer are metal lithium sheets.
进一步地，所述外壳为扣式电池的外壳。Further, the casing is a casing of a button battery.
一种制备如上所述的四电极锂硫电池的方法，包括如下步骤：A method for preparing the above-mentioned four-electrode lithium-sulfur battery includes the following steps:
准备顶壳和底壳，并在所述顶壳上开设开孔；Prepare a top shell and a bottom shell, and open holes in the top shell;
制备所述第一负极材料层、所述第一隔膜层、所述第一正极材料层、所述第一铝带、所述第二隔膜层、所述第二铝带、所述第二正极材料层、所述第三隔膜层和所述第二负极材料层；Preparation of 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, and the second positive electrode Material layer, the third separator layer and the second negative electrode material layer;
在手套箱中由下至上依次安装所述底壳、所述第一负极材料层、所述第一隔膜层、所述第一正极材料层、所述第一铝带、所述第二隔膜层、所述第二铝带、所述第二正极材料层、所述第三隔膜层和所述第二负极材料层，在安装所述第一隔膜层、所述第一正极材料层、所述第二隔膜层、所述第二正极材料层和所述第三隔膜层时，先注入电解液然后再安装；Install the bottom case, the first negative electrode material layer, the first diaphragm layer, the first positive electrode material layer, the first aluminum tape, and the second diaphragm layer in the glove box from bottom to top , The second aluminum tape, the second positive electrode material layer, the third separator layer, and the second negative electrode material layer are installed after the first separator layer, the first positive electrode material layer, and the When the second separator layer, the second positive electrode material layer and the third separator layer are used, the electrolyte is injected first and then installed;
将所述第一铝带和所述第二铝带从所述开孔引出；Leading the first aluminum strip and the second aluminum strip from the opening;
在所述第二负极材料层上安装金属垫片，并在所述金属垫片上安装金属弹簧片；Installing a metal gasket on the second negative electrode material layer, and installing a metal spring sheet on the metal gasket;
将所述顶壳扣合在所述底壳上，使所述金属弹簧片弹性抵压在所述顶壳内侧顶部与所述金属垫片之间，并与所述顶壳电连接；Buckle the top shell on the bottom shell, so that the metal spring sheet elastically presses between the inner top of the top shell and the metal gasket, and is electrically connected to the top shell;
利用绝缘材料将所述开孔密封，使所述第一铝带和所述第二铝带与所述顶壳绝缘。The opening is sealed with an insulating material to insulate the first aluminum strip and the second aluminum strip from the top case.
进一步地，所述第一正极材料层和所述第二正极材料层的制备方法均包括：Further, the preparation methods of the first positive electrode material layer and the second positive electrode material layer both include:
采用多孔碳纸作为集流体，用丙酮清洗干净后，将其切成圆片，添加硫粉在圆片上，并加热到120度，使硫粉溶化被碳纸吸收。Use porous carbon paper as the current collector, clean it with acetone, cut it into discs, add sulfur powder on the disc, and heat it to 120 degrees to melt the sulfur powder and be absorbed by the carbon paper.
进一步地，安装所述第一铝带和所述所述第二铝带时，将所述第一铝带固定连接在所述第一正极材料层的边缘，将所述第二铝带固定连接在所述第二正极材料层的边缘。Further, when installing the first aluminum strip and the second aluminum strip, 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 At the edge of the second positive electrode material layer.
进一步地，所述绝缘材料为树脂。Further, the insulating material is resin.
