WO2019196193A1 - 储能设备充电状态光纤在线监测系统及方法 - Google Patents

储能设备充电状态光纤在线监测系统及方法 Download PDF

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Publication number
WO2019196193A1
WO2019196193A1 PCT/CN2018/090809 CN2018090809W WO2019196193A1 WO 2019196193 A1 WO2019196193 A1 WO 2019196193A1 CN 2018090809 W CN2018090809 W CN 2018090809W WO 2019196193 A1 WO2019196193 A1 WO 2019196193A1
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Prior art keywords
fiber
capacitor
sensor probe
electrochemical
charge
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English (en)
French (fr)
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郭团
麦文杰
劳家杰
孙鹏
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Jinan University
University of Jinan
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Jinan University
University of Jinan
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Priority to JP2020555868A priority Critical patent/JP2021532335A/ja
Priority to EP18914084.1A priority patent/EP3779483A4/en
Publication of WO2019196193A1 publication Critical patent/WO2019196193A1/zh
Priority to US17/067,748 priority patent/US20210025945A1/en
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28—Electrolytic cell components
    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
    • G01N27/305—Electrodes, e.g. test electrodes; Half-cells optically transparent or photoresponsive electrodes
    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02J—ELECTRIC POWER NETWORKS; CIRCUIT ARRANGEMENTS OR SYSTEMS FOR SUPPLYING OR DISTRIBUTING ELECTRIC POWER; SYSTEMS FOR STORING ELECTRIC ENERGY
    • H02J7/00—Circuit arrangements for charging or discharging batteries or for supplying loads from batteries
    • H02J7/80—Circuit arrangements for charging or discharging batteries or for supplying loads from batteries including monitoring or indicating arrangements
    • H02J7/82—Control of state of charge [SOC]
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01D—MEASURING NOT SPECIALLY ADAPTED FOR A SPECIFIC VARIABLE; ARRANGEMENTS FOR MEASURING TWO OR MORE VARIABLES NOT COVERED IN A SINGLE OTHER SUBCLASS; TARIFF METERING APPARATUS; MEASURING OR TESTING NOT OTHERWISE PROVIDED FOR
    • G01D5/00—Mechanical means for transferring the output of a sensing member; Means for converting the output of a sensing member to another variable where the form or nature of the sensing member does not constrain the means for converting; Transducers not specially adapted for a specific variable
    • G01D5/26—Mechanical means for transferring the output of a sensing member; Means for converting the output of a sensing member to another variable where the form or nature of the sensing member does not constrain the means for converting; Transducers not specially adapted for a specific variable characterised by optical transfer means, i.e. using infrared, visible, or ultraviolet light
    • G01D5/32—Mechanical means for transferring the output of a sensing member; Means for converting the output of a sensing member to another variable where the form or nature of the sensing member does not constrain the means for converting; Transducers not specially adapted for a specific variable characterised by optical transfer means, i.e. using infrared, visible, or ultraviolet light with attenuation or whole or partial obturation of beams of light
    • G01D5/34—Mechanical means for transferring the output of a sensing member; Means for converting the output of a sensing member to another variable where the form or nature of the sensing member does not constrain the means for converting; Transducers not specially adapted for a specific variable characterised by optical transfer means, i.e. using infrared, visible, or ultraviolet light with attenuation or whole or partial obturation of beams of light the beams of light being detected by photocells
    • G01D5/353—Mechanical means for transferring the output of a sensing member; Means for converting the output of a sensing member to another variable where the form or nature of the sensing member does not constrain the means for converting; Transducers not specially adapted for a specific variable characterised by optical transfer means, i.e. using infrared, visible, or ultraviolet light with attenuation or whole or partial obturation of beams of light the beams of light being detected by photocells influencing the transmission properties of an optical fibre
    • G01D5/35306—Mechanical means for transferring the output of a sensing member; Means for converting the output of a sensing member to another variable where the form or nature of the sensing member does not constrain the means for converting; Transducers not specially adapted for a specific variable characterised by optical transfer means, i.e. using infrared, visible, or ultraviolet light with attenuation or whole or partial obturation of beams of light the beams of light being detected by photocells influencing the transmission properties of an optical fibre using an interferometer arrangement
    • G01D5/35309—Mechanical means for transferring the output of a sensing member; Means for converting the output of a sensing member to another variable where the form or nature of the sensing member does not constrain the means for converting; Transducers not specially adapted for a specific variable characterised by optical transfer means, i.e. using infrared, visible, or ultraviolet light with attenuation or whole or partial obturation of beams of light the beams of light being detected by photocells influencing the transmission properties of an optical fibre using an interferometer arrangement using multiple waves interferometer
    • G01D5/35316—Mechanical means for transferring the output of a sensing member; Means for converting the output of a sensing member to another variable where the form or nature of the sensing member does not constrain the means for converting; Transducers not specially adapted for a specific variable characterised by optical transfer means, i.e. using infrared, visible, or ultraviolet light with attenuation or whole or partial obturation of beams of light the beams of light being detected by photocells influencing the transmission properties of an optical fibre using an interferometer arrangement using multiple waves interferometer using a Bragg gratings
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28—Electrolytic cell components
    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
    • G01N27/307—Disposable laminated or multilayered electrodes
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/416—Systems
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/416—Systems
    • G01N27/4163—Systems checking the operation of, or calibrating, the measuring apparatus
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/416—Systems
    • G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
    • G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
    • G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
    • G01R31/3644—Constructional arrangements
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
    • G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
    • G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
    • G01R31/382—Arrangements for monitoring battery or accumulator variables, e.g. SoC
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
    • G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
    • G01R31/50—Testing of electric apparatus, lines, cables or components for short-circuits, continuity, leakage current or incorrect line connections
    • G01R31/64—Testing of capacitors
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/02—Optical fibres with cladding with or without a coating
    • G02B6/02057—Optical fibres with cladding with or without a coating comprising gratings
    • G02B6/02076—Refractive index modulation gratings, e.g. Bragg gratings
    • G02B6/0208—Refractive index modulation gratings, e.g. Bragg gratings characterised by their structure, wavelength response
    • G02B6/02085—Refractive index modulation gratings, e.g. Bragg gratings characterised by their structure, wavelength response characterised by the grating profile, e.g. chirped, apodised, tilted, helical
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/02—Optical fibres with cladding with or without a coating
    • G02B6/02057—Optical fibres with cladding with or without a coating comprising gratings
    • G02B6/02076—Refractive index modulation gratings, e.g. Bragg gratings
    • G02B6/02123—Refractive index modulation gratings, e.g. Bragg gratings characterised by the method of manufacture of the grating
    • G02B6/02133—Refractive index modulation gratings, e.g. Bragg gratings characterised by the method of manufacture of the grating using beam interference
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/08—Structural combinations, e.g. assembly or connection, of hybrid or EDL capacitors with other electric components, at least one hybrid or EDL capacitor being the main component
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/14—Arrangements or processes for adjusting or protecting hybrid or EDL capacitors
    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02J—ELECTRIC POWER NETWORKS; CIRCUIT ARRANGEMENTS OR SYSTEMS FOR SUPPLYING OR DISTRIBUTING ELECTRIC POWER; SYSTEMS FOR STORING ELECTRIC ENERGY
    • H02J2207/00—Details of circuit arrangements for charging or discharging batteries or supplying loads from batteries
    • H02J2207/50—Charging of capacitors, supercapacitors, ultra-capacitors or double layer capacitors
    • 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
    • Y02E60/13—Energy storage using capacitors

Definitions

  • the invention relates to a charging state online monitoring system and method, in particular to an energy storage device charging state optical fiber online monitoring system and method, belonging to the field of optical fiber electrochemical sensor design.
  • the earth's energy faces enormous challenges.
  • the energy supply structure of human society must be developed from non-renewable energy to renewable energy to solve the problem of energy depletion and rising sea level. Whether these problems can be solved depends mainly on the effective use and management of energy equipment systems.
