CN110190325A - Four electrode lithium-sulfur cells, preparation method and electrode electro Chemical characteristic monitoring method - Google Patents
Four electrode lithium-sulfur cells, preparation method and electrode electro Chemical characteristic monitoring method Download PDFInfo
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- CN110190325A CN110190325A CN201910388254.8A CN201910388254A CN110190325A CN 110190325 A CN110190325 A CN 110190325A CN 201910388254 A CN201910388254 A CN 201910388254A CN 110190325 A CN110190325 A CN 110190325A
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- 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
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—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
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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
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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
- H01M10/48—Accumulators combined with arrangements for measuring, testing or indicating the condition of cells, e.g. the level or density of the electrolyte
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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
- 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
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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
- 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
- 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
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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 of a single cell or a single battery
- H01M50/102—Primary casings, jackets or wrappings of a single cell or a single battery characterised by their shape or physical structure
- H01M50/109—Primary casings, jackets or wrappings of a single cell or a single battery characterised by their shape or physical structure of button or coin shape
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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
- H01M50/50—Current conducting connections for cells or batteries
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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
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/543—Terminals
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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
- 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
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- 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
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- 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
Abstract
The invention discloses a kind of four electrode lithium-sulfur cells, preparation method and electrode electro Chemical characteristic monitoring methods.Four electrode lithium-sulfur cells have four electrode structures, wherein top shell and bottom case are two cathode, two aluminium strips draw from the aperture in top shell and are used as two anodes, two cathode are mounted on the two sides up and down of lithium-sulfur cell, two anodes are clipped in the middle, meanwhile being separated between positive electrode and negative electrode with diaphragm, it is also separated with diaphragm between two anodes.The lithium-sulfur cell has four electrode structures, it can be under the premise of not destroying battery structure, the anode of battery and the electrochemical impedance of cathode are acquired simultaneously, solve the problems, such as that current conventional commercial two terminal battery and three-electrode battery can not accurately obtain unitary electrode Electrochemistry Information.The present invention can be used for the research and development of new electrode materials.
Description
Technical field
The present invention relates to battery preparation and detection techniques, more particularly to one kind to be based on four electrode lithium-sulfur cells, its preparation side
Method and electrode electro Chemical characteristic monitoring method.
Background technique
Electric vehicle in recent years and personal electronic equipments it is universal, be unable to do without high performance lithium battery.However, current lithium
Ion battery energy density is already close to theoretical value.Commercialized lithium ion battery is with LiFePO4 (LiFePO4), nickel cobalt mangaic acid
Lithium (NMC) and nickel cobalt lithium aluminate (NCA) etc. are anode, and graphite is cathode, and capacity is generally in 250Wh/kg or so.Want further
Energy density is improved, then needs to change the material of positive and negative anodes, this is the developing direction of next-generation lithium battery.Lithium-sulfur cell is great latent
The lithium ion battery competitor of power.It is positive electrode that the battery system, which uses elemental sulfur (theoretical specific capacity 1675mAh/g), with
Lithium metal does cathode, and average output voltage is 2567Wh/kg up to 2.1V, the theoretical energy density of system, about traditional lithium
10 times of ion battery.Although elemental sulfur is extensive in distributed in nature, reserves are big, at low cost, however the big rule of lithium-sulfur cell at present
Commercially producing for mould is challenged there are also very much.Such as capacitance loss caused by the dissolution of polysulfide, the electric conductivity of active material
Difference causes output voltage low, and battery capacity is lower than theoretical value.These all have direct connection with the internal resistance of battery.
Electrochemical impedance spectroscopy is one of the classical way for studying the internal resistance of cell.It can not only characterize the conductivity of ion, also
It can be carried out the electrochemical reaction dynamics research of electrode.But common full battery, testing obtained is anode, electrolyte
With the superposition of cathode impedance, and it is difficult to distinguish the respective impedance of this three parts.If obtaining the resistance of single electrode
Anti-, there are two types of currently used methods.One is multiple batteries are disassembled, anode and positive (or cathode and cathode) group again
Dress up two electrode Symmetrical cells.Second is to be added a reference electrode, is made into three-electrode battery.