基于如上所述的四电极锂硫电池的电极电化学特性监测方法，包括如下步骤：The method for monitoring the electrochemical characteristics of electrodes based on the four-electrode lithium-sulfur battery as described above includes the following steps:
将第一铝带和第二铝带通过第一双刀双掷开关连接至充放电测试仪的正极和阻抗谱测试仪的一端，将顶壳和底壳通过第二双刀双掷开关连接至所述充放电测试仪的负极和所述阻抗谱测试仪的另一端；Connect the first aluminum strip and the second aluminum strip to the positive electrode of the charge-discharge tester and one end of the impedance spectrum tester through the first double-pole double-throw switch, and connect the top and bottom cases to the second double-pole double-throw switch. The negative electrode of the charge and discharge tester and the other end of the impedance spectrum tester;
通过所述第一双刀双掷开关能够将所述第一铝带和所述第二铝带同时与所述充放电测试仪的正极连接，或者将所述第一铝带和所述第二铝带同时与所述阻抗谱测试仪的一端连接，通过所述第二双刀双掷开关能够将所述顶壳和所述底壳同时与所述充放电测试仪的负极连接，或者将所述顶壳和所述底壳同时与所述阻抗谱测试仪的另一端连接；将所述第一铝带和所述第二铝带同时与所述充放电测试仪的正极连接，同时将所述顶壳和所述底壳同时与所述充放电测试仪的负极连接后，能够进行恒电流充放电测试，将所述第一铝带和所述第二铝带同时与所述阻抗谱测试仪的一端连接，同时将所述顶壳和所述底壳同时与所述阻抗谱测试仪的另一端连接后，能够进行阻抗谱测试；Through the first double-pole double-throw switch, the first aluminum strip and the second aluminum strip can be simultaneously connected to the positive electrode of the charge and discharge tester, or the first aluminum strip and the second aluminum strip can be connected The aluminum strip is connected to one end of the impedance spectrum tester at the same time, and the top case and the bottom case can be simultaneously connected to the negative electrode of the charge and discharge tester through the second double-pole double-throw switch, or all The top case and the bottom case are simultaneously connected to the other end of the impedance spectrum tester; the first aluminum strip and the second aluminum strip are simultaneously connected to the positive electrode of the charge-discharge tester, and all After the top case and the bottom case are simultaneously connected to the negative electrode of the charge and discharge tester, a constant current charge and discharge test can be performed, and the first aluminum strip and the second aluminum strip are simultaneously tested with the impedance spectrum After connecting one end of the instrument, and simultaneously connecting the top shell and the bottom shell to the other end of the impedance spectrum tester, impedance spectrum testing can be performed;
根据预设程序对所述四电极锂硫电池进行恒电流充放电测试和阻抗谱测试，并记录相应电压曲线和阻抗谱曲线。Perform constant current charge and discharge test and impedance spectrum test on the four-electrode lithium-sulfur battery according to a preset program, and record the corresponding voltage curve and impedance spectrum curve.
与现有技术相比，本发明提供了一种四电极锂硫电池、其制备方法及电极电化学特性监测方法。四电极锂硫电池具有四电极结构，其中顶壳和底壳为两个负极，两条铝带为两个正极，两个负极安装在锂硫电池的上下两侧，将两个正极夹在中间，同时，正极与负极间用隔膜隔开，两个正极之间也用隔膜隔开。该锂硫电池具有四电极结构，可在不破坏电池结构的前提下，同时采集电池的正极和负极的电化学阻抗，解决了目前传统商用两电极电池和三电极电池无法精确获得单一电极电化学信息的问题。本发明可用于新型电极材料的研发。Compared with the prior art, the present 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, in which the top shell and the bottom shell are two negative electrodes, two aluminum strips are two positive electrodes, and the two negative electrodes are installed on the upper and lower sides of the lithium-sulfur battery, sandwiching the two positive electrodes in the middle At the same time, the positive electrode and the negative electrode are separated by a separator, and the two positive electrodes are also separated by a separator. The lithium-sulfur battery has a four-electrode structure, which can collect the electrochemical impedance of the positive and negative electrodes of the battery at the same time without damaging the structure of the battery. This solves the problem that traditional commercial two-electrode batteries and three-electrode batteries cannot accurately obtain single-electrode electrochemistry. Information problem. The invention can be used for the research and development of new electrode materials.
发明的有益效果The beneficial effects of the invention
对附图的简要说明Brief description of the drawings
附图说明Description of the drawings
图1是本发明实施例四电极锂硫电池的组成原理示意图；1 is a schematic diagram of the composition principle of a four-electrode lithium-sulfur battery according to an embodiment of the present invention;
图2是本发明实施例四电极锂硫电池的电化学特性测试连接示意图；2 is a schematic diagram of the electrochemical characteristics test connection diagram of a four-electrode lithium-sulfur battery in an embodiment of the present invention;
图3是用恒电流方法对四电极电池进行充放电的电压曲线图；Figure 3 is a voltage curve diagram of charging and discharging a four-electrode battery using a constant current method;
图4是典型的电池正极和负极的阻抗谱曲线图；Figure 4 is a graph of impedance spectra of a typical battery positive and negative electrodes;
图5是电池的电解液、正极和负极的内阻在电池放电时的变化曲线图。Fig. 5 is a graph showing changes in the internal resistance of the electrolyte, the positive electrode and the negative electrode of the battery when the battery is discharged.
发明实施例Invention embodiment
本发明的实施方式Embodiments of the invention
为使本发明的目的、技术方案和优点更加清楚明白，下面结合实施例和附图，对本发明作进一步详细说明。In order to make the objectives, technical solutions, and advantages of the present invention clearer, the following further describes the present invention in detail with reference to embodiments and drawings.