  • Contemporary technology has achieved rapid development in the fields of information science and electronic technology in the last two or three decades.
  • the power supply system is equipped with a traditional lithium-ion battery.
  • the complex housing package in the traditional lithium-ion battery manufacturing will be limited to the miniaturization of the volume and weight of the mobile phone, in other traditional lithium.
  • Supercapacitors have received extensive attention due to their fast charge and discharge speed, long service life, good temperature characteristics, and environmental protection.
  • the detection method for supercapacitors is "offline" type detection, that is, it is impossible to measure the state of charge of the capacitor while charging and discharging, but it is necessary to wait for the capacitor to stop working and then test the electrode with an electrochemical workstation. Whether the electrochemical performance is attenuated or damaged.
  • the object of the present invention is to solve the above drawbacks of the prior art, and to provide an on-line monitoring system for an energy storage device charging state optical fiber, which utilizes a fine fiber-like optical fiber sensing probe to transmit optical signals and transmit optical signals.
  • the light wave information can be obtained to monitor the potential of the supercapacitor during charging and discharging and the real-time storage of the power information in real time.
  • Another object of the present invention is to provide an on-line monitoring method for an energy storage device in a state of charge, which can be implanted in a small space to realize in-situ measurement, and simultaneously measure multiple parameter changes in real time, such as state of charge and potential.
  • the method also inherits the low-loss transmission characteristics of the optical fiber.
  • the sensor probe and the optical transmission path are both optical fibers, which can realize long-distance online real-time monitoring.
  • Energy storage device charging state optical fiber online monitoring system including light source, polarizer and polarization controller, further comprising a fiber circulator, a fiber sensor probe, an electrochemical supercapacitor device, a fiber spectrometer and an electrochemical workstation, the light source, a polarizer, a polarization controller, a fiber optic circulator, and a fiber optic sensor probe are connected in series, the fiber optic spectrometer being coupled to a fiber optic circulator, the electrochemical supercapacitor device being coupled to an electrochemical workstation, the fiber optic sensor probe being disposed in an electrical Inside the chemical supercapacitor unit.
  • the optical fiber sensor probe comprises an optical fiber, the optical fiber is engraved with an inclined fiber grating, and the outer surface of the optical fiber cladding is plated with a metal film of a uniform thickness of nanometer order, and the light emitted by the light source is sequentially passed through a polarizer and polarization control.
  • the fiber circulator is incident on the fiber sensor probe, and the cladding mode generated in the fiber of the fiber sensor probe is coupled to the metal film on the outer surface of the fiber cladding to excite the surface plasmon resonance of the metal film;
  • the plasmon resonance wave is embodied In the reflection spectrum of the fiber spectrometer is an absorption envelope, the dielectric constant of the metal film changes under the charge and discharge of the capacitor, and the amplitude of the plasmon resonance wave absorption envelope also changes accordingly.
  • the oblique fiber grating in the optical fiber is written by an excimer laser and a phase mask, or is written by a double beam interference method; the tilt angle of the oblique fiber grating is 5 ⁇ 25 degrees, the axial length is about 10 ⁇ 20mm.
  • the end face of the optical fiber is plated with a metal reflective film having a thickness of 200 nm or more.
  • the outer surface of the optical fiber cladding layer is first plated with a chromium thin film transition layer of 2 to 3 nm thickness by magnetron sputtering or thermal evaporation, and then plated with a metal of a uniform thickness of nanometer order.
  • the film is subjected to a tempering treatment of the optical fiber coated with the metal film.
  • the electrochemical supercapacitor device is filled with an electrolyte and has two capacitor electrodes, a part of which is placed in an electrolyte, and the fiber sensor probe is closely packed with one of the capacitor electrodes .
  • the electrochemical workstation has a counter electrode, a reference electrode and a working electrode, and the counter electrode and the reference electrode are connected to one of the capacitor electrodes of the electrochemical supercapacitor device, and the working electrode is connected to the electrochemical supercapacitor device Another capacitor electrode.
  • An energy storage device charging state optical fiber online monitoring method comprising the following steps:
  • the fiber sensor probe is closely packed with one of the electrodes of the electrochemical supercapacitor device, the electrochemical supercapacitor device is filled with electrolyte, and the light output light is converted into polarized light by the polarizer, and passes through the polarization controller. Adjusting the polarization direction of the input polarized light to coincide with the direction in which the oblique fiber grating is written in the fiber sensor probe;
  • the electrochemical supercapacitor device After setting up the optical path and the electrochemical supercapacitor device, the electrochemical supercapacitor device is connected to the electrochemical workstation, the electrochemical workstation and the optical fiber spectrometer are connected to the computer, the relevant parameters are set, and the polarization controller is adjusted to make the incident fiber sensor probe The incident light is in a polarization state of the plasmon resonance of the surface of the excited metal film;
  • the electrochemical supercapacitor device is placed under natural conditions, and the whole process of the state of charge of the capacitor during charging, discharging, storage and release of electrical energy is monitored by optical and electrochemical methods;
  • the polarized light is polarized light parallel to the writing direction of the oblique fiber grating, and the polarization direction of the polarized light is determined by the surface plasmon resonance peak amplitude, that is, the surface parallel to the oblique fiber grating writing direction.
  • the plasmon resonance peak has the largest amplitude.
  • step S3 the optical and electrochemical methods are used to monitor the whole process of the state of charge change of the capacitor during charging, discharging, storage and release of electrical energy, and specifically includes:
  • the capacitor is charged and discharged under the excitation of the electrochemical workstation.
  • the ions in the electrolyte form an electric double layer to store electric energy on the surface of the capacitor electrode, and the electric charge is further accumulated on the capacitor electrode along with the oxidation reaction of the electrode material.
  • the energy stored in the capacitor reaches a peak value; when the capacitor is discharged, the electrode material undergoes a reduction reaction, and ions accumulated on the surface of the capacitor electrode to form an electric double layer charge will diffuse back to the electrolyte in a reverse process opposite to the charging process. in;
  • the fiber sensor probe will monitor the real-time charge change of the capacitor.
  • the electrochemical workstation and the fiber spectrometer record the whole process of capacitor charging power rise and discharge power drop, and draw a one-to-one correspondence. The graph.
  • the detection result recorded by the optical fiber spectrometer is corrected by the wavelength shift amount and the amplitude variation of the fiber core mode.
  • step S4 specifically includes:
  • the density of negative ions at the electrode tip of the capacitor packaged with the fiber sensor probe will increase, the metal film will be in an electronically polarized state; when a negative potential is applied, it is packaged with the fiber sensor probe.
  • the density of positive ions at the electrode tip of the capacitor will increase and the metal film will be in a polarization state of opposite polarity.
  • the change in the charge density generated on the surface of the fiber sensor probe is detected by the intensity variation of the oblique fiber grating cladding mode corresponding to the wavelength of the plasmon resonance wave absorption envelope wavelength drift modulation plasma resonance wave absorption envelope, thereby The amount of charge information stored by the capacitor is converted into an electrochemical-optical signal for detection.
  • the invention utilizes a fiber-optic sensing probe with a fine hairline to transmit optical signals and obtain optical wave information to monitor the potential of the supercapacitor during charging and discharging and real-time storage of electric quantity information in real time. Implanted into a small space for in-situ measurement, while simultaneously measuring multiple parameter changes in real time, such as state of charge, potential, temperature and other information.
  • the outer surface of the optical fiber cladding of the optical fiber sensing probe of the present invention is coated with a metal film, and the optical fiber sensing probe couples the energy of the surface plasmon resonance wave generated by the metal film to the external environment outside the metal film, and the plasmon resonance The wave interacts with the electrode material that is in close contact with the surface of the metal film to produce energy loss and resonance center wavelength drift.
  • This phenomenon is reflected in the fiber optic spectrometer as an absorption envelope by using this multi-domain technology (electrochemical technology ( The combination of Electrochemical technology and Surface Plasmon Resonance technology has enabled real-time, in-situ monitoring of the charge and discharge behavior of supercapacitors, providing monitoring of the operating conditions of various energy storage devices. New use prospects.
