CN110988089B - Wide-range digital electrochemical analysis device and detection method - Google Patents
Wide-range digital electrochemical analysis device and detection method Download PDFInfo
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Abstract
The invention relates to a wide-range digital electrochemical analysis device and a detection method thereof. An electrochemical analysis device includes: the device comprises a microcontroller, a digital-to-analog converter, an analog-to-digital converter, an amplifier, a working electrode, an auxiliary electrode and a reference electrode; the microcontroller is respectively connected with one end of the digital-to-analog converter and one end of the analog-to-digital converter; the other end of the digital-to-analog converter is connected with the working electrode; the analog-to-digital converter comprises a plurality of analog-to-digital converters; the amplifier comprises a plurality of amplifiers which are connected in series to form an amplifier series string; the first input end of each amplifier is respectively connected with the other end of one analog-to-digital converter; the second input end of the first amplifier is connected with the auxiliary electrode; and the output end of the last amplifier is connected with the reference electrode and then grounded. The electrochemical analysis device and the detection method thereof provided by the invention can select a proper detection range on line and improve the current detection precision.
Description
Technical Field
The invention relates to the field of electrochemical detection devices, in particular to a wide-range digital electrochemical analysis device and a detection method.
Background
An electrochemical analyzer, also called an electrochemical workstation, an electrochemical detector, an electrochemical sensor, etc., detects according to electrochemical principles and electrochemical properties of substances, is used for measuring the change of electric signals of the substances, and can detect compounds with redox properties, such as organic compounds containing nitro, amino, etc., and inorganic anions, cations, etc., by using the electrochemical detector. The electrochemical detection is mainly used for detecting reaction current released in the oxidation-reduction reaction of a substance to be detected in the electrochemical reaction; the magnitude of the reaction current highly depends on the type and concentration of the substance to be detected, the range of the reaction current cannot be predicted in advance or the variation range is large, the unit is from pico ampere to ampere, and the span of the measuring range reaches 12 times of 10. The existing electrochemical analysis devices often have the following problems:
the problem that the bandwidth of a signal to be measured is larger than the measuring range of measuring equipment occurs not only in electrochemical detection but also in other signal detection, and increasing the measuring range inevitably reduces the measuring precision, so the measuring range is narrow, and the measuring range needs to be manually set in advance; the equipment cannot be converted into a proper measuring range on line in the detection process; when the measuring range is changed in the detection process, the data is discontinuous, or the change trend of the data is discontinuous.
Disclosure of Invention
The invention aims to provide a wide-range digital electrochemical analysis device and a detection method, which are used for solving the problems that the conventional electrochemical analysis device has narrow detection range, cannot be converted into a proper range on line and has discontinuous data during range conversion.
In order to achieve the purpose, the invention provides the following scheme:
a wide-range digital electrochemical analysis device, comprising: the device comprises a microcontroller, a digital-to-analog converter, an analog-to-digital converter, an amplifier, a working electrode, an auxiliary electrode and a reference electrode;
the microcontroller is respectively connected with one end of the digital-to-analog converter and one end of the analog-to-digital converter; the other end of the digital-to-analog converter is connected with the working electrode; the analog-to-digital converter comprises a plurality of analog-to-digital converters; the amplifier comprises a plurality of amplifiers which are connected in series to form an amplifier series string; the first input end of each amplifier is respectively connected with the other end of one analog-to-digital converter; the second input end of the first amplifier is connected with the auxiliary electrode; and the output end of the last amplifier is connected with the reference electrode and then grounded.
Optionally, the amplifier specifically includes: an operational amplifier and a plurality of resistors;
the resistors are connected in series and connected with the first input end and the output end of the operational amplifier; the second input terminal of the operational amplifier is grounded.
Optionally, the amplifier is a current amplifier.
Optionally, the wide-range digital electrochemical analysis device is connected with a remote server in a serial port communication manner.
The serial port communication mode is a wired transmission mode or a wireless transmission mode.
A detection method of a wide-range digital electrochemical analysis device comprises the following steps:
acquiring the detection range of each amplifier;
determining a first detection range of the detected current value based on the detection ranges of all the current amplifiers;
determining a current observation compensation vector according to the first detection range;
determining a current measurement fitting value according to the current observation compensation vector;
determining an electrochemical current measurement value from the current measurement fit value.
Optionally, the determining a current observation compensation vector according to the first detection range specifically includes:
according to the formula OIi＝aj*OIj+bjDetermining a current observation compensation vector; wherein, OIiIs a first detection range; OI (oil in oil) devicejIs an observed value; a isjIs the current coefficient; bjIs a constant; [ a ] Aj，bj]The compensation vector is observed for the current.
