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**Hongqing Cao', Jingxian Yuz ,Lishan Kang'
**

$ate Key Laboratory of Software Engineering; Wuhan University, Wuhan 430072, China -email: (jxyu, kang)@whu,edu.cn 1 -Depanment of Chemistry, Wuhan University, Wuhan 430072, China email: jxyu@whu.edu.cn least.square method [3][41. But Some problems exist in using this method, like the sensitivity to initial values, the difficulty to compute the partial derivative expression of each parameter for some complex circuits and the great likelihwd to trap into local optima. In view of all above analysis, we consider that the most desirable way to analyze electrochemical impedance data is to build the equivalent circuit model automatically as well as optimize the component parameters simultaneously by using some intelligent approach. Hence this paper proposes a hybrid evolutionary modeling algorithm (HEMA) to approach this modeling task. Its main idea is to embed a genetic algorithm (CA) in gene expression programming (GEP) where GEP is employed to discover and optimize the structure of a circuit, while the CA is employed to optimize the parameters of all the electric components contained in the circuit.

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Abstract- This paper proposes an evolutionary approach to build the equivalent circuit model for electrochemical impedance spectroscopy. It works by using a hybrid evolutionary modeling algorithm (HEMA) whose main idea is tn embed a genetic algorithm (GA) in gene expression programming (GEP) where GEP is employed to discoverand optimize the structure of a circuit, while the GA is employed to optimize the parameters of all the electric components contained in the circuit. By running the HEMA, the computer can automatically find suitable circuit structures as well as optimize the component parameters simultaneously. Compared with most available methods, it has the advantages of automation . of modeling process, great diversity of model,structnres, high stability and efficiency of parameter optimization.

1 Introduction .

. . , . With ths development of electrochemical measurement technique, the acquisition of impedance data has become much easier than before. On the contrary, how to analyze and interpret those data is considered as a complicated and arduous task. Usually the interpretation of electrochemical impedance data includes three steps. First an equivalent circuit model for the examined system is built based on the measursd electrochemical impedance spectroscopy and relevant electrochemical knowledge. Second the parameter values of all components contained in the circuit are determined by using some curve-fitting methods. Finally some lanetic parameters in the electrode, reaction are calculated according to the circuit structure and the component parameters [I]. Among those, how to build a suitable model is the most crucial step. Among the available modeling software for equivalent circuits a1 present, the EQUIVCRT software developed by Boukamp [ 2 ] is applied most widely. However the EQUlVCRT software. requires the users to have abundant electrochemical professional knowledge and research experience, which limits its application range in some degree. As for the second step, people have done much work in this field. The most popular approach adopted by people to fit the impedance datais the complex non-linear

**2 Hybrid Evolutionary Modeling Algorithm
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Gene Expression Programming (GEP) is a linear genetic programming (GP) [5-71 with fixad length invented by Ferreira [8][9] in 2001. It is the natural combination of chromosomes of GP and GA [IO] in which the genotype and the phenotype are separated. In GEP the individuals are encoded as symbolic strings of fixed length (genotype) which are then expressed as non-linear expression trees (ETS) of different sizes and shapes (phenotype). In comparison with GP, the most advantage of GEP lies in that it allows the modification of the genome using any genetic operator without restrictions, producing always syntactically correct programs. But it has a major drawback in GEP, namely the inconvenience to handle numerical constants [9]. While for our case, when building an equivalent circuit model for electrochemical impedance, it involves not only the structure of the circuit, but also the parameters of all electric components contained in the circuit. Moreover the electrochemical impedance of a circuit is rather sensitive to the values of those parameters. Hence it is expected to achieve desirable results if we can deal with those parameters separately. Based on all above considerations, we propose a hybrid evolutionary modeling algorithm (HEMA) to approach the