  • the high-sensitivity surface plasmon resonance technology of the present invention replaces the conventional tens of millimeter-scale triangular prism with a compact optical fiber sensing probe of only a hundred micrometer scale, thereby realizing miniaturization of the sensor probe, so that it can In-situ detection is performed in a space that is difficult to reach with conventional sensors.
  • the sensor probe of the present invention is the same fiber as the fiber for conducting signals. Due to the low loss characteristic of the fiber, even the transmission at a long distance is hardly attenuated, so that the detection precision of the sensor is greatly improved, and it can be applied to a long distance. Online real-time monitoring overcomes the shortcomings of existing "offline" testing.
  • the thickness of the metal film on the outer surface of the fiber cladding of the optical fiber sensor probe of the present invention is a uniform thickness of nanometer order, which ensures that the plasma resonance is excited with an optimum efficiency, and the metal film is both a plasmon resonance optical signal carrier and It also has good electrical conductivity and becomes a micro-current transmission carrier.
  • the fiber end face of the optical fiber sensor probe of the present invention is plated with a metal reflective film having a thickness of 200 nm or more, and the metal reflective film can reflect the optical signal to realize probe type measurement.
  • the outer surface of the fiber cladding of the optical fiber sensor probe of the present invention is coated with a chromium thin film transition layer of 2 to 3 nm thickness by magnetron sputtering prior to plating the nano-thickness metal film to increase the metal film and
  • the adhesion of the surface of the fiber cladding layer is tempered after the metal film is plated, the adhesion of the metal film is increased, and the residual stress during the coating process is released.
  • the fiber core mode of the fiber sensor probe is only sensitive to temperature and is not sensitive to the refractive index of the environment; therefore, by detecting the fiber core mode, real-time measurement of temperature information can be realized, thereby eliminating temperature variation and measuring
  • the effect of the result, as well as its amplitude variation to calibrate the interference experienced in the optical system, has a self-calibration function.
  • FIG. 1 is a schematic diagram of an apparatus for an on-line monitoring system for an energy storage device in a state of charge according to the present invention.
  • FIG. 2 is a schematic diagram showing the operation of a fiber optic sensor probe in an apparatus for charging an optical fiber on-line monitoring system of an energy storage device according to the present invention.
  • Figure 3 (a) is a cyclic voltammogram of an electrochemical supercapacitor device of the present invention at a scan rate of 10 mV/s.
  • Fig. 3(b) is a graph showing the relationship between the plasma resonance intensity and the capacitor potential in the optical fiber sensor probe of the present invention.
  • FIG. 4 is a graph showing the core mode and the amplitude of the SPR mode to be tested in the corresponding sensor probe of the electrochemical supercapacitor device of the present invention under cyclic voltammetry test charging and discharging.
  • Figure 5 (a) is a cyclic voltammogram of an electrochemical supercapacitor device of the present invention at a series of scan rates.
  • Fig. 5(b) is a graph showing changes in the stored charge amount of the capacitor of the electrochemical supercapacitor device of the present invention under a series of scanning rate cyclic volt-ampere charge and discharge tests (Fig. 5(a)).
  • Fig. 5(c) is a graph showing the amplitude variation of the SPR mode to be tested corresponding to the fiber-optic sensor probe of the present invention under a series of scanning rate cyclic volt-ampere charge and discharge tests (Fig. 5(a)).
  • Fig. 5(d) is a graph showing the constant current charge and discharge test of the electrochemical supercapacitor device in different current magnitudes according to the present invention.
  • Fig. 5(e) is a graph showing changes in the stored charge amount of the capacitor of the electrochemical supercapacitor device of the present invention under different current and magnitude constant current charge and discharge tests (Fig. 5(d)).
  • Fig. 5(f) is a graph showing the amplitude variation of the SPR mode to be tested corresponding to the current sensor of the present invention under the constant current charge and discharge test of different current magnitudes (Fig. 5(d)).
  • Fig. 5(g) is a graph showing the constant current charging of the electrochemical supercapacitor at different high potentials in the present invention.
  • Fig. 5(h) is a graph showing changes in the stored charge amount of the capacitor in the electrochemical supercapacitor device of the present invention under different high potential constant current charging tests (Fig. 5(g)).
  • Fig. 5(i) is a graph showing the amplitude variation of the SPR mode to be tested corresponding to the fiber-optic sensor probe under the constant current charging test of different high potentials (Fig. 5(g)).
  • 1-light source 2-polarizer, 3-polarization controller, 4-fiber circulator, 5-fiber sensor probe, 6-electrochemical supercapacitor device, 7-fiber spectrometer, 8-electrochemical workstation, 9-capacitor electrode, 10-working electrode, 11-counting electrode, 12-reference electrode, 13-tilted fiber grating, 14-metal film, 15-plasma resonance wave, 16-capacitor electrode material, 17-ion, 18 - Metal reflective film.
  • tilted fiber gratings have become a research hotspot in recent years.
  • the tilted fiber grating can excite hundreds of different modes of sensitivity to the surrounding environment.
  • a metal film such as gold or silver
  • a tilted fiber grating cladding mode that satisfies the phase matching condition can be coupled to the metal film to form a plasmon resonance. wave.
  • the plasmon resonance wave is very sensitive to changes in the dielectric constant, the electrode potential, and the charge density of the metal thin film.
  • the plasmon resonance wave has higher detection sensitivity, and the related monitoring field has become a research hotspot at home and abroad.
  • the embodiment provides an on-line optical fiber monitoring system for an energy storage device, the system comprising a light source 1, a polarizer 2, a polarization controller 3, a fiber circulator 4, and a fiber sensor probe 5.
  • the electrochemical supercapacitor device 6, the optical fiber spectrometer 7 and the electrochemical workstation 8, the light source 1, the polarizer 2, the polarization controller 3, the optical fiber circulator 4 and the optical fiber sensor probe 5 are sequentially connected, and the optical fiber spectrometer 7 and the optical fiber circulator 4
  • the connection, the electrochemical supercapacitor device 6 is connected to the electrochemical workstation 8, and the fiber optic sensor probe 5 is disposed within the electrochemical supercapacitor device 6.
  • the electrochemical supercapacitor device 6 is filled with an electrolyte and has two capacitor electrodes 9, a portion of which is placed in an electrolyte, a fiber sensor probe 5 and one of the capacitor electrodes 9
  • the electrochemical workstation 8 has a counter electrode 10, a reference electrode 11 and a working electrode 12, and the counter electrode 10 and the reference electrode 11 are connected in common to one of the capacitor electrodes 9 of the electrochemical supercapacitor device, the working electrode 12 is connected to the other capacitor electrode 9 of the electrochemical supercapacitor device 6 by a wire.
  • the optical fiber sensor probe 5 includes an optical fiber, the optical fiber is engraved with an inclined fiber grating 13, and the outer surface of the optical fiber cladding is plated with a metal film 14 of a uniform thickness of nanometer order, and the metal film 14 is
  • the plasmon resonance optical signal carrier has good electrical conductivity characteristics and becomes a micro current transmission carrier.
  • the light emitted by the light source 1 passes through the polarizer 2, the polarization controller 3 and the fiber circulator 4, and then enters the fiber sensor probe 5
  • the cladding mode generated in the fiber of the fiber sensor probe 5 is coupled to the metal film 14 on the outer surface of the fiber cladding to excite the surface plasmon resonance of the metal film 14; the fiber sensor probe 5 will contain the light of the plasmon resonance wave 15.
  • the capacitor electrode material 16 modified on the surface of the capacitor electrode 9 interacts, and the ions 17 in the electrolyte enter the two-dimensional or three-dimensional space of the capacitor electrode material 16 to undergo oxidation-reduction reaction.