如图1所示，本发明实施例一提供的四电极锂硫电池，包括外壳和封装在外壳内的电池组件，外壳包括金属底壳1和扣合在底壳1上的金属顶壳2，顶壳2与底壳1绝缘，电池组件由下至上包括第一负极材料层3、第一隔膜层4、第一正极材料层5、第一铝带6、第二隔膜层7、第二铝带8、第二正极材料层9、第三隔膜层10和第二负极材料层11。As shown in Fig. 1, the four-electrode lithium-sulfur battery provided in the first embodiment of the present invention includes a shell and a battery assembly enclosed in the shell. The shell includes a metal bottom shell 1 and a metal top shell 2 fastened to the bottom shell 1. The top case 2 is insulated from the bottom case 1, and the battery assembly includes a first negative electrode material layer 3, a first separator layer 4, a first positive electrode material layer 5, a first aluminum strip 6, a second separator layer 7, and a second aluminum from bottom to top. Belt 8, second positive electrode material layer 9, third separator layer 10, and second negative electrode material layer 11.
第一负极材料层3安装在底壳1内侧底部，并与底壳1电连接，第二负极材料层11上安装有与第二负极材料层11电连接的金属垫片12，金属垫片12上安装有与金属垫片12电连接的金属弹簧片13，金属弹簧片13弹性抵压在顶壳2内侧顶部与金属垫片12之间，并与顶壳2电连接。The first negative electrode material layer 3 is installed on the inner bottom of the bottom case 1 and is electrically connected to the bottom case 1. The second negative electrode material layer 11 is equipped with a metal gasket 12 electrically connected to the second negative electrode material layer 11, and the metal gasket 12 A metal spring sheet 13 electrically connected to the metal washer 12 is installed on it. The metal spring sheet 13 is elastically pressed between the inner top of the top shell 2 and the metal washer 12 and is electrically connected to the top shell 2.
第一铝带6与第一正极材料层5电连接，第二铝带8与第二正极材料层9电连接，顶壳2上开设有开孔14，第一铝带6和第二铝带8从开孔14引出，并与顶壳2绝缘。The first aluminum strip 6 is electrically connected to the first positive electrode material layer 5, the second aluminum strip 8 is electrically connected to the second positive electrode material layer 9, the top case 2 is provided with an opening 14, the first aluminum strip 6 and the second aluminum strip 8 leads from the opening 14 and is insulated from the top case 2.
该四电极锂硫电池作为一种四电极对称电池，可直接采用扣式电池的外壳作为其外壳。例如，可直接采用CR2032扣式不锈钢电池的外壳来封装电池组件，只需要对其外壳的负极(即顶壳2)稍作调整，切开一个小洞作为引出第一铝带6和第二铝带8的开孔14。第一正极材料层5和第二正极材料层9采用多孔碳纸作为集流体，厚度为0.28毫米，用丙酮将多孔碳纸清洗干净后，将其切成直径为14毫米的圆片，添加一定量的硫粉在圆片上，加热到120度，使硫粉溶化被碳纸吸收。第一隔膜层4、第二隔膜层7和第三隔膜层10均可采用商用的锂离子电池的隔膜，厚度为25微米，切成直径为15毫米的圆片。第一铝带6和第二铝带8可由铝箔剪成细长的带状制成，第一铝带6固定连接在第一正极材料层5的边缘，第二铝带8固定连接在第二正极材料层9的边缘。第一负极材料层3和第二负极材料层11均为金属锂片，厚度0.5毫米，直径14毫米。各正极材料层和各隔膜层中注入的电解液是1，3-二氧戊环(DOL)和1，2-二甲氧基乙烷(DME)的等比例混合溶剂，内含1M双(三氟甲烷)磺酰亚胺(LiTFSI)。制得的四电极锂硫电池具有两 个正极和两个负极共四个电极，其中顶壳2和底壳1为两个负极，两条铝带为两个正极，两个负极安装在锂硫电池的上下两侧，将两个正极夹在中间，同时，正极与负极间用隔膜隔开，两个正极之间也用隔膜隔开。该锂硫电池由于具有四电极结构，可在不破坏电池结构的前提下，同时采集电池的正极和负极的电化学阻抗，解决了目前传统商用两电极电池和三电极电池无法精确获得单一电极电化学信息的问题。As a four-electrode symmetrical battery, the four-electrode lithium-sulfur battery can directly use the shell of the button cell as its shell. For example, the shell of CR2032 button-type stainless steel battery can be directly used to encapsulate the battery assembly, and the negative electrode of the shell (ie, the top shell 2) needs to be adjusted slightly, and a small hole is cut to lead out the first aluminum strip 6 and the second aluminum Opening 14 with 8 The first positive electrode material layer 5 and the second positive electrode material layer 9 use porous carbon paper as the current collector with a thickness of 0.28 mm. After the porous carbon paper is cleaned with acetone, it is cut into 14 mm diameter discs, and a certain amount is added. The amount of sulfur powder is heated to 120 degrees on the wafer, so that the sulfur powder is dissolved and absorbed by the carbon paper. The first diaphragm layer 4, the second diaphragm layer 7 and the third diaphragm layer 10 can all be commercial lithium-ion battery diaphragms with a thickness of 25 microns and cut into discs with a diameter of 15 mm. The first aluminum strip 6 and the second aluminum strip 8 can be made by cutting aluminum foil 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 second The edge of the positive electrode material layer 9. The first negative electrode material layer 3 and the second negative electrode material layer 11 are both metal lithium sheets, with a thickness of 0.5 mm and a diameter of 14 mm. The electrolyte injected into each cathode material layer and each separator layer is a mixed solvent of 1,3-dioxolane (DOL) and 1,2-dimethoxyethane (DME) in equal proportions, containing 1M bis( Trifluoromethane)sulfonimide (LiTFSI). The prepared four-electrode lithium-sulfur battery has two positive electrodes and two negative electrodes, a total of four electrodes, in which the top shell 2 and the bottom shell 1 are two negative electrodes, the two aluminum strips are two positive electrodes, and the two negative electrodes are installed on the lithium sulfur The upper and lower sides of the battery are sandwiched between the two positive electrodes. At the same time, the positive electrode and the negative electrode are separated by a separator, and the two positive electrodes are also separated by a separator. Due to the four-electrode structure of the lithium-sulfur battery, the electrochemical impedance of the positive and negative electrodes of the battery can be collected at the same time without destroying the battery structure, which solves the problem that the current traditional commercial two-electrode batteries and three-electrode batteries cannot accurately obtain a single electrode. The question of chemical information.
