CN110133089A - A kind of automatic internal calibration system of electrochemical sensor and calibration method - Google Patents
A kind of automatic internal calibration system of electrochemical sensor and calibration method Download PDFInfo
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Abstract
The present invention provides a kind of automatic internal calibration systems of electrochemical sensor, comprising: microprocessor, sensor module, base modules, tension excitation circuitry, amplifying circuit, digital analog converter, analog-digital converter, microprocessor is connect with digital analog converter and analog-digital converter, and digital analog converter is connect with tension excitation circuitry, and tension excitation circuitry and sensor module connect electrode, analog-digital converter is connect with amplifying circuit, and amplifying circuit is connect with sensor module working electrode；Base modules are consistent with sensor module connection circuit as built-in calibration module；The invention further relates to a kind of automatic internal calibration methods of electrochemical sensor.The automatic internal calibration system of electrochemical sensor of the invention realizes autonomous judgement, independently determines intelligent automaticization internal calibration；It can be calibrated while work, and it is not necessary that sensor to be placed in external perimysium reference analyte, calibration range is wide, and calibration accuracy is higher.
Description
Technical field
The present invention relates to the automatic internal calibration system of electrochemical sensor, further relate to a kind of electrochemical sensor automatically in school
Quasi- method.
Background technique
Electrochemical sensor is more common sensor in research work and daily life, is generally used for measurement target point
The electricity and electrochemical properties of son or substance are the electrifications based on determinand to carry out qualitative and quantitative analysis and measurement
Characteristic is learned, and converts a kind of sensor device that electrical quantities carry out sensing detection for the chemical quantity of determinand.
The primary element of one typical electrochemical sensor are as follows: work (or sensing) electrode, one to electrode, lead to
It often further include a reference electrode.Above-mentioned electrode invests in sensor, is lined with electrolyte.Electrode is located at the inner face of one piece of diffusion barrier
On, have it is porous passed through for detection substance, but electrolyte can not permeate.Measured matter diffuses into sensor and passes through film and reaches
After electrode, electrochemical reaction will occur --- or be oxidation, or be reduction, depending on material type.Oxidation reaction keeps electronics logical
External circuit is crossed to flow to from working electrode to electrode；In contrast, reduction reaction makes electronics flow to working electrode to electrode.It is above-mentioned
Electron stream constitutes electric current, and mutually proportional to gas concentration.Circuit is detected and is put to electric current in sensor module and instrument
Greatly, final to realize other to species to be measured and concentration measurement and export result.
Electrochemical sensor is small in size, and detection speed is fast, at low cost, the application for being suitble to scene directly to detect and continuously detect
Scene, in gas detection, water quality detection, the fields such as biological detection are widely used.But since electrochemical sensor is
It is detected by directly being contacted with test substance, during sensor use, sensor often absorbs pollutant, and remains in
On diffusion barrier, or even on the electrode, pollutant can reduce electrode area, influence the diffusion admittance of analyte；On the other hand, electric
The evaporation and pollution of pole matter, also influence whether sensor performance.In practical applications, electrochemical sensor is in the inspection using initial stage
Survey the result is that precisely and stable, but in use after the phase, data become uncontrollable, may result in detection data have it is very big
Deviation even results in detection data failure.
For this electrochemical sensor limitation, current general technology coping style includes: more emat sensor；According to warp
Data are tested, the artificial amount of bias that is arranged is modified；Manual calibration, sensor settings in standard analyte environment, to biography
Sensor output valve is modified.However the above technology coping style, the following limitations exist: more emat sensor increases cost and band
It is inconvenient to come；Need manpower intervention, cannot in time, accurate judgement data deviation even fail, cause misjudgement to be judged by accident, or even cause not
Repairable loss.
Patent CN201 draws 0291057.7 and discloses a kind of gas sensor automated calibration system and its gas sensor school
Sensor is arranged in the measured matter environment of external certain concentration quasi- method, special only with reference to acquisition single-point or limited several points
Value indicative calibrates sensor, and efficiency is lower, and calibration effect is limited, cannot function as the calibration method of accurate simplicity.
