CN102253100A - Solid electrolyte-type hydrogen detector and detection method of hydrogen concentration realized by the hydrogen detector - Google Patents

Abstract

The invention relates to a solid electrolyte-type hydrogen detector and a detection method of hydrogen concentration realized by the hydrogen detector, and belongs to the detection field; the invention solves the problems of high-temperature operation, short life, low sensitivity, long response time, and poor stability of present hydrogen sensor detectors. The hydrogen detector of the invention comprises a solid electrolyte-type hydrogen sensor, a voltage follower, an A/D conversion circuit, and a single-chip microcomputer; the solid electrolyte-type hydrogen sensor ionizes the hydrogen in environment to be detected; an electromotive force signal generated by the solid electrolyte-type hydrogen sensor is outputted to the voltage follower; the voltage follower outputs a following electromotive force signal to the A/D conversion circuit; the A/D conversion circuit converts the inputted simulated following electromotive force signal into a digital signal, and outputs the converted digital electromotive force signal to the single-chip microcomputer; the single-chip microcomputer outputs the hydrogen concentration of the environment to be detected based on the inputted digital electromotive force signal.

Description

Solid electrolyte type hydrogen detector and adopt this hydrogen detector to realize the detection method of density of hydrogen

Technical field

The present invention relates to a kind of solid electrolyte type hydrogen detector and adopt this hydrogen detector to realize the detection method of density of hydrogen, belong to detection range.

Background technology

Hydrogen energy source is as a kind of new green power, have widely distributed (having water to get final product hydrogen manufacturing), renewable never exhausted, pollution-free, energy density is big and wide application etc. more and more is subjected to people's favor, and obtains Application and Development widely in industries such as chemical industry, space flight, military projects.

Hydrogen is flammable explosive gas, very easily blasts with air mixed.In order to ensure the industrial processes that there are hydrogen and the security of use, need hydrogen gas sensor to detect, and send control information.One of basic gordian technique that the hydrogen detection technique develops as hydrogen energy source, its research and development becomes more and more important, and national 921 manned astro-engineerings are classified the continuous 0-2% density of hydrogen that shows as research topic.Therefore, study the important need that high performance hydrogen gas sensor has become national economy field and national defence.

At present, also there are many technical matterss in the hydrogen gas sensor that use in market, as the semi-conductor type hydrogen gas sensor need under hot conditions, heat, power consumption is big, and can only qualitative detection, can't realize the accurate measurement of concentration; The catalytic combustion-type hydrogen gas sensor also is a kind of hot type element of hot operation, and its shortcoming is easy poisoning, and power consumption is big, and stability is bad; Galvanochemistry type hydrogen gas sensor does not need heating work, but operating temperature range is narrower, and electrolytic solution is easily dry, and the life-span is short; The optical type hydrogen gas sensor is that the quick material of hydrogen is coated onto on the optical device, and this sensor is prone to delamination, foaming phenomenon after repeatedly circulating, thereby serviceable life is shorter.In addition, at present also there is following shortcoming in hydrogen gas sensor in the practical application: 1. can not produce in wide density of hydrogen scope and the linear response of the quick concentration of hydrogen, insufficient sensitivity height, response time are long; 2. can not solve the influence of temperature, humidity, pressure etc. well; 3. stable bad.For solving the problem that the sensor exists.

Summary of the invention

The present invention seeks to provides a kind of solid electrolyte type hydrogen detector and has adopted this hydrogen detector to realize the detection method of density of hydrogen in order to solve existing hydrogen gas sensor detector hot operation, the life-span is short, sensitivity is not high, the response time is long, stability is bad problem.