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1 The binary tree structure of GEP gene (a) and h e correpondenicircuit (bj 2.chromosome as the mutation points. I(b). and the two possible ways to connect them are parallel and series. despite its fixed length. For example. In multi-point mutation multiple points are randomly chosen from the ECS of the parent. n). According to the binary tree. any symbol can change into another (function or terminal). and all the new individuals produced by mutation are structurally correct programs. initialize the circuit population. CPE. C . end 21 Structure Optimization Pmcess of Circuit Models . the length of the segment and the insertion point. So. constant phase elements CPE(w. k 2 . Thus the length of the gene is 4 + 5 = 9. In this way. as linear symbolic strings of fixed length. the possible electric components include resistors (R). Thus we define the set of terminals T = {R. terminals can only change into terminals. 1:=0 below: -+R~50~~-L~82mH~R~O. the ECS of each gene is underlined and the tail of a gene is shown in bold. end output the best circuit model.represent the series connection and the parallel connection respectively. Each gene is composed of a head and a tail. the correspondent circuit can he obtained easily. in the tails. ](a) which corresponds to a circuit illustrated in Fig. we first convert it into a binary tree stmture of GP by following some rules descrikd in Ref. the structural organization of chromosomes is remained intact. we use two kinds of crossover: one-pint crossover and two-point crossover and two kinds of mutation are adopted as well: multi-point mutation and segment-insenion mutation. For distinction.the electric components contained in the circuit.1. One such gene is shown Fig.1 Representation of Chromosomes The chromosomes in GEP are represented. Using GEP 2. while the GA is employed to optimize the parameters of all.O 2) It can be convened into a tree structure shown in Fig. the length of the bead h is chosen. if we'chose an h = 4. then r = 5 . When mapping a GEP gene into a circuit. whereas the length of the tail I is a function of h and the number of arguments of the function with more arguments k. whereas the tail contains only terminals. In the heads.3n)C(ZUF1C~2~C(4~)CPE~lO~.modeling task of the equivalent circuit for electrochemical impedance. In segment-insertion mutation a segment is randomly chosen throughout the parent chromosome. while ( I < MAXGEP) do begin structure optimization process of circuit models using G E P parameter optimization process of electric components using GA. A copy of the segment is made and inserted at any position in the head of the chromosome. The structure of the HEMA can be described as follows: Procedure HEMA begin input observed data of electrochemical impedance.1. and is evaluated by the equation: t=h(k-l)t I (1) As far as the equivalent circuit for electrochemical impedance is concerned. The head contains symbols that represent both functions and terminals. except the first position.O. For each problem. 1820 . -1 where + and . r:=t+1. LJ and the set of functions F = {+. capacitors (C) and inductors (L). [9]. This operator involves in the selections of the start of the segment. Its main idea is to embed a GA in GEP where GEP is employed to discover and optimize the structure of a circuit. Obviously in this case. each gene has an effective coding segment (ECS) whose length equals to the number of nodes in the binary tree.2 Genetic Operators In the HEMA.

the lower the fitness value. P.. a segment with as many symbols as the inserted segment is deleted at the end of the head of the parent chromosome. Suppose there are k parameters in total. in GA population. electric components) in the ECS of the individual gene and their types. The formulae for calculating the electrochemical impedance of each electric component are listed as follows: (a) the impedance of a resistor: R. z2 When calculating the fitness value of an individual.experiments. We first determine the total number of the parameters to be optimized according to the number of terminals (i. whereas the insertion point can only be chosen from-the head except the first element and the ECS of the chromosome. . When the components are series-connected or. w(0-IOOQ).5. That is. Finally we can calculate the fitness value of p by using Eq.. 6 > 1) and CO. 2.. the equation is the Warburg impedance caused by the semi-infinite diffusion process. but on the other hand.. the inserted segment becomes duplicated. are and the imaginary part of the electrochemical impedance under a given frequency. we first assign the parameter values in P to the correspondent components in the GEP parent chromosome one by one and then follow the same procedure in Section 2. the number . Then for each input frequency f . Afterwards we trace back upward to access the tree level by level until the total impedance' of the whole equivalent circuit is achieved. a one-dimensional line vector written in the form of P = b . C . Accordingly produce M random coefficients where 2. namely the real part and the imaginary part..The former two can be chosen randomly. It adopts a novel crossover operator which performs by the non-convex combination of multiple parents. the better the individual. P. segment insertion are syntactically correct programs.= -+ z 2 .3 to figure out the fitness value of I l l (b) Z1-22 parallel connection: . + Z2. The algorithm to do the parameter optimization in the HEMA is a genetic algorithm based on the subspace search. Each time we randomly select M different individuals from the old population (M>2) denoted as P. 2.2 Parameter Optimization Process of Electric Components Using GA This parameter optimization process is done for each individual in the current circuit population. parallel-connected. the fitting values of the impedance under all other input frequencies can be computed..(2) based on those fitting values. we can calculate the sum of the least-square errors of those two parts as the fitness value of an individual. F. C(0-0. P2. 1 (c) the impedance of a capacitor: . then abandon this invalid individual and recreate a new one by reproducing a new set of ai and following the Eq. Pne.1.. is out of its range of definition. the formulae for calculating the impedance are: (a) Z..'. In our . p . n(0-I). m is the number of input frequencies. = (p. If any parameter in P.-Z? series connection: Z = Z.. on the one hand.001F) and L(0-IH). (3) until a valid individual is generated..p X ) where p .M ) and k is the total number of parameters to be optimized. f. This value is just the fitting value of the electrochemical impedance for p under the given frequency f .' and Z ? the actual values of the real part . which contains two p e s . Obviously. Thus the fithess function.j . Note that. Each pi has its own range of definition in terms of the component it 'corresponds to. Thus. 5 6 ( a < 0 .and 2. Py where P. is produced by the non-convex linear combination of those M individuals: 2nfc (d) the impedance of an inductor: .<. ~ ( R . Similarly 2. we predefine the ranges of these parameters as R(O-IOOQ). despite the insertion. L ) ( i :I-k). (b) the impedance of a constant phase element CPE(w.e. n . the tail of the parent chromosome remains unchanged after insertion.of data points. and therefore all the new individuals created by. is defined by the following equation: from the bottom level of the tree and figure out the electrochemical impedance of all branch circuits by using the formulae described above. the structural organization of chromosomes is maintained.. . we start 0-7803-7804-0 1031$17. n): When I I is 0. is encoded as an ordered set of k floating numbers. ~ a. 2@. j . w .. M = iil Thus a new individual. which satisfies a < a. p 2 . respectively.e. in GEP population we first convert it into the correspondent tree structure.1.3 Calculation of Fitness Values As the electrochemical impedance of a circuit consists of a real part and an imaginary part.00 02003 IEEE 1821 . By following the same procedure. When calculating the fitness value of an individual. i.p r ) ( i : l . Then each individual in the parameter population. p 2 .1." are the correspondent fitting values.

