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POLYMER GEL ELECTROLYTES

Ing. Vtzslav HEKERLE, Doctoral Degree Programme (1) Dept. of Electrical and Electronic Technology, FEEC, BUT E-mail: hekerlej@selfnet.cz Supervised by: Dr. Ji Vondrk

ABSTRACT The survey on solid ionic conductors, the fundamentals of gel polymers electrolytes conductivity and preparation, and on methods of conductivity measurements are given in the first theoretical part. The preparation of electrolytes by ultra-violet forming is described in the second, experimental part. 1 INTRODUCTION

During the last years there was a lot of effort done on the electrochemical preparation of polymer gel electrolytes. These materials are often used as electrolytes in lithium batteries, super capacitors and elektrochromic components. Even when these materials are known for a longer time already, studies of their properties are being accomplished as late as in the recent years. The easiest way to create a polymer gel electrolyte is by polymerizing polymethylmetacrylate (PMMA) with addition of electrolyte. For real application of polymer gel electrolyte its parameters have to be known. Most important parameter in this case is electrical resistance or electrical conductivity, capacity or real and imaginary part of impedance. 2 ION CONDUCTORS

The reason of ion conductivity is mobility of ions in crystals. It is caused by the existence of cavities, tunnels or other empty spaces in the matrix or cause it by difference in comparing to the ideal structure. In gel polymer electrolytes however, the ions migrate in the liquid phase which is immobilized by the polymer macromolecules. In the absence of electrical field ions in crystal are doing random thermal movement. As soon as there are electrodes in contact with the electrolyte and an external voltage is connected to them, the electric field will cause orientation of the movement of disengaged ions. Positive ions will move to the negative electrode and negative ions will move to the positive electrode. Electric current will pass through the electrolyte. At the start it will be small current but it will disappear soon. Permanent current will be emerged after breaking an

electric boundary Vr called decomposition voltage. For voltage V bigger than the decomposition voltage Vr the current is approximately linear, so it is:
V = Vr + R I

(1)

where R is a constant with stable temperature and it is called an electrolyte resistance. 2.1 ELECTROLYTES

By the dissolution of electrolyte (usually a salt able to carry the electric current) in the proper solvent , liquid electrolyte is formed. In the common language is electrolyte often used in meaning of liquid electrolyte. Under the category electrolyte we include those conducting systems where electric current is joined with material transporting. The layer of ionic conductor is used as ion source for implementing them to the active layer or as a base for their subtracting. Thats why electrolyte must be able of fast ion transport between layers or between electrodes. High conductivity is required for electrolytes in practical applications (it should be somewhere above 10-12 S.cm-1). Ratio of cations and/or anions on the whole charge Q in the liquid of electrolyte is different and it is expressed by transference numbers defined by equations: tC = tA = QC Q QA Q (2) (3)

where tC and tA are transference numbers, QC and QA is charge transferred by positive and negative ions and Q is total charge transferred during the process. 2.2 SOLID ELECTROLYTES

Ion conducting polymers were first tried as solid electrolytes in the end of 7th decade of last century (seventy?). These electrolytes involve solid polymers (often used polypropylen or polyethylene), lithium salts (lithium perchlorate) and ceramic oxides. Cation transference number depends on the amount of added ceramic. By experiments was found that size of Al2O3 have to be smaller than 0,3 m to build a material with high transference numbers, but it is hard to create as thin layers as they are very unstable when left in places with higher air humidity. It is also possible to use dielectric or insulator cellular layer to absorb humidity from the air. When the layer is embedded between two electrodes and electric voltage is higher than 1.3 V, water is decomposed on H2 and O2. 2.3 LIQUID ELECTROLYTES

Materials conducting electric current are divided into two groups ionofors and ionogens. Ionofor is a material compact from ions only. Conductivity of ionofor depends on concentration, dielectric constant and viscosity of dissolver. Ionogen is a material which crystals are compounded from molecules creating ions while being affected by dissolver. By other words, inofors contains ions while to make ions from ionogen material we have to use dissolver.

2.4

GEL ELECTROLYTES

Gel electrolytes are electrolytes with polymer addition with balanced ratio so polymeration will produce gel structure. Between often used materials to create gel polymers we can find polymers polypropylene, plyethylene oxide (PEO), polymethyl methacrylate (PMMA) known in R as Dentacryl, polyvinylpyrrolidone and polyvinylpyridine (PVP), prolypropyleglycol-methylmethacrylate (PPG-PMMA) etc. Electrolyte is usually created from alcalic salts, often used is lithium perchlorate (LiClO4). 3 POLYMER GEL ELECTROLYTES

Polymer electrolytes are defined as solid ion conductors formed with dissolving salt in polymer having fitting high molecular weight. Based on the method of holding ions in the polymer they can be divided into two groups: 3.1 polyelectrolytes gel electrolytes GELATION