Solid electrolyte type hydrogen detector of the present invention, it comprises solid electrolyte type hydrogen gas sensor, voltage follower, A/D change-over circuit and single-chip microcomputer,

Hydrogen in the solid electrolyte type hydrogen gas sensor ionization environment to be measured, the electromotive force signal that the solid electrolyte type hydrogen gas sensor produces is exported to voltage follower, voltage follower will be followed electromotive force signal and be exported to the A/D change-over circuit, the electromotive force signal of following of the simulation that the A/D change-over circuit will be imported converts digital signal to, and the digitalized electric gesture signal after will changing exports to single-chip microcomputer, and single-chip microcomputer is exported density of hydrogen in the environment to be measured according to the digitalized electric gesture signal of input.

The method that adopts above-mentioned solid electrolyte type hydrogen detector to realize that density of hydrogen detects is:

Adopt the hydrogen in the solid electrolyte type hydrogen gas sensor ionization environment to be measured, the electromotive force signal that this solid electrolyte type hydrogen gas sensor produces is E;

The electromotive force signal E that the single-chip microcomputer basis receives is a density of hydrogen that obtains in the environment to be measured by formula:

Formula one: $P=g(\left(\underset{m=1}{\overset{K}{\mathrm{\Σ}}}{V}_{m}f(W_{m}E+b_{1m})\right)+b_2),$

In the formula: P is a density of hydrogen;

F (.) is the hidden layer activation function, and hidden layer is selected the logarithmic activation function for use:

G (.) is the output layer activation function, and output layer is selected linear function for use: y=ax+b;

W _mWeight coefficient for the input layer activation function;

V _mWeight coefficient for the hidden layer activation function;

b _1mBe the hidden layer deviation;

b ₂Be the output layer deviation;

The weight coefficient W of training input layer activation function _m, the hidden layer activation function weight coefficient V _m, hidden layer deviation b _1mWith output layer deviation b ₂, and then error of calculation e, when error stops training during less than error threshold T, T=0.01～0.03, and with the W of output _m, V _m, b _1m, b ₂Net result substitution formula one in obtain density of hydrogen in the environment to be measured.

The weight coefficient W of input layer activation function _m, the hidden layer activation function weight coefficient V _m, hidden layer deviation b _1mWith output layer deviation b ₂Training process be:

b ₂Be the output layer deviation, and by formula

Training is obtained,

Wherein,

For error function to b ₂Partial derivative,

In the formula,

Be neuron number;

W _mBe the weight coefficient of input layer activation function, and by formula

Training is obtained,

Wherein,

For error function to W _mPartial derivative, P (e in the formula _i) ' _Wm=a * V _m* f ¹' * e _i, f wherein ¹' be that logarithmic function is to input layer Q (i)=W _me _i+ b _1mThe local derviation value,

V _mBe the weight coefficient of hidden layer activation function, and by formula

Training is obtained,

Wherein,

P (e in the formula _i) ' _Vm=a * f (Wm * e _i+ b _1m);

b _1mBe the hidden layer deviation, and by formula

Training is obtained,

Wherein,

For error function to b _1mPartial derivative,

In the formula $P{\left(e_i\right)}_{b_{1m}}^{\′}=a\×V_m\×f^{1\′}.$

Error e is obtained by following formula:

$e=\frac{1}{N}\underset{i=1}{\overset{N}{\mathrm{\Σ}}}{(P_{\left({e_i}^{\′}\right)}-{P_i}^{\′})}^2$

In the formula:

Be training output result, P _i' be the sample point output valve, e _iBe the sample point input value, N is a sample number.

Advantage of the present invention: solid electrolyte type hydrogen detector of the present invention is operated under the normal temperature state, has advantage highly sensitive, that the response time short, the life-span is long, main performance index:

(1) need not heating, can work at normal temperatures, effectively reduce power consumption, increase explosion-proof security, effectively reduce failure mode, the long service life that material causes under hot conditions;

(2) sensitivity is less than 100PPm;

(3) response time is less than 10s;

(4) life-span was greater than 5 years;

(5) the designed solid electrolyte hydrogen detector based on the adaptive algorithm model, that adopts that processor realizes electromotive force and density of hydrogen separates measurement range 0-5%.