  • the spectrometer 7 shows that the plasmon resonance wave 15 is embodied as an absorption envelope in the reflection spectrum or transmission spectrum of the fiber spectrometer 7.
  • the metal film 14 is electronically polarized under the charging of the capacitor, its dielectric constant will change.
  • the absorption envelope amplitude of the plasmon resonance wave 15 also changes accordingly, and the amount of change has a corresponding relationship with the amount of stored charge of the capacitor, so that the system can simultaneously obtain the electrochemical quantity and the optical quantity, and the intrinsic of both. relationship.
  • the output spectrum of the light source 1 is 1500 to 1620 nm, and the range of the output spectrum of the light source 1 matches the envelope range of the oblique fiber grating reflection spectrum in the fiber sensor probe 5.
  • the oblique fiber grating 13 of the fiber sensor probe 5 is written by an excimer laser and a phase mask. It can be understood that the oblique fiber grating 13 can also be written by double beam interference.
  • the tilted fiber grating 13 has an inclination of 5 to 25 degrees and an axial length of about 10 to 20 mm.
  • the fiber end face of the fiber sensor probe 5 is plated with a metal reflective film 18 having a thickness of about 200 nm or more, and the metal reflective film 18 is used for reflecting the optical signal to realize probe type measurement.
  • the outer surface of the fiber cladding of the fiber sensor probe 5 is first plated with a chrome film transition layer of 2 to 3 nm thickness by magnetron sputtering or thermal evaporation to increase the surface of the metal film and the fiber cladding.
  • the adhesion is further plated with a metal film 14 of a uniform thickness on the order of nanometers.
  • the metal film 14 is a gold film, which can effectively excite plasmon resonance waves, has good electrical conductivity, and has stable physical chemistry.
  • the metal film 14 has a thickness of 40 to 50 nm, which ensures that the plasma resonance is excited with an optimum efficiency; after the metal film 14 is plated, the metal film-coated optical fiber is subjected to a tempering treatment, preferably at 300 ° C. The tempering treatment is carried out for more than 3 hours to increase the adhesion of the metal film 14 and release the residual stress during the coating process.
  • the embodiment further provides an online monitoring method for the energy state of the energy storage device, the method comprising the following steps:
  • the fiber sensor probe 5 is closely packed with one of the electrodes 6 of the electrochemical supercapacitor device 6.
  • the electrochemical supercapacitor device 6 is filled with electrolyte, and the output light of the light source 1 is converted into polarization by the polarizer 2.
  • the polarization direction of the input polarized light is adjusted by the polarization controller 3 to coincide with the direction in which the oblique fiber grating 13 is written in the fiber sensor probe 5.
  • the polarized light is polarized light parallel to the writing direction of the oblique fiber grating 13, and the polarization direction of the polarized light is determined by the surface plasmon resonance peak amplitude, that is, the surface plasma is parallel to the writing direction of the oblique fiber grating 13.
  • the body resonance peak has the largest amplitude.
  • the electrochemical supercapacitor device 6 is placed under natural conditions, and the whole process of the state of charge of the capacitor during the process of charging, discharging, storing and releasing electrical energy is monitored by using optical and electrochemical methods, including:
  • the capacitor is charged and discharged under the excitation of the electrochemical workstation.
  • the ions 17 in the electrolyte form an electric double layer to store electrical energy on the surface of the capacitor electrode 9, and the charge is further accumulated along with the oxidation reaction of the capacitor electrode material 16.
  • the energy stored in the capacitor reaches a peak after the capacitor is charged; when the capacitor is discharged, the capacitor electrode material 16 undergoes a reduction reaction, and at the same time, the ion 17 accumulated on the surface of the capacitor electrode 9 to form an electric double layer charge is charged and charged.
  • the reverse process of the process is diffused back into the electrolyte;
  • the fiber sensor probe 5 will monitor the real-time charge change of the capacitor, and the electrochemical workstation 8 and the fiber spectrometer 7 record the whole process of the capacitor charging power rise and the discharge power drop, and draw One-to-one corresponding graph;
  • the small disturbance of the light source energy, the optical path system and the ambient temperature may bring certain errors to the detection results of the electrochemical workstation and the optical fiber spectrometer, while the optical fiber core mode is only sensitive to temperature, and the environmental refractive index and the metal film 14 The change of dielectric constant is not sensitive. Therefore, by detecting the wavelength and amplitude of the fiber core mode, real-time measurement of temperature information and light source energy can be realized. The error is corrected by the wavelength and amplitude variation of the fiber core mode, thereby eliminating temperature changes.
  • the influence of external interference on the detection result has a self-calibration function.
  • the density of negative ions at the electrode end of the capacitor packaged with the fiber sensor probe 5 will increase, and the metal film 14 will be in an electronically polarized state; when a negative potential is applied, the fiber-optic sensor probe will be transmitted. 5
  • the density of positive ions at the electrode end of the packaged capacitor will increase, and the metal film 14 will be in a polarization state of opposite polarity; when the capacitor is charged, the energy is two-dimensionally entered into the electrode surface of the electrode by the electrochemical reaction. Or in a three-dimensional space, a large amount of charge is stored in the electrode, and when discharged, the ions are returned to the electrolyte, and the stored charge is released, and the fiber sensor probe 5 can be used to detect the charge density. Change to determine the state of charge of the supercapacitor.
  • the optical fiber sensor probe 5 ejects the light containing the plasmon resonance wave 13 into the external environment other than the metal film 14, interacts with the capacitor electrode material 16 modified on the surface of the capacitor electrode 9, and the ions 17 in the electrolyte enter the capacitor.
  • the redox reaction occurs in the two-dimensional or three-dimensional space of the electrode material and the charge density near the capacitor electrode changes.
  • the energy loss of the plasmon resonance wave 13 and the resonance center wavelength shift which is shown in the fiber spectrometer 7, the specific change As shown in Fig. 3(a)-3(b), in Fig.
  • the capacitor is subjected to cyclic voltammetry charging and discharging at a scanning rate of 10 mV/s under the excitation of an electrochemical workstation, correspondingly, in Fig. 3 ( b), the plasmon resonance (SPR) amplitude at the asterisk "*" corresponding to the absorption envelope of the plasmon resonance (SPR) varies with the potential of the capacitor; in Figure 3(b), when the capacitor is charged and discharged At the time, the core mode does not change, indicating that the detection process is performed under a stable optical path system and temperature environment conditions.
  • SPR plasmon resonance
  • the change of the plasma resonance intensity during the charging and discharging of the capacitor is recorded more completely, which is basically consistent with the change trend of the stored charge of the capacitor.
  • the intensity change of the core correction mode is also recorded. It is marked by a red curve in Fig. 4, indicating that the ambient temperature has hardly changed during the whole monitoring process, or if there is a temperature-induced deviation of the detection result and instability of the light source and the optical path, the core mode can be used. Correction.
  • the supercapacitor performs Cyclic Voltammetry (CV) charge and discharge at a series of scanning rates.
  • CV Cyclic Voltammetry
  • the real-time change of the stored capacity of the capacitor is calculated by the CV curve (Fig. 5(b). )), as shown in Figure 5(c), while the capacitor is charged and discharged, the fiber optic spectrometer records the real-time variation of the amplitude of the corresponding SPR mode; similarly, as shown in Figure 5(d), the supercapacitor has a different current.
  • Carrying out constant current (Galvanostatic Charge-Discharge, GCD) charge and discharge, the real-time change of the stored capacity of the capacitor storage is calculated by the GCD curve (Fig.
  • the optical fiber spectrometer records the real-time variation curve corresponding to the amplitude of the SPR mode; further, as shown in Fig. 5(g), the supercapacitor performs high-potential constant current at different high potentials (Galvanostatic Charge and Voltage Holding, GCVH) Charging, the real-time change of the stored capacity of the capacitor storage is calculated by the GCVH curve (Fig. 5(h)). As shown in Fig. 5(i), the capacitor is kept at a high potential. At the same time as the flow charging, the fiber optic spectrometer records the real-time curve corresponding to the amplitude of the SPR mode.
