CN107688048A - Reverse addition type potentiostat and IV converted measurement circuit available for electrochemical measurement - Google Patents
Reverse addition type potentiostat and IV converted measurement circuit available for electrochemical measurement Download PDFInfo
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Abstract
The present invention proposes a kind of reverse addition type potentiostat and IV converted measurement circuit available for electrochemical measurement, including：Potentiostat, IV conversion circuit, electrolytic cell, wherein, the positive input and function generator of potentiostat is connected, and the reverse input and output end of potentiostat is connected with electrolytic cell, to be made up of the closed loop of negative-feedback amplification, output polarization electric current potentiostat and electrolytic cell；The negative input of IV conversion circuit connects electrolytic cell, the positive input ground connection of IV conversion circuit, the output end of IV conversion circuit is connected with follow-up reception signal acquisition circuit, polarization current for electrolytic cell to be exported in electrochemical reaction process is converted into voltage signal, so that follow-up reception signal acquisition circuit carries out data acquisition and processing (DAP).The present invention has higher stability and conversion accuracy under the control voltage of high speed；Current measurement high resolution, it is reproducible.
Description
Technical field
It is more particularly to a kind of high-precision available for the reverse of electrochemical measurement the present invention relates to potentiostat technical field
Addition type potentiostat and IV converted measurement circuits.
Background technology
Existing potentiostat circuit is there is stability is poor, conversion accuracy and resolution ratio are low, poor repeatability, anti-interference energy
The problems such as power is weak.
The content of the invention
The purpose of the present invention is intended at least solve one of described technological deficiency.
Therefore, it is an object of the invention to propose a kind of reverse addition type potentiostat and IV available for electrochemical measurement
Converted measurement circuit.
To achieve these goals, embodiments of the invention provide a kind of reversely addition type potentiostat and IV converted measurements
Circuit, including：Potentiostat, IV conversion circuit, electrolytic cell, wherein,
The positive input and function generator of the potentiostat is connected, the potentiostat it is reverse input and defeated
Go out end to be connected with the electrolytic cell, it is defeated to be made up of the closed loop of negative-feedback amplification the potentiostat and the electrolytic cell
Go out polarization current；
The negative input of the IV conversion circuit connects the electrolytic cell, and the positive input of the IV conversion circuit connects
Ground, the output end of the IV conversion circuit are connected with follow-up reception signal acquisition circuit, for by the electrolytic cell in electrification
Learn the polarization current exported in course of reaction and be converted into voltage signal, so that the follow-up reception signal acquisition circuit enters line number
According to collection and processing.
Further, the potentiostat and the IV conversion circuit use integrated operational amplifier.
Further, the potentiostat includes the first operational amplifier, is inputted with the negative sense of first operational amplifier
Hold first resistor, second resistance and the 3rd resistor being respectively connected with, the positive input ground connection of first operational amplifier, structure
Into reverse add circuit, the reverse add circuit includes three branch roads, and the electric current of three branch roads is in the first operational amplifier
Reverse input end add and, each electric current sum of inflow is zero.
Further, three branch roads include：
Tie point：The input of first operational amplifier receives control voltage EOUT, through the first rheostat and institute
State the reverse input end that first resistor acts on first operational amplifier；
Second branch road：The output end of second operational amplifier is connected with the 3rd resistor, forms voltage follower conduct
Backfeed loop is connected to reference electrode, and the feedback signal of the reference electrode current potential is through the second operational amplifier and the 3rd electricity
Resistance acts on the reverse input end of first operational amplifier；
3rd branch road：External+5V a reference sources are linked into described by the second rheostat and the second resistance in circuit
The reverse input end of first operational amplifier, to be returned to zero to system.
Further, in addition to：First to the 3rd analog switch, first analog switch and first operational amplifier
Output end be connected with an electrode of the electrolytic cell, the forward direction of second analog switch and second operational amplifier
Input is connected with another electrode of the electrolytic cell, the 3rd analog switch and the IV conversion circuit and the electrolysis
Another electrode in pond is connected, for by switch control the conducting of the three of potentiostat electrode connecting ends and electrolytic cell with
It is no.
