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WO2013191578A1 - Élément électrochimique économique - Google Patents

Élément électrochimique économique Download PDF

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Publication number
WO2013191578A1
WO2013191578A1 PCT/RU2012/000628 RU2012000628W WO2013191578A1 WO 2013191578 A1 WO2013191578 A1 WO 2013191578A1 RU 2012000628 W RU2012000628 W RU 2012000628W WO 2013191578 A1 WO2013191578 A1 WO 2013191578A1
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WO
WIPO (PCT)
Prior art keywords
potential
ions
electrochemical cell
electrodes
cell
Prior art date
Application number
PCT/RU2012/000628
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English (en)
Russian (ru)
Inventor
Игорь Витальевич БУЗМАКОВ
Original Assignee
Buzmakov Igor Vitalyevich
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Buzmakov Igor Vitalyevich filed Critical Buzmakov Igor Vitalyevich
Publication of WO2013191578A1 publication Critical patent/WO2013191578A1/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
    • H01M8/184—Regeneration by electrochemical means
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the invention relates to the electrical industry and can be used for the electrolysis of electrolytes and / or for generating electricity.
  • An electrochemical cell is a device for producing electric current due to electrochemical reactions. Electric current may flow as a result of the circuit of an electrochemical cell formed by electrodes and an electrolyte, or under the influence of an applied external potential difference, in the latter case, electrochemical reactions result from the flow of electrical current through the electrochemical cell.
  • Electric current may flow as a result of the circuit of an electrochemical cell formed by electrodes and an electrolyte, or under the influence of an applied external potential difference, in the latter case, electrochemical reactions result from the flow of electrical current through the electrochemical cell.
  • I. I. Gerasimov "The course of physical chemistry.” Tutorial: For universities. In 2 t. ETC. - 2nd ed., Rev., the publishing house “Chemistry” Moscow 1973. - 624 s, p. 488 - 489, 573 /
  • Electrochemical cells are known, the main characteristic of which is an electromotive force equal to the difference in electrode potentials, depending in general on the nature of the substances used, their activities, temperature and pressure. /TO. Fetter "Electrochemical Kinetics", translated from German with the author's additions for the Russian edition edited by Corr. USSR Academy of Sciences prof. Kolotyrkina Ya.M., Chemistry Publishing House Moscow 1967. - 856 p., Pp. 32 - 44 /
  • the amount of transmitted energy depends on the electromotive force. energy load, and when working as a cell - the amount of energy expended by an external source.
  • electrochemical cells such physical phenomena as the Donnan potential and the internal contact potential difference of conductors of the first kind are not used as sources of additional electromotive force.
  • the invention is an electrochemical cell (hereinafter referred to as Element), using Donnan potential and / or internal contact potential difference (hereinafter CRP) as sources of additional electromotive force (hereinafter emf) to increase the efficiency of electrolysis processes, when voltage is applied from an external of the power supply to the Element electrodes, and in the load connected to the Element electrodes, the net electricity generated by electrochemical reactions on the surfaces of the electrodes, in the absence of eshnego power.
  • Element electrochemical cell
  • CRP internal contact potential difference
  • emf additional electromotive force
  • the technical result of the invention is to increase the efficiency of the processes of electrolysis and the production of electricity, i.e. increase of the coefficient of performance (hereinafter the efficiency) of the Element
  • the Element uses the Donnan potential and / or internal PKK of parts of electrodes for obtaining additional emf. in a chain and, as a result, increase in efficiency.
  • the Donnan potential of electrolytes and the internal ⁇ of conductors of the first kind are rather small, therefore a significant increase in the efficiency of the Element can be expected, for example, when its performance decreases by reducing the voltage supplied to the element from an external power source, during its operation as electrolyzer, and reduce the difference of standard electrode potentials (ie, the voltage on the electrodes), when it works as a current source.
  • the internal contact potential difference is equal to the Fermi energy difference of the contacting conductors, referred to the electron charge value.
  • the internal ⁇ is a potential difference caused by the diffusion of electrons from a conductor with their greater concentration (and, accordingly, with a higher Fermi energy) into a conductor with a lower concentration (and, accordingly, with a lower Fermi energy).
  • the electromotive force is the integral of the field strength of external forces in the area containing the current source (in other words, it is the work of external forces in moving a single charge).
  • the external forces in the galvanic cells act on the boundaries between the electrolytes and the electrodes. They