Summary of the invention
In view of the above-mentioned problems, the present invention provides a kind of automatic internal calibration system of electrochemical sensor, the present invention is also related to
A kind of and automatic internal calibration method of electrochemical sensor.
The automatic internal calibration system of electrochemical sensor provided by the invention, comprising:
Microprocessor: included A D interface and DA interface, the DA interface export analog signal, and the A D interface acquires number
According to；
Sensor module, tension excitation circuitry, amplifying circuit, digital analog converter, analog-digital converter, the microprocessor with
The digital analog converter is connected with the analog-digital converter, and the digital analog converter is connect with the tension excitation circuitry, described
Tension excitation circuitry connect electrode with the sensor module, and the analog-digital converter is connect with the amplifying circuit, described
Amplifying circuit is connect with the sensor module working electrode；
Base modules, tension excitation circuitry, amplifying circuit, digital analog converter, analog-digital converter, the microprocessor and institute
It states digital analog converter to connect with the analog-digital converter, the digital analog converter is connect with the tension excitation circuitry, the electricity
Pressure exciting circuit connect electrode with the base modules, and the analog-digital converter is connect with the amplifying circuit, the amplification
Circuit is connect with the base modules working electrode.
Further, the base modules are one in the mould group form of redundancy electrode, equivalent circuit, intrinsic parameter constant
Kind.
Further, the base modules Seal and preservation keeps electrochemical properties to stablize constant not with external contact.
Further, the base modules and sensing mould group original state energy with uniformity or error are acceptable
In range.
Further, the amplifying circuit, the digital analog converter and the analog-digital converter parameter are consistent with model, electricity
Road connection type is consistent.
Further, calibration algorithm built in the microprocessor, for comparing the sensor module and the benchmark mould
Group output data difference and corresponding excitation waveform data, calculate calibration factor, correct the biography using the calibration factor
Sensor mould group output data makes it approach the benchmark mould group output data, until between the two data difference control it is specific can
In the range of receiving.
The automatic internal calibration method of electrochemical sensor provided by the invention, comprising:
(1) the quantized data sequence of the microprocessor output specific voltage waveform, is converted via the digital analog converter
At specific voltage waveform, by the tension excitation circuitry, the voltage waveform is applied to the sensor module to electrode,
The voltage drive to the sensor module is formed, the waveform of voltage drive is generated by the microprocessor programming Control, described
Sensor module working electrode output signal is adopted by the amplifying circuit and the analog-digital converter by the microprocessor
Collect output data；
(2) the quantized data sequence of the microprocessor output specific voltage waveform, is converted via the digital analog converter
At specific voltage waveform, by the tension excitation circuitry, voltage waveform is applied to the base modules to electrode, formation pair
The waveform of the voltage drive of the base modules, voltage drive is generated by the microprocessor programming Control.The base modules
Working electrode output signal collects output number by the microprocessor by the amplifying circuit and the analog-digital converter
According to；
(3) by parser preset in the microprocessor, according to different excitation voltage waveforms and the comparison biography
The output data difference of sensor mould group and the base modules calculates calibration factor and handles, according to the base modules data
It is modified, the above steps are repeated, and imposes different voltage waveform modes, until the collected data of the sensor module
In a certain range with the collected data deviation control of the benchmark mould group, to realize automatic calibration.
In the initial state, it imposes the same voltage waveform to sensor and calibration module respectively to motivate, due to sensor
Consistent with characteristic under calibration module original state, output data is also the same.After sensor characteristics changes, and base
Quasi-mode block maintains intrinsic characteristic in sensor internal, and the characteristic of the two will form difference.When process is calibrated in starting, micro process
Device control imposes the same voltage waveform to sensor and calibration module respectively and motivates, and the data of output will form certain poor
It is different.The present invention is modified using the values of disparity between sensor and calibration module, realizes automatic calibration.
