The storage battery with bipolar membranes

doi:10.1016/S0376-7388(97)00306-2

Journal of Membrane Science

Volume 141, Issue 2, 15 April 1998, Pages 231-243

https://doi.org/10.1016/S0376-7388(97)00306-2 Get rights and content

Abstract

The storage battery consists of a three-compartment electrodialysis cell with a bipolar membrane. The main characteristics of the electric energy source are evaluated when applied to the regimes of charge, discharge and self-discharge. These regimes are subjected to the experimental study to verify the theoretical predictions. The experimentally obtained values of the performance of the battery are compared with that of the known battery types. The comparison of the yield density of 0.5 and 80 W/kg (lead battery) makes it obvious that an industrial application is scarcely conceivable. Membranes with better permselectivity are needed.

Introduction

Ion-exchange membranes' function is to transport ions. Sometimes, however, their behavior may be compared to electrode properties as they can be regarded as a sort of reversible electrodes. For example, the concentration potential of a membrane corresponds to the potential difference between the same electrodes being in contact with solutions of different electrolyte concentrations, provided that the solutions are connected by a salt bridge. Also electro membrane purification (electrodialysis) of water from salt pollution is analogous to electrolysis purification.

The electrochemistry of electrodes deals with obtaining substances using an external electric energy supply (several types of electrolysis) as well as producing electric energy by using free energy of chemical transformations (electrochemical batteries). Membrane technology mostly has to do with processes belonging to the first group (electrodialysis). As to electrochemical energy sources, some types of them use membranes only as charge transferring media as well as reactant separators 1, 2, 3. A sort of battery where membranes perform the function of electrode has been proposed rather long ago 4, 5 referred to as reverse electrodialysis. In simple, it is a batch of membranes with transfer numbers 1 and 0 for cations (0 and 1 for anions) in series (Fig. 1). Each membrane separates two compartments that are supplied either with solutions of high or low electrolyte concentration. These solutions may be of natural origin (river and sea water for example [6]) or prepared artificially with the help of natural energy sources (by solar energy [7]). For the case of a 1–1 electrolyte and ideally selective membranes the system shown in Fig. 1 can provide an open circuit voltage (OCV)) E $E= RT F ·N ln C_{h} C_{l}$ where the subscripts h and l stand for high and low binary electrolyte concentrations in the corresponding compartments which are used instead of activities; N is the whole number of the membranes in the system; R, T and F are the gas constant, the absolute temperature and the Faraday constant.

The system shown in Fig. 1 can also work as a storage battery. The initial state can be restored after levelling the concentrations by carrying out conventional electrodialysis. There is, however, one significant disadvantage of the system when it may be used as a storage battery. A system with a high ratio C_h/C_l should be established when high OCV is required. However, high concentrations reduce the membrane permselectivity, but low concentrations create a high resistance within the low-concentration compartment. This can be overcome by reducing the thickness d of the corresponding compartments [7]. Yet, this method is not fit because it leads to reducing the capacity whose maximum value can be estimated as the value of the electric charge to be transferred across the system in order to equalize the concentrations in all compartments. In other words, trying to reach a sufficient value of the electromotoric force (EMF) the internal resistance must be increased or the capacity decreased.

However, another version of the system can be provided enabling to overcome the aforementioned difficulties. The proposal is not to use the “reverse electrodialysis”, but the “reverse bipolar membrane electrodialysis”. The “direct” one is the method of applying electrodialysis to produce bases and acids 8, 9. The other method makes use of this system as a storage battery which is described in this paper.

Section snippets

Principles of the work

The system in consideration consists of a multiple set of a three compartment cell (Fig. 2(a)–(c)) which usually is employed in the electrodialysis technology for base and acid production 8, 9. In general, there are base and acid solutions in the compartments separated from each other by a bipolar membrane (BM). BM is the essential component in the system. It consists of cation and anion exchange layers in close contact with each other 8, 9. The base compartment (BC) and the acid compartment

Essential characteristics

The quantitative characteristics of a storage battery work 11, 12 are chosen on the assumption that any high value of current and voltage can be achieved by increasing the area crossed by a current and by using a sufficient number of cells connected in series. Therefore, only the specific characteristics calculated per unit of a battery mass (m) or volume are indicative. The discharge regime is described with the help of specific capacity (q_dch), energy density (w_dch) and power density (p). The

Self-discharge

Self-discharge is mainly caused by a leakage of protons and hydroxyl ions across monopolar membranes in the open circuit regime. An alternative mechanism is associated with cation and anion transport across the bipolar membrane. However, for approximately equal thickness of all membranes the order of the ratio between the two fluxes in question is about J_s(1)/J_s(0)≅P²≪1 because each self-discharge flux is approximately equal to coion diffusion flux across the corresponding membrane. It enables

Materials

The monopolar membranes used in the experiments were Selemion-type CMV (cation exchange) and AMV (anion exchange). The bipolar membrane was obtained from Stantech, Hamburg, Germany. The characterization of the membranes was carried out in the normal way as described in [13]. The results are shown in Table 1. The analytical grade chemicals were obtained from Fluka, Neu-Ulm, Germany.

For the measurements a conventional electrodialysis cell with some modifications was used. It is a four compartment

Discussion and conclusion

The results obtained by the experiments can be classified by three groups. All are concerned with experimental verification of the theoretical prediction for discharge, charge and self-discharge. In the case that the theory can successfully be proved with regard to the curves a conclusion can be made on the correctness of the calculation of the main figures as following from , , , , , , , .

The first group of the results deals with the self-discharge. Each experimentally obtained curve contains

Acknowledgements

The grant from the Deutsche Forschungsgemeinschaft for E.Z. is highly appreciated.

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The storage battery with bipolar membranes

Abstract

Introduction

Section snippets

Principles of the work

Essential characteristics

Self-discharge

Materials

Discussion and conclusion

Acknowledgements

J. Membr. Sci.

J. Membr. Sci.

Elektrische Leitfähigkeit von Kationenaustauschermembranen

Z. Physik. Chem.

Production of electric power by mixing fresh and salt water in the hydroelectric pile

Nature