本发明实施例二提供了一种制备如上的四电极锂硫电池的方法，包括如下步骤：The second embodiment of the present invention provides a method for preparing the above four-electrode lithium-sulfur battery, which includes the following steps:
准备顶壳2和底壳1，并在顶壳2上开设开孔14；Prepare top shell 2 and bottom shell 1, and open holes 14 on top shell 2;
制备第一负极材料层3、第一隔膜层4、第一正极材料层5、第一铝带6、第二隔膜层7、第二铝带8、第二正极材料层9、第三隔膜层10和第二负极材料层11；Preparation of the first negative electrode material layer 3, the first separator layer 4, the first positive electrode material layer 5, the first aluminum tape 6, the second separator layer 7, the second aluminum tape 8, the second positive electrode material layer 9, and the third separator layer 10 and the second negative electrode material layer 11;
在手套箱中由下至上依次安装底壳1、第一负极材料层3、第一隔膜层4、第一正极材料层5、第一铝带6、第二隔膜层7、第二铝带8、第二正极材料层9、第三隔膜层10和第二负极材料层11，在安装第一隔膜层4、第一正极材料层5、第二隔膜层7、第二正极材料层9和第三隔膜层10时，先注入电解液然后再安装；Install the bottom case 1, the first negative electrode material layer 3, the first diaphragm layer 4, the first positive electrode material layer 5, the first aluminum tape 6, the second diaphragm layer 7, and the second aluminum tape 8 in the glove box from bottom to top. , The second positive electrode material layer 9, the third separator layer 10 and the second negative electrode material layer 11 are installed in the first separator layer 4, the first positive electrode material layer 5, the second separator layer 7, the second positive electrode material layer 9 and the first When the three diaphragm layer is 10, inject electrolyte first and then install;
将第一铝带6和第二铝带8从开孔14引出；Lead the first aluminum strip 6 and the second aluminum strip 8 from the opening 14;
在第二负极材料层11上安装金属垫片12，并在金属垫片12上安装金属弹簧片13；A metal gasket 12 is installed on the second negative electrode material layer 11, and a metal spring sheet 13 is installed on the metal gasket 12;
将顶壳2扣合在底壳1上，使金属弹簧片13弹性抵压在顶壳2内侧顶部与金属垫片12之间，并与顶壳2电连接；Fasten the top shell 2 on the bottom shell 1, so that the metal spring sheet 13 is elastically pressed between the top inside the top shell 2 and the metal gasket 12, and is electrically connected to the top shell 2;
利用绝缘材料15将开孔14密封，使第一铝带6和第二铝带8与顶壳2绝缘。本实施例中绝缘材料15采用树脂，采用液压封口机密封开孔14。The opening 14 is sealed with an insulating material 15 to insulate the first aluminum strip 6 and the second aluminum strip 8 from the top case 2. In this embodiment, the insulating material 15 is made of resin, and the opening 14 is sealed by a hydraulic sealer.