Description of drawings

Fig. 1 is the structural representation of solid electrolyte type hydrogen detector of the present invention.

Embodiment

Embodiment one: below in conjunction with Fig. 1 present embodiment is described, the described solid electrolyte type hydrogen of present embodiment detector comprises solid electrolyte type hydrogen gas sensor 1, voltage follower 2, A/D change-over circuit 3 and single-chip microcomputer 4,

Hydrogen in the solid electrolyte type hydrogen gas sensor 1 ionization environment to be measured, the electromotive force signal that solid electrolyte type hydrogen gas sensor 1 produces is exported to voltage follower 2, voltage follower 2 will be followed electromotive force signal and be exported to A/D change-over circuit 3, the electromotive force signal of following of the simulation that A/D change-over circuit 3 will be imported converts digital signal to, and the digitalized electric gesture signal after will changing exports to single-chip microcomputer 4, and single-chip microcomputer 4 is exported density of hydrogen in the environment to be measured according to the digitalized electric gesture signal of input.

Solid electrolyte type hydrogen gas sensor 1 has normal electrode and contrast electrode, and described normal electrode is selected platinum electrode for use, and contrast electrode is selected tungsten electrode for use, and electrolyte adopts phosphotungstic acid.

Problem at present hydrogen gas sensor existence, carry out the research of solid electrolyte hydrogen gas sensor, this electrode and electrolyte and signal processing technology are done comprehensive research, design and to work, have high sensitivity, the response time is short, the life-span is long solid electrolyte hydrogen measuring instrument at normal temperatures.

The electrochemical reaction of solid electrolyte type hydrogen gas sensor 1 mainly is to occur in three places of practising physiognomy.Three practise physiognomy is the intersection of electrolyte, electrode and ambient gas environment, after hydrogen touches platinum electrode in the surrounding environment, hydrogen molecule can be H+ and electronics by catalytic decomposition, and electronics can be sent on the contrast electrode through electrolyte, will cause the variation of electromotive force between two electrodes like this.

Embodiment two: present embodiment is described further embodiment one, the described solid electrolyte type hydrogen of present embodiment detector also comprises EEPROM5 and LCD display 6, the storage output terminal of single-chip microcomputer 4 links to each other with the input end of EEPROM5, and the demonstration output terminal of single-chip microcomputer 4 links to each other with the input end of LCD display.

The EEPROM5 that present embodiment increased, the enforcement storage that can realize surveying measurement data.

The LCD display 6 that present embodiment increased can realize the real-time demonstration of measurement data.

Embodiment three: present embodiment is described further embodiment one, the described solid electrolyte type hydrogen of present embodiment detector also comprises linear voltage stabilization module 7 and reference source 8, the input termination AC power of linear voltage stabilization module 7, first power output end of linear voltage stabilization module 7 links to each other with the power input of single-chip microcomputer 4, the second source output terminal of linear voltage stabilization module 7 links to each other with the power input of A/D change-over circuit 3, the 3rd power output end of linear voltage stabilization module 7 links to each other with the input end of reference source 8, and the output terminal of reference source 8 links to each other with the reference power supply input end of A/D change-over circuit 3.

Embodiment four: present embodiment is described to be to adopt embodiment one, two or three described solid electrolyte type hydrogen detectors to realize the detection method of density of hydrogen, and the process of this method is:

Adopt the hydrogen in the solid electrolyte type hydrogen gas sensor 1 ionization environment to be measured, the electromotive force signal that this solid electrolyte type hydrogen gas sensor 1 produces is E;

The electromotive force signal E that single-chip microcomputer 4 bases receive is a density of hydrogen that obtains in the environment to be measured by formula,

Formula one: $P=g(\left(\underset{m=1}{\overset{K}{\mathrm{\Σ}}}{V}_{m}f(W_{m}E+b_{1m})\right)+b_2),$