twenty independent runs are conducted by .&3 produce M random coefficients (Yj ( i: I-W. for j := 0 to S do . '3.).600000)+((R(5. )CPE(43. 0. It differs from a simple GA in that the search space of crossover is determined by multiple points (M parents) rather than by only two points used in a painvise crossover. MAXGA. a. 2 (b).000061 )C(0.. calculate the fitness of the population F(P(r)) = (F(P... The settings of their optimal values depend upon the property of the specific problem.000420))) Model 2: +R(4. := Q. we observe that.b=1.0. : llilN Fnm:= F ( P n m 3 := m a F ( I : if (F(Q) < Fm.S=20. [ N is the population size) N=50.P. 2 Simulated Circuit I (a) and its complex plane impedance plot (b) From the experimental results.popsize = 100. We list some of them below: Model I : 3. of the 20 NnS: 2 Results and Discussions (a) There are 13 runs that the HEMA can find the same circuit model as the original one. and generate the simulated data based on them. (a) ).600~O)+CPE(3. end F(Q) := min ~ ( 8 .000773)C(0.5. -. Pdr)). we obtain 100 data points (Z:. .2Circuit I while (f < MAXCA) do The original circuit used to generate the simulated data is begin shown in Fig.0 00840)L(0.input data file.356660)C(0.82431I ) a (R(4. (il-99). All the experiments are performed on a Pentium Ill PC (IGHz) and programmed by C language. . 1822 .. i 3 10 IS 20 T i ollm (b) Fig. Then the structure of the GA can be described as follows: Procedure GA begin Z which are used to set up'thr. r:=r+1. be 1. I:=% The parameter settings ofthe HEMA are as follows: in initialize the parameter 'population P ( I ) = ( P ~ ( I ) . F(P2).3 then P. we design two relatively complex circuits (including the parameter values of components) with distinct complex plane impedance plots by ourselves.600000)-C(0.a=-0. For each : ) data'file. the GEP.927744. The fitness values of all those circuits equal to 0.&. b.20~00. begin CI420. is 0.1 Generation of Simulated Data and Parameter Settings of HEMA To test the effectiveness of the HEMA. Moreover more than one point (S offspring) are produced from the subspace and the best one is chosen to replace the worst individual in the original parameter population. Its complex plane impedance plot is shown in Fig. Not only the structure of the circuit but also the component parameters are exactly consistent with Circuit I. The adjustable control parameters in the GA include N . generate a new individual Qi := calculate F(Qj). MAXGEP = 5 0 in the GA.5.. Suppose the fitness function is F(x).using the 'HEMA. P2(t). To be specific. we assume the initial frequency.MAXGA=1000.p.2 folds of f i .0IHz and let f.0. M.500000))-C(0.000420)+R(5.600000)CPE~320CO00.. . By calculating the values of the electrochemical impedance under each frequency f. from PO). S. end end The essence of the GA lies in the random search to the subspace determined by multiple parents. Wj'Z 2 1=1 *.M=8. . F(P$). 2(a) which is a typical circuit for the simple randomly select M different individuals P i ( L1-W electron transfer reaction with concentration polarization. h = 8.