The production of two electrode Symmetrical cells is cumbersome, needs to dismantle on battery and re-assemblies, and this battery cannot continue charge and discharge
Electricity.And the process dismantled inevitably destroys electrode, and electrolyte also has loss, these factors can all cause
Measurement result inaccuracy.Although three-electrode battery is frequently used to the impedance of test unitary electrode, but early there are some researches prove it
Inherent electrochemistry is asymmetric, will affect measuring accuracy.
In the case where not destroying battery, and the method that can accurately measure anode and cathode impedance, it yet there are no report
Road.
Summary of the invention
Present invention is primarily aimed at provide four electrode lithium-sulfur cells of one kind, preparation method and electrode electro Chemical characteristic
Monitoring method can measure accurate anode and cathode impedance spectrum in the case where not disassembling battery.
The present invention is achieved through the following technical solutions:
A kind of four electrode lithium-sulfur cells, including shell and the battery component being encapsulated in the shell, the shell includes
Metal bottom shell and the metal top shell being fastened on the bottom case, the top shell and the bottom case insulate, and the battery component is under
Supreme includes the first negative electrode material layer, the first membrane layer, the first positive electrode material layer, the first aluminium strip, the second membrane layer, the second aluminium
Band, the second positive electrode material layer, third membrane layer and the second negative electrode material layer；
First negative electrode material layer is mounted on the bottom case inside bottom, and is electrically connected with the bottom case, described second
The metal gasket being electrically connected with second negative electrode material layer is installed on negative electrode material layer, be equipped on the metal gasket with
The metallic spring of metal gasket electrical connection, the metallic spring elasticity be pressed on the top shell inside top with it is described
Between metal gasket, and it is electrically connected with the top shell；
First aluminium strip is electrically connected with first positive electrode material layer, second aluminium strip and second positive electrode
Layer electrical connection, first aluminium strip and second aluminium strip insulate, and offer aperture, first aluminium strip and institute in the top shell
It states the second aluminium strip to draw from the aperture, first aluminium strip, second aluminium strip and the top shell three mutually insulated.
Further, first positive electrode material layer and second positive electrode material layer use porous carbon paper as afflux
Body.
Further, first aluminium strip is fixedly connected on the edge of first positive electrode material layer, second aluminium strip
It is fixedly connected on the edge of second positive electrode material layer.
Further, first negative electrode material layer and second negative electrode material layer are metal lithium sheet.
Further, the shell is the shell of button cell.
A method of four electrodes lithium-sulfur cell as described above is prepared, is included the following steps:
Prepare top shell and bottom case, and opens up aperture in the top shell；
Prepare first negative electrode material layer, first membrane layer, first positive electrode material layer, first aluminium
Band, second membrane layer, second aluminium strip, second positive electrode material layer, the third membrane layer and described second negative
Pole material layer；
Successively installed from the bottom to top in glove box the bottom case, first negative electrode material layer, first membrane layer,
First positive electrode material layer, first aluminium strip, second membrane layer, second aluminium strip, second positive electrode
Layer, the third membrane layer and second negative electrode material layer are installing first membrane layer, first positive electrode
When layer, second membrane layer, second positive electrode material layer and the third membrane layer, first injects electrolyte and then pacify again
Dress；
First aluminium strip and second aluminium strip are drawn from the aperture；
Metal gasket is installed on second negative electrode material layer, and metallic spring is installed on the metal gasket；
The top shell is fastened on the bottom case, the metallic spring elasticity is made to be pressed on the top shell inside top
It is electrically connected between the metal gasket, and with the top shell；
The aperture is sealed using insulating materials, when sealing makes first aluminium strip, second aluminium strip and the top
Shell three's mutually insulated.
Further, the preparation method of first positive electrode material layer and second positive electrode material layer includes:
Using porous carbon paper as collector, after being cleaned up with acetone, it is cut into disk, adds sulphur powder in disk
On, and 120 degree are heated to, it dissolves sulphur powder and is absorbed by carbon paper.
Further, when first aluminium strip and second aluminium strip are installed, first aluminium strip is fixedly connected
At the edge of first positive electrode material layer, second aluminium strip is fixedly connected on to the edge of second positive electrode material layer.
Further, the insulating materials is resin.
