Online monitoring device for state of charge of flow battery based on ultraviolet spectrum

Abstract

The invention discloses an online monitoring device for the state of charge of a flow battery based on ultraviolet spectrum, and relates to the technical field of flow batteries, the online monitoring device comprises a light shielding case, the light shielding case is internally provided with a pipeline integration module, a light source module, a spectral analysis unit and a data processing system; under a continuous operation condition, a feature extraction algorithm based on a multi-stage signal processing architecture can significantly improve the spectral signal-to-noise ratio, an embedded real-time analysis model is matched, the SOC detection response time is effectively shortened, and the detection reliability under a wide temperature range condition is improved; compared with the prior art, the modular framework is connected through flanges and is designed through a standardized interface modular linkage mechanism, so that the maintenance time of optical elements is greatly shortened, online replacement can be completed without interrupting electrolyte circulation, the stability and reliability of the system can be kept in the long-term operation process, and the service life of the system is prolonged. The service life of the battery is effectively prolonged, the operation cost is reduced, and the industrial application prospect is wide.

Description

Technical Field

[0001] This invention relates to the field of flow battery technology, specifically to an online monitoring device for the state of charge of flow batteries based on ultraviolet spectroscopy. Background Technology

[0002] Flow batteries offer advantages such as high safety, large-scale energy storage, and long cycle life, and have been widely used in renewable energy grid connection and peak shaving / valley filling. However, in practical use, flow batteries are susceptible to problems such as capacity decay, electrolyte concentration imbalance, and volume changes due to factors like transmembrane migration of active materials, irreversible side reactions, and environmental factors, leading to a decline in battery performance. To maintain high system efficiency and stability, real-time monitoring and management of the flow battery's state of charge (SOC) and health status, such as active material concentration and capacity decay, are necessary.

[0003] Traditional monitoring methods such as potentiometric titration, open-circuit voltage method, and coulometric measurement suffer from insufficient accuracy, complex operation, or long processing times in long-term, online detection. In recent years, online detection methods based on spectrophotometry have gradually gained attention. By measuring the changes in absorbance or transmittance of active substances in the electrolyte at specific wavelengths, real-time detection of SOC and electrolyte health can be achieved.

[0004] However, current optical monitoring devices can only measure single wavelengths or a small number of discrete bands, failing to accurately acquire full-spectrum information. This makes it difficult to comprehensively analyze nonlinear absorption or multi-component coupling effects in high-concentration electrolytes. To address this need, this invention proposes a monitoring device installed on a pipeline based on spectrophotometry. By measuring the full-spectrum absorption spectrum of the electrolyte and combining it with a calibration model, it achieves accurate and real-time monitoring of SOC and health status.

[0005] Therefore, an online monitoring device for the state of charge of flow batteries based on ultraviolet spectroscopy was proposed to solve the above problems. Summary of the Invention

[0006] In view of this, the technical problem to be solved by the present invention is to propose an online monitoring device for the state of charge of flow batteries based on ultraviolet spectroscopy. This device uses spectrophotometry to monitor the optical absorption characteristics of the electrolyte in the pipeline, and then calculates the SOC of the electrolyte and judges the health status of the battery.

[0007] To achieve the above objectives, the present invention provides the following technical solution: an online monitoring device for the state of charge of a flow battery based on ultraviolet spectroscopy, comprising a light shield, wherein a pipeline integration module, a light source module, a spectral analysis unit, and a data processing system are respectively installed in the light shield; Preferably, the light shield is made of black anodized aluminum or rigid polyvinyl chloride, and the inside of the light shield has a frosted surface.

[0008] Pipeline integration module; The integrated piping module includes, from the outside to the inside, a union connector, a straight-insertion rigid pipe, a male threaded connector, a through-plate connector, and a transparent observation pipe. The integrated piping module is used for through-plate liquid or gas pipeline connections within the enclosure. Light source module; The light source module includes a collimating lens, a sliding module, and a heat dissipation device. The collimating lens is located in the middle of the light shield and is on the same horizontal plane as the center of the transparent observation channel. The sliding module is located on the inner wall of the light shield and includes a guide rail system and a linkage adjustment rod. The collimating lens is fixed through a pre-drilled hole on the linkage adjustment rod. The heat dissipation device is installed on the outside of the light shield. The light source module is used to adjust the light intensity and dissipate heat. Spectral analysis unit and data processing system; The spectral analysis unit and data processing system include a miniature spectrometer, which is installed in a light shield and electrically connected to a collimating lens via an optical fiber. The spectral analysis unit and data processing system are used for data analysis, processing, and storage.

