CN108398446B - In-situ device for testing synchrotron radiation X-ray absorption spectrum of battery electrode material - Google Patents
In-situ device for testing synchrotron radiation X-ray absorption spectrum of battery electrode material Download PDFInfo
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- CN108398446B CN108398446B CN201810439974.8A CN201810439974A CN108398446B CN 108398446 B CN108398446 B CN 108398446B CN 201810439974 A CN201810439974 A CN 201810439974A CN 108398446 B CN108398446 B CN 108398446B
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- 238000012360 testing method Methods 0.000 title claims abstract description 37
- 239000007772 electrode material Substances 0.000 title claims abstract description 30
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 28
- 230000005469 synchrotron radiation Effects 0.000 title claims abstract description 27
- 238000000862 absorption spectrum Methods 0.000 title claims abstract description 24
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 30
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 30
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 28
- 238000009421 internal insulation Methods 0.000 claims abstract description 9
- 230000005540 biological transmission Effects 0.000 claims description 7
- 238000009413 insulation Methods 0.000 claims description 4
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 10
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 abstract description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 8
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 8
- 238000004146 energy storage Methods 0.000 abstract description 6
- 238000010249 in-situ analysis Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- 238000000833 X-ray absorption fine structure spectroscopy Methods 0.000 description 8
- 229910052744 lithium Inorganic materials 0.000 description 8
- 238000007789 sealing Methods 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
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- 239000006230 acetylene black Substances 0.000 description 4
- 238000011066 ex-situ storage Methods 0.000 description 4
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 4
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- 229910052786 argon Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052790 beryllium Inorganic materials 0.000 description 2
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 2
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- 239000002904 solvent Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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- 229910052802 copper Inorganic materials 0.000 description 1
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Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/02—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by transmitting the radiation through the material
- G01N23/06—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by transmitting the radiation through the material and measuring the absorption
- G01N23/083—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by transmitting the radiation through the material and measuring the absorption the radiation being X-rays
-
- 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
Abstract
The invention discloses an in-situ device for testing the synchrotron radiation X-ray absorption spectrum of a battery electrode material, which comprises a negative electrode part, an internal insulation and pressure part and a positive electrode part; the negative electrode part comprises a negative electrode a, a beryllium sheet a, a rubber ring a, a negative electrode b and four insulating sleeves, the internal insulation and pressure part comprises a rubber ring b, a polytetrafluoroethylene sleeve, a spring, a top sheet and a beryllium sheet b, the positive electrode part comprises a positive electrode a, a rubber ring c, a beryllium sheet c and a positive electrode b, and the positive electrode a and the positive electrode b are respectively provided with a threaded through hole and a light-transmitting through hole. The detachable and washable connecting structure has the characteristics of good tightness and internal insulation, realizes the advantages of high repeatability of in-situ test, simple operation, convenient carrying and reduced cost, is suitable for collecting data of in-situ analysis electrode materials by synchrotron radiation X rays, and can be used for researching the physical and chemical properties of various energy storage devices such as lithium ion batteries, sodium ion batteries, supercapacitors and the like.
Description
Technical Field
The invention relates to a lithium ion, sodium ion and magnesium ion battery material and an electrochemical technology, in particular to an in-situ device for testing a synchrotron radiation X-ray absorption spectrum of a battery electrode material.
Background
Secondary batteries such as lithium ion, sodium ion and magnesium ion play an important role in energy storage technology. Lithium ion batteries have been commercialized and widely used in consumer electronics markets and in new energy automobiles. Compared with Li, na has the advantages of richer resources and lower price, and the sodium ion battery provides a better solution for the large-scale application of the sodium ion battery in the field of large-scale energy storage systems. However, there are many problems in the migration of sodium ions and the structural transformation of electrode materials, which need to be resolved by advanced test means. Magnesium ion batteries are currently in the laboratory research stage, and the early electrochemical mechanism is very poorly studied. Therefore, searching for an effective test means to study the structural properties of electrode materials is a necessary way to further develop high performance batteries.
X-ray absorption fine structure spectroscopy (XAFS) is favored by many field scientists in terms of material structure measurement characterization, can detect the local structure of a material, is sensitive to the chemical environment of an atom, and can give structural information of several neighboring coordination layers around an absorption atom on an atomic scale. Moreover, synchrotron radiation XAFS technology has been rapidly developed since the advent of synchrotron radiation light sources with high brightness, high beam power, and continuously adjustable wavelengths. In recent years, XAFS technology has greatly driven the recognition of structural changes in battery materials during charge and discharge in microstructure.