需要指出的是，手套箱的含水量需不高于1ppm。同时，上述各步骤之间并没有绝对的先后顺序，有些步骤之间执行不相冲突，可以同步执行，也可以先后执行或调换执行顺序，具体能否同步执行或调换执行顺序依实际情况而定。将开孔14密封后四电极锂硫电池就组装完成了，四电极锂硫电池组装完成后需要静置8小时，让树脂彻底固化后再从手套箱中取出。组装好的四电极锂硫电池，其四电极对称结构如图1所示。It should be pointed out that the moisture content of the glove box should not be higher than 1 ppm. At the same time, there is no absolute sequence between the above steps. Some steps do not conflict with each other. They can be executed synchronously, or they can be executed one after the other or the order of execution can be changed. The specific whether they can be executed synchronously or the order of execution depends on the actual situation. . After the opening 14 is sealed, the four-electrode lithium-sulfur battery is assembled. After the four-electrode lithium-sulfur battery is assembled, it needs to stand for 8 hours to allow the resin to completely cure before taking it out of the glove box. The assembled four-electrode lithium-sulfur battery has a four-electrode symmetrical structure as shown in Figure 1.
本实施例中，第一正极材料层5和第二正极材料层9的制备方法为：In this embodiment, the preparation methods of the first positive electrode material layer 5 and the second positive electrode material layer 9 are:
采用多孔碳纸作为集流体，用丙酮清洗干净后，将其切成圆片，添加硫粉在圆片上，并加热到120度，使硫粉溶化被碳纸吸收。Use porous carbon paper as the current collector, clean it with acetone, cut it into discs, add sulfur powder on the disc, and heat it to 120 degrees to melt the sulfur powder and be absorbed by the carbon paper.
在安装第一铝带6和第二铝带8时，将第一铝带6固定连接在第一正极材料层5的边缘，将第二铝带8固定连接在第二正极材料层9的边缘。When installing the first aluminum strip 6 and the second aluminum strip 8, 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 .
本发明实施例三提供了一种基于如上的四电极锂硫电池的电极电化学特性监测方法，包括如下步骤：The third embodiment of the present invention provides an electrode electrochemical characteristic monitoring method based on the above four-electrode lithium-sulfur battery, which includes the following steps:
将第一铝带6和第二铝带8通过第一双刀双掷开关16连接至充放电测试仪19的正极和阻抗谱测试仪18的一端，将顶壳2和底壳1通过第二双刀双掷开关17连接至充放电测试仪19的负极和阻抗谱测试仪18的另一端；Connect the first aluminum strip 6 and the second aluminum strip 8 to the positive electrode of the charge and discharge tester 19 and one end of the impedance spectrum tester 18 through the first double-pole double-throw switch 16, and pass the top case 2 and the bottom case 1 through the second The double pole double throw switch 17 is connected to the negative electrode of the charge and discharge tester 19 and the other end of the impedance spectrum tester 18;
通过第一双刀双掷开关16能够将第一铝带6和第二铝带8同时与充放电测试仪19的正极连接，或者将第一铝带6和第二铝带8同时与阻抗谱测试仪18的一端连接，通过第二双刀双掷开关17能够将顶壳2和底壳1同时与充放电测试仪19的负极连接，或者将顶壳2和底壳1同时与阻抗谱测试仪18的另一端连接；将第一铝带6和第二铝带8同时与充放电测试仪19的正极连接，同时将顶壳2和底壳1同时与充放电测试仪19的负极连接后，能够进行恒电流充放电测试，将第一铝带6和第二铝带8同时与阻抗谱测试仪18的一端连接，同时将顶壳2和底壳1同时与阻抗谱测试仪18的另一端连接后，能够进行阻抗谱测试；Through the first double-pole double-throw switch 16, the first aluminum strip 6 and the second aluminum strip 8 can be connected to the positive electrode of the charge and discharge tester 19 at the same time, or the first aluminum strip 6 and the second aluminum strip 8 can be connected to the impedance spectrum at the same time. One end of the tester 18 is connected, and the top case 2 and the bottom case 1 can be connected to the negative electrode of the charge and discharge tester 19 at the same time through the second double-pole double-throw switch 17, or the top case 2 and the bottom case 1 can be simultaneously tested with the impedance spectrum The other end of the meter 18 is connected; the first aluminum strip 6 and the second aluminum strip 8 are simultaneously connected to the positive electrode of the charge and discharge tester 19, and the top case 2 and the bottom case 1 are simultaneously connected to the negative electrode of the charge and discharge tester 19 , Can perform constant current charge and discharge test, connect the first aluminum strip 6 and the second aluminum strip 8 to one end of the impedance spectrum tester 18 at the same time, and simultaneously connect the top shell 2 and the bottom shell 1 to the other end of the impedance spectrum tester 18 After one end is connected, impedance spectrum test can be performed;
根据预设程序对四电极锂硫电池进行恒电流充放电测试和阻抗谱测试，并记录相应电压曲线和阻抗谱曲线。Perform constant current charge and discharge test and impedance spectrum test on the four-electrode lithium-sulfur battery according to the preset program, and record the corresponding voltage curve and impedance spectrum curve.