Electrode electro Chemical characteristic monitoring method based on four electrodes lithium-sulfur cell as described above, includes the following steps:
First aluminium strip and the second aluminium strip are connected to anode and the resistance of charge-discharge test instrument by the first double-point double-throw switch
Top shell and bottom case, are connected to the cathode of the charge-discharge test instrument by one end of anti-spectrum tester by the second double-point double-throw switch
With the other end of the impedance spectrum tester；
First aluminium strip and second aluminium strip can be filled with described simultaneously by first double-point double-throw switch
The anode connection of discharge tester, or by first aluminium strip and second aluminium strip simultaneously with the impedance spectrum tester
One end connection, by second double-point double-throw switch can by the top shell and the bottom case simultaneously with the charge-discharge test
The cathode of instrument connects, or the top shell and the bottom case are connect with the other end of the impedance spectrum tester simultaneously；By institute
It states the first aluminium strip and second aluminium strip to connect with the anode of the charge-discharge test instrument simultaneously, while by the top shell and described
After bottom case is connect with the cathode of the charge-discharge test instrument simultaneously, it is able to carry out constant current charge-discharge test, by first aluminium
Band and second aluminium strip are connect with one end of the impedance spectrum tester simultaneously, while simultaneously by the top shell and the bottom case
After connecting with the other end of the impedance spectrum tester, it is able to carry out impedance spectrum test；
Constant current charge-discharge test is carried out to the four electrodes lithium-sulfur cell according to pre-set programs and impedance spectrum is tested, and is remembered
Picture recording answers voltage curve and impedance spectrum curve.
Compared with prior art, the present invention provides a kind of four electrode lithium-sulfur cells, preparation method and electrode electro Chemicals
Characteristic monitoring method.Four electrode lithium-sulfur cells have four electrode structures, and wherein top shell and bottom case are two cathode, and two aluminium strips are
Two anodes, two cathode are mounted on the two sides up and down of lithium-sulfur cell, and two anodes are clipped in the middle, meanwhile, positive electrode and negative electrode
Between separated with diaphragm, also separated with diaphragm between two anodes.The lithium-sulfur cell has four electrode structures, can not destroy battery
Under the premise of structure, while the anode of battery and the electrochemical impedance of cathode are acquired, solves current two electrode of conventional commercial electricity
The problem of pond and three-electrode battery can not accurately obtain unitary electrode Electrochemistry Information.The present invention can be used for new electrode materials
Research and development.
Detailed description of the invention
Fig. 1 is the theory of constitution schematic diagram of four electrode lithium-sulfur cell of the embodiment of the present invention；
Fig. 2 is the electrochemical properties test connection schematic diagram of four electrode lithium-sulfur cell of the embodiment of the present invention；
Fig. 3 is the voltage curve that with constant current process four electrode batteries are carried out with charge and discharge；
Fig. 4 is the impedance spectrum curve figure of typical anode and cathode；
Fig. 5 is change curve of the internal resistance of the electrolyte of battery, anode and cathode in battery discharge.
Specific embodiment
To make the objectives, technical solutions, and advantages of the present invention clearer, below with reference to embodiment and attached drawing, to this
Invention is described in further detail.
As shown in Figure 1, the four electrode lithium-sulfur cells that the embodiment of the present invention one provides, including shell and encapsulate inside the shell
Battery component, shell include metal bottom shell 1 and the metal top shell 2 that is fastened on bottom case 1, and top shell 2 and bottom case 1 insulate, battery pack
Part includes the first negative electrode material layer 3, the first membrane layer 4, the first positive electrode material layer 5, the first aluminium strip 6, the second diaphragm from the bottom to top
The 7, second aluminium strip 8 of layer, the second positive electrode material layer 9, third membrane layer 10 and the second negative electrode material layer 11.
First negative electrode material layer 3 is mounted on 1 inside bottom of bottom case, and is electrically connected with bottom case 1, on the second negative electrode material layer 11
The metal gasket 12 being electrically connected with the second negative electrode material layer 11 is installed, is equipped on metal gasket 12 and is electrically connected with metal gasket 12
The metallic spring 13 connect, 13 elasticity of metallic spring is pressed between 2 inside top of top shell and metal gasket 12, and and top shell
2 electrical connections.