The beneficial effects of the present invention are:
(1) the automatic internal calibration method of electrochemical sensor disclosed by the invention independently determines sensing data accuracy, has
Effect property, and independently intelligent, auto-calibration is realized in triggering, does not need manpower intervention；
(2) the automatic internal calibration method of electrochemical sensor disclosed by the invention detects interval insertion calibration in sensing data
Mode, side work, side calibration do not need interrupt sensors work；
(3) the automatic internal calibration system of electrochemical sensor disclosed by the invention is built-in in the sensor calibrates benchmark mould group,
It is not necessary that sensor to be placed in external perimysium reference analyte, internal self calibration can be completed；
(4) the automatic internal calibration method calibration range of electrochemical sensor disclosed by the invention is wide, and calibration accuracy is higher, no
It is limited to several characteristic point value revision calibrations.
Detailed description of the invention
The attached drawing constituted part of this application is used to provide further understanding of the present invention, schematic reality of the invention
It applies example and its explanation is used to explain the present invention, do not constitute improper limitations of the present invention.In the accompanying drawings:
Fig. 1 is the structure chart of the automatic internal calibration system of electrochemical sensor in the embodiment of the present invention；
Fig. 2 is gas sensors electrode structure signal of the redundancy electrode as calibration base modules in the embodiment of the present invention
Figure；
Fig. 3 is sensor module electrode structure schematic diagram in the embodiment of the present invention；
Fig. 4 is the automatic internal calibration system knot of sensor normal electrode and base modules redundancy electrode in the embodiment of the present invention
Structure schematic diagram；
Fig. 5 is processing of the redundancy electrode as the gas sensor system calibration of calibration base modules in the embodiment of the present invention
Flow chart；
Fig. 6 is gas sensors electrode structure signal of the electrical equivalent of the embodiment of the present invention as calibration base modules
Figure；
Fig. 7 is the automatic internal calibration system knot of sensor normal electrode and base modules equivalent circuit in the embodiment of the present invention
Structure schematic diagram.
Specific embodiment
Below by specific embodiment, technical scheme of the present invention will be described in further detail.
Embodiment 1:
Redundancy electrode is made to calibrate the formaldehyde gas sensor of base modules and automatic internal calibration system:
As shown in figure 3, gas sensor includes substrate, electrolyte, electrode plate, diffusion barrier, shell and air hole.
As shown in Fig. 2, gas sensors electrode plate includes normal electrode and redundancy electrode.The two electrode pattern, electrode system
Make technique, electrode catalyst modification process is just the same.The electrolyte of normal electrode and redundancy electrode, the material and work of diffusion barrier
Skill is just the same.The two difference is the band air hole of the shell above normal electrode, and redundancy electrode upper shell is without saturating
Stomata, redundancy electrode part are believed that complete and external sealing and isolation.
Since normal electrode and redundancy electrode material and technique are consistent and parallel progress, when original state, the two characteristic
It answers almost the same or in certain tolerance interval.And air-tight state at redundancy electrode, it can be tieed up in the middle and later periods performance of sensor
It keeps steady fixed and does not change.
As shown in figure 4, normal electrode and redundancy electrode have independent a set of voltage input excitation and output amplification data respectively
Acquisition Circuit, two sets of circuit designs and parameter are consistent.It is high that integrated level simultaneously may be selected, carry the micro process of AD and DA interface
Device, such as STM32F051K6U6.DA export analog signal by amplifier to Sensor Reference electrode and to electrode impose voltage swash
It encourages.Working electrode exports after accurate amplifier and secondary amplification, carries out AD sampling, acquires working sensor electrode output numerical value.
Voltage excitation signals generate waveform quantization sequence by microprocessor program, and the waveform of generation can be various frequencies
The wave sequences such as sinusoidal waveform, triangular wave, square wave, pulse.