Further, the IV conversion circuit uses feedback type electric flow measuring method, including the 3rd operational amplifier and the 4th
Operational amplifier, wherein, the 3rd operational amplifier forms current follower, output voltage homopolarity galvanic current with feedback resistance
Proportional, the polarization current signal that will be measured changes into voltage signal, by the four-operational amplifier, obtains and controls
Voltage parameters of the voltage EOUT with phase change.
Further, in addition to：Multiway analog switch, the multiway analog switch is connected with the feedback resistance, for selecting
Select the feedback resistance for switching different resistances.
Further, to the power supply in reversely addition type potentiostat and the IV converted measurement circuits, digitally and mould
Intend isolated and separately connected up, including, by analog power, analog element and simulation with digital power, digital element and
Digitally carry out magnetic bead isolation.
The embodiment of the present invention also provides a kind of electro-chemical measuring apparatus, including：Function generator, above-described embodiment provide
Reverse addition type potentiostat and IV converted measurements circuit, reception signal acquisition circuit and microcontroller, wherein, the function hair
The input of raw device is connected with the microcontroller, the output end of the function generator and the high-precision reverse addition type
The input of potentiostat and IV converted measurement circuits is connected, for producing required control voltage；It is described it is high-precision reversely plus
The output end of French potentiostat and IV converted measurement circuits is connected with the reception signal acquisition circuit, for according to the control
Voltage processed performs the control and measurement of signal, and the polarization current exported in electrochemical reaction process is converted into voltage signal；Institute
The output end for stating reception signal acquisition circuit is connected with the microcontroller, for receiving the signal after measuring.
Further, the function generator uses DA digital analog converters, and the reception signal acquisition circuit uses AD moduluses
Converter.
Reverse addition type potentiostat and IV converted measurements electricity available for electrochemical measurement according to embodiments of the present invention
Road, have the advantages that：
(1) under the control voltage of high speed, there is higher stability and conversion accuracy；
(2) current measurement high resolution, it is reproducible；
(3) good Anti-interference Design is provided, so as to ensure that the job stability of circuit.
The additional aspect of the present invention and advantage will be set forth in part in the description, and will partly become from the following description
Obtain substantially, or recognized by the practice of the present invention.
Brief description of the drawings
The above-mentioned and/or additional aspect and advantage of the present invention will become in the description from combination accompanying drawings below to embodiment
Substantially and it is readily appreciated that, wherein：
Fig. 1 is the schematic diagram according to reverse addition type potentiostat and IV the converted measurement circuit of the embodiment of the present invention；
Fig. 2 is the circuit theory diagrams changed according to the potentiostat and its IV of the embodiment of the present invention；
Fig. 3 is the schematic diagram according to the sensitivity selection circuit of the embodiment of the present invention；
Fig. 4 is the Anti-interference Design schematic diagram according to the embodiment of the present invention；
Fig. 5 is the system block diagram according to the electro-chemical measuring apparatus of the embodiment of the present invention.
Embodiment
Embodiments of the invention are described below in detail, the example of embodiment is shown in the drawings, wherein identical from beginning to end
Or similar label represents same or similar element or the element with same or like function.Retouched below with reference to accompanying drawing
The embodiment stated is exemplary, it is intended to for explaining the present invention, and is not considered as limiting the invention.
As shown in figure 1, reverse addition type potentiostat and IV the converted measurement circuit of the embodiment of the present invention, including：Permanent electricity
Position device 100, IV conversion circuit 200, electrolytic cell 300.In one embodiment of the invention, potentiostat 100 and IV conversion electricity
Road 200 uses integrated operational amplifier.Function generator uses DA digital analog converters, and reception signal acquisition circuit uses AD moulds
Number converter.
In general electrochemical reaction process, polarization current maximum magnitude is mA levels, and current measurement resolution ratio is less than 1nA.