Fig.00.5- ? $ 0. -0. In other words.5 0-1 . I 2 1 ?I Generation Our experimental results show that as for this circuit. the HEMA can find the circuit models whose structure and. C(4. in most runs. II . . I n addition. by running the HEMA. of the 20 runs. from the fact that those parameter values are exactly the same as the original circuit.the minimum 000000MN)2. it demonstrates that the genetic algorithm used to do parameter optimization is stable and effective. being the maximum 0. 3 The evolving curves of Model I-Model 5 for Circuit I (c) There are another 4 runs that the HEMA can find such models that have slight difference with the original circuit i n the structure but have a small fitness value.3 Circuit I1 The original circuit used to generate the simulated data is shown in Fig. as for Circuit I.5- L- - 1. the computer can discover the suitable circuit structure automatically as well as optimize the component parameters simultaneously according to the input data of electrochemical impedance. In summary. 4 1 . . . 3. 2 3 4 5 6 Z /ohm 2 -0. . 4(b) illustrates its complex plane impedance plot. 4(a) and Fig.71lFj U966nI.5 1.I) 2. .0039298495.64 (b) Fig.0 - 1. 4 Simulated Circuit I1 (a) and its complex plane impedance plot (b) I .0-0. there are only one run that the HEMA can find the model that has the exactly same structure as the 1823 .pararneters both exactly coincide with the original circuit. .

864127)R(2.OOO323)CPE(39.999705~C(O.000207)L(0.096000)))) F = 0.282573.0. we observe that this circuit can fit the simulated data very well and its fitness value is very close to 0. 47063.864130)R(3 1.597639)R(S5. Its fitness value is 0. k 4 R.0.800000)+((U0.999706)C~O a new equivalent circuit for Circuit II which has not is .683 136)+(R(6. they all can be 7 simplified into the circuit structure shown in Fig.000005)-((R(6. with 0.800000)+(C(0.435266))-(R(2. the HEMA finds the models (R(2.5659 11)+L(0.255279)C(0.000005)))) 331) 3 (R(1. (a) 1.OOOM)5)-(R(2.8952 19)C(O.000005)C(0.95353 We depict the evolving curves of those six models above 0. Its complex plane impedance plot is shown in Fig. From Fig.000005)) +(R(1.000318)CPE(78.0.799999)+-I R(3.001175) 0. 183 153 for Circuit 11 in Fig.864127))))) Model 9 Z'lohm (b) Fig. 6.778953)L(0. 5(b).O002l8)C(O.0. +R(? XO0~K)0r-Ct01~000051-K12 9997061+Rth 001177rLtO BM127lCPFt6 00027 I .692722)R(98.001178)+L(O. 5 The circuit that occurs most frequently when evolving Circuit II (a) and its complex plane impedance plot (b) From the case that this kind of model turns up so frequently and its fitness is almost 0.458685)L(0. Model 6 +R(I . 954) In the remaining two runs. of the 20 ruis there are 17 runs that the HEMA finds another kind of circuit structure shown in Fig.999706)-C(0.0. 800000~-+-+R(5. 5(b).000995) 3 (R(2.800000)+((R(6.43526~R(2. Model I O - i +RO.original circuit and whose parameters are almost identical with the original one. we surmise that this +R(2.618154)C( 3 (R(2. 52)C(O.644502.000001 )C(O.800000)+(C(O.01178)L(0. Below we list some of them: Model 7: CISuF) R 2 811) ( O------l R(2 999706Q) 0 .953301)C(0. 102541)R(6.800000)-+-R(6.769643)UO.I80991)))-(R(2. Xa).224784)CPE(47..O960001CPE(7.0.O00005)))) M d e l 11.864127))-R(2.0000000000 and 0. .799999)+((R(3.780889)L(0.000000oMK) Most surprisingly.466461 IR(83.5 - 1 Simulated curve Fining data A 76)R(83.800000)+(((R(0.999706)))) M o _. But the -(R(2. 5(a) and their parameters only have the difference of mantissa with this circuit.348435.413373)R(41.2258 18)L(0.2 1 I)CPE( 19.0000000001 respectively.00003 I)L(0.001175) +L(0.001177)+L(0.864130)) 1824 .891787)L(0.702 793)L(O.742320)C (0.518849.000000)L(O.0005)))) fitness values of those two models are both minor.000M)I )-C(0.0. The model is: +R(5.6166l3)R(12.825903) 3 (R(2.0.0.OM)OO5)CPE(53. Although the specific representations of those 1 models are not completely same.999706) -(R(6.999706)-C(0.864127)) having different structures with the previous two.999705)-C(O.O 000100rClO 000015rLtO 657127 )CPE(7.47 1400) 704573.000000)-U0.487394.O00005)R(I.577338)CPE(83.442W0.56591 1)L(0.8 been realized by people yet.6 69721)L(0.000005)CPE(lI .411747) 3 (R(2.O00005~R( 0.402 +L(O.