First aluminium strip 6 is electrically connected with the first positive electrode material layer 5, and the second aluminium strip 8 is electrically connected with the second positive electrode material layer 9, top
It offers aperture 14, the first aluminium strip 6 and the second aluminium strip 8 on shell 2 to draw from aperture 14, the first aluminium strip 6, the second aluminium strip 8, top shell 2
Three's mutually insulated.It can be separately connected carbon paper on first aluminium strip 6 and the second aluminium strip 8, by carbon paper by the first aluminium strip 6 and the second aluminium
Band 8 is drawn from aperture 14, with the carbon paper that connects on the first aluminium strip 6 and the second aluminium strip 8 as two anodes.
The four electrodes lithium-sulfur cell can directly adopt the shell of button cell as it as a kind of four electrode Symmetrical cells
Shell.For example, the shell of CR2032 button stainless steel battery can be directlyed adopt to encapsulate battery component, it is only necessary to its shell
Cathode (i.e. top shell 2) slightly adjusts, and cuts a duck eye as the aperture 14 for drawing the first aluminium strip 6 and the second aluminium strip 8.First just
Pole material layer 5 and the second positive electrode material layer 9 will be porous with acetone with a thickness of 0.28 millimeter as collector using porous carbon paper
After carbon paper cleans up, it is cut into the disk that diameter is 14 millimeters, a certain amount of sulphur powder is added on disk, is heated to 120
Degree, dissolves sulphur powder and is absorbed by carbon paper.Commercial lithium can be used in first membrane layer 4, the second membrane layer 7 and third membrane layer 10
The diaphragm of ion battery is cut into the disk that diameter is 15 millimeters with a thickness of 25 microns.First aluminium strip 6 and the second aluminium strip 8 can be by aluminium
Foil be cut into it is elongated it is band-like be made, the first aluminium strip 6 is fixedly connected on the edge of the first positive electrode material layer 5, and the second aluminium strip 8 is fixed to be connected
It connects at the edge of the second positive electrode material layer 9.First negative electrode material layer 3 and the second negative electrode material layer 11 are metal lithium sheet, thickness
0.5 millimeter, 14 millimeters of diameter.The electrolyte injected in each positive electrode material layer and each membrane layer be 1,3- dioxolanes (DOL) and
The equal proportion mixed solvent of 1,2- dimethoxy-ethane (DME) includes bis- (fluoroform) sulfimides (LiTFSI) of 1M.It is made
Four electrode lithium-sulfur cells tool there are two anodes and two cathode totally four electrodes, wherein top shell 2 and bottom case 1 are two cathode,
Two aluminium strips are two anodes, and two cathode are mounted on the two sides up and down of lithium-sulfur cell, two anodes are clipped in the middle, meanwhile,
It is separated between positive electrode and negative electrode with diaphragm, is also separated with diaphragm between two anodes.The lithium-sulfur cell due to have four electrode structures,
It can be under the premise of destroying battery structure, while the anode of battery and the electrochemical impedance of cathode are acquired, solve current biography
The problem of commercial two terminal battery of system and three-electrode battery can not accurately obtain unitary electrode Electrochemistry Information.
Second embodiment of the present invention provides a kind of methods for preparing four electrode lithium-sulfur cells as above, include the following steps:
Prepare top shell 2 and bottom case 1, and opens up aperture 14 in top shell 2；
Prepare the first negative electrode material layer 3, the first membrane layer 4, the first positive electrode material layer 5, the first aluminium strip 6, the second membrane layer
7, the second aluminium strip 8, the second positive electrode material layer 9, third membrane layer 10 and the second negative electrode material layer 11；
Bottom case 1, the first negative electrode material layer 3, first the 4, first anode of membrane layer are successively installed from the bottom to top in glove box
Material layer 5, the first aluminium strip 6, the second membrane layer 7, the second aluminium strip 8, the second positive electrode material layer 9, third membrane layer 10 and second are negative
Pole material layer 11 is installing the first membrane layer 4, the first positive electrode material layer 5, the second membrane layer 7, the second positive electrode material layer 9 and the
When three membrane layers 10, first injects electrolyte and then install again；
First aluminium strip 6 and the second aluminium strip 8 are drawn from aperture 14；
Metal gasket 12 is installed on the second negative electrode material layer 11, and metallic spring 13 is installed on metal gasket 12；
Top shell 2 is fastened on bottom case 1,13 elasticity of metallic spring is made to be pressed on 2 inside top of top shell and metal gasket
Between 12, and it is electrically connected with top shell 2；
Aperture 14 is sealed using insulating materials 15, when sealing keeps the first aluminium strip 6, the second aluminium strip 8,2 three of top shell mutual
Insulation.Insulating materials 15 uses resin in the present embodiment, using hydraulic sealing machine seal and opening 14.