Conventional operational amplifier all has the current output capability of mA levels.To prevent the wave distortion of control voltage, to potentiostat
100 and IV conversion circuit 200 in the selection of amplifier, it is necessary to emphatically consider index be input offset voltage, input biased electrical
Stream and open-loop gain.Therefore, the integrated chip AD8627 that is used in potentiostat 100 of the invention, IV conversion circuit 200 and
AD8608, for its input offset voltage in uV levels, input bias current is pA levels, and open-loop gain is more than 100Db, in coincident circuit
Requirement.
Preferably, integrated operational amplifier chip of the potentiostat 100 from model AD8627；IV conversion circuit 200
From model AD8608 integrated operational amplifier chip.
Specifically, the positive input and function generator of potentiostat 100 is connected, the reverse input of potentiostat 100
And output end be connected with electrolytic cell 300, with by potentiostat 100 and electrolytic cell 300 formed negative-feedback amplification closed loop,
So that reference voltage changes with the regulation of control voltage, and compared with the constant reference voltage of working electrode, obtain model
The scanning voltage of ± 2V changes is trapped among, finally realizes that polarization current exports.
Fig. 2 is the circuit theory diagrams changed according to the potentiostat 100 and its IV of the embodiment of the present invention.Wherein, WE, RE,
CE represents working electrode, reference electrode and auxiliary electrode respectively, and polarization current i is cathodic reduction electric current, and provides cathode current
For just.
As shown in Fig. 2 potentiostat 100 includes the first operational amplifier A 2, it is defeated with the negative sense of the first operational amplifier A 2
Enter first resistor R1, second resistance R2 and 3rd resistor R3 that end is respectively connected with, the positive input of the first operational amplifier A 2
Ground connection, forms reverse add circuit, the reverse add circuit includes three branch roads, and the electric current of three branch roads is in the first operation amplifier
Device A2 reverse input end add and, each electric current sum of inflow is zero.
Specifically, three branch roads include：
Tie point：The input of first operational amplifier A 2 receives control voltage EOUT, through the first rheostat RW1 and the
One resistance R1 acts on the first operation amplifier A2 reverse input end；
Second branch road：The output end of second operational amplifier A 2 is connected with 3rd resistor R3, forms voltage follower conduct
Backfeed loop is connected to reference electrode.Because operational amplifier has high input impedance, therefore do not had on reference electrode big
Electric current flows through, so as to avoid the interference of the electrode system to being surveyed.The feedback signal of reference electrode current potential is put through the second computing
Big device A1 and 3rd resistor R3 acts on the reverse input end of the first operational amplifier A 2.
3rd branch road：External+5V a reference sources are linked into first by the second rheostat RW2 and second resistance R2 in circuit
The reverse input end of operational amplifier A 2, to be returned to zero to system.
Specifically, the bias current of amplifier, solution resistance can produce certain influence to control voltage in loop, therefore,
External+5V a reference sources are linked into A2 reverse input end by rheostat RW2 and resistance R2 in circuit, so as to be carried out to system
Zeroing.In the circuit of this part, operational amplifier A 2 and A3 in-phase input end+2.5V a reference sources, while be also work electricity
The constant potential point of pole.When input signal EOUT changes between 1V to 4V, the voltage change range of reference electrode for 4.5V~
0.5V, equivalent working electrode are -2V~2V relative to the potential change scope of reference electrode, so as to meet scanning voltage ±
The design requirement changed between 2V.
With reference to figure 2, the negative input of IV conversion circuit 200 connects electrolytic cell 300, the positive input of IV conversion circuit 200
End ground connection, the output end of IV conversion circuit 200 is connected with follow-up reception signal acquisition circuit, for by electrolytic cell 300 in electricity
The polarization current exported in chemical reaction process is converted into voltage signal, so that follow-up reception signal acquisition circuit carries out data
Collection and processing.
Specifically, as shown in Fig. 2 IV conversion circuit 200 uses feedback type electric flow measuring method, including the 3rd operation amplifier
Device A3B and four-operational amplifier A3C, wherein, the 3rd operational amplifier A 3B and feedback resistance Rf forms current follower, defeated
Go out voltage same polarization current in proportion, the polarization current signal that will be measured changes into voltage signal, by the 4th operation amplifier
Device A3C, obtain the voltage parameter with phase change with control voltage EOUT.