Ex-situ X-ray absorption fine structure spectrum (Ex-situ XAFS), also known as "semi-in-situ" XAFS, allows quasi-dynamic observation of changes in the local structure and valence state of transition metal elements of the battery material during delithiation/delithiation. After the battery is charged and discharged on a test system, the battery is disassembled in a glove box, an electrode plate is taken out, surface electrolyte is cleaned, and the battery is packaged by a 3M adhesive tape. Pelliccione et al tested the local atomic structure of the two-dimensional material CuxMnOy.nH2O in the charge and discharge process by using semi-in-situ XAFS, which shows that MnO in the compound 6 The octahedral structure disappears upon discharge and recovers upon charge. Cu in oxide 2+ Is reduced to elemental copper during discharging and oxidized to Cu during charging 2+ . Thus further demonstrating the excellent cycling stability of the material (Phys. Chem. Phys.2008, 18:2959-2967).
However, due to the voltage hysteresis, the semi-in-situ X-ray absorption spectrum is difficult to analyze and test in real time. Therefore, with the growing understanding of the reaction mechanism of electrode materials and the urgent need for the development of next-generation battery materials, the development of In-situ X-ray absorption spectroscopy (In-site XAFS) is imperative. Lim et al characterized LiFePO in situ by utilizing high-resolution X-ray absorption spectrum based on synchrotron radiation in situ light source 4 Single nanoparticle charging and dischargingElectrical variation, in order to enable time-space resolution, a set of in-situ battery devices is designed: liFePO to be a monolithic layer 4 Coating on Au current collector, clamping SiN with a distance of 75nm between upper and lower parts x And the middle part is filled with electrolyte by a polymer conduit, the negative lithium sheet is arranged in an injector, and the injector is filled with the electrolyte and is arranged outside the testing device. Experimental results found LiFePO 4 The material has very small domains, which preferentially intercalate lithium when discharged, resulting in non-uniformity in the composition of the material, and mechanical internal stresses, resulting in capacity loss (Science 2016; 353:566-571).
Although the in-situ battery experiment based on the synchrotron radiation technology is widely applied, compared with the traditional battery testing device, the device has the advantages of poor performance, poor stability and short service life, and cannot be used for testing high multiplying power.
Disclosure of Invention
The invention aims to provide an in-situ device for testing the synchrotron radiation X-ray absorption spectrum of battery electrode materials.
The invention aims at realizing the following technical scheme:
the in-situ device for testing the synchrotron radiation X-ray absorption spectrum of the battery electrode material comprises a negative electrode part, an internal insulation and pressure part and a positive electrode part;
the negative electrode part comprises a negative electrode a, a beryllium sheet a, a rubber ring a, a negative electrode b and four insulating sleeves, wherein threaded through holes, insulating sleeve through holes and light-transmitting through holes are formed in the negative electrode a and the negative electrode b, the beryllium sheet a is positioned at the light-transmitting through hole between the negative electrode a and the negative electrode b, and the insulating sleeves are embedded in the insulating sleeve through holes and are fixed to an insulating fixing device;
the inner insulation and pressure part comprises a rubber ring b, a polytetrafluoroethylene sleeve, a spring, a top sheet and a beryllium sheet b, wherein the spring and the top sheet are nested in the polytetrafluoroethylene sleeve, and the rubber ring b, the polytetrafluoroethylene sleeve and the beryllium sheet b are fixed at a light-transmitting through hole between a negative electrode b and a positive electrode a;
the positive electrode part comprises a positive electrode a, a rubber ring c, a beryllium sheet c and a positive electrode b, wherein the positive electrode a and the positive electrode b are respectively provided with a threaded through hole and a light-transmitting through hole, and the beryllium sheet c is positioned at the light-transmitting through hole between the positive electrode a and the positive electrode b.
According to the technical scheme provided by the invention, the in-situ device for testing the synchrotron radiation X-ray absorption spectrum of the battery electrode material provided by the embodiment of the invention adopts a detachable and washable connecting structure, has the characteristics of good sealing property and internal insulation, overcomes the problems of unrepeatability and complex operation of the existing similar devices, realizes the advantages of high in-situ test repeatability, simplicity in operation, convenience in carrying and cost reduction, is suitable for collecting data of in-situ analysis electrode material by synchrotron radiation X-rays, and can be used for researching the physical and chemical properties of various energy storage devices such as lithium ion batteries, sodium ion batteries, supercapacitors and the like.