Optionally, the determining a current measurement fitting value according to the current observation compensation vector specifically includes:
according to the formula
Determining a current measurement fitting value; wherein, IoFitting values for the current measurements;
is a constant coefficient weight vector.
According to the specific embodiment provided by the invention, the invention discloses the following technical effects: the invention provides a wide-range digital electrochemical analysis device and a detection method, wherein the purpose of mutual compensation of the ranges of a plurality of amplifiers is to enable a total range to cover all possible ranges to be detected, the wide range is dispersed into a plurality of relatively narrow ranges, the ranges are simultaneously subjected to signal acquisition, and the acquired data are calculated by using a mathematical method to obtain a signal value to be detected, so that a proper detection range is selected on line, and the detection precision is improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without inventive exercise.
FIG. 1 is a schematic diagram of a wide-range digital electrochemical analyzer according to the present invention;
FIG. 2 is a circuit diagram of an exemplary amplifier provided by the present invention;
FIG. 3 is a circuit diagram of an amplifier provided by the present invention;
FIG. 4 is a schematic diagram of digital communication of a wide-range electrochemical analysis device provided by the present invention;
FIG. 5 is a schematic diagram of an electrochemical three-electrode system in accordance with the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention aims to provide a wide-range digital electrochemical analysis device and a detection method thereof, which can select a proper detection range on line and improve the current detection precision.
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in further detail below.
Fig. 1 is a structural diagram of a wide-range digital electrochemical analysis device provided by the present invention, and as shown in fig. 1, the wide-range digital electrochemical analysis device includes: a Microcontroller (MCU), a Digital-to-Analog Converter (DAC), an Analog-to-Digital Converter (AD), an Amplifier (AMP), a working electrode, an auxiliary electrode, and a reference electrode. The microcontroller is respectively connected with one end of the digital-to-analog converter and one end of the analog-to-digital converter; the other end of the digital-to-analog converter is connected with the working electrode; the analog-to-digital converter comprises a plurality of analog-to-digital converters; the amplifier comprises a plurality of amplifiers which are connected in series to form an amplifier series string; the first input end of each amplifier is respectively connected with the other end of one analog-to-digital converter; the second input end of the first amplifier is connected with the auxiliary electrode; the output end of the last amplifier is connected with the reference electrode and then Grounded (GND); the invention also comprises a transmitting Data unit (TXD), a receiving Data unit (RXD) and a power supply module (VCC). The analog-to-digital converter AD is used for converting an analog voltage input signal into a digital signal; the digital-to-analog converter DAC is used for converting the digital signal into an analog voltage signal and outputting the analog voltage signal; the amplifier AMP is used to convert the trickle current into an amplified voltage signal for use or detection by the back end.
Fig. 2 is a circuit diagram of a typical amplifier provided by the present invention, as shown in fig. 2, the amplification factor is changed by changing the internal resistance of the amplifier, and with such an amplifier circuit, the detection range is narrow, the range needs to be manually set in advance, and the current cannot be quickly and accurately detected. Fig. 3 is a circuit diagram of the amplifier according to the present invention, as shown in fig. 3, a plurality of resistors are connected in series and connected to the first input terminal and the output terminal of the operational amplifier; the second input end of the operational amplifier is grounded; by connecting the amplifiers in series, the ranges of the amplifiers are mutually compensated and compensated, and all possible ranges of the range to be detected are covered, so that the range does not need to be set, and a more accurate measurement value is obtained; wherein the ratio of the range of each shift amplifier is equal to the ratio of the accumulated resistance value on the left side of the measuring line. All ranges work simultaneously in the operation of the equipment, if a certain range acquisition signal is larger than the maximum value of the range, data overflow, and the weight is set to zero; if the signal collected in a certain range is not greater than the maximum value, giving a weight; the most suitable range is that the signal collected in a certain range is about half of the maximum value of the range, and a larger weight can be given, and the sum of the weights of all ranges is 1, so that the proper range is converted on line without manually adjusting the range.
Fig. 4 is a schematic diagram of digital communication of the wide-range electrochemical analysis device provided by the present invention, fig. 5 is a schematic diagram of an electrochemical three-electrode system in practical application provided by the present invention, as shown in fig. 4-5, the wide-range electrochemical analysis device is used as a lower computer to communicate with other upper computers through serial ports using TXD and RXD data exchange ports on the MCU, and the wide-range electrochemical analysis device receives control signals of the upper computers and transmits obtained digital detection information to the upper computers; the serial communication in fig. 4 can be connected by wire or wirelessly through bluetooth, WIFI, 3G \4G, etc.; DAC in FIG. 1 is connected to working electrode clamp, reaction current is generated in auxiliary electrode in FIG. 5, and connected to amplifier in FIG. 1, and reference electrode clamp is connected to GND.