When drawing the first aluminium strip 6 and the second aluminium strip 8 from aperture 14, can distinguish on the first aluminium strip 6 and the second aluminium strip 8
Carbon paper is connected, the first aluminium strip 6 and the second aluminium strip 8 are drawn from aperture 14 by carbon paper, sealed aperture 14 after extraction, by first
The carbon paper connected on aluminium strip 6 and the second aluminium strip 8 is as two anodes.
It should be pointed out that the water content of glove box need to be not higher than 1ppm.Meanwhile there is no absolutely between above steps
Sequencing, execute between some steps and do not collide, execution can be synchronized, successively can also execute or exchange execute it is suitable
Can sequence specifically synchronize execution or exchange execution sequence depending on actual conditions.Four electrode lithium-sulfur cells after aperture 14 is sealed
It is just completed, four electrode lithium-sulfur cells need to stand 8 hours after being completed, again from glove box after allowing resin thoroughly to solidify
Middle taking-up.Assembled four electrodes lithium-sulfur cell, four electrode symmetrical structures are as shown in Figure 1.
In the present embodiment, the first positive electrode material layer 5 and the second positive electrode material layer 9 the preparation method comprises the following steps:
Using porous carbon paper as collector, after being cleaned up with acetone, it is cut into disk, adds sulphur powder in disk
On, and 120 degree are heated to, it dissolves sulphur powder and is absorbed by carbon paper.
When installing the first aluminium strip 6 and the second aluminium strip 8, the first aluminium strip 6 is fixedly connected on to the side of the first positive electrode material layer 5
Second aluminium strip 8 is fixedly connected on the edge of the second positive electrode material layer 9 by edge.
The embodiment of the present invention three provides a kind of electrode electro Chemical characteristic monitoring based on four electrode lithium-sulfur cells as above
Method includes the following steps:
First aluminium strip 6 and the second aluminium strip 8 are being connected to charge-discharge test instrument 19 just by the first double-point double-throw switch 16
Top shell 2 and bottom case 1 are connected to charge-discharge test by the second double-point double-throw switch 17 by one end of pole and impedance spectrum tester 18
The cathode of instrument 19 and the other end of impedance spectrum tester 18；
By the first double-point double-throw switch 16 can by the first aluminium strip 6 and the second aluminium strip 8 simultaneously with charge-discharge test instrument 19
Anode connection, or the first aluminium strip 6 and the second aluminium strip 8 are connect with one end of impedance spectrum tester 18 simultaneously, pass through second
Top shell 2 and bottom case 1 can be connect with the cathode of charge-discharge test instrument 19 by double-point double-throw switch 17 simultaneously, or by 2 He of top shell
Bottom case 1 is connect with the other end of impedance spectrum tester 18 simultaneously；By the first aluminium strip 6 and the second aluminium strip 8 while and charge-discharge test
The anode connection of instrument 19, while by top shell 2 and bottom case 1 while after being connect with the cathode of charge-discharge test instrument 19, it is able to carry out perseverance
First aluminium strip 6 and the second aluminium strip 8 are connect with one end of impedance spectrum tester 18 by current charge-discharge electrical testing simultaneously, while will top
After shell 2 and bottom case 1 are connect with the other end of impedance spectrum tester 18 simultaneously, it is able to carry out impedance spectrum test；
Constant current charge-discharge test is carried out to four electrode lithium-sulfur cells according to pre-set programs and impedance spectrum is tested, and records phase
Answer voltage curve and impedance spectrum curve.
Specific test can carry out as follows:
Charge-discharge test instrument 19 is using Arbin BT2000, and impedance spectrum tester 18 is using Zahner IM6 electricity
Chem workstation.It is attached according to fig. 2, when the first double-point double-throw switch 16 and the second double-point double-throw switch 17 are switched to the left side
When position, which connect with charge-discharge test instrument 19, when the first double-point double-throw switch 16 and the second double-pole are double
When throw switch 17 is switched to location right, which connect with impedance spectrum tester 18.