1994. I . The Applicability and Power of Complex Nonlinear Least Squares for the Analysis of Impedance and Admittance Data. The user himself can control the structure types and the complexity of the circuits flexibly by defining the sets of functions and terminals and the length of tail of a GEP gene. [7] I. 2001. [6] I. Compared with most available methods. ( 2 ) The models have great diversity. R.131. MA: MIT Press. Solid State lonics. Lehnen. Journal of Electroanalytical Chemistry. R. H. Cambridge. 1996. 1825 . 31-44.24. the HEMA can find the models which are in . Boukamp. MA: MIT Press. 2002CB211800).pp. We need to further test . 2002. Gene expression programming in problem solving. [2] B. and M. (3) The result of parameter optimization is stable and effective. ' Acknowledgements This work was supported by National Natural Science Foundation of China (No. Cha. . A Nonlinear Least Squares Fit Procedure for Analysis of I~~~~~~~~~ Data of Electrochemical Systems. some preliminary work of evolving Chemical Circuits by using GEP. Cambridge. But sometimes it also finds some new structure that has not been recognized by people yet. 1999. Complex Systems. and A.the efticacy of the HEMA in larger circuits which contain more components and parameters in the future. Ferreira. Mitchell. Impedance Spectroscopy: Old Problems and New Developments. [3] J. This paper is. Macdoald. only if the structure of circuit eventually found is identical. Electrochimica Acta. September 10. ~ . 2001. [8] C. P. Once the electrochemical impedance data are provided. Koza. S . 1990. 77-95. Koza. The authors wish to thank the anonymous referees for their helpful suggestions for this paper. by running the HEMA. Genetic Programming Ill: Darwinian Invention and Problem Solving. [ 5 ] J. Koza. 20. Bejing: Science Press. 87-129. F. 1992. In most runs. 6 The evolving curves of Model 6-Model I I for Circuit I I [ I ] C. The whole modeling process needs not the manual intervention. ~~~ -. R. R. Genetic Programming II: Automatic Discovery of Reusable Programs. An Introduction to Genetic Algorithm. invited tutorial of the 6th online World Conference' on Soft Computing in Industrial Applications. 13(2). pp. it has some advantages: 1 I) The whole modeline nrccess is done automaticalh.being optimized are always consistent. Andre. . [4] J.. the component parameters. Schoonman. J. 1982. Genetic Programming: On the Programming of Computers by Means of Natural Selection. Macdoald. MA: MIT Press. R. 1986. Ferreira. the computer can search suitable circuit structures as well as optimize the component parameters simultaneously by itself. 1483-1492. Cambridge. [9] C. agreement with the original circuit. Bennett 111. . pp. pp. Meanwhile we will conduct some similar expenm'ents by using standard GP and compare the results with those of this paper. CA: Morgan Kaufmann Publishers. Introduction' to Kinetics of Electrode Processes (Third Edition). Keane. As for different runs. Model 8 VI e -10 I 11 References 21 31 41 Generation Fig. A. D. A. ' [IOIM. 4 Conclusions and Future Work The hybrid evolutionary modeling algorithm (HEMA) based on the combination of Gene Expression Programming (GEP) and genetic algorithm (CA) proposed in this paper i s a new evolutionary approach to build the equivalent circuit model for electrochemical impedance. San Francisco. Gene Expression Programming: A New Adaptive Algorithm for Solving Problems. 60133010) and the Special Funds for Major State Basic Research Projects of China (No. 35.0 . .

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An Evolutionary Approach for Modeling the Equivalent Circuit for electrochemical impedance spectroscopy

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