In practical applications, the amplifier is a current amplifier.
Based on the wide-range digital electrochemical analysis device, the invention provides a detection method of the wide-range digital electrochemical analysis device, which comprises the following steps:
acquiring the detection range of each amplifier;
determining a first detection range of the detected current value based on the detection ranges of all the current amplifiers;
determining a current observation compensation vector according to the first detection range;
determining a current measurement fitting value according to the current observation compensation vector;
determining an electrochemical current measurement value from the current measurement fit value.
Note n independent Current Scale (Current Scale) IS ═ ISl，ISh]Wherein ISlIndicating the minimum value of the measuring range, IShIndicating the maximum value of the range.
Detection range IS of ith current amplifieri＝[ISli，IShi](i-1, 2 …, n) with ISli<IShi-1&&IShi＞ISli+1(i-1≥1&&i +1 is less than or equal to n), namely, the adjacent two ranges have partial detection ranges which are overlapped.
When the ith measurement range is the most suitable measurement range and the measurement value (observer current) is OIiThen, the jth detection range also detects an observable OIjThe two observed values conform to the formula OIi＝aj*OIj+bj. An observation compensation vector [ a ] can be obtainedj，bj]。
Can establish proper constant coefficient weight vector W, the norm of W is constant 1, | W | ≡ 1, the measurement fitting value of current
Generally, the most suitable detection range is determined according to the proximity degree of the observed value and the range median, and the distribution method of the constant coefficient weight vector can be different under the condition that the above conditions are met, such as linear distribution according to the relative proximity degree of the constant coefficient weight vector and the range median or linear distribution of three digits with the highest relative proximity degree of the constant coefficient weight vector and the range median.
The measuring method ensures that the electrochemical current measuring value can be measured in a wide range and the measuring value is continuous.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other.
The principles and embodiments of the present invention have been described herein using specific examples, which are provided only to help understand the method and the core concept of the present invention; meanwhile, for a person skilled in the art, according to the idea of the present invention, the specific embodiments and the application range may be changed. In view of the above, the present disclosure should not be construed as limiting the invention.
Claims (5)
1. A wide-range digital electrochemical analysis device, comprising: the device comprises a microcontroller, a digital-to-analog converter, an analog-to-digital converter, an amplifier, a working electrode, an auxiliary electrode and a reference electrode;
the microcontroller is respectively connected with one end of the digital-to-analog converter and one end of the analog-to-digital converter; the other end of the digital-to-analog converter is connected with the working electrode; the analog-to-digital converter comprises a plurality of analog-to-digital converters; the amplifier comprises a plurality of amplifiers which are connected in series to form an amplifier series string; the first input end of each amplifier is respectively connected with the other end of one analog-to-digital converter; the second input end of the first amplifier is connected with the auxiliary electrode; the output end of the last amplifier is connected with the reference electrode and then grounded; the amplifier specifically includes: an operational amplifier and a plurality of resistors; the resistors are connected in series and connected with the first input end and the output end of the operational amplifier; the second input terminal of the operational amplifier is grounded.
2. The wide-range digital electrochemical analyzer of claim 1, wherein the amplifier is a current amplifier.
3. The wide-range digital electrochemical analyzer of claim 1, wherein the wide-range digital electrochemical analyzer is connected to a remote server via serial communication.
4. The wide-range digital electrochemical analysis device according to claim 3, wherein the serial communication mode is a wired transmission mode or a wireless transmission mode.
5. A detection method of a wide-range digital electrochemical analyzer, which is applied to the wide-range digital electrochemical analyzer according to any one of claims 1 to 4, the detection method comprising:
acquiring the detection range of each amplifier;
determining a first detection range of the detected current value based on the detection ranges of all the amplifiers;
determining a current observation compensation vector according to the first detection range, which specifically comprises: according to the formula OIi＝aj*OIj+bjDetermining a current observation compensation vector; wherein, OIiIs a first detection range; OI (oil in oil) devicejIs an observed value; a isjIs the current coefficient; bjIs a constant; [ a ] Aj，bj]A compensation vector is observed for the current;
determining a current measurement fitting value according to the current observation compensation vector, which specifically comprises: according to the formula
Determining a current measurement fitting value; wherein, IoFitting values for the current measurements;
is a constant coefficient weight vector;
determining an electrochemical current measurement value from the current measurement fit value.
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