In the formula: P is a density of hydrogen;

F (.) is the hidden layer activation function, and hidden layer is selected the logarithmic activation function for use:

G (.) is the output layer activation function, and output layer is selected linear function for use: y=ax+b;

W _mWeight coefficient for the input layer activation function;

V _mWeight coefficient for the hidden layer activation function;

b _1mBe the hidden layer deviation;

b ₂Be the output layer deviation;

The weight coefficient W of training input layer activation function _m, the hidden layer activation function weight coefficient V _m, hidden layer deviation b _1mWith output layer deviation b ₂, and then error of calculation e, when error stops training during less than error threshold T, T=0.01～0.03, and with the W of output _m, V _m, b _1m, b ₂Net result substitution formula one in obtain density of hydrogen in the environment to be measured.

When error meets the demands, train and stop.Thereby obtain W _m, V _m, b _1m, b ₂Net result.Utilize this result can obtain the density of hydrogen under the different electromotive force in the environment.

The weight coefficient W of input layer activation function _m, the hidden layer activation function weight coefficient V _m, hidden layer deviation b _1mWith output layer deviation b ₂Training process be:

b ₂Be the output layer deviation, and by formula Training is obtained,

Wherein,

For error function to b ₂Partial derivative,

In the formula, Be neuron number;

W _mBe the weight coefficient of input layer activation function, and by formula

Training is obtained,

Wherein,

For error function to W _mPartial derivative,

P (e in the formula _i) ' _Wm=a * V _m* f ¹' * e _i, f wherein ¹' be that logarithmic function is to input layer Q (i)=W _me _i+ b _1mThe local derviation value,

V _mBe the weight coefficient of hidden layer activation function, and by formula

Training is obtained,

Wherein,

P (e in the formula _i) ' _Vm=a * f (Wm * e _i+ b _1m);

b _1mBe the hidden layer deviation, and by formula

Training is obtained,

Wherein,

For error function to b _1mPartial derivative,

In the formula $P{\left(e_i\right)}_{b_{1m}}^{\′}=a\×V_m\×f^{1\′}.$

Error e is obtained by following formula:

$e=\frac{1}{N}\underset{i=1}{\overset{N}{\mathrm{\Σ}}}{(P_{\left({e_i}^{\′}\right)}-{P_i}^{\′})}^2$

In the formula: Be training output result, P _i' be the sample point output valve, e _iBe the sample point input value, N is a sample number.

Claims (7)

1. solid electrolyte type hydrogen detector is characterized in that, it comprises solid electrolyte type hydrogen gas sensor (1), voltage follower (2), A/D change-over circuit (3) and single-chip microcomputer (4),

Hydrogen in solid electrolyte type hydrogen gas sensor (1) the ionization environment to be measured, the electromotive force signal that solid electrolyte type hydrogen gas sensor (1) produces is exported to voltage follower (2), voltage follower (2) will be followed electromotive force signal and be exported to A/D change-over circuit (3), the electromotive force signal of following of the simulation that A/D change-over circuit (3) will be imported converts digital signal to, and the digitalized electric gesture signal after will changing exports to single-chip microcomputer (4), and single-chip microcomputer (4) is exported density of hydrogen in the environment to be measured according to the digitalized electric gesture signal of input.

2. solid electrolyte type hydrogen detector according to claim 1, it is characterized in that, it also comprises EEPROM (5) and LCD display (6), the storage output terminal of single-chip microcomputer (4) links to each other with the input end of EEPROM (5), and the demonstration output terminal of single-chip microcomputer (4) links to each other with the input end of LCD display.

3. solid electrolyte type hydrogen detector according to claim 2, it is characterized in that, it also comprises linear voltage stabilization module (7) and reference source (8), the input termination AC power of linear voltage stabilization module (7), first power output end of linear voltage stabilization module (7) links to each other with the power input of single-chip microcomputer (4), the second source output terminal of linear voltage stabilization module (7) links to each other with the power input of A/D change-over circuit (3), the 3rd power output end of linear voltage stabilization module (7) links to each other with the input end of reference source (8), and the output terminal of reference source (8) links to each other with the reference power supply input end of A/D change-over circuit (3).

