In-situ multi-spectroscopy and mass spectrometry testing device for gas cell

Abstract

The application discloses a kind of gas battery in-situ multispectral and mass spectrum combined testing device, including gas reaction chamber, gas reaction chamber is arranged between positive electrode component and negative electrode component, and is fixedly connected with positive electrode component and negative electrode component, first circuit connecting wire is equipped on negative electrode component, second circuit connecting wire is equipped on positive electrode component, and first circuit connecting wire and second circuit connecting wire are conducted through external circuit;Gas reaction chamber is provided with carrier gas inlet and carrier gas outlet, carrier gas outlet is directed to positive electrode component, and carrier gas is conveyed to electrochemical differential mass spectrometer by sweeping positive electrode side to carry out real-time on-line monitoring in gas reaction chamber.The device can realize real-time, synchronous, in-situ monitoring of electrode crystal structure, electronic structure evolution, material local coordination environment and gas phase product in the electrochemical reaction process of gas battery, which provides strong technical support for revealing the reaction mechanism and multidimensional structure-activity relationship of various gas batteries related to gas catalytic reaction.

Description

Technical Field

[0001] This invention relates to the field of gas battery technology, and more specifically, to an in-situ multispectral and mass spectrometry testing device for gas batteries. Background Technology

[0002] Lithium-air batteries boast an extremely high theoretical energy density (approximately 3500 Wh / kg). -1 With its superior performance (far exceeding that of existing lithium-ion batteries) and environmentally friendly characteristics, lithium-carbon dioxide (LCC) batteries have shown enormous application potential and broad development prospects in the field of next-generation high-energy-density energy storage systems. As an important branch of lithium-air batteries, LCC batteries can capture and convert CO2 while simultaneously providing electrical energy output, offering an innovative solution for the coordinated development of energy and environment under the "dual-carbon" strategic goal. However, due to the complex gas-liquid-solid three-phase reaction interface and the challenge of highly reversible CO2 reduction / evolution reactions, the reaction kinetics of LCC batteries are generally slow, leading to problems such as high overpotential, poor reversibility, and poor cycle stability, severely restricting their practical application. The insulating properties of discharge products (such as Li2CO3 or Li2C2O4) and their irreversible accumulation on the electrode surface further exacerbate electrode polarization and reduce energy efficiency. Therefore, in-depth understanding of the dynamic evolution of electrode structure, the evolution of product morphology and composition, and intermediate information in the gas reaction process of LCC batteries under operating conditions is of significant scientific importance and research value for understanding the reaction mechanism, guiding the design of efficient catalysts, and promoting the practical development of LCC batteries.

[0003] In-situ characterization techniques provide crucial experimental evidence for a deeper understanding of battery working mechanisms and revealing the essence of performance degradation by directly observing the structural evolution of electrode materials, interface behavior, and the dynamic generation and consumption of products under operating conditions. For lithium-carbon dioxide batteries, the electrochemical reaction involves complex CO2 reduction and precipitation processes, accompanied by the reversible generation and decomposition of discharge products (such as Li2CO3 or Li2C2O4) and the dynamic evolution of the electrode surface microstructure. In-situ synchrotron X-ray diffraction, with its high throughput, high energy resolution, and deep penetration, can track the evolution of electrode crystal structure, electronic states, and local coordination environment during the charging and discharging process of lithium-carbon dioxide batteries in real time, providing important information for revealing the nucleation, growth, and decomposition mechanisms of discharge products. In-situ differential electrochemical mass spectrometry (DEMS) can perform qualitative and quantitative analysis of gaseous reactant consumption and product generation in the CO2 reduction / precipitation reaction on a millisecond timescale, capturing information on reaction intermediates and elucidating gas evolution pathways. However, traditional single in-situ characterization methods often only reflect one aspect of the electrode process. Furthermore, differences in electrode configuration, gas atmosphere, and testing environment among different testing devices can lead to discrepancies between experimental results and actual battery operation, making it difficult to achieve precise correlation and mutual verification of multi-dimensional information on "structural evolution, gas-phase products, and electrochemical behavior." Therefore, developing an in-situ characterization device for lithium-carbon dioxide batteries that can simultaneously perform multi-spectral and mass spectrometry is of significant scientific and engineering application value for systematically elucidating reaction mechanisms, establishing structure-activity relationships between electrode microstructure and macroscopic electrochemical performance, and guiding the design and optimization of efficient catalyst systems.