[0009] Preferably, a broadband LED array and a CCD camera are uniformly installed in the sliding module. The broadband LED array covers the 400-1000nm wavelength band, and the light intensity stability is ensured by a constant current drive circuit and pulse modulation technology. The wavelength of the broadband LED array is adjusted to 740-780nm for VOC detection. 2+ Absorption characteristics; the wavelength of the broadband LED array is tuned to 580-590 nm for detecting V. 3+ Absorption characteristics; the wavelength of the broadband LED array is tuned to 275-300nm for detecting V. 5+ Its absorption characteristics.

[0010] Preferably, the spectral analysis unit and data processing system further include a front-end signal processing module, a feature extraction module, and an embedded computing unit equipped with a pre-training module. The front-end signal processing module performs noise suppression and baseline correction on the original spectrum based on wavelet transform and moving average algorithms. The feature extraction module identifies characteristic absorption peaks through analysis and simultaneously extracts near-infrared scattering intensity to assess electrolyte turbidity. The embedded computing unit, equipped with a pre-training module, maps characteristic absorbance to SOC values ​​and compares the currently measured concentration with the initial calibration value to determine whether there is a significant imbalance of active substances or transmembrane migration, thereby outputting the SOH index.

[0011] Preferably, the light source module is a fiber-coupled miniature spectrometer, whose input end is connected to a collimating lens via a fiber optic jumper. The miniature spectrometer has a built-in CCD sensor and transmits raw spectral data to the spectral analysis unit and data processing system via a USB interface.

[0012] Preferably, the transparent observation pipe is made of high-transmittance corrosion-resistant glass or rigid polyvinyl chloride material. The surface of the transparent observation pipe is treated with an anti-glare coating and coated with a hydrophobic nano-coating to reduce the adhesion of electrolyte residue. Both ends of the transparent observation pipe are fixed to the sides of the light shield by straight-insertion joints. The through-plate joint is externally connected to an external threaded connector via a threaded connection. Fluororubber O-rings are embedded at both ends of the through-plate joint. The external threaded connector receives a section of straight-insertion rigid tube, which is externally connected to a union joint.

[0013] Preferably, the auxiliary adjustment mechanism includes slide rails installed on the inner wall and bottom of the light shield. A sliding module is slidably mounted on the slide rails on the inner wall and bottom of the light shield. An integrated n-shaped adjustment plate is fixedly connected to the sliding module. Two sliders are fixed to the two ends of the integrated n-shaped adjustment plate, and a lead screw is threaded into the middle of the integrated n-shaped adjustment plate. Both ends of the lead screw are rotatably connected to the light shield, and an adjustment block is fixedly connected to one end of the lead screw. A collimating lens pre-drilled hole is made parallel to the horizontal center of the transparent observation channel on the integrated n-shaped adjustment plate. The collimating lens is fixed within the pre-drilled hole.

[0014] Compared with the prior art, the present invention provides an online monitoring device for the state of charge of flow batteries based on ultraviolet spectroscopy, which has the following beneficial effects: (1) The online monitoring device for the state of charge and health of a flow battery based on ultraviolet spectroscopy proposed in this patent achieves real-time non-invasive measurement of electrolyte state parameters by innovatively coupling the optical detection module with the circulation pipeline structure. Its beneficial effects are specifically reflected in the following aspects: (2) From the structural features analysis, the invention adopts a composite module design that integrates a transparent observation pipe and a light shield with equal diameter fluid channels of through-plate joint and live joint. By eliminating the turbulence effect and optical path refraction distortion caused by sudden changes in pipe diameter, it ensures the stability of optical signal acquisition while maintaining the laminar flow state of the electrolyte. Compared with the traditional bypass sampling or external probe detection method, it effectively avoids the signal baseline drift problem caused by fluid disturbance. (3) The synergistic effect of the low-reflection material inside the light shield and the dedicated fixing mechanism, combined with the fine-tuning mechanism of the light source module, can greatly reduce the interference of stray light in the environment. Through the tight adjustment of the auxiliary adjustment mechanism, it provides structural guarantee for the signal coupling efficiency between the broadband continuous light source and the spectrometer.