具体测试可按照如下方法进行：The specific test can be carried out as follows:
充放电测试仪19采用的是Arbin BT2000，阻抗谱测试仪18采用的是Zahner IM6电化学工作站。根据图2进行连接，当第一双刀双掷开关16和第二双刀双掷开关17切换到左边位置时，该四电极锂硫电池与充放电测试仪19连接，当第一双刀双掷开关16和第二双刀双掷开关17切换到右边位置时，该四电极锂硫电池与阻抗谱测试仪18连接。The charge and discharge tester 19 uses Arbin BT2000, and the impedance spectrum tester 18 uses Zahner IM6 electrochemical workstation. Connect according to Figure 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. When the 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.
将该四电极锂硫电池接入Arbin BT2000，进行恒电流充放电测试，检测电池的可用性。放电和充电电流为177mA(0.1mA/cm2)，放电截止电压为1.7V，充电 截止电压为2.8V。充放电的同时记录充放电电压，记录的电压曲线如图3所示，其中在2.3V的高电位放电平台和在2.1V的低电位放电平台，是典型的双放电平台，与相关研究报道的一致。说明该新组装的四电极锂硫电池能正常工作，是有效的。The four-electrode lithium-sulfur battery was connected to Arbin BT2000, and the constant current charge and discharge test was performed to check the usability of the battery. The discharge and charge current is 177mA (0.1mA/cm2), the discharge cut-off voltage is 1.7V, and the charge cut-off voltage is 2.8V. The charge and discharge voltage was recorded at the same time of charging and discharging. The recorded voltage curve is shown in Figure 3. Among them, the high-potential discharge platform at 2.3V and the low-potential discharge platform at 2.1V are typical dual-discharge platforms. Consistent. It shows that the newly assembled four-electrode lithium-sulfur battery can work normally and is effective.
将四电极锂硫电池进行阻抗谱测试可得到电池的在线阻抗谱。首先将该电池充满电，然后在Arbin BT2000设定单次放电容量，开始恒电流放电，放电过程中记录电池电压。此时图2中第一双刀双掷开关16和第二双刀双掷开关17在左边位置。放电到达设定容量时，暂停放电，将第一双刀双掷开关16和第二双刀双掷开关17切换到右边位置，将电池接Zahner IM6电化学工作站进行阻抗谱测试。设定开路电压为测试信号的电压，振幅为10mV，频率从1MHz到0.1Hz，得到正极和负极的阻抗谱。得到的正极和负极的阻抗谱如图4所示。测试完成后，重新将第一双刀双掷开关16和第二双刀双掷开关17切换到左边位置，继续放电并记录电池电压。重复上述步骤直到电池的放电电压降低到1.7V。图5中黑色曲线是以单次50mAh/g作为放电容量的电压曲线图。图5中由上至下的三个填充图分别是电池在放电过程中正极、负极和电解液的阻抗变化情况。The impedance spectrum test of the four-electrode lithium-sulfur battery can obtain the online impedance spectrum of the battery. First, fully charge the battery, then set the single discharge capacity in Arbin BT2000, start constant current discharge, and record the battery voltage during the discharge process. At this time, the first double-pole double-throw switch 16 and the second double-pole double-throw switch 17 in FIG. 2 are in the left position. When the discharge reaches the set capacity, pause the discharge, switch the first double-pole double-throw switch 16 and the second double-pole double-throw switch 17 to the right position, and connect the battery to the Zahner IM6 electrochemical workstation for impedance spectroscopy test. Set the open circuit voltage as the voltage of the test signal, the amplitude is 10mV, the frequency is from 1MHz to 0.1Hz, and the impedance spectra of the positive and negative electrodes are obtained. The impedance spectra of the positive and negative electrodes obtained are shown in Figure 4. After the test is completed, switch the first double pole double throw switch 16 and the second double pole double throw switch 17 to the left position again, continue to discharge and record the battery voltage. Repeat the above steps until the discharge voltage of the battery drops to 1.7V. The black curve in Figure 5 is a voltage curve with a single discharge capacity of 50 mAh/g. The three filling diagrams from top to bottom in Figure 5 are the impedance changes of the positive electrode, negative electrode, and electrolyte of the battery during discharge.
上述实施例仅为优选实施例，并不用以限制本发明的保护范围，在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。The above-mentioned embodiments are only preferred embodiments, and are not intended to limit the scope of protection of the present invention. Any modification, equivalent replacement and improvement made within the spirit and principle of the present invention shall be included in the scope of protection of the present invention. .