[0004] Therefore, how to achieve real-time, synchronous, multi-dimensional in-situ monitoring of the evolution of electrode microstructure and dynamic generation of gaseous products during the complex gas-solid interface reaction process of lithium carbon dioxide batteries, especially the accurate capture of the structure-property relationship between the nucleation / decomposition pathways and gas consumption / precipitation behavior of discharge products under CO2 atmosphere, and overcome the limitations of existing single in-situ characterization techniques in the resolution of "gas-solid coupling", has become a technical problem that urgently needs to be solved by those skilled in the art. Summary of the Invention

[0005] Therefore, the purpose of this invention is to provide an in-situ multispectral and mass spectrometry testing device for gas batteries, which solves the technical problem of real-time, synchronous, and multi-dimensional in-situ monitoring of the dynamic evolution of electrode microstructure and gas-phase products during the complex gas-solid interface reaction of lithium carbon dioxide batteries. It enables real-time correlation analysis of electrode crystal structure, electronic state evolution, and gas consumption / emission behavior during the reaction process, so as to reveal the kinetic mechanism of reversible generation and decomposition of discharge products, and provide reliable technical support for the design and optimization of highly reversible lithium carbon dioxide battery catalyst systems and various gas batteries.

[0006] To achieve the above objectives, the present invention provides the following technical solution:

[0007] A gas battery in-situ multispectral and mass spectrometry testing device includes a gas reaction chamber, a negative electrode component, and a positive electrode component;

[0008] The gas reaction chamber is located between the positive electrode component and the negative electrode component, and is fixedly connected to both components. The negative electrode component is provided with a first circuit connection line, and the positive electrode component is provided with a second circuit connection line. The first and second circuit connection lines are connected through an external circuit. The gas reaction chamber is provided with a carrier gas inlet and a carrier gas outlet. The carrier gas outlet points towards the positive electrode component. The carrier gas is used to purge the positive electrode side to deliver the reaction tail gas in the gas reaction chamber to an electrochemical differential mass spectrometer for real-time online monitoring.

[0009] Further technology of the present invention:

[0010] Preferably, the gas reaction chamber is provided with a first threaded hole, and the positive electrode component is provided with a second threaded hole that mates with the first threaded hole, and the two are connected by bolts; the gas reaction chamber is provided with a third threaded hole, and the negative electrode component is provided with a fourth threaded hole that mates with the third threaded hole, and the two are connected by bolts.

[0011] Preferably, a first sealing ring is provided between the positive electrode component and the gas reaction chamber; a second sealing ring is provided between the gas reaction chamber and the negative electrode component.

[0012] Preferably, the negative electrode component is provided with a negative electrode window, the negative electrode component is provided with a fifth threaded hole, and the negative electrode window is provided with a sixth threaded hole for connection, and the two are connected by bolts.

[0013] Preferably, a gas electrode is provided on the positive electrode component, and a negative electrode is provided on the negative electrode component;

[0014] An elastic conductive component is provided in the gas reaction chamber. The elastic conductive component includes a conductive pad and an elastic reset member. The conductive pad is in contact with the negative electrode. One end of the elastic reset member abuts or connects to the conductive pad, and the other end abuts or connects to the gas electrode. The elastic conductive component presses the gas electrode and the negative electrode together on both sides of the gas reaction chamber to form a tight electrochemical interface.

[0015] Preferably, the positive electrode component is provided with a radiation light inlet that passes through the gas electrode, the negative electrode component is provided with a radiation light channel, the negative electrode window is provided with a radiation light outlet, and the conductive pad is provided with a cavity for synchrotron radiation to pass through. The radiation light inlet, radiation light channel, cavity, and radiation light outlet are coaxially arranged.

[0016] Compared with the prior art, the present invention provides an in-situ multispectral and mass spectrometry coupled testing device for gas batteries, which has the following advantages:

[0017] Through the coordinated design of the positive electrode, negative electrode, and gas reaction chamber, the gas electrode in the gas reaction chamber is connected to the negative electrode to achieve battery charge-discharge cycles, thereby obtaining a real electrochemical reaction process. By setting radiation light entrance and radiation light exit on the positive and negative electrode components respectively, a "light in, light out" penetration path is provided for synchrotron X-rays, enabling in-situ monitoring of the crystal structure evolution, electronic state changes, and local coordination environment evolution of the electrode materials during battery charge-discharge. The gas reaction chamber is equipped with a carrier gas inlet and a carrier gas outlet, providing a "gas in, gas out" path for the carrier gas. Electrochemical differential mass spectrometry can simultaneously perform qualitative and quantitative analysis of gaseous intermediate and final products in the CO2 reduction / evolution reaction process, providing technical support for real-time monitoring of the gas evolution path during the reaction process. Attached Figure Description