  • the change of the plasma resonance intensity in the sensor probe is basically consistent with the change trend of the real-time storage and discharge of the capacitor, indicating that the real-time state of charge of the supercapacitor during charging and discharging can be utilized.
  • the light signal of the sensor probe is monitored.
  • the present invention utilizes a fiber-optic sensing probe that is as thin as a hairline to transmit optical signals and obtain optical wave information to monitor the potential of the supercapacitor during charging and discharging and real-time storage of power in real time.
  • Information can be implanted in a small space to achieve in-situ measurement, while simultaneously measuring multiple parameter changes in real time, such as state of charge, potential, temperature, etc.; in addition, the fiber-optic sensing probe of the present invention is outside the fiber cladding
  • the surface is plated with a metal film, and the fiber sensing probe couples the energy of the surface plasmon resonance wave generated by the metal film to the external environment outside the metal film, and the plasmon resonance wave interacts with the electrode material closely attached to the surface of the metal film to generate Energy loss and resonance center wavelength drift, this phenomenon is reflected in the fiber optic spectrometer is an absorption envelope, through this multi-domain technology (electrochemical technology (Electrochemical technology) and plasmon resonance technology (Surface Plas

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Abstract

一种储能设备充电状态光纤在线监测系统及方法，系统包括光源（1）、起偏器（2）和偏振控制器（3）、光纤环形器（4）、光纤传感器探针（5）、电化学超级电容器装置（6）、光纤光谱仪（7）和电化学工作站（8），光源（1）、起偏器（2）、偏振控制器（3）、光纤环形器（4）和光纤传感器探针（5）依次连接，光纤光谱仪（7）与光纤环形器（4）连接，电化学超级电容器装置（6）与电化学工作站（8）连接，光纤传感器探针（5）设置在电化学超级电容器装置（6）内。光纤传感探针（5），既可传输光信号，又能充当传感探针获取光波信息，从而实时原位监测超级电容器充放电过程中的电势大小和实时存储电量信息，可植入狭小空间实现原位测量，同时又能同步实时地测量多个参量变化，如荷电状态、电势、温度等信息。

Description

储能设备充电状态光纤在线监测系统及方法 技术领域
本发明涉及一种充电状态在线监测系统及方法，尤其是一种储能设备充电状态光纤在线监测系统及方法，属于光纤电化学传感器设计领域。
背景技术
目前，地球能源面临着各种巨大的挑战。随着石油、煤炭和天然气等化石燃料的消耗和温室气体的过渡排放，人类社会的能源供给结构必须由不可再生能源向可再生能源发展，以解决能源枯竭和地球海平面上升问题。能否解决这些问题主要依赖于能源设备系统的有效使用和管理。当代科技在信息科学和电子技术等领域在最近的二三十年取得了迅猛的发展。在现阶段已经应用成熟的商用手机中，配备的供电系统选用的是传统锂离子电池，传统锂离子电池制造中复杂的外壳封装将会限制到手机的体积和重量微型化发展，在其它传统锂离子电池的应用领域同样会有遇到这样的问题，因此，开发新型柔性能源器件是能源设备领域中急需解决的研究课题。在一系列需求的推动下，超级电容器技术应运而生。超级电容器，也称电化学电容器，是近年来快速发展的一种新型储能器件，其工作原理是利用电极表面形成的双电层或发生的二维或准二维法拉第反应存储电能。研究领域涉及能源、材料、化学及电子器件等，成为交叉学科的研究热点之一。
超级电容器以其充放电速度快、使用寿命长、温度特性好、绿色环保等特点，受到了广泛关注。目前，针对超级电容器的检测方式都是“脱机”式的检测，即无法在电容器充放电工作的同时对它的荷电情况进行测量，而是需要等待电容器停止工作之后用电化学工作站测试电极的电化学性能是否有衰减或者损坏。当然，也可以利用透射电镜或者冷冻电镜等设备对电容器边工作边进行测试，但由于透射电镜和冷冻电镜等设备极其昂贵，也不适用于现场原位的测量，所以使得超级电容器的原位在线监测技术无法得到发展和大规模的普及应用。
发明内容
本发明的目的是为了解决上述现有技术的缺陷，提供一种储能设备充电状态光纤在线监测系统，该系统利用一根细如发丝的光纤传感探针，既可传输光信号，又能获取光波信息从而实时原位监测超级电容器充放电过程中的电势大小和实时存储电量信息。
本发明的另一目的在于提供一种储能设备充电状态光纤在线监测方法，该方法可植入狭小空间实现原位测量，同时又能同步实时地测量多个参量变化，如荷电状态、电势、温度等信息；此外，该方法还继承了光纤低损耗传输特点，传感器探针与传光通路均为光纤，可实现远距离在线实时监测。
本发明的目的可以通过采取如下技术方案达到：
储能设备充电状态光纤在线监测系统，包括光源、起偏器和偏振控制器，还包括光纤环形器、光纤传感器探针、电化学超级电容器装置、光纤光谱仪和电化学工作站，所述光源、起偏器、偏振控制器、光纤环形器和光纤传感器探针依次连接，所述光纤光谱仪与光纤环形器连接，所述电化学超级电容器装置与电化学工作站连接，所述光纤传感器探针设置在电化学超级电容器装置内。
进一步的，所述光纤传感器探针包括光纤，所述光纤刻有倾斜光纤光栅，且光纤包层外表面镀有纳米量级均匀厚度的金属膜，光源发出的光依次经过起偏器、偏振控制器和光纤环形器后入射到光纤传感器探针中，光纤传感器探针的光纤中产生的包层模耦合至光纤包层外表面的金属膜，激发金属膜表面等离子体共振；等离子体共振波体现在光纤光谱仪的反射光谱上是一个吸收包络，金属膜的介电常数在电容器充放电作用下发生改变，等离子体共振波吸收包络的幅度也会随之发生相应的变化。