Specifically, the electric current for flowing into working electrode is converted into voltage signal by IV conversion circuit 200, is turned for AD acquisition circuits
Change digital quantity into.The present invention use feedback type electric flow measuring method, and the operational amplifier of selection is that internal have integrating for 4 amplifiers
Chip AD8608,2 tunnel therein amplifier has been used in circuit, has been A3B and A3C respectively.By operational amplifier A 3B and feedback electricity
Resistance Rf constitutes current follower, the influence very little of operational amplifier A D8608 Low-bias Current to polarization current i, can neglect
Slightly.Therefore the 3rd operational amplifier A 3B output voltage same polarization current in proportion, so as to the polarization current signal that will be measured
Voltage signal is changed into, by four-operational amplifier A3C, can obtain the voltage parameter with phase change with EOUT.When control electricity
When pressure EOUT changes between 1V to 4V, the output voltage range for now measuring the 3rd operational amplifier A 3B is 5V-0V, through anti-
Output area is 0V-2.5V after to scaling circuit A3C, by AD acquisition circuit measuring operational amplifiers A3C output voltage
The measurement to polarization current and record can be achieved.
In electrochemical analysis test, polarization current size to be measured is often not under different electrochemical system test conditions
With, it is therefore desirable to user selects suitable sensitivity according to actual conditions, so as to ensure the accuracy of current detecting.For not
Same sensitivity can use different feedback resistance Rf.In one embodiment of the invention, in addition to：Multi-channel analog is opened
Close, multiway analog switch is connected with feedback resistance, for selecting the feedback resistance of the different resistances of switching.
Preferably, multiway analog switch selects model MAX4617.
Specifically, the switching to Rf is realized using multiway analog switch MAX4617, and in Rf both ends parallel filtering electric capacity Cf
To form low pass filter, schematic diagram is as shown in figure 3, the circuit of this part is linked into Fig. 2 with IWE and OWE end points, and is substituted
Rf and Cf loops in Fig. 2.
In addition, as shown in Fig. 2 present invention additionally comprises：First to the 3rd analog switch, the first analog switch and the first computing
The output end of amplifier is connected with an electrode of electrolytic cell 300, and the second analog switch is positive defeated with the second operational amplifier
Enter end with another electrode of electrolytic cell 300 to be connected, the 3rd analog switch and IV conversion circuit 200 and electrolytic cell 300 it is another
Individual electrode is connected, for by switch control the conducting of the three of potentiostat 100 electrode connecting ends and electrolytic cell 300 with
It is no.
Specifically, in order to control test process, also need to control the three of potentiostat 100 electrode connecting ends by switching
Whether is conducting with electrolytic cell 300.Realize that such function can be realized by analog switch, first in this circuit to
3rd analog switch is using low on-resistance, the DG419 of response quickly.As shown in Fig. 2 the first to the 3rd analog switch distinguishes Ei
D1, D2 and D3., can be in the external AD of output end of operational amplifier A 1 because operational amplifier has the output impedance of very little
Acquisition Circuit, realize to the real-time measurement of scanning voltage and record.
The whole loop of the present invention is made up of the analog device of analog device and a part of Digital Signals, and is simulated
The anti-interference of device is poor, therefore when carrying out PCB design, power supply should be carried out, digitally with the isolation on simulation ground and point
Open wiring, and insulating power supply.As shown in figure 5, to the power supply in reverse addition type potentiostat 100 and IV converted measurement circuits
Ground, digitally isolated with simulation and separately connected up, including, it is by analog power, analog element and simulation electric with numeral
Source, digital element and digitally progress magnetic bead isolation, realize Anti-interference Design.
As shown in figure 5, the electro-chemical measuring apparatus of the embodiment of the present invention, including：Function generator 2, above-described embodiment carry
Reverse addition type potentiostat and IV converted measurements circuit 1, reception signal acquisition circuit 3 and the microcontroller 4 supplied.