Claims (10)

  1. 一种四电极锂硫电池，包括外壳和封装在所述外壳内的电池组件，所述外壳包括金属底壳和扣合在所述底壳上的金属顶壳，所述顶壳与所述底壳绝缘，其特征在于，所述电池组件由下至上包括第一负极材料层、第一隔膜层、第一正极材料层、第一铝带、第二隔膜层、第二铝带、第二正极材料层、第三隔膜层和第二负极材料层；A four-electrode lithium-sulfur battery, comprising an outer shell and a battery assembly encapsulated in the outer shell, the outer shell including a metal bottom shell and a metal top shell buckled on the bottom shell, the top shell and the bottom shell Case insulation, characterized in that the battery assembly includes a first negative electrode material layer, a first separator layer, a first positive electrode material layer, a first aluminum tape, a second separator layer, a second aluminum tape, and a second positive electrode from bottom to top. Material layer, third separator layer and second negative electrode material layer;
    所述第一负极材料层安装在所述底壳内侧底部，并与所述底壳电连接，所述第二负极材料层上安装有与所述第二负极材料层电连接的金属垫片，所述金属垫片上安装有与所述金属垫片电连接的金属弹簧片，所述金属弹簧片弹性抵压在所述顶壳内侧顶部与所述金属垫片之间，并与所述顶壳电连接；The first negative electrode material layer is installed on the inner bottom of the bottom case and is electrically connected to the bottom case, and the second negative electrode material layer is installed with a metal gasket electrically connected to the second negative electrode material layer, The metal washer is equipped with a metal spring sheet electrically connected to the metal washer, and the metal spring sheet is elastically pressed between the inner top of the top shell and the metal washer, and is connected to the top Shell electrical connection;
    所述第一铝带与所述第一正极材料层电连接，所述第二铝带与所述第二正极材料层电连接，所述顶壳上开设有开孔，所述第一铝带和所述第二铝带从所述开孔引出，并与所述顶壳绝缘。The first aluminum strip is electrically connected to the first positive electrode material layer, the second aluminum strip is electrically connected to the second positive electrode material layer, the top case is provided with openings, and the first aluminum strip And the second aluminum strip is led out from the opening and insulated from the top case.
  2. 如权利要求1所述的四电极锂硫电池，其特征在于，所述第一正极材料层和所述第二正极材料层采用多孔碳纸作为集流体。The four-electrode lithium-sulfur battery according to claim 1, wherein the first positive electrode material layer and the second positive electrode material layer use porous carbon paper as a current collector.
  3. 如权利要求2所述的四电极锂硫电池，其特征在于，所述第一铝带固定连接在所述第一正极材料层的边缘，所述第二铝带固定连接在所述第二正极材料层的边缘。The four-electrode lithium-sulfur battery according to claim 2, wherein 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 second positive electrode. The edge of the material layer.
  4. 如权利要求1所述的四电极锂硫电池，其特征在于，所述第一负极材料层和所述第二负极材料层为金属锂片。8. The four-electrode lithium-sulfur battery according to claim 1, wherein the first negative electrode material layer and the second negative electrode material layer are metal lithium sheets.
  5. 如权利要求3所述的四电极锂硫电池，其特征在于，所述外壳为扣式电池的外壳。The four-electrode lithium-sulfur battery according to claim 3, wherein the casing is a button cell casing.
  6. 一种制备权利要求1至5中任一所述的四电极锂硫电池的方法，其特征在于，包括如下步骤：A method for preparing the four-electrode lithium-sulfur battery according to any one of claims 1 to 5, characterized in that it comprises the following steps:
    准备顶壳和底壳，并在所述顶壳上开设开孔；Prepare a top shell and a bottom shell, and open holes in the top shell;
    制备所述第一负极材料层、所述第一隔膜层、所述第一正极材料 层、所述第一铝带、所述第二隔膜层、所述第二铝带、所述第二正极材料层、所述第三隔膜层和所述第二负极材料层；Preparation of 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, and the second positive electrode Material layer, the third separator layer and the second negative electrode material layer;
    在手套箱中由下至上依次安装所述底壳、所述第一负极材料层、所述第一隔膜层、所述第一正极材料层、所述第一铝带、所述第二隔膜层、所述第二铝带、所述第二正极材料层、所述第三隔膜层和所述第二负极材料层，在安装所述第一隔膜层、所述第一正极材料层、所述第二隔膜层、所述第二正极材料层和所述第三隔膜层时，先注入电解液然后再安装；Install the bottom case, the first negative electrode material layer, the first diaphragm layer, the first positive electrode material layer, the first aluminum tape, and the second diaphragm layer in the glove box from bottom to top , The second aluminum tape, the second positive electrode material layer, the third separator layer and the second negative electrode material layer are installed in the first separator layer, the first positive electrode material layer, and the When the second separator layer, the second positive electrode material layer and the third separator layer are used, the electrolyte is injected first and then installed;
    将所述第一铝带和所述第二铝带从所述开孔引出；Leading the first aluminum strip and the second aluminum strip from the opening;
    在所述第二负极材料层上安装金属垫片，并在所述金属垫片上安装金属弹簧片；Installing a metal gasket on the second negative electrode material layer, and installing a metal spring sheet on the metal gasket;
    将所述顶壳扣合在所述底壳上，使所述金属弹簧片弹性抵压在所述顶壳内侧顶部与所述金属垫片之间，并与所述顶壳电连接；Buckle the top shell on the bottom shell, so that the metal spring sheet elastically presses between the inner top of the top shell and the metal gasket, and is electrically connected to the top shell;
    利用绝缘材料将所述开孔密封，使所述第一铝带和所述第二铝带与所述顶壳绝缘。The opening is sealed with an insulating material to insulate the first aluminum strip and the second aluminum strip from the top case.