[0015] (4) Under continuous operation, the feature extraction algorithm based on the multi-level signal processing architecture can significantly improve the spectral signal-to-noise ratio. Combined with the embedded real-time analytical model, it can effectively shorten the SOC detection response time. Furthermore, through the active temperature control of the heat dissipation system of heat pipe and heat dissipation fin composite heat dissipation system in the heat dissipation device, the spectral shift of the light source module under high temperature environment is significantly reduced, thereby improving the detection reliability under wide temperature range conditions.

[0016] (5) Compared with the existing technology, its modular architecture, through flange connection and standardized interface modular linkage mechanism design, greatly shortens the maintenance time of optical components, and can complete online replacement without interrupting electrolyte circulation. Moreover, it can maintain the stability and reliability of the system during long-term operation, effectively extend battery life and reduce operating costs, and has broad industrial application prospects. Attached Figure Description

[0017] Figure 1 This is a schematic diagram of the front structure of the electrolyte image acquisition device of the present invention; Figure 2 This is a schematic diagram of the rear structure of the electrolyte image acquisition device of the present invention; Figure 3 This is a schematic diagram of the connection relationship of the auxiliary adjustment mechanism structure of the present invention; Figure 4 This is a schematic diagram illustrating the connection relationship of the auxiliary adjustment mechanism structure of the present invention.

[0018] In the picture: 1. Light shield; 11. Sealing plate; 12. Transparent observation tube; 14. Collimating lens; 15. Miniature spectrometer; 16. Sliding module; 17. Heat dissipation device; 2. Auxiliary adjustment mechanism; 21. Slide rail; 22. Integrated n-shaped adjustment plate; 23. Adjustment block; 24. Through-plate connector; 25. External threaded connector; 26. Straight-insertion rigid tube; 27. Union connector; 29. ​​Lead screw. Detailed Implementation

[0019] 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. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention. The embodiments are shown in the appendix. Figure 1 To be continued Figure 4 An online monitoring device for the state of charge of a flow battery based on ultraviolet spectroscopy includes a light shield 1, in which a pipeline integration module, a light source module, a spectral analysis unit, and a data processing system are installed respectively. Pipeline integration module; The integrated piping module includes, from the outside to the inside, a union joint 27, a straight-insertion rigid pipe 26, an external threaded joint 25, a through-plate joint 24, and a transparent observation pipe 12, connected sequentially. The integrated piping module is used for through-plate liquid or gas pipeline connections within the enclosure. Light source module; The light source module includes a collimating lens 14, a sliding module 16, and a heat dissipation device 17. The collimating lens 14 is located in the middle of the light shield 1, at the same horizontal plane as the center of the transparent observation channel 12. The sliding module 16 is located on the inner wall of the light shield 1 and includes a guide rail system and a linkage adjustment rod. The collimating lens 14 is fixed through a pre-drilled hole on the linkage adjustment rod. The heat dissipation device 17 is installed on the outside of the light shield 1. The light source module is used to adjust the light intensity and dissipate heat. Spectral analysis unit and data processing system; The spectral analysis unit and data processing system include a miniature spectrometer 15, which is installed in the optical shield 1. The miniature spectrometer 15 is electrically connected to the collimating lens 14 via optical fiber. The spectral analysis unit and data processing system are used for data analysis, processing and storage. The light shield 1 is made of matte rigid polyvinyl chloride with a frosted interior. Pipe holes are provided on both sides of the light shield 1, which is clamped and fixed by through-plate connectors 24. O-rings are provided at both ends of the connectors, made of fluororubber or EPDM rubber. The inner side and bottom of the light shield 1 are fixed with slide rails 21 via threaded holes and hexagonal bolts. The slide rails 21 on the inner wall of the light shield 1 cooperate with the sliding module 16, fixing the LED light source mounted on the sliding module 16 to the side wall of the light shield 1, ensuring that the LED light source can be adjusted along the axial direction of the pipes. A heat dissipation device 17 is welded to the outer side. The heat dissipation device 17 integrates an aluminum heat dissipation substrate and a copper heat dissipation pipe. The sliding module 16 is made of aluminum, coated with thermal grease, and tightly attached to the LED module. A copper heat dissipation pipe is welded to the outer side of the aluminum heat dissipation substrate, and heat dissipation fins are welded to the outside of the heat dissipation pipe. An axial fan is installed next to the heat dissipation fins to achieve efficient heat dissipation and ensure spectral consistency of the light source over a wide temperature range.