During the research of second polymer electrolyte type it was found that one of most important things is increasing conductivity of electrolytes at room temperature. Principe of this is holding liquid polymer with high dielectric constant involving dissolved alkali salt in the chemical or electrochemical polymer inert matrix in the base polymer. Target is using good properties of inert form and size stability and liquid electrolyte with high conductivity. Basically it is thickening up (or immobilization) of liquid electrolyte by appropriate polymer material. Ions of alkali salts are moving in the gaps between macromolecular chains. These electrolytes are called gel electrolytes. They can be prepared by three methods: 3.2 thermal formation (polymerization) formation by light (polymerization) chemical forming (polymerization) PROPERTIES AND USABILITY OF GEL POLYMER ELECTROLYTES

Polymer gel electrolytes are very progressive materials. They can be prepared in semisolid or solid form, which is a cheap and reliable process when they are manufactured. Between requests for wide-usability of gel electrolytes is high conductancy. Polymer electrolytes and in recent days especially gel polymer electrolytes can be used in several different cases. In accumulators and supercapacitors they can replace liquid electrolytes, as they are more stable in the meaning of chemical and electric stability and also in electrochromic displays and devices as it is very handful to prevent devices from drying out or leaking electrolyte. 4 RESULTS

In the recent years there were several gel electrolytes prepared already. During the time and after consulting with people from the Institute of Inorganic Chemistry in Prague we have

decided to try to prepare our gel electrolyte by another method than by chemical formation. While the method used before were done from Dentracryl, lithium perchlorate and propylencarbonate, we have tried to make similar process but by the polarization induced by the ultra-violet radioation. As before, our basic structure was propylencarbonate, salt of lithium perchlorate and methylmethacrylate. The liquid substances were purified by distillation in nitrogen. The initiator for was added in order to guarantee a good polymerization process. Then it was shaken for a while to ensure dissolution of lithium perchlorate and initiator in the solvent and then exposed to ultra-violet light. In our case ultra-violet light was obtained by Tesla RVK 125 W mercury discharge tube, as we knew it is used in Prague in the Institute of Macromolecular Chemistry. All mentioned chemicals were bought from Sigma Aldrich except of Dentacryl that is often used in dental surgery and can be purchased with requested quality in pharmacy. For preparing mixtures we have used chemical equipment like Petris dishes, chemistry scales with accuracy 10-4 gram, and hypodermics for measuring liquids. 4.1 SAMPLES

After several gels had been prepared in Prague we have decided to create similar gels at our laboratory. For first tries we have used similar ratios of chemicals as in Prague but decided to not use networking agent to try how much the target gel is affected by missing component. During the process we have noticed several mistakes made during the process. In the first glance we set exposition time too long. This resulted into the fact that first two samples were compact or they were missing transparency and softness. Then polymerization time was shortened but later we have noticed the final target weight is significantly lower than weight of the prepared mixture. It seems that components tend to evaporize during the process. To prevent this we had closed Petris dishes starting from the 6th experiment. From the 7th sample we were able to create a material similar to the starting gel made from Dentacryl by chemical polymerization. After testing its properties we have noticed that results properties especially conductivity is too bad for using this as polymer gel electrolyte. 4.2 DISCUSSION OF RESULTS

At this time we have stopped and started discussing what we were able to understand from the made samples being made. Electrolyte have to be closed in the mould when prepared to prevent vaporizing radicals It seems that the gel cant be prepared without a neworking agent. Even when we know the network agent makes targets properties worse, without it the result ing conductivity is so low that electrolyte cannot work properly Used ultra-violet source is not very good. Its power is too low which results into the fact that gel has to be exposed for too a long time, heats itself and radicals decompose or recombine again. Another reason is that electrolyte can be overheated which will result into color change.

CONCLUSION

From the main idea to prepare polymer gel electrolyte by using ultra-violet light polymerization method instead of chemical forming weve learned several facts about preparing them. Although the whole idea isnt probably bad, weve failed to create electrolyte with requested properties. After discussing the results we were able to find better methods how to prepare whole polymer. In next days well try to prepare them with network agent. Another ultra-violet light source will replace current one between ideas what to use there was also suggestion to use device for preparing PCB (print on board device). Advantage of this is exhausting system PCB device posses as well as very high power used which will result into lowering time used for one sample which will greatly speed-up time needed to prepare a polymer gel electrolyte. AKNOWLEDGMENT This article is being supported by the grant projects of Grant Agency of Czech Republic (No. 104-02-0731), of Grant Agency of Czech Academy of Sciences (No. A 403-02-002) and Ministry of Education REFERENCES [1] Kalakov A., Toukov A.: Chmia a fyziklna chmia pro elektrotechnikov [2] Touek J., Toukov A., andera J.: Fyzika a technologie materil IV elektrochemick technologie [3] Novek T.: Gelov elektrolyty, technical project VUT Brno 2001 [4] Conway B. E.: Elektrochemical supercapacitors [5] Borick T.: Elektrochemick superkondenztor VUT Brno 2002 [6] Canaud J.: Energy reservoirs and super capacitors