进一步的，所述光纤传感器探针中，光纤中的倾斜光纤光栅通过准分子激光器及相位掩膜板方式写制而成，或通过双光束干涉方式写制而成；倾斜光纤光栅的倾角为5～25度，轴向长度约为10～20mm。
进一步的，所述光纤传感器探针中，光纤端面镀有厚度为200nm以上的金属反射膜。
进一步的，所述光纤传感器探针中，光纤包层外表面先通过磁控溅射 方式或热蒸镀方式镀上2～3nm厚度的铬薄膜过渡层，再镀上纳米量级均匀厚度的金属膜，并对镀上金属膜的光纤进行褪火处理。
进一步的，所述电化学超级电容器装置内充满电解液，且具有两个电容器电极，两个电容器电极的一部分置于电解液中，所述光纤传感器探针与其中一个电容器电极紧贴封装在一起。
进一步的，所述电化学工作站具有计数电极、参比电极和工作电极，所述计数电极和参比电极连接电化学超级电容器装置的其中一个电容器电极，所述工作电极连接电化学超级电容器装置的另一个电容器电极。
本发明的另一目的可以通过采取如下技术方案达到：
储能设备充电状态光纤在线监测方法，所述方法包括以下步骤：
S1、将光纤传感器探针与电化学超级电容器装置的其中一个电极紧贴封装在一起，电化学超级电容器装置内充满电解液，光源输出光经过起偏器后转变成偏振光，通过偏振控制器把输入偏振光的偏振方向调节成与光纤传感器探针内倾斜光纤光栅写制方向相一致；
S2、搭建好光路和电化学超级电容器装置后，将电化学超级电容器装置与电化学工作站连接，电化学工作站和光纤光谱仪连接到计算机，设置好相关参数，调节偏振控制器使入射光纤传感器探针的入射光处在激发金属膜表面等离子体共振的偏振态下；
S3、在自然条件下静置电化学超级电容器装置，同时利用光学和电化学方法监测电容器在充放电存储释放电能过程中荷电状态变化的全过程；
S4、通过对电化学超级电容器装置施加不同电位来控制电容器存储电荷极性和电荷量大小，从而控制在光纤传感器探针表面的电荷密度变化，以检测电容器内电荷存储释放过程。
进一步的，步骤S1中，所述偏振光为平行于倾斜光纤光栅写制方向的偏振光，偏振光的偏振方向由表面等离子体共振峰幅度来确定，即平行于倾斜光纤光栅写制方向时表面等离子体共振峰幅度最大。
进一步的，步骤S3中，所述利用光学和电化学方法监测电容器在充放电存储释放电能过程中荷电状态变化的全过程，具体包括：
电容器在电化学工作站的激励下进行充放电，当电容器充电时，电解 液中的离子在电容器电极表面会形成双电层存储电能，伴随着电极材料发生氧化反应，电荷进一步地积累到电容器电极上，电容器充电完成后电容器存储的能量达到峰值；当电容器放电时，电极材料发生还原反应，同时在电容器电极表面聚集形成双电层电荷的离子将会以与充电过程相反的逆过程扩散回电解液中；
在电容器充放电的全过程中，光纤传感器探针将对电容器的实时荷电变化进行监测，电化学工作站和光纤光谱仪将电容器充电电能上升和放电电能下降的全过程记录下来，绘制成一一对应的曲线图。
进一步的，所述光纤光谱仪记录的检测结果通过光纤纤芯模的波长漂移量和幅度变化量进行校正。
进一步的，步骤S4，具体包括：
当施加正电位时，与光纤传感器探针封装在一起的电容器电极端负离子的密度将会增大，金属膜将处于电子极化状态；当施加负电位时，与光纤传感器探针封装在一起的电容器电极端正离子的密度将会增大，金属膜将处于相反极性的极化状态。
进一步的，所述光纤传感器探针表面产生的电荷密度的变化由等离子体共振波吸收包络波长漂移调制等离子体共振波吸收包络对应波长的倾斜光纤光栅包层模强度变化来检测，从而将电容器存储释的电荷信息量转变为电化学-光学信号进行检测。
本发明相对于现有技术具有如下的有益效果：
1、本发明利用一根细如发丝的光纤传感探针，既可传输光信号，又能获取光波信息从而实时原位监测超级电容器充放电过程中的电势大小和实时存储电量信息，可植入狭小空间实现原位测量，同时又能同步实时地测量多个参量变化，如荷电状态、电势、温度等信息。
2、本发明的光纤传感探针的光纤包层外表面镀有金属膜，光纤传感探针将金属膜产生表面等离子体共振波的能量耦合到金属膜以外的外界环境中，等离子体共振波与紧贴在金属膜表面的电极材料相互作用而产生能量损失与共振中心波长漂移，这一现象体现在光纤光谱仪中是一个吸收包络，通过将这种多领域的技术(电化学技术(Electrochemical technology)和等离子体共振技术(Surface Plasmon Resonance technology))相结合交 叉应用，已经实现了对超级电容器的充放电行为进行光谱实时、原位监测，为各种能源存储设备的工作状况监测提供了新的使用前景。
3、本发明的高灵敏度表面等离子体共振技术将仅有百微米尺度的紧凑型光纤传感探针来替代传统的数十毫米尺度的三角棱镜，实现了传感器探针的小型化，使得它可以插入传统传感器难以到达的空间中进行原位检测。
4、本发明的传感器探针与传导信号的光纤为同一根光纤，由于光纤的低损耗特性，即使远距离的传输也几乎不会衰减，使传感器的检测精度大大提高，且可以运用于长距离的在线实时监测，克服了现有的需要“脱机”才能测试的缺陷。
5、本发明的光纤传感器探针的光纤包层外表面金属膜厚度为纳米量级均匀厚度，可确保等离子体共振以最佳效率激发，并且这层金属膜既是等离子体共振光学信号载体，同时又有良好的导电特性，成为微电流传输载体。
6、本发明的光纤传感器探针的光纤端面镀有厚度为200nm以上的金属反射膜，通过金属反射膜可以反射光信号进而实现探针式测量。
7、本发明的光纤传感器探针的光纤包层外表面在镀上纳米级厚度的金属膜之前，先通过磁控溅射方式镀上2～3nm厚度的铬薄膜过渡层，以增加金属膜与光纤包层表面的粘附力，在镀完金属膜后，对光纤进行褪火处理，增加金属膜的附着力，释放镀膜过程中的残留应力。
8、本发明由于光纤传感器探针的光纤纤芯模式仅对温度敏感，而对环境折射率不敏感；因此，通过检测光纤纤芯模式，可实现温度信息的实时测量，进而消除温度变化对测量结果的影响，同时还可以利用它的幅度变化来校准光路系统中受到的干扰，具有自校准功能。
附图说明
图1为本发明的储能设备充电状态光纤在线监测系统装置的原理图。
图2为本发明的储能设备充电状态光纤在线监测系统装置中光纤传感器探针的工作原理图。
图3(a)为本发明中的电化学超级电容器装置在10mV/s扫描速率下循 环伏安图。
图3(b)为本发明的光纤传感器探针中等离子体共振强度和电容器电位的关系图。
图4为本发明中的电化学超级电容器装置在循环伏安测试充放电下对应的传感器探针中纤芯模式和待测SPR模式幅度变化曲线。
图5(a)为本发明中电化学超级电容器装置在系列扫描速率下循环伏安图。
图5(b)为本发明中电化学超级电容器装置在系列扫描速率循环伏安充放电测试下(图5(a))电容器存储电荷量变化曲线。
图5(c)为本发明中光纤传感器探针在系列扫描速率循环伏安充放电测试下(图5(a))对应的待测SPR模式幅度变化曲线。
图5(d)为本发明中电化学超级电容器装置在不同电流大小恒电流充放电测试图。
图5(e)为本发明中电化学超级电容器装置在不同电流大小恒电流充放电测试下(图5(d))电容器存储电荷量变化曲线。
图5(f)为本发明中光纤传感器探针在不同电流大小恒电流充放电测试下(图5(d))对应的待测SPR模式幅度变化曲线。
图5(g)为本发明中电化学超级电容器在不同高电位保持恒电流充电测试图。
图5(h)为本发明中电化学超级电容器装置在不同高电位保持恒电流充电测试下(图5(g))电容器存储电荷量变化曲线。
图5(i)为本发明中光纤传感器探针在不同高电位保持恒电流充电测试下(图5(g))对应的待测SPR模式幅度变化曲线。
其中，1-光源，2-起偏器，3-偏振控制器，4-光纤环形器，5-光纤传感器探针，6-电化学超级电容器装置，7-光纤光谱仪，8-电化学工作站，9-电容器电极，10-工作电极，11-计数电极，12-参比电极，13-倾斜光纤光栅，14-金属膜，15-等离子体共振波，16-电容器电极材料，17-离子，18-金属反射膜。