[0020] The sealing plate 11 has a cable outlet hole for connecting the miniature spectrometer 15 to the data processing system. A sealing ring groove is added around the hole to prevent light leakage. There are two axial fan mounting holes on the back of the light shield 1 for installing the heat dissipation device 17. The sealing plate 11 and the light shield 1 are fixedly connected by bolts and threaded holes, which facilitates the installation and disassembly of internal components.

[0021] A broadband LED array and a CCD camera are evenly installed in the sliding module 16. The broadband LED array covers the 400-1000nm wavelength band, and the light intensity stability is ensured by a constant current drive circuit and pulse modulation technology. The wavelength of the broadband LED array is adjusted to 740-780nm for the detection of VOCs. 2+ Absorption characteristics; broadband LED array wavelength adjustable to 580-590nm for V detection 3+ Absorption characteristics; broadband LED array wavelength tuning in the turbine 275-300nm for V detection 5+ Absorption characteristics; The spectral analysis unit and data processing system also include a front-end signal processing module, a feature extraction module, and an embedded computing unit equipped with a pre-training module. The front-end signal processing module performs noise suppression and baseline correction on the original spectrum based on wavelet transform and moving average algorithms. The feature extraction module locks the characteristic absorption peaks through analysis and simultaneously extracts the near-infrared scattering intensity to assess the electrolyte turbidity. The embedded computing unit is equipped with a pre-training module, which maps the characteristic absorbance to the SOC value and compares the currently measured concentration with the initial calibration value to determine whether there is a significant imbalance of active substances or transmembrane migration, and outputs the SOH index. The light source module uses a fiber-coupled miniature spectrometer 15, whose input end is connected to the transparent observation tube 12 via a fiber optic jumper. The miniature spectrometer 15 has a built-in CCD sensor and transmits the raw spectral data to the spectral analysis unit and data processing system via a USB interface. The transparent observation pipe 12 is made of rigid polyvinyl chloride (PVC) material. The surface of the transparent observation pipe is treated with an anti-glare coating and coated with a hydrophobic nano-coating to reduce the adhesion of electrolyte residue. Both ends of the transparent observation pipe are fixed to the sides of the light shield by straight insertion into the through-plate connector 24. The through-plate connector 24 is externally connected to an external threaded connector 25 through a threaded connection. Both ends of the through-plate connector 24 are embedded with fluororubber O-rings. The external threaded connector 25 inserts a section of straight-inserted rigid pipe 26, and the straight-inserted rigid pipe 26 is externally connected to a union connector 27.

[0022] Each interface utilizes fluororubber or EPDM rubber sealing gaskets and anti-loosening bolts to ensure long-term stability of the device under vibration or temperature changes. This design supports quick disassembly and maintenance without interrupting electrolyte circulation, making it suitable for various flow battery systems, including vanadium redox flow, zinc-bromine, and iron-chromium flow batteries.