[0018] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0019] Figure 1 This is a schematic diagram of an in-situ multispectral and mass spectrometry testing device for a gas battery disclosed in an embodiment of the present invention;

[0020] Figure 2 This is an exploded view of an in-situ multispectral and mass spectrometry testing device for gas batteries disclosed in an embodiment of the present invention;

[0021] Figure 3 This is a schematic diagram of the gas reaction chamber disclosed in an embodiment of the present invention;

[0022] Figure 4 This is a schematic diagram of the negative electrode component disclosed in an embodiment of the present invention;

[0023] Figure 5 This is a schematic diagram of the negative electrode window structure disclosed in an embodiment of the present invention;

[0024] Figure 6 This is an assembly diagram of the positive electrode component disclosed in an embodiment of the present invention;

[0025] Figure 7 This is a schematic diagram of the structure of the elastic conductive component disclosed in an embodiment of the present invention. Detailed Implementation

[0026] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0027] like Figure 1-7 This embodiment provides an in-situ multispectral and mass spectrometry testing device for gas batteries, including a gas reaction chamber 100, a negative electrode component 200, and a positive electrode component 400;

[0028] The gas reaction chamber 100 is disposed between the positive electrode component 400 and the negative electrode component 200, and is fixedly connected to the positive electrode component 400 and the negative electrode component 200.

[0029] The gas reaction chamber 100 is provided with a first threaded hole 102, and the positive electrode component 400 is provided with a second threaded hole 401 that mates with the first threaded hole 102. The two are connected by bolts. The gas reaction chamber 100 is provided with a third threaded hole 101, and the negative electrode component 200 is provided with a fourth threaded hole 201 that mates with the third threaded hole 101. The two are connected by bolts.

[0030] The positive electrode component 400 is provided with a gas electrode 404 (i.e., the positive electrode of a lithium carbon dioxide battery, usually a carbon cloth, carbon paper or other gas diffusion layer loaded with a catalyst), and the negative electrode component 200 is provided with a negative electrode 205 (lithium metal).

[0031] A first sealing ring 106 is provided between the positive electrode component 400 and the gas reaction chamber 100; a second sealing ring 104 is provided between the gas reaction chamber 100 and the negative electrode component 200. This ensures that CO2 or carrier gas atmosphere does not leak out, while preventing outside air (especially moisture) from entering the battery.

[0032] The negative electrode component 200 is provided with a first circuit connection line 202, and the positive electrode component 400 is provided with a second circuit connection line 402. The first circuit connection line 202 and the second circuit connection line 402 are connected to the electrochemical workstation through an external circuit to form a complete charge and discharge circuit.

[0033] The gas reaction chamber 100 is provided with a carrier gas inlet 103 and a carrier gas outlet 105. The carrier gas outlet 105 points to the positive electrode component 400. The carrier gas is used to purge the positive electrode side to deliver the reaction tail gas in the gas reaction chamber to the electrochemical differential mass spectrometer for real-time online monitoring.

[0034] The negative electrode component 200 is provided with a negative electrode window 300, a fifth threaded hole 203, and a sixth threaded hole 301 for connection. The two are connected by bolts.

[0035] The positive electrode component 400 is provided with a radiation light inlet 403, which passes through the gas electrode 404. The negative electrode component 200 is provided with a radiation light channel 204. The negative electrode window 300 is provided with a radiation light outlet 302. The conductive pad 503 is provided with a cavity 501 for synchrotron radiation to pass through. The radiation light inlet 403, the radiation light channel 204, the cavity 501 and the radiation light outlet 302 are coaxially arranged.

[0036] To enable multi-spectral characterization, this embodiment integrates replaceable window components on the sealed housing, specifically providing four independent optical channels.

[0037] Laser Raman spectroscopy testing window (first optical window): A first optical window for laser incident and signal collection is provided on the side of the positive electrode component 400 or the gas reaction chamber 100. This window is made of quartz or sapphire glass to facilitate the transmission of 532 nm, 632 nm, or 785 nm lasers. During testing, the laser is focused onto the surface of the gas electrode through this window, and the electrode material (such as catalyst) and discharge products (Li2CO3, Li2C) are collected in real time. 2O4 Raman characteristic peaks (e.g., ) are used to analyze the chemical structural evolution of surface species.