Embodiment further includes calibration algorithm.Calibration algorithm is preset in microprocessor operation program, controls sensor excitation
The generation of waveform, data after acquisition sensor output amplification, calibration algorithm compare sensor module and benchmark mould group output data
Difference and corresponding excitation waveform data, calculate calibration factor, correct sensor module output data using calibration factor, make
It approaches benchmark mould group output data, until data difference control between the two is in specific acceptable range.
For the parameter attribute of the present embodiment formaldehyde gas sensor, treatment process such as Fig. 5 institute of sensing system calibration
Show.Data acquisition process is successively called in calibration, and acquisition driving frequency can successively be set as 10khz, 9khz, 8khz~1khz,
900hz, 800hz~100hz, 10hz, 9hz~0.1hz, 0.5hz, 0.1hz.After the completion of every frequency point data acquisition, calibration algorithm 1
Sensor module and the collected data of benchmark mould group are analyzed respectively, calculate and store corresponding single acquisition ginseng
Number.After the completion of all frequency point data acquisitions, calibration algorithm 2 carries out comprehensive analysis to each frequency point acquisition parameter, compares sensor die
The analysis result difference of group and benchmark mould group generates calibration factor, and calibration factor is substituted into the acquisition of sensor module data and is calculated
In method, data gathering algorithm is modified.Above procedure is repeated, final calibration factor is generated, makes sensor module and base
Within an acceptable range, calibration process terminates the analysis of data collected parameter differences of quasi-mode group.
Embodiment 2:
Equivalent circuit makees the automatic internal calibration system of electrochemical sensor of calibration base modules:
As shown in fig. 6, the present embodiment is using equivalent-circuit model as benchmark mould group.Electrochemical sensor internal structure is not
Become, when sensor original state, log-on data collecting flowchart acquires each frequency point output data.Equivalent circuit algorithm is according to each frequency
Point output data calculates equivalent-circuit model, and equivalent circuit parameter is cured to base by adjustable resistance, capacitor, inductance
It in quasi- modular circuit, and is fixed by physical means, is no longer changed.
In use for some time, Parameters variation occurs for sensor module, and the benchmark mould group being made of equivalent circuit is simultaneously
It does not change, by calibration algorithm, compares the acquisition parameter difference of sensor module and benchmark mould group, generate calibration factor.
Specific calibration algorithm such as embodiment 1.
As the supplement of 1 scheme of embodiment, separate microprocessor discrete device side is can be used in analog-to-digital conversion or digital-to-analogue conversion
Case, by independent modulus conversion chip or analog-digital chip special disposal, microprocessor mainly completes overall flow control, number
According to analysis, the work such as calibration, as shown in Figure 7.
It will be appreciated by those skilled in the art that the accompanying drawings are only schematic diagrams of a preferred implementation scenario, module in attached drawing or
Process is not necessarily implemented necessary to the present invention.
To the present invention it should be understood that embodiment described above, to the purpose of the present invention, technical solution and beneficial to effect
Fruit has carried out further details of explanation, and the above is only the embodiment of the present invention, are not intended to limit the present invention, it is all
Within spiritual principles of the invention, made any modification, equivalent substitution, improvement and etc. should be included in protection of the invention
Within the scope of, the scope of protection of the present invention shall be subject to the scope of protection defined by the claims.
Claims (10)
1. a kind of automatic internal calibration system of electrochemical sensor characterized by comprising
Microprocessor: possessing A D interface and DA interface, and the DA interface exports analog signal, and the A D interface acquires data；
Sensor module system to be calibrated: sensor module, tension excitation circuitry, amplifying circuit, digital analog converter, analog-to-digital conversion
Device, the microprocessor are connect with the digital analog converter and the analog-digital converter, the digital analog converter and the voltage
Exciting circuit connection, the tension excitation circuitry connect electrode with the sensor module, the analog-digital converter with it is described
Amplifying circuit connection, the amplifying circuit are connect with the sensor module working electrode；
Base modules system: base modules, tension excitation circuitry, amplifying circuit, digital analog converter, analog-digital converter are described micro-
Processor is connect with the digital analog converter and the analog-digital converter, and the digital analog converter and the tension excitation circuitry connect
It connecing, the tension excitation circuitry connect electrode with the base modules, and the analog-digital converter is connect with the amplifying circuit,
The amplifying circuit is connect with the base modules working electrode.