The four electrodes lithium-sulfur cell is accessed into Arbin BT2000, carries out constant current charge-discharge test, that detects battery can
The property used.Electric discharge and charging current are 177mA (0.1mA/cm2), discharge cut-off voltage 1.7V, charge cutoff voltage 2.8V.
Charging/discharging voltage is recorded while charge and discharge, the voltage curve of record is as shown in figure 3, wherein in the high potential discharge platform of 2.3V
It is typical double discharge platforms with the low potential discharge platform in 2.1V, it is consistent with correlative study report.Illustrate the new assembling
Four electrode lithium-sulfur cells can work normally, be effective.
Four electrode lithium-sulfur cells, which are carried out impedance spectrum test, can be obtained the online impedance spectrum of battery.The battery is full of first
Then electricity sets individual discharge capacities in Arbin BT2000, start constant current discharge, record cell voltage in discharge process.
At this time in Fig. 2 the first double-point double-throw switch 16 and the second double-point double-throw switch 17 in left position.When electric discharge reaches setting capacity,
Pause electric discharge, is switched to location right for the first double-point double-throw switch 16 and the second double-point double-throw switch 17, battery is connect
Zahner IM6 electrochemical workstation carries out impedance spectrum test.Set open-circuit voltage as test signal voltage, amplitude 10mV,
Frequency obtains the impedance spectrum of anode and cathode from 1MHz to 0.1Hz.The impedance spectrum of obtained anode and cathode is as shown in Figure 4.It surveys
After the completion of examination, the first double-point double-throw switch 16 and the second double-point double-throw switch 17 are switched to left position again, continue to discharge
And record cell voltage.It steps be repeated alternatively until that the discharge voltage of battery is reduced to 1.7V.Black curve is with single in Fig. 5
Voltage curve of the 50mAh/g as discharge capacity.Three blank maps in Fig. 5 from top to bottom are battery respectively in discharge process
The impedance variations situation of middle anode, cathode and electrolyte.
Above-described embodiment is only preferred embodiment, the protection scope being not intended to limit the invention, in spirit of the invention
With any modifications, equivalent replacements, and improvements made within principle etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of four electrode lithium-sulfur cells, including shell and the battery component being encapsulated in the shell, the shell includes gold
The metal top shell for belonging to bottom case and being fastened on the bottom case, the top shell and the bottom case insulate, which is characterized in that the battery
Component include from the bottom to top the first negative electrode material layer, the first membrane layer, the first positive electrode material layer, the first aluminium strip, the second membrane layer,
Second aluminium strip, the second positive electrode material layer, third membrane layer and the second negative electrode material layer；
First negative electrode material layer is mounted on the bottom case inside bottom, and is electrically connected with the bottom case, second cathode
The metal gasket being electrically connected with second negative electrode material layer is installed in material layer, be equipped on the metal gasket with it is described
The metallic spring of metal gasket electrical connection, the metallic spring elasticity are pressed on the top shell inside top and the metal
Between gasket, and it is electrically connected with the top shell；
First aluminium strip is electrically connected with first positive electrode material layer, second aluminium strip and second positive electrode material layer electricity
Connection, first aluminium strip and second aluminium strip insulate, and offer aperture in the top shell, first aluminium strip and described the
Two aluminium strips are drawn from the aperture, first aluminium strip, second aluminium strip and the top shell three mutually insulated.
2. four electrodes lithium-sulfur cell as described in claim 1, which is characterized in that first positive electrode material layer and described second
Positive electrode material layer is using porous carbon paper as collector.
3. four electrodes lithium-sulfur cell as claimed in claim 2, which is characterized in that first aluminium strip is fixedly connected on described
The edge of one positive electrode material layer, second aluminium strip are fixedly connected on the edge of second positive electrode material layer.
4. four electrodes lithium-sulfur cell as described in claim 1, which is characterized in that first negative electrode material layer and described second
Negative electrode material layer is metal lithium sheet.
5. four electrodes lithium-sulfur cell as claimed in claim 3, which is characterized in that the shell is the shell of button cell.