Specifically, the input of function generator 2 is connected with microcontroller 4, the output end and high accuracy of function generator 2
The input of reverse addition type potentiostat and IV converted measurements circuit 1 be connected, for producing required control voltage.High accuracy
The output end of reverse addition type potentiostat and IV converted measurements circuit 1 be connected with reception signal acquisition circuit 3, for basis
Control voltage performs the control and measurement of signal, and the polarization current exported in electrochemical reaction process is converted into voltage signal.
The output end of reception signal acquisition circuit 3 is connected with microcontroller, for receiving the signal after measuring.Microcontroller 4 is mainly adopted
By the use of Embedded microprocessor as master controller, the work(such as realization automatically controls, data acquisition, data processing, display and transmission
Energy.
In one embodiment of the invention, function generator 2 uses DA digital analog converters, reception signal acquisition circuit 3
Using AD analog-digital converters.
Reverse addition type potentiostat and IV converted measurements electricity available for electrochemical measurement according to embodiments of the present invention
Road, have the advantages that：
(1) under the control voltage of high speed, there is higher stability and conversion accuracy；
(2) current measurement high resolution, it is reproducible；
(3) good Anti-interference Design is provided, so as to ensure that the job stability of circuit.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or the spy for combining the embodiment or example description
Point is contained at least one embodiment or example of the present invention.In this manual, to the schematic representation of above-mentioned term not
Necessarily refer to identical embodiment or example.Moreover, specific features, structure, material or the feature of description can be any
One or more embodiments or example in combine in an appropriate manner.
Although embodiments of the invention have been shown and described above, it is to be understood that above-described embodiment is example
Property, it is impossible to limitation of the present invention is interpreted as, one of ordinary skill in the art is not departing from the principle and objective of the present invention
In the case of above-described embodiment can be changed within the scope of the invention, change, replace and modification.The scope of the present invention
By appended claims and its equivalent limit.
Claims (10)
1. a kind of reversely addition type potentiostat and IV converted measurement circuits, it is characterised in that including：Potentiostat, IV conversions
Circuit, electrolytic cell, wherein,
The positive input and function generator of the potentiostat is connected, the reverse input and output end of the potentiostat
It is connected with the electrolytic cell, to be made up of the closed loop of negative-feedback amplification, output stage the potentiostat and the electrolytic cell
Galvanic current；
The negative input of the IV conversion circuit meets the electrolytic cell, the positive input ground connection of the IV conversion circuit, institute
The output end for stating IV conversion circuit is connected with follow-up reception signal acquisition circuit, for by the electrolytic cell in electrochemical reaction
During the polarization current that exports be converted into voltage signal, so that the follow-up reception signal acquisition circuit carries out data acquisition
And processing.
2. reversely addition type potentiostat and IV converted measurement circuits as claimed in claim 1, it is characterised in that the permanent electricity
Position device and the IV conversion circuit use integrated operational amplifier.
3. reversely addition type potentiostat and IV converted measurement circuits as claimed in claim 1, it is characterised in that the permanent electricity
Position device includes the first operational amplifier, the first resistor being respectively connected with the negative input of first operational amplifier, the
Two resistance and 3rd resistor, the positive input ground connection of first operational amplifier, form reverse add circuit, this reversely adds
Method circuit includes three branch roads, and the electric current of three branch roads adds with inflow in the reverse input end of the first operational amplifier
Each electric current sum is zero.
4. reversely addition type potentiostat and IV converted measurement circuits as claimed in claim 3, it is characterised in that described three
Branch road includes：
Tie point：The input of first operational amplifier receives control voltage EOUT, through the first rheostat and described the
One resistance acts on the reverse input end of first operational amplifier；
Second branch road：The output end of second operational amplifier is connected with the 3rd resistor, forms voltage follower as feedback
Loop is connected to reference electrode, and the feedback signal of the reference electrode current potential is made through the second operational amplifier and the 3rd resistor
Reverse input end for first operational amplifier；
3rd branch road：External+5V a reference sources are linked into described first by the second rheostat and the second resistance in circuit
The reverse input end of operational amplifier, to be returned to zero to system.