[0023] Specifically, such as Figures 3 to 4As shown, slide rails 21 are respectively installed on the inner wall and bottom of the light shield 1. A sliding module 16 is slidably installed on the slide rails 21 on the inner wall of the light shield 1. An integrated n-shaped adjusting plate 22 is fixedly connected to the sliding module 16. Both ends of the integrated n-shaped adjusting plate 22 are fixed to two sliders respectively. A lead screw is threadedly connected to the middle of the integrated n-shaped adjusting plate. Both ends of the lead screw are rotatably connected to the light shield 1. An adjusting block 23 is fixedly connected to one end 29 of the lead screw. When the adjusting block 23 is rotated, the integrated n-shaped adjusting plate 22 moves horizontally in tandem with the two sliders. A collimating lens pre-drilled hole is opened on the integrated n-shaped adjusting plate 22 parallel to the horizontal center position of the transparent observation pipe 12. The collimating lens is fixed inside the pre-drilled hole. The specific adjustment process for installing the pipeline integration module in the above embodiments is as follows: First, insert the external threaded sections of the two through-plate connectors 24 into the insertion holes on both sides of the light shield 1. Then, connect both ends of the transparent observation pipe 12 to the external threaded sections of the two through-plate connectors 24 by straight insertion. Install the transparent observation pipe 12 in the light shield 1, and ensure good airtightness when the through-plate connectors 24 are connected to the light shield 1 through the sealing gaskets on both sides of the transparent observation pipe 12. At this time, install the locking nuts of the two through-plate connectors 24 to the external threaded sections of the through-plate connectors 24 again, so that both ends of the transparent observation pipe 12 are tightly fitted with the through-plate connectors 24 at both ends of the light shield 1. Next, insert the outer end of the through-plate connector 24 into the straight insertion rigid tube 26 for cooperation. Finally, add the union 27 to the outer end to achieve modular and flexible assembly and disassembly with the electrolyte pipeline.

[0024] Furthermore, by adjusting the knob on one side of the light shield 1, the screw 29 can be rotated. The rotation of the screw 29 can move the integrated n-shaped adjustment plate 22 within the light shield 1. The movement of the n-shaped adjustment plate 22 can directly adjust the position of the sliding module 16 and the collimating lens 14 within the light shield 1.

[0025] This design not only enables rapid adjustment of the collimating lens 14, but also reduces the impact of the optical axis on the experiment. Compared to the traditional method of adjusting the collimating lens 14 by tightening or loosening bolts, which is not only more complex to operate, but also makes it difficult to ensure the accuracy of manual operation, this design reduces the impact of the optical axis on the experiment.

[0026] From a structural perspective, the device employs a composite module design that integrates a through-plate connector 24, a constant-diameter fluid channel, a transparent observation pipe 12, and a light shield 1. By eliminating turbulence and optical path refraction distortion caused by abrupt changes in pipe diameter, it maintains the laminar flow state of the electrolyte while ensuring the stability of optical signal acquisition. Compared to traditional bypass sampling or external probe detection methods, it effectively avoids signal baseline drift caused by fluid disturbance. Compared to existing technologies, its modular architecture, through the integrated pipe module design, significantly shortens the maintenance time of optical components and allows for online replacement without interrupting electrolyte circulation. Moreover, it maintains system stability and reliability during long-term operation, effectively extending battery life and reducing operating costs, thus possessing broad industrial application prospects.

[0027] It should be noted that the term "comprising" or any other variation thereof is 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.

[0028] 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. An online monitoring device for the state of charge of a flow battery based on ultraviolet spectroscopy, characterized in that, It includes a light shield (1), in which a pipeline integration module, a light source module, a spectral analysis unit, and a data processing system are respectively installed; Pipeline integration module; The integrated pipeline module includes, from the outside to the inside, a union (27), a straight-insertion rigid pipe (26), an external threaded connector (25), a through-plate connector (24), and a transparent observation pipe (12); the integrated pipeline module is used for through-plate liquid or gas pipeline connections in the enclosure. Light source module; The light source module includes a collimating lens (14), a sliding module (16), and a heat dissipation device (17). The collimating lens (14) is located in the middle of the light shield (1) and is on the same horizontal plane as the center of the transparent observation pipe (12). The sliding module (16) is located on the inner wall of the light shield (1) and includes a guide rail system and a linkage adjustment rod. The collimating lens (14) is fixed through a reserved hole on the linkage adjustment rod. The heat dissipation device (17) is installed on the outside of the light shield (1). The light source module is used to adjust the light intensity and dissipate heat. Spectral analysis unit and data processing system; The spectral analysis unit and data processing system include a miniature spectrometer (15), which is installed in a light shield (1). The miniature spectrometer (15) is electrically connected to the collimating lens (14) via an optical fiber. The spectral analysis unit and data processing system are used for data analysis, processing and storage.