具体实施方式
下面结合实施例及附图对本发明作进一步详细的描述，但本发明的实施方式不限于此。
实施例1：
在光纤生化传感研究的相关报道中，倾斜光纤光栅成为近些年的研究热点。倾斜光纤光栅可激发数百个对周围环境敏感度不同的模式，通过在光纤表面镀金、银等金属薄膜，可将满足相位匹配条件的倾斜光纤光栅包层模耦合至金属薄膜，形成等离子体共振波。等离子体共振波对金属薄膜的介电常数、电极电势大小、电荷密度等变化非常敏感。较传统倏逝场效应的光纤传感方式，等离子体共振波具有更高的检测灵敏度，相关监测领域已成为国内外研究热点。
如图1所示，本实施例提供了一种储能设备充电状态光纤在线监测系统，该系统包括光源1、起偏器2、偏振控制器3、光纤环形器4、光纤传感器探针5、电化学超级电容器装置6、光纤光谱仪7和电化学工作站8，光源1、起偏器2、偏振控制器3、光纤环形器4和光纤传感器探针5依次连接，光纤光谱仪7与光纤环形器4连接，电化学超级电容器装置6与电化学工作站8连接，光纤传感器探针5设置在电化学超级电容器装置6内。
本实施例中，所述电化学超级电容器装置6内充满电解液，且具有两个电容器电极9，两个电容器电极9的一部分置于电解液中，光纤传感器探针5与其中一个电容器电极9紧贴封装在一起；所述电化学工作站8具有计数电极10、参比电极11和工作电极12，计数电极10和参比电极11共同连接电化学超级电容器装置的其中一个电容器电极9，工作电极12通过导线连接电化学超级电容器装置6的另一个电容器电极9。
如图1和图2所示，所述光纤传感器探针5，包括光纤，光纤刻有倾斜光纤光栅13，且光纤包层外表面镀有纳米量级均匀厚度的金属膜14，金属膜14既是等离子体共振光学信号载体，同时又有良好的导电特性，成为微电流传输载体，光源1发出的光依次经过起偏器2、偏振控制器3和光纤环形器4后入射到光纤传感器探针5中，光纤传感器探针5的光纤中产生的包层模耦合至光纤包层外表面的金属膜14，激发金属膜14表面等离子体共振；光纤传感器探针5将含有等离子体共振波15的光倏逝到 金属膜14以外的外界环境中，与修饰在电容器电极9表面的电容器电极材料16相互作用，同时电解液中的离子17进入电容器电极材料16的二维或三维空间中发生氧化还原反应和电容器电极附近的电荷密度发生变化，此时等离子体共振波13能量损失与共振中心波长漂移，这一现象在光纤光谱仪7中显示，等离子体共振波15体现在光纤光谱仪7的反射光谱或透射谱上是一个吸收包络，当金属膜14在电容器充电作用下电子极化时其介电常数将会发生变化，等离子体共振波15的吸收包络幅度也随之发生相应的变化，其改变量与电容器存储电荷量大小具有对应关系，因此该系统可同时获得电化学量和光学量，以及两者的内在关系。
本实施例中，光源1的输出光谱为1500～1620nm，光源1的输出光谱的范围与光纤传感器探针5中的倾斜光纤光栅反射光谱的包络范围相匹配。
本实施例中，光纤传感器探针5的倾斜光纤光栅13通过准分子激光器及相位掩膜板方式写制而成，可以理解的是，倾斜光纤光栅13也可以通过双光束干涉方式写制而成；倾斜光纤光栅13的倾角为5～25度，轴向长度约为10～20mm。
本实施例中，光纤传感器探针5的光纤端面镀上厚度约为200nm以上的金属反射膜18，该金属反射膜18用于反射光信号进而实现探针式测量。
本实施例中，光纤传感器探针5的光纤包层外表面先通过磁控溅射方式或热蒸镀方式镀上2～3nm厚度的铬薄膜过渡层，以增加金属膜与光纤包层表面的粘附力，再镀上纳米级量级均匀厚度的金属膜14，优选地，金属膜14为金膜，既可有效激发等离子体共振波，又有良好的导电特性，并且具备稳定的物理化学特性，金属膜14的厚度为40～50nm，可确保等离子体共振以最佳效率激发；在镀完金属膜14后，将镀上金属膜的光纤进行褪火处理，优选地，在300℃条件下褪火处理3小时以上，以增加金属膜14的附着力，释放镀膜过程中的残留应力。
本实施例还提供了一种储能设备充电状态光纤在线监测方法，该方法包括以下步骤：
S1、将光纤传感器探针5与电化学超级电容器装置6的其中一个电极 6紧贴封装在一起，电化学超级电容器装置6内充满电解液，光源1输出光经过起偏器2后转变成偏振光，通过偏振控制器3把输入偏振光的偏振方向调节成与光纤传感器探针5内倾斜光纤光栅13写制方向相一致。
本步骤中，所述偏振光为平行于倾斜光纤光栅13写制方向的偏振光，偏振光的偏振方向由表面等离子体共振峰幅度来确定，即平行于倾斜光纤光栅13写制方向时表面等离子体共振峰幅度最大。
S2、搭建好光路和电化学超级电容器装置6后，将电化学超级电容器装置6与电化学工作站8连接，电化学工作站8和光纤光谱仪7连接到计算机，设置好相关参数，调节偏振控制器3使入射光纤传感器探针5的入射光处在激发金属膜14表面等离子体共振的偏振态下；
S3、在自然条件下静置电化学超级电容器装置6，同时利用光学和电化学方法监测电容器在充放电存储释放电能过程中荷电状态变化的全过程，具体包括：
电容器在电化学工作站的激励下进行充放电，当电容器充电时，电解液中的离子17在电容器电极9表面会形成双电层存储电能，伴随着电容器电极材料16发生氧化反应，电荷进一步地积累到电容器电极9上，电容器充电完成后电容器存储的能量达到峰值；当电容器放电时，电容器电极材料16发生还原反应，同时在电容器电极9表面聚集形成双电层电荷的离子17将会以与充电过程相反的逆过程扩散回电解液中；
在电容器充放电的全过程中，光纤传感器探针5将对电容器的实时荷电变化进行监测，电化学工作站8和光纤光谱仪7将电容器充电电能上升和放电电能下降的全过程记录下来，绘制成一一对应的曲线图；
其中，光源能量、光路系统和环境温度的微小扰动均可能会对电化学工作站和光纤光谱仪的检测结果带来一定的误差，而光纤纤芯模仅对温度敏感，而对环境折射率和金属膜14介电常数变化不敏感，因此通过检测光纤纤芯模的波长和幅度，可实现温度信息和光源能量的实时测量，通过光纤纤芯模波长和幅度变化量对误差进行校正，进而消除温度变化和外界干扰对检测结果的影响，具有自校准功能。
S4、在人为条件下，通过对电化学超级电容器装置6施加不同电位来控制电容器存储电荷极性和电荷量大小，从而控制在光纤传感器探针5表 面的电荷密度变化，在光纤传感器探针5表面产生的电荷密度的变化由等离子体共振波15吸收包络波长漂移调制等离子体共振波15吸收包络对应波长的倾斜光纤光栅13包层模强度变化来检测，从而将电容器存储释的电荷信息量转变为电化学-光学信号进行检测，用以检测电容器内电荷存储释放过程，具体包括：
当施加正电位时，与光纤传感器探针5封装在一起的电容器电极端负离子的密度将会增大，金属膜14将处于电子极化状态；当施加负电位时，与传光纤感器探针5封装在一起的电容器电极端正离子的密度将会增大，金属膜14将处于相反极性的极化状态；电容器充电时能量是离子通过电化学反应进入电极表面活性氧化物体相中的二维或三维空间中，大量的电荷就被存储在电极中，放电时，这些离子又会重新回到电解液中，同时所存储的电荷被释放出来，利用该光纤传感器探针5可以检测电荷密度的变化来判断出超级电容器的荷电状态。
光纤传感器探针5将含有等离子体共振波13的光倏逝到金属膜14以外的外界环境中，与修饰在电容器电极9表面的电容器电极材料16相互作用，同时电解液中的离子17进入电容器电极材料的二维或三维空间中发生氧化还原反应和电容器电极附近的电荷密度发生变化，此时等离子体共振波13能量损失与共振中心波长漂移，这一现象在光纤光谱仪7中显示，具体变化如图3(a)-3(b)所示，在图3(a)中，电容器在电化学工作站的激励下以10mV/s扫描速率进行循环伏安充放电，对应地，在图3(b)中，等离子体共振(SPR)的吸收包络所对应的星号“*”处的等离子体共振(SPR)幅度随电容器电位变化而变化；在图3(b)中，当电容器充放电时，纤芯模式不会改变，说明检测过程是在稳定的光路系统和温度环境条件下进行。在图4中，较完整地记录了在电容器充放电过程中等离子体共振强度变化，与电容器存储释放电量的变化趋势基本一致，在这个过程中，纤芯校正模式的强度变化也记录了下来，在图4中由红色曲线标出，说明在整个监测过程中环境温度几乎没有发生改变，或者说如果有温度引起的检测结果的偏差及光源和光路的不稳定因素，均可以利用纤芯模式进行校正。