[0038] X-ray diffraction testing window (second optical window): A second optical window for X-ray diffraction is provided on the positive electrode component 400. This window is typically a beryllium window or a Kapton thin film window, which has low absorption of high-energy X-rays. Synchrotron radiation X-rays enter through the radiation light entrance port 403, pass through the gas electrode, and exit through the radiation light exit port 302. By acquiring diffraction signals, changes in the crystal structure of the electrode material, such as catalyst phase transitions or changes in product crystallinity, can be analyzed in real time.

[0039] X-ray absorption spectroscopy testing window (third optical window): A third optical window for the passage of incident X-ray absorption spectroscopy light is also provided on the positive electrode component 400. This window is usually a beryllium window or a Kapton thin film window, which has low absorption of high-energy X-rays. Together with the radiation light inlet 403 and outlet 302, it constitutes the optical path for X-ray absorption fine structure spectroscopy testing. By analyzing the near-edge structure and extended fine structure of X-ray absorption, the valence state changes of metal elements (such as Ru and Mn in catalysts) and their local coordination environment (such as bond length and coordination number) in the electrode can be monitored in real time.

[0040] X-ray scattering spectroscopy testing window (fourth optical window): To further analyze the short-range ordered structure and nanoscale morphology of the products, a fourth optical window is also provided on the device for the passage of incident light for X-ray scattering spectroscopy. By combining high-energy X-rays and collecting the scattering signal and performing Fourier transform, information on the atomic pair distribution function can be obtained. This has a unique advantage for resolving the local structure of amorphous or nanoscale discharge products.

[0041] To facilitate adjustments to the testing modes, the four windows described above can be modularly designed, meaning they are fixed to replaceable window components. Users can quickly replace different window components as needed without disassembling the battery unit, enabling switching or simultaneous testing of Raman, XRD, XAFS, and PDF.

[0042] Furthermore, to ensure good electrical contact between the electrodes during charging and discharging, an elastic conductive component 500 is provided inside the gas reaction chamber 100. The elastic conductive component 500 includes a conductive pad 503 and an elastic reset member 502. The conductive pad 503 is in contact with the negative electrode 205, and one end of the elastic reset member 502 abuts or connects to the conductive pad 503, while the other end abuts or connects to the gas electrode 404. The conductive component 500 presses the gas electrode 404 and the negative electrode 205 together on both sides of the gas reaction chamber 100 to form a tight electrochemical interface.

[0043] During pressing, the component can automatically compensate for assembly tolerances, forming a stable electrochemical interface. At the same time, it connects the negative electrode and the negative electrode component 200 to form a negative electrode current path, ensuring the accuracy of electrochemical signal acquisition.

[0044] The gas path system design of this embodiment includes a carrier gas inlet 103 and a carrier gas outlet 105 on the carrier gas delivery and mass spectrometry coupled gas reaction chamber 100. This provides a "gas in, gas out" pathway for the carrier gas, allowing the electrochemical differential mass spectrometer to simultaneously perform qualitative or quantitative analysis of gaseous or volatile intermediate and final products of the electrochemical reaction, providing technical support for real-time monitoring of gaseous products during the reaction process. The in-situ synchrotron radiation and electrochemical differential mass spectrometry coupled device for gas batteries disclosed in this embodiment can perform real-time, synchronous, and in-situ monitoring of electrode microstructure and gas evolution during the electrochemical reaction process, thereby providing a multi-dimensional and high-precision experimental platform for the study of the energy storage mechanism of gas batteries.

[0045] Taking lithium carbon dioxide batteries as an example:

[0046] Electrochemical excitation: The battery is subjected to constant current charge-discharge or cyclic voltammetry scanning using an electrochemical workstation. Gas inlet path: During gas inlet, a three-way valve is installed at the front end of the inlet, one of which carries a high-purity carrier gas (such as high-purity Ar or He) at a rate of 3 mL / min. -1One input is a three-way valve, and the other is the reaction gas CO2, which is input at a rate of 0.09 mL / min. The two gas streams merge before entering the apparatus, and the other end extends into the gas reaction chamber 100, passing through the carrier gas outlet 105 near the gas electrode. The gas outlet path: The carrier gas outlet 105 passes through the positive electrode side, and the other end connects to the electrochemical differential mass spectrometer. Through continuous purging with carrier gas, the gaseous products consumed or generated by the electrochemical reaction are blown into the mass spectrometer for quantitative determination.