2. the automatic internal calibration system of electrochemical sensor according to claim 1, which is characterized in that the base modules
It is one of the mould group form of redundancy electrode, equivalent circuit, intrinsic parameter constant.
3. the automatic internal calibration system of electrochemical sensor according to claim 2, which is characterized in that the base modules
For redundancy electrode, the redundancy electrode and the sensor module electrode are in electrode pattern, Fabrication Technology of Electrode, electrode catalyst
Modification process is just the same, electrolyte, and the material and technique of diffusion barrier are also just the same.
4. the automatic internal calibration system of electrochemical sensor according to claim 2, which is characterized in that the base modules
For equivalent circuit, acquire the sensor module initial condition data, calculate equivalent-circuit model, and by adjustable resistance,
Capacitor, inductance are cured in the benchmark modular circuit in the recent period, are fixed by physical means.
5. according to the automatic internal calibration system of electrochemical sensor as claimed in claim 2, which is characterized in that the base modules envelope
Preservation is closed, not with external contact, electrochemical properties are remained unchanged.
6. the automatic internal calibration system of any electrochemical sensor according to claim 1~5, which is characterized in that described
Base modules and sensing mould group original state energy with uniformity or error are within an acceptable range.
7. the automatic internal calibration system of electrochemical sensor according to claim 1, which is characterized in that the biography to be calibrated
The tension excitation circuitry that sensor module system and the base modules system respectively use, the amplifying circuit, the number
Mode converter and the analog-digital converter parameter are consistent with model, and circuit connecting mode is consistent.
8. the automatic internal calibration system of electrochemical sensor according to claim 1, which is characterized in that the microprocessor
Built-in calibration algorithm, for comparing the sensor module and the benchmark mould group output data difference and corresponding excitation waveform
Data calculate calibration factor, correct the sensor module output data using the calibration factor, it is made to approach the base
Quasi-mode group output data, until data difference control between the two is in specific acceptable range.
9. using the automatic internal calibration side of the electrochemical sensor of the automatic internal calibration system of electrochemical sensor in claim 1
Method, which is characterized in that method includes the following steps:
S1: the quantized data sequence of the microprocessor output specific voltage waveform is converted into spy via the digital analog converter
The voltage waveform is applied to the sensor module to electrode, is formed by constant voltage waveform by the tension excitation circuitry
To the voltage drive of the sensor module, the waveform of voltage drive is generated by the microprocessor programming Control, the sensing
Device mould group working electrode output signal is collected by the amplifying circuit and the analog-digital converter by the microprocessor
Output data；
S2: the quantized data sequence of the microprocessor output specific voltage waveform is converted into spy via the digital analog converter
Voltage waveform is applied to the base modules to electrode, is formed to described by constant voltage waveform by the tension excitation circuitry
The waveform of the voltage drive of base modules, voltage drive is generated by the microprocessor programming Control.The base modules work
Electrode output signal collects output data by the microprocessor by the amplifying circuit and the analog-digital converter；
S3: by parser preset in the microprocessor, according to different excitation voltage waveforms and the comparison sensor
The output data difference of mould group and the base modules calculates calibration factor and handles, carried out according to the base modules data
Amendment, the above steps are repeated, and imposes different voltage waveform modes, until the collected data of the sensor module and institute
The collected data deviation control of benchmark mould group is stated in a certain range, to realize automatic calibration.
10. the automatic internal calibration method of electrochemical sensor according to claim 9, which is characterized in that the micro process
Device exports the quantized data sequence of specific voltage waveform, and the voltage waveform can be sinusoidal waveform, triangular wave, square wave, pulse
At least one of.
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