5. reversely addition type potentiostat and IV converted measurement circuits as claimed in claim 4, it is characterised in that also include：
First to the 3rd analog switch, the output end of first analog switch and first operational amplifier and the electrolytic cell
One electrode is connected, the positive input of second analog switch and second operational amplifier and the electrolytic cell it is another
One electrode is connected, and the 3rd analog switch is connected with another electrode of the IV conversion circuit and the electrolytic cell, uses
In whether controlling the conducting of the three of potentiostat electrode connecting ends and electrolytic cell by switching.
6. reversely addition type potentiostat and IV converted measurement circuits as claimed in claim 1, it is characterised in that the IV turns
Change circuit and use feedback type electric flow measuring method, including the 3rd operational amplifier and four-operational amplifier, wherein, the described 3rd
Operational amplifier forms current follower, output voltage same polarization current in proportion, the polarization electricity that will be measured with feedback resistance
Stream signal changes into voltage signal, by the four-operational amplifier, obtains the voltage with phase change with control voltage EOUT
Parameter.
7. reversely addition type potentiostat and IV converted measurement circuits as claimed in claim 6, it is characterised in that also include：
Multiway analog switch, the multiway analog switch are connected with the feedback resistance, for selecting the feedback for switching different resistances electric
Resistance.
8. reversely addition type potentiostat and IV converted measurement circuits as claimed in claim 1, it is characterised in that to described anti-
Power supply into addition type potentiostat and IV converted measurement circuits, digitally isolated with simulation and separately connected up,
Including, by analog power, analog element and simulation with digital power, digital element and digitally carry out magnetic bead isolate.
A kind of 9. electro-chemical measuring apparatus, it is characterised in that including：Any one of function generator, claim 1-8 are described reversely
Addition type potentiostat and IV converted measurements circuit, reception signal acquisition circuit and microcontroller, wherein,
The input of the function generator is connected with the microcontroller, the output end of the function generator with it is described high-precision
The input of reverse addition type potentiostat and IV the converted measurement circuit of degree is connected, for producing required control voltage；
The high-precision reversely output end of addition type potentiostat and IV converted measurement circuits gathers with the reception signal
Loop is connected, for performing the control and measurement of signal, the pole that will be exported in electrochemical reaction process according to the control voltage
Galvanic current is converted into voltage signal；
The output end of the reception signal acquisition circuit is connected with the microcontroller, for receiving the signal after measuring.
10. electro-chemical measuring apparatus as claimed in claim 9, it is characterised in that the function generator is turned using DA digital-to-analogues
Parallel operation, the reception signal acquisition circuit use AD analog-digital converters.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110646494A (en) * | 2018-06-27 | 2020-01-03 | 英飞凌科技股份有限公司 | Circuit arrangement for operating an electrochemical cell and corresponding method |
| CN111693582A (en) * | 2020-05-26 | 2020-09-22 | 杭州电子科技大学 | Portable front end device of electrochemistry detection high accuracy |
| CN112630287A (en) * | 2020-12-14 | 2021-04-09 | 山东理工大学 | Multi-channel organophosphorus pesticide rapid detector and detection method based on Internet of things |
| CN115061523A (en) * | 2022-05-20 | 2022-09-16 | 山西大学 | Portable high-resolution constant potential system |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110646494A (en) * | 2018-06-27 | 2020-01-03 | 英飞凌科技股份有限公司 | Circuit arrangement for operating an electrochemical cell and corresponding method |
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| CN111693582A (en) * | 2020-05-26 | 2020-09-22 | 杭州电子科技大学 | Portable front end device of electrochemistry detection high accuracy |
| CN112630287A (en) * | 2020-12-14 | 2021-04-09 | 山东理工大学 | Multi-channel organophosphorus pesticide rapid detector and detection method based on Internet of things |
| CN115061523A (en) * | 2022-05-20 | 2022-09-16 | 山西大学 | Portable high-resolution constant potential system |
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| CN107688048B (en) | 2024-07-30 |
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