[0047] Multispectral acquisition process. Gas analysis: The carrier gas continuously purges the gas reaction chamber, carrying the gaseous products generated during the reaction (such as O2, CO, and unreacted CO2) into the electrochemical differential mass spectrometer. The mass spectrometer performs real-time, high-sensitivity qualitative and quantitative analysis of the gas. Data correlation: By aligning the acquired electrochemical signals (voltage / current-time curves), multispectral structural information (characteristic peak shifts / intensity changes), and mass spectrometry gas signals (ion current intensity) along the time axis, real-time correlation and mutual verification between "structure-product-electrochemical performance" can be achieved.

[0048] Through the above design, this device successfully solves the problem of simultaneously acquiring multi-dimensional information in battery research, and provides a reliable experimental platform for a deeper understanding of the gas reduction / evolution reaction mechanism.

[0049] It should be noted that in this embodiment, the gas reaction chamber 100, negative electrode component 200, negative electrode window 300, positive electrode component 400, and elastic conductive component 500 are all disposed inside the sealed housing.

[0050] In this document, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one..." does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes said element.

[0051] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A gas battery in-situ multispectral and mass spectrometry coupled testing device, characterized in that: It includes a gas reaction chamber (100), a negative electrode component (200), and a positive electrode component (400); The gas reaction chamber (100) is disposed between the positive electrode component (400) and the negative electrode component (200) and is fixedly connected to the positive electrode component (400) and the negative electrode component (200). The negative electrode component (200) is provided with a first circuit connection line (202), and the positive electrode component (400) is provided with a second circuit connection line (402). The first circuit connection line (202) and the second circuit connection line (402) are connected through an external circuit. The gas reaction chamber (100) is provided with a carrier gas inlet (103) and a carrier gas outlet (105). The carrier gas outlet points to the positive electrode component (400). The carrier gas is used to purge the positive electrode side to deliver the reaction tail gas in the gas reaction chamber to the electrochemical differential mass spectrometer for real-time online monitoring.

2. The in-situ multispectral and mass spectrometry coupled testing device for gas batteries according to claim 1, characterized in that: The gas reaction chamber (100) is provided with a first threaded hole (102), and the positive electrode component (400) is provided with a second threaded hole (401) that mates with the first threaded hole (102). The two are connected by bolts. The gas reaction chamber (100) is provided with a third threaded hole (101), and the negative electrode component (200) is provided with a fourth threaded hole (201) that mates with the third threaded hole (101). The two are connected by bolts.

3. The in-situ multispectral and mass spectrometry testing device for gas batteries according to claim 1, characterized in that: A first sealing ring (106) is provided between the positive electrode component (400) and the gas reaction chamber (100); a second sealing ring (104) is provided between the gas reaction chamber (100) and the negative electrode component (200).

4. The in-situ multispectral and mass spectrometry coupled testing device for gas batteries according to claim 1, characterized in that: The negative electrode component (200) is provided with a negative electrode window (300), the negative electrode component (200) is provided with a fifth threaded hole (203), and the negative electrode window (300) is provided with a sixth threaded hole (301) for connection, and the two are connected by bolts.

5. The in-situ multispectral and mass spectrometry coupled testing device for gas batteries according to claim 1, characterized in that: A gas electrode (404) is provided on the positive electrode component (400), and a negative electrode (205) is provided on the negative electrode component (200). An elastic conductive component (500) is provided inside the gas reaction chamber (100). The elastic conductive component (500) includes a conductive pad (503) and an elastic reset member (502). The conductive pad (503) is in contact with the negative electrode (205). One end of the elastic reset member (502) abuts or connects to the conductive pad (503), and the other end abuts or connects to the gas electrode (404). The elastic conductive component (500) presses the gas electrode (404) and the negative electrode (205) together on both sides of the gas reaction chamber (100) to form a tight electrochemical interface.

6. The in-situ multispectral and mass spectrometry coupled testing device for gas batteries according to claim 5, characterized in that: The positive electrode component (400) is provided with a radiation light inlet (403), which passes through the gas electrode (404). The negative electrode component (200) is provided with a radiation light channel (204). The negative electrode window (300) is provided with a radiation light outlet (302). The conductive pad (503) is provided with a cavity (501) for synchrotron radiation to pass through. The radiation light inlet (403), radiation light channel (204), cavity (501) and radiation light outlet (302) are coaxially arranged.

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