2. The online monitoring device for the state of charge of a flow battery based on ultraviolet spectroscopy according to claim 1, characterized in that: A broadband LED array is uniformly mounted on the sliding module (16). The broadband LED array covers the 400-1000nm wavelength band. The light intensity stability is ensured by a constant current driving circuit and pulse modulation technology. The wavelength of the broadband LED array is adjusted to 740-780nm for the detection of VO. 2+ Absorption characteristics; the wavelength of the broadband LED array is tuned to 580-590 nm for detecting V. 3 + Absorption characteristics; the wavelength of the broadband LED array is tuned to 275-300nm for detecting V. 5+ Its absorption characteristics.

3. The online monitoring device for the state of charge of a flow battery based on ultraviolet spectroscopy according to claim 1, characterized in that: The spectral analysis unit and data processing system also include a front-end signal processing module, a feature extraction module, and an embedded computing unit equipped with a pre-training module. The front-end signal processing module performs noise suppression and baseline correction on the original spectrum based on wavelet transform and moving average algorithms. The feature extraction module identifies characteristic absorption peaks through analysis and simultaneously extracts near-infrared scattering intensity to assess electrolyte turbidity. The embedded computing unit, equipped with a pre-training module, maps characteristic absorbance to SOC values ​​and compares the currently measured concentration with the initial calibration value to determine whether there is a significant imbalance of active substances or transmembrane migration, thereby outputting the SOH index.

4. The online monitoring device for the state of charge of a flow battery based on ultraviolet spectroscopy according to claim 1, characterized in that: The light source module uses a fiber-coupled micro spectrometer (15), whose input end is connected to a collimating lens (14) via a fiber optic jumper. The micro spectrometer (15) has a built-in CCD sensor and transmits the raw spectral data to the spectral analysis unit and data processing system via a USB interface.

5. The online monitoring device for the state of charge of a flow battery based on ultraviolet spectroscopy according to claim 1, characterized in that: The transparent observation pipe (12) is made of high light transmittance corrosion-resistant glass or rigid polyvinyl chloride material. The two ends of the through-plate connector (24) are embedded with fluororubber O-rings. The surface of the transparent observation pipe (12) is treated with an anti-glare coating and coated with a hydrophobic nano coating to reduce the adhesion of electrolyte residue. The two ends of the transparent observation pipe (12) are respectively fixed to the two sides of the light shield by the through-plate connector (24) through a straight insertion method. The through-plate connector (24) is connected to an external threaded connector (25) through a threaded connection. The external threaded connector (25) is inserted into a straight rigid tube (26). The straight rigid tube (26) is connected to a union connector (27).

6. The online monitoring device for the state of charge of a flow battery based on ultraviolet spectroscopy according to claim 1, characterized in that: An auxiliary adjustment mechanism (2) is provided in the light shield (1). The auxiliary adjustment mechanism (2) includes a slide rail (21). The slide rail (21) is installed on the inner wall of the light shield (1) and the bottom of the light shield (1). The sliding module (16) is slidably installed on the slide rail (21) on the inner wall and bottom of the light shield (1). An integrated n-shaped adjustment plate (22) is fixedly connected to the sliding module (16). The two ends of the integrated n-shaped adjustment plate (22) are fixed to two sliders respectively. A lead screw (29) is threadedly connected to the middle of the n-shaped adjustment plate (22). The two ends of the lead screw (29) are rotatably connected in the light shield (1). An adjustment block (23) is fixedly connected to one end of the lead screw (29). The integrated n-shaped adjustment plate (22) has a collimating lens reserved hole parallel to the horizontal center position of the transparent observation pipe (12). The collimating lens is fixed in the reserved hole.

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