Drawings
Fig. 1 is a schematic diagram of a disassembled structure of an in-situ apparatus for testing a synchrotron radiation X-ray absorption spectrum of a battery electrode material according to an embodiment of the present invention;
FIG. 2 is a schematic diagram of an assembly structure of an in-situ apparatus for testing synchrotron radiation X-ray absorption spectra of battery electrode materials according to an embodiment of the present invention;
fig. 3 is a schematic structural diagram of a negative electrode a according to an embodiment of the present invention;
fig. 4 is a schematic structural diagram of a negative electrode b according to an embodiment of the present invention;
FIG. 5 is a schematic structural diagram of an anode a according to an embodiment of the present invention;
FIG. 6 is a schematic structural diagram of a positive electrode b according to an embodiment of the present invention;
FIG. 7 example of the measurement of V using the device of the present invention 2 C-Sn is used as a charge-discharge curve of the working electrode;
FIG. 8 shows charge and discharge curves measured under the same conditions using a button cell apparatus commonly used in the laboratory at present;
fig. 9 shows the data of the X-ray absorption spectrum of Sn tested by the device of the present invention at the beam line experiment station of the Beijing synchrotron radiation light source 1W 2B.
In the figure:
1. an insulating sleeve;
2. a negative electrode a;2-1, semi-arc through holes; 2-2, threaded through holes; 2-3, insulating sleeve through holes; 2-4, a light-transmitting through hole; 2-5, an inner layer groove; 2-6, an outer layer groove;
3. beryllium sheet a;
4. a rubber ring a;
5. a negative electrode b;5-1, an annular groove; 5-2, semi-arc through holes; 5-3, a light-transmitting through hole; 5-4, an insulating sleeve through hole outer layer groove; 5-5, insulating sleeve through holes; 5-6, threaded through holes; 5-7, a negative electrode lead hole;
6. a rubber ring b;
7. a polytetrafluoroethylene sleeve;
8. a top sheet;
9. a spring;
10. beryllium sheet b;
11. a positive electrode a;11-1, threaded through holes; 11-2, semi-arc through holes; 11-3, layer grooves; 11-4, a light-transmitting through hole; 11-5, an anode lead hole;
12. a rubber ring c;
13. beryllium sheet c;
14. a positive electrode b;14-1, threaded through holes; 14-2, an outer layer groove; 14-3, a light-transmitting through hole; 14-4, inner layer groove.
Detailed Description
Embodiments of the present invention will be described in further detail below. What is not described in detail in the embodiments of the present invention belongs to the prior art known to those skilled in the art.
The invention relates to an in-situ device for testing the synchrotron radiation X-ray absorption spectrum of a battery electrode material, which comprises the following preferred specific embodiments:
comprises a negative electrode part, an internal insulation and pressure part and a positive electrode part;
the negative electrode part comprises a negative electrode a, a beryllium sheet a, a rubber ring a, a negative electrode b and four insulating sleeves, wherein threaded through holes, insulating sleeve through holes and light-transmitting through holes are formed in the negative electrode a and the negative electrode b, the beryllium sheet a is positioned at the light-transmitting through hole between the negative electrode a and the negative electrode b, and the insulating sleeves are embedded in the insulating sleeve through holes and are fixed to an insulating fixing device;
the inner insulation and pressure part comprises a rubber ring b, a polytetrafluoroethylene sleeve, a spring, a top sheet and a beryllium sheet b, wherein the spring and the top sheet are nested in the polytetrafluoroethylene sleeve, and the rubber ring b, the polytetrafluoroethylene sleeve and the beryllium sheet b are fixed at a light-transmitting through hole between a negative electrode b and a positive electrode a;
the positive electrode part comprises a positive electrode a, a rubber ring c, a beryllium sheet c and a positive electrode b, wherein the positive electrode a and the positive electrode b are respectively provided with a threaded through hole and a light-transmitting through hole, and the beryllium sheet c is positioned at the light-transmitting through hole between the positive electrode a and the positive electrode b.
The apertures of the light-transmitting through holes of the negative electrode a and the negative electrode b meet the size of the beam line light spot of the synchronous radial line station.
The beryllium sheet a is positioned between the negative electrode a and the negative electrode b, is placed in a through hole groove in the inner layer of the negative electrode b, and is fixed through the rubber ring a.
The polytetrafluoroethylene sleeve is nested in the groove of the inner layer of the positive electrode a, and the rubber ring b is sleeved outside the polytetrafluoroethylene sleeve.
The beryllium sheet b is embedded in the through hole groove of the top sheet, the spring is arranged above the top sheet, and the top sheet is arranged in the polytetrafluoroethylene sleeve.
In the invention, the beryllium sheet can ensure the normal penetration of X rays. The polytetrafluoroethylene sleeve is nested in the inner layer groove of the positive electrode a, and the rubber ring b is sleeved outside the sleeve to play a role in sealing and fastening. The beryllium sheet b can ensure that the internal pressure of the electrode material is uniform, and the spring can fix the top sheet and the beryllium sheet b and buffer the internal air pressure of the battery so as to keep a sealing state all the time. The positive electrode and the negative electrode are respectively provided with a through hole cylindrical through hole for fixing, and the insulating sleeve is placed in the through hole cylindrical body and used for preventing the screw from directly connecting the positive electrode and the negative electrode to cause short circuit of the battery. The insulating sleeve is made of Polytetrafluoroethylene (PTFE). The fixed connection is screw connection. An O-shaped sealing ring is arranged between the screw and all the contact surfaces.
The in-situ device for testing the synchrotron radiation X-ray absorption spectrum of the battery electrode material is suitable for testing X-ray absorption spectrum data of the battery material in transmission and fluorescence modes and can be used repeatedly. The device is used for measuring the X-ray absorption spectrum data of the electrode material of the lithium ion, sodium ion or magnesium ion battery by an X-ray transmission type or fluorescent in-situ experiment method.
Compared with the prior art, the invention is convenient to unpick and wash and replace electrode materials after the experiment is finished, and can be reused, thereby reducing the cost and shortening the experiment period. And can be used for in-situ test methods of transmission type and fluorescent type X-ray absorption spectra, so that the method can be widely applied to research on the charge and discharge processes of electrode materials of energy storage devices such as various lithium ion batteries, sodium ion batteries and magnesium ion batteries.
The invention is a synchrotron radiation X-ray absorption spectrum device for in-situ analysis of the electrochemical performance of electrode materials, adopts a detachable and washable connection structure, has the characteristics of good sealing performance and internal insulation, overcomes the problems of unrepeatable and complex operation of the existing similar devices, realizes the advantages of high in-situ test repeatability, simple operation, convenient carrying and cost reduction, is suitable for acquisition of data of in-situ analysis of the electrode materials by synchrotron radiation X-rays, and can be used for research of the physical and chemical performances of energy storage devices such as various lithium ion batteries, sodium ion batteries, supercapacitors and the like.
Specific examples:
as shown in fig. 1 to 6, the present invention provides a synchrotron radiation X-ray absorption spectrum device for analyzing electrochemical properties of an electrode material, comprising: a negative electrode portion, an internal insulation and pressure portion, and a positive electrode portion. The negative electrode part comprises a negative electrode a, a beryllium sheet a, a rubber ring a, a negative electrode b and four insulating sleeves, wherein the negative electrode a and the negative electrode b are respectively provided with a threaded through hole, an insulating sleeve through hole and a light-transmitting through hole; the beryllium sheet a is positioned at the position of the light-transmitting through hole between the negative electrode a and the negative electrode b, and the insulating sleeve is used for insulating and fixing the whole device. The inner insulation and pressure part comprises a rubber ring b, a polytetrafluoroethylene sleeve, a spring, a top piece and a beryllium piece b, wherein the beryllium piece b is fixed at a light transmission through hole of the anode a by the top piece, the spring and the top piece are nested in the polytetrafluoroethylene sleeve, the polytetrafluoroethylene sleeve is fixed between the cathode b and the anode a, and the rubber ring b is arranged between the cathode b and the anode a for better sealing and protecting effects. The positive electrode part comprises a positive electrode a, a rubber ring c, a beryllium sheet c and a positive electrode b, threaded through holes are formed in the positive electrode a and the positive electrode b, the beryllium sheet c is located at the position of a light-transmitting through hole between the positive electrode a and the positive electrode b and is fixed through screws, and the rubber ring c is arranged between the positive electrode a and the positive electrode b for better sealing and protecting effects.