  7. 如权利要求6所述的方法，其特征在于，所述第一正极材料层和所述第二正极材料层的制备方法均包括：8. The method of claim 6, wherein the preparation methods of the first positive electrode material layer and the second positive electrode material layer both comprise:
    采用多孔碳纸作为集流体，用丙酮清洗干净后，将其切成圆片，添加硫粉在圆片上，并加热到120度，使硫粉溶化被碳纸吸收。Use porous carbon paper as the current collector, clean it with acetone, cut it into discs, add sulfur powder on the disc, and heat it to 120 degrees to melt the sulfur powder and be absorbed by the carbon paper.
  8. 如权利要求6所述的方法，其特征在于，安装所述第一铝带和所述所述第二铝带时，将所述第一铝带固定连接在所述第一正极材料层的边缘，将所述第二铝带固定连接在所述第二正极材料层的边缘。The method of claim 6, wherein 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 , The second aluminum strip is fixedly connected to the edge of the second positive electrode material layer.
  9. 如权利要求6所述的方法，其特征在于，所述绝缘材料为树脂。The method according to claim 6, wherein the insulating material is resin.
  10. 基于权利要求1至5中任一所述的四电极锂硫电池的电极电化学特性监测方法，其特征在于，包括如下步骤：The method for monitoring the electrochemical characteristics of electrodes of a four-electrode lithium-sulfur battery according to any one of claims 1 to 5, characterized in that it comprises the following steps:
    将第一铝带和第二铝带通过第一双刀双掷开关连接至充放电测试仪的正极和阻抗谱测试仪的一端，将顶壳和底壳通过第二双刀双 掷开关连接至所述充放电测试仪的负极和所述阻抗谱测试仪的另一端；Connect the first aluminum strip and the second aluminum strip to the positive electrode of the charge-discharge tester and one end of the impedance spectrum tester through the first double-pole double-throw switch, and connect the top and bottom cases to the second double-pole double-throw switch. The negative electrode of the charge and discharge tester and the other end of the impedance spectrum tester;
    通过所述第一双刀双掷开关能够将所述第一铝带和所述第二铝带同时与所述充放电测试仪的正极连接，或者将所述第一铝带和所述第二铝带同时与所述阻抗谱测试仪的一端连接，通过所述第二双刀双掷开关能够将所述顶壳和所述底壳同时与所述充放电测试仪的负极连接，或者将所述顶壳和所述底壳同时与所述阻抗谱测试仪的另一端连接；将所述第一铝带和所述第二铝带同时与所述充放电测试仪的正极连接，同时将所述顶壳和所述底壳同时与所述充放电测试仪的负极连接后，能够进行恒电流充放电测试，将所述第一铝带和所述第二铝带同时与所述阻抗谱测试仪的一端连接，同时将所述顶壳和所述底壳同时与所述阻抗谱测试仪的另一端连接后，能够进行阻抗谱测试；Through the first double-pole double-throw switch, the first aluminum strip and the second aluminum strip can be connected to the positive electrode of the charge and discharge tester at the same time, or the first aluminum strip and the second aluminum strip can be connected The aluminum strip is connected to one end of the impedance spectrum tester at the same time, and the top case and the bottom case can be simultaneously connected to the negative electrode of the charge and discharge tester through the second double-pole double-throw switch, or all The top case and the bottom case are simultaneously connected to the other end of the impedance spectrum tester; the first aluminum strip and the second aluminum strip are simultaneously connected to the positive electrode of the charge-discharge tester, and all After the top case and the bottom case are simultaneously connected to the negative electrode of the charge and discharge tester, a constant current charge and discharge test can be performed, and the first aluminum strip and the second aluminum strip are simultaneously tested with the impedance spectrum After connecting one end of the instrument, and simultaneously connecting the top shell and the bottom shell to the other end of the impedance spectrum tester, impedance spectrum testing can be performed;
    根据预设程序对所述四电极锂硫电池进行恒电流充放电测试和阻抗谱测试，并记录相应电压曲线和阻抗谱曲线。Perform constant current charge and discharge test and impedance spectrum test on the four-electrode lithium-sulfur battery according to a preset program, and record the corresponding voltage curve and impedance spectrum curve.
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