4. solid electrolyte type hydrogen detector according to claim 1, it is characterized in that solid electrolyte type hydrogen gas sensor (1) has normal electrode and contrast electrode, described normal electrode is selected platinum electrode for use, contrast electrode is selected tungsten electrode for use, and electrolyte adopts phosphotungstic acid.

5. adopt the detection method of the density of hydrogen of the described solid electrolyte type hydrogen of claim 1 detector realization, it is characterized in that the process of this method is:

Adopt the hydrogen in solid electrolyte type hydrogen gas sensor (1) the ionization environment to be measured, the electromotive force signal that this solid electrolyte type hydrogen gas sensor (1) produces is E;

The electromotive force signal E that single-chip microcomputer (4) basis receives is a density of hydrogen that obtains in the environment to be measured by formula,

Formula one: $P=g(\left(\underset{m=1}{\overset{K}{\mathrm{\Σ}}}{V}_{m}f(W_{m}E+b_{1m})\right)+b_2),$

In the formula: P is a density of hydrogen;

F (.) is the hidden layer activation function, and hidden layer is selected the logarithmic activation function for use:

G (.) is the output layer activation function, and output layer is selected linear function for use: y=ax+b;

W _mWeight coefficient for the input layer activation function;

V _mWeight coefficient for the hidden layer activation function;

b _1mBe the hidden layer deviation;

b ₂Be the output layer deviation;

The weight coefficient W of training input layer activation function _m, the hidden layer activation function weight coefficient V _m, hidden layer deviation b _1mWith output layer deviation b ₂, and then error of calculation e, when error stops training during less than error threshold T, T=0.01～0.03, and with the W of output _m, V _m, b _1m, b ₂Net result substitution formula one in obtain density of hydrogen in the environment to be measured.

6. the detection method of density of hydrogen according to claim 5 is characterized in that, the weight coefficient W of input layer activation function _m, the hidden layer activation function weight coefficient V _m, hidden layer deviation b _1mWith output layer deviation b ₂Training process be:

b ₂Be the output layer deviation, and by formula Training is obtained,

Wherein,

For error function to b ₂Partial derivative,

In the formula,

Be neuron number;

W _mBe the weight coefficient of input layer activation function, and by formula

Training is obtained,

Wherein, For error function to W _mPartial derivative,

P (e in the formula _i) ' _Wm=a * V _m* f ¹' * e _i, f wherein ¹' be that logarithmic function is to input layer Q (i)=W _me _i+ b _1mThe local derviation value,

V _mBe the weight coefficient of hidden layer activation function, and by formula

Training is obtained,

Wherein, $\▿\mathrm{EVm}=\frac{2}{N}\underset{i=1}{\overset{k}{\mathrm{\Σ}}}\left[(P\left(e_i\right)-P_i^{\′})P{\left(e_i\right)}_{\mathrm{Vm}}^{\′}\right],$

P (e in the following formula _i) ' _Vm=a * f (Wm * e _i+ b _1m);

b _1mBe the hidden layer deviation, and by formula

Training is obtained,

Wherein, For error function to b _1mPartial derivative,

In the formula $P{\left(e_i\right)}_{b_{1m}}^{\′}=a\×V_m\×f^{1\′}.$

7. the detection method of density of hydrogen according to claim 5 is characterized in that, error e is obtained by following formula:

$e=\frac{1}{N}\underset{i=1}{\overset{N}{\mathrm{\Σ}}}{(P_{\left({e_i}^{\′}\right)}-{P_i}^{\′})}^2$

In the formula:

Be training output result, P _i' be the sample point output valve, e _iBe the sample point input value, N is a sample number.

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