The rubber ring is a ring-shaped silica gel pad or a fluorine rubber pad.
The insulating sleeve is made of Polytetrafluoroethylene (PTFE) or organic glass.
And sealing the electrode to be tested in the polytetrafluoroethylene sleeve between the negative electrode b and the positive electrode a, connecting one lead wire to the positive electrode lead wire hole of the positive electrode b to serve as a positive electrode, and connecting the other lead wire to the negative electrode lead wire hole of the negative electrode a to serve as a negative electrode.
Example 1:
in V form 2 C-Sn is used as an active substance of a working electrode, N-methylpyrrolidone (NMP) is used as a solvent, the N-methylpyrrolidone (NMP) is ground and mixed with a conductive agent Acetylene Black (AB) and a binder vinylidene fluoride (PVDF) uniformly, the slurry is coated on an aluminum foil uniformly, the aluminum foil is dried in a vacuum drying oven at 110 ℃ for overnight, the aluminum foil is rolled on a tablet press to be compact, and finally an electrode plate with the diameter of 16mm is cut on a slicer. When the cell is assembled, the following steps are required to be operated in a glove box filled with high purity argon, and the water content and the oxygen content are both less than 0.1ppm. Firstly, combining the positive electrode a with the positive electrode b, and screwing four screws of the positive electrode part; clamping a polytetrafluoroethylene sleeve into a groove of an anode a, putting a cut electrode slice into the polytetrafluoroethylene sleeve of the device, sequentially putting a diaphragm (Celegard 2400) and a counter electrode lithium slice, and then dripping a small amount of electrolyte (LiPF) 6 EC, dmc=1:1, v/v), and then placing a spring piece on the lithium piece, so that the positive electrode and the negative electrode can be fully contacted, the positive electrode and the negative electrode can be prevented from shaking, the top piece is placed on the lithium piece to be compacted, and a rubber ring b is placed on the top piece; finally, the negative electrode a and the negative electrode b are assembled and fixed, the negative electrode part is installed on the parts, and four screws are screwed. The assembled device structure is shown in fig. 2.
And in the test, setting a potential window of 0.2C multiplying power and 0-3.5V on the Land battery test system for circulation to obtain a charge-discharge specific capacity and voltage change curve.
To control the experimental results, it is necessary to perform a test in which the battery is mounted in a button cell with the same electrode material.
FIG. 7 is a schematic illustration of the measurement of V using the apparatus of the present invention in example 1 2 C-Sn is used as a charge-discharge curve of a working electrode, the test current is 0.12mA, and the electrode mass is 0.6220mg;
fig. 8 is a charge-discharge curve measured under the same conditions using a button cell apparatus commonly used in the laboratory at present, the test current was 0.14mA, and the electrode mass was 0.6960mg.
As can be seen in connection with fig. 7 and 8: the experimental device can test the relation curve of specific capacitance and voltage under the condition of completely exposing air to basically coincide with the button cell of the charge and discharge testing device commonly used in the laboratory at present.
Example 2:
in V form 2 C-Sn is used as an active substance of a working electrode, N-methylpyrrolidone (NMP) is used as a solvent, the N-methylpyrrolidone (NMP) is ground and mixed with a conductive agent Acetylene Black (AB) and a binder vinylidene fluoride (PVDF) uniformly, the slurry is coated on an aluminum foil uniformly, the aluminum foil is dried in a vacuum drying oven at 110 ℃ for overnight, the aluminum foil is rolled on a tablet press to be compact, and finally an electrode plate with the diameter of 16mm is cut on a slicer. When the cell is assembled, the following steps are required to be operated in a glove box filled with high purity argon, and the water content and the oxygen content are both less than 0.1ppm. Firstly, combining the positive electrode a with the positive electrode b, and screwing four screws of the positive electrode part; clamping a polytetrafluoroethylene sleeve into a groove of an anode a, putting a cut electrode sheet into the polytetrafluoroethylene sleeve of the device, sequentially putting a diaphragm (Celegard 2400) and a counter electrode lithium sheet, then dripping a small amount of electrolyte (LiPF 6, EC: DMC=1:1, v/v), putting a spring sheet on the lithium sheet, so that the anode and the cathode can be fully contacted, preventing the anode and the cathode from shaking, putting a top sheet on the device to be compacted, and putting a rubber ring b on the top sheet; finally, the negative electrode a and the negative electrode b are assembled and fixed, the negative electrode part is installed on the parts, and four screws are screwed. The assembled device structure is shown in fig. 2.
FIG. 9 shows the data of the absorption spectrum of Sn, electrode material, tested by the device of the invention at the Beijing synchrotron radiation light source 1W2B beam line experiment stationThe material is V 2 C-Sn. As can be seen from the figure, the original device can perform transmission type X-ray test in the process of charging and discharging, and the test result is more accurate and reliable than the result obtained by the traditional ex-situ test method.
In addition, the device can be applied to ex-situ test, and the device is detachable, so that the in-situ device is conveniently opened at any time, and electrode materials are taken out for other tests.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions easily contemplated by those skilled in the art within the scope of the present invention should be included in the scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.
Claims (4)
1. An in-situ apparatus for testing the synchrotron radiation X-ray absorption spectrum of a battery electrode material, which is characterized by comprising a negative electrode part, an internal insulation and pressure part and a positive electrode part;
the negative electrode part comprises a negative electrode a, a beryllium sheet a, a rubber ring a, a negative electrode b and four insulating sleeves, wherein threaded through holes, insulating sleeve through holes and light-transmitting through holes are formed in the negative electrode a and the negative electrode b;
the beryllium sheet a is positioned at the position of the light-transmitting through hole between the negative electrode a and the negative electrode b, is placed in a through hole groove of the inner layer of the negative electrode b, and is fixed through the rubber ring a;
the insulating sleeve is embedded in the insulating sleeve through hole and is fixed on the insulating fixing device;
the inner insulation and pressure part comprises a rubber ring b, a polytetrafluoroethylene sleeve, a spring, a top sheet and a beryllium sheet b, wherein the spring and the top sheet are nested in the polytetrafluoroethylene sleeve, and the rubber ring b, the polytetrafluoroethylene sleeve and the beryllium sheet b are fixed at a light-transmitting through hole between a negative electrode b and a positive electrode a;
the positive electrode part comprises a positive electrode a, a rubber ring c, a beryllium sheet c and a positive electrode b, wherein the positive electrode a and the positive electrode b are respectively provided with a threaded through hole and a light transmission through hole, and the beryllium sheet c is positioned at the light transmission through hole between the positive electrode a and the positive electrode b;
the rubber ring b is arranged between the negative electrode b and the positive electrode a;
the rubber ring c is arranged between the positive electrode a and the positive electrode b.
2. The in situ apparatus for testing the synchrotron radiation X-ray absorption spectrum of battery electrode materials according to claim 1, wherein the apertures of the light transmitting through holes of the negative electrode a and the negative electrode b satisfy the size dimension of the beam spot of the synchrotron radiation station.
3. An in situ apparatus for testing the synchrotron radiation X-ray absorption spectrum of a battery electrode material as claimed in claim 2, wherein,
the polytetrafluoroethylene sleeve is nested in the groove of the inner layer of the positive electrode a, and the rubber ring b is sleeved outside the polytetrafluoroethylene sleeve.
4. An in situ apparatus for testing the synchrotron radiation X-ray absorption spectrum of a battery electrode material according to claim 3, wherein the beryllium sheet b is embedded in a through-hole groove of a top sheet, a spring is placed over the top sheet, and the top sheet is placed in the polytetrafluoroethylene sleeve.
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| CN109856170A (en) * | 2018-12-14 | 2019-06-07 | 深圳先进技术研究院 | Battery in-situ synchronization radiation X ray absorption spectra test device |
| CN109839594A (en) * | 2019-01-28 | 2019-06-04 | 西安交通大学 | A kind of electrode slice charge and discharge pressure control device, control system and its application method |
| CN111638233B (en) * | 2020-04-26 | 2021-05-07 | 山东大学 | In-situ battery reaction chamber of multifunctional X-ray diffractometer and application |
| CN112151898A (en) * | 2020-09-09 | 2020-12-29 | 中国原子能科学研究院 | Neutron in-situ device |
| CN114035088B (en) * | 2021-11-10 | 2023-04-07 | 哈尔滨工业大学 | A battery testing arrangement for normal position synchrotron radiation formation of image |
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