6. a kind of method for preparing any four electrode lithium-sulfur cells in claim 1 to 5, which is characterized in that including such as
Lower step:
Prepare top shell and bottom case, and opens up aperture in the top shell；
Prepare first negative electrode material layer, first membrane layer, first positive electrode material layer, first aluminium strip, institute
State the second membrane layer, second aluminium strip, second positive electrode material layer, the third membrane layer and second negative electrode material
Layer；
The bottom case, first negative electrode material layer, first membrane layer, described is successively installed from the bottom to top in glove box
First positive electrode material layer, first aluminium strip, second membrane layer, second aluminium strip, second positive electrode material layer, institute
Third membrane layer and second negative electrode material layer are stated, first membrane layer, first positive electrode material layer, described is being installed
When the second membrane layer, second positive electrode material layer and the third membrane layer, first injects electrolyte and then install again；
First aluminium strip and second aluminium strip are drawn from the aperture；
Metal gasket is installed on second negative electrode material layer, and metallic spring is installed on the metal gasket；
The top shell is fastened on the bottom case, the metallic spring elasticity is made to be pressed on the top shell inside top and institute
It states between metal gasket, and is electrically connected with the top shell；
The aperture is sealed using insulating materials, when sealing makes first aluminium strip, second aluminium strip and the top shell three
Person's mutually insulated.
7. method as claimed in claim 6, which is characterized in that first positive electrode material layer and second positive electrode material layer
Preparation method include:
Using porous carbon paper as collector, after being cleaned up with acetone, it is cut into disk, adds sulphur powder on disk, and
120 degree are heated to, sulphur powder is dissolved and is absorbed by carbon paper.
8. method as claimed in claim 6, which is characterized in that when first aluminium strip and second aluminium strip are installed,
First aluminium strip is fixedly connected on to the edge of first positive electrode material layer, second aluminium strip is fixedly connected on described
The edge of second positive electrode material layer.
9. method as claimed in claim 6, which is characterized in that the insulating materials is resin.
10. based on the electrode electro Chemical characteristic monitoring method of the four electrode lithium-sulfur cells any in claim 1 to 5,
It is characterized in that, includes the following steps:
First aluminium strip and the second aluminium strip are connected to the anode and impedance spectrum of charge-discharge test instrument by the first double-point double-throw switch
Top shell and bottom case are connected to cathode and the institute of the charge-discharge test instrument by one end of tester by the second double-point double-throw switch
State the other end of impedance spectrum tester；
By first double-point double-throw switch can by first aluminium strip and second aluminium strip simultaneously with the charge and discharge
The anode connection of tester, or one end with the impedance spectrum tester simultaneously by first aluminium strip and second aluminium strip
Connection, by second double-point double-throw switch can by the top shell and the bottom case simultaneously with the charge-discharge test instrument
Cathode connection, or the top shell and the bottom case are connect with the other end of the impedance spectrum tester simultaneously；By described
One aluminium strip and second aluminium strip are connect with the anode of the charge-discharge test instrument simultaneously, while by the top shell and the bottom case
Simultaneously connect with the cathode of the charge-discharge test instrument after, be able to carry out constant current charge-discharge test, by first aluminium strip with
Second aluminium strip is connect with one end of the impedance spectrum tester simultaneously, at the same by the top shell and the bottom case simultaneously with institute
After the other end connection for stating impedance spectrum tester, it is able to carry out impedance spectrum test；
Constant current charge-discharge test is carried out to the four electrodes lithium-sulfur cell according to pre-set programs and impedance spectrum is tested, and records phase
Answer voltage curve and impedance spectrum curve.
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| CN201910388254.8A CN110190325B (en) | 2019-05-10 | 2019-05-10 | Four-electrode lithium-sulfur battery, preparation method thereof and electrode electrochemical characteristic monitoring method |
| DE112019000208.2T DE112019000208T5 (en) | 2019-05-01 | 2019-10-14 | Four-electrode lithium-sulfur battery, manufacturing method therefor and method for monitoring the electrochemical properties of the electrodes |
| PCT/CN2019/111055 WO2020228234A1 (en) | 2019-05-10 | 2019-10-14 | Four-electrode lithium-sulfur battery and preparation method therefor, and electrode electrochemical property monitoring method |
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| CN201910388254.8A CN110190325B (en) | 2019-05-10 | 2019-05-10 | Four-electrode lithium-sulfur battery, preparation method thereof and electrode electrochemical characteristic monitoring method |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110618175A (en) * | 2019-10-09 | 2019-12-27 | 哈尔滨工业大学 | Electrochemical detection device and method for soluble polysulfide in metal/sulfur battery |
| WO2020228234A1 (en) * | 2019-05-10 | 2020-11-19 | 深圳技术大学 | Four-electrode lithium-sulfur battery and preparation method therefor, and electrode electrochemical property monitoring method |
| CN113138345A (en) * | 2021-03-22 | 2021-07-20 | 万向一二三股份公司 | Method for evaluating performance of lithium ion battery by using symmetric battery |
| CN113702245A (en) * | 2021-08-06 | 2021-11-26 | 清华大学 | Method, device, equipment and medium for measuring diffusion coefficient of battery anode material |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2023003730A1 (en) * | 2021-07-23 | 2023-01-26 | Celgard, Llc | Improved batteries, cells, components, and testing thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2717036Y (en) * | 2004-03-01 | 2005-08-10 | 惠州Tcl金能电池有限公司 | A lithium battery |
| CN202454648U (en) * | 2012-02-25 | 2012-09-26 | 佛山市顺德区精锐电池科技有限公司 | Novel easy-to-process lithium battery |
| CN202601766U (en) * | 2012-05-29 | 2012-12-12 | 深圳市博亿能科技有限公司 | Lithium ion battery with staggered tabs |
| CN203434241U (en) * | 2013-05-13 | 2014-02-12 | 深圳市比里通电子科技有限公司 | High-capacity ultra-thin lithium battery |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070015051A1 (en) * | 2005-07-18 | 2007-01-18 | Shen Ko C | Secondary battery |
| CN101465441B (en) * | 2009-01-06 | 2010-11-10 | 清华大学 | Preparation method of lithium sulphur battery using graphite as cathode |
| CN104617247B (en) * | 2015-01-20 | 2017-04-12 | 浙江大学 | Preparation method of tandem laminated lithium-sulfur battery |
| CN106935863A (en) * | 2015-12-30 | 2017-07-07 | 科源（天津）电源部品有限公司 | A kind of novel lithium battery |
| CN110190325B (en) * | 2019-05-10 | 2020-10-27 | 深圳技术大学 | Four-electrode lithium-sulfur battery, preparation method thereof and electrode electrochemical characteristic monitoring method |
-
2019
- 2019-05-10 CN CN201910388254.8A patent/CN110190325B/en active Active
- 2019-10-14 WO PCT/CN2019/111055 patent/WO2020228234A1/en active Application Filing
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2717036Y (en) * | 2004-03-01 | 2005-08-10 | 惠州Tcl金能电池有限公司 | A lithium battery |
| CN202454648U (en) * | 2012-02-25 | 2012-09-26 | 佛山市顺德区精锐电池科技有限公司 | Novel easy-to-process lithium battery |
| CN202601766U (en) * | 2012-05-29 | 2012-12-12 | 深圳市博亿能科技有限公司 | Lithium ion battery with staggered tabs |
| CN203434241U (en) * | 2013-05-13 | 2014-02-12 | 深圳市比里通电子科技有限公司 | High-capacity ultra-thin lithium battery |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020228234A1 (en) * | 2019-05-10 | 2020-11-19 | 深圳技术大学 | Four-electrode lithium-sulfur battery and preparation method therefor, and electrode electrochemical property monitoring method |
| CN110618175A (en) * | 2019-10-09 | 2019-12-27 | 哈尔滨工业大学 | Electrochemical detection device and method for soluble polysulfide in metal/sulfur battery |
| CN113138345A (en) * | 2021-03-22 | 2021-07-20 | 万向一二三股份公司 | Method for evaluating performance of lithium ion battery by using symmetric battery |
| CN113138345B (en) * | 2021-03-22 | 2023-08-15 | 万向一二三股份公司 | Method for evaluating performance of lithium ion battery by using symmetrical battery |
| CN113702245A (en) * | 2021-08-06 | 2021-11-26 | 清华大学 | Method, device, equipment and medium for measuring diffusion coefficient of battery anode material |
| CN113702245B (en) * | 2021-08-06 | 2022-04-08 | 清华大学 | Method, device, equipment and medium for measuring diffusion coefficient of battery anode material |
Also Published As
| Publication number | Publication date |
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| WO2020228234A1 (en) | 2020-11-19 |
| DE112019000208T5 (en) | 2021-01-07 |
| CN110190325B (en) | 2020-10-27 |
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