如图5(a)所示，超级电容器在系列扫描速率下进行循环伏安(Cyclic Voltammetry，CV)充放电，此过程电容器存储释放电量的实时变化情况 通过CV曲线计算得出(图5(b))，如图5(c)所示，在电容器充放电的同时，光纤光谱仪记录了对应SPR模式幅度的实时变化曲线；类似地，如图5(d)所示，超级电容器以不同大小电流进行恒电流(Galvanostatic Charge–Discharge，GCD)充放电，此过程电容器存储释放电量的实时变化情况通过GCD曲线计算得出(图5(e))，如图5(f)所示，在电容器恒电流充放电的同时，光纤光谱仪记录了对应SPR模式幅度的实时变化曲线；更进一步地如图5(g)所示，超级电容器以不同高电位进行高电位保持恒电流(Galvanostatic Charge and Voltage Holding，GCVH)充电，此过程电容器存储释放电量的实时变化情况通过GCVH曲线计算得出(图5(h))，如图5(i)所示，在电容器高电位保持恒电流充电的同时，光纤光谱仪记录了对应SPR模式幅度的实时变化曲线。电容器在CV、GCD、GCVH这三种充放电测试中，传感器探针中等离子体共振强度变化与电容器实时存储释放电量的变化趋势基本一致，表明超级电容器充放电时的实时荷电状态可利用该传感器探针的光信号来进行监测。
综上所述，本发明利用一根细如发丝的光纤传感探针，既可传输光信号，又能获取光波信息从而实时原位监测超级电容器充放电过程中的电势大小和实时存储电量信息，可植入狭小空间实现原位测量，同时又能同步实时地测量多个参量变化，如荷电状态、电势、温度等信息；此外，本发明的光纤传感探针的光纤包层外表面镀有金属膜，光纤传感探针将金属膜产生表面等离子体共振波的能量耦合到金属膜以外的外界环境中，等离子体共振波与紧贴在金属膜表面的电极材料相互作用而产生能量损失与共振中心波长漂移，这一现象体现在光纤光谱仪中是一个吸收包络，通过将这种多领域的技术(电化学技术(Electrochemical technology)和等离子体共振技术(Surface Plasmon Resonance technology))相结合交叉应用，已经实现了对超级电容器的充放电行为进行光谱实时、原位监测，为各种能源存储设备的工作状况监测提供了新的使用前景。
以上所述，仅为本发明专利较佳的实施例，但本发明专利的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明专利所公开的范围内，根据本发明专利的技术方案及其发明构思加以等同替换或改变，都属于本发明专利的保护范围。

Claims (10)

  1. 储能设备充电状态光纤在线监测系统，包括光源、起偏器和偏振控制器，其特征在于：还包括光纤环形器、光纤传感器探针、电化学超级电容器装置、光纤光谱仪和电化学工作站，所述光源、起偏器、偏振控制器、光纤环形器和光纤传感器探针依次连接，所述光纤光谱仪与光纤环形器连接，所述电化学超级电容器装置与电化学工作站连接，所述光纤传感器探针设置在电化学超级电容器装置内。
  2. 根据权利要求1所述的储能设备充电状态光纤在线监测系统，其特征在于：所述光纤传感器探针包括光纤，所述光纤刻有倾斜光纤光栅，且光纤包层外表面镀有纳米量级均匀厚度的金属膜，光源发出的光依次经过起偏器、偏振控制器和光纤环形器后入射到光纤传感器探针中，光纤传感器探针的光纤中产生的包层模耦合至光纤包层外表面的金属膜，激发金属膜表面等离子体共振；等离子体共振波体现在光纤光谱仪的反射光谱或透射谱上是一个吸收包络，金属膜的介电常数在电容器充放电作用下发生改变，等离子体共振波吸收包络的幅度也会随之发生相应的变化。
  3. 根据权利要求2所述的储能设备充电状态光纤在线监测系统，其特征在于：所述光纤传感器探针中，光纤中的倾斜光纤光栅通过准分子激光器及相位掩膜板方式写制而成，或通过双光束干涉方式写制而成；倾斜光纤光栅的倾角为5～25度，轴向长度约为10～20mm。
  4. 根据权利要求2所述的储能设备充电状态光纤在线监测系统，其特征在于：所述光纤传感器探针中，光纤端面镀有厚度为200nm以上的金属反射膜。
  5. 根据权利要求2所述的储能设备充电状态光纤在线监测系统，其特征在于：所述光纤传感器探针中，光纤包层外表面先通过磁控溅射方式或热蒸镀方式镀上2～3nm厚度的铬薄膜过渡层，再镀上纳米量级均匀厚度的金属膜，并对镀上金属膜的光纤进行褪火处理。
  6. 根据权利要求1所述的储能设备充电状态光纤在线监测系统，其特征在于：所述电化学超级电容器装置内充满电解液，且具有两个电容器电极，两个电容器电极的一部分置于电解液中，所述光纤传感器探针与其 中一个电容器电极紧贴封装在一起。
  7. 根据权利要求6所述的储能设备充电状态光纤在线监测系统，其特征在于：所述电化学工作站具有计数电极、参比电极和工作电极，所述计数电极和参比电极连接电化学超级电容器装置的其中一个电容器电极，所述工作电极连接电化学超级电容器装置的另一个电容器电极。
  8. 储能设备充电状态光纤在线监测方法，其特征在于：所述方法包括以下步骤：
    S1、将光纤传感器探针与电化学超级电容器装置的其中一个电极紧贴封装在一起，电化学超级电容器装置内充满电解液，光源输出光经过起偏器后转变成偏振光，通过偏振控制器把输入偏振光的偏振方向调节成与光纤传感器探针内倾斜光纤光栅写制方向相一致；
    S2、搭建好光路和电化学超级电容器装置后，将电化学超级电容器装置与电化学工作站连接，电化学工作站和光纤光谱仪连接到计算机，设置好相关参数，调节偏振控制器使入射光纤传感器探针的入射光处在激发金属膜表面等离子体共振的偏振态下；
    S3、在自然条件下静置电化学超级电容器装置，同时利用光学和电化学方法监测电容器在充放电存储释放电能过程中荷电状态变化的全过程；
    S4、通过对电化学超级电容器装置施加不同电位来控制电容器存储电荷极性和电荷量大小，从而控制在光纤传感器探针表面的电荷密度变化，以检测电容器内电荷存储释放过程。
  9. 根据权利要求8所述的储能设备充电状态光纤在线监测方法，其特征在于：步骤S3中，所述利用光学和电化学方法监测电容器在充放电存储释放电能过程中荷电状态变化的全过程，具体包括：
    电容器在电化学工作站的激励下进行充放电，当电容器充电时，电解液中的离子在电容器电极表面会形成双电层存储电能，伴随着电极材料发生氧化反应，电荷进一步地积累到电容器电极上，电容器充电完成后电容器存储的能量达到峰值；当电容器放电时，电极材料发生还原反应，同时在电容器电极表面聚集形成双电层电荷的离子将会以与充电过程相反的逆过程扩散回电解液中；
    在电容器充放电的全过程中，光纤传感器探针将对电容器的实时荷电变化进行监测，电化学工作站和光纤光谱仪将电容器充电电能上升和放电电能下降的全过程记录下来，绘制成一一对应的曲线图。
  10. 根据权利要求8所述的储能设备充电状态光纤在线监测方法，其特征在于：步骤S4，具体包括：
    当施加正电位时，与光纤传感器探针封装在一起的电容器电极端负离子的密度将会增大，金属膜将处于电子极化状态；当施加负电位时，与光纤传感器探针封装在一起的电容器电极端正离子的密度将会增大，金属膜将处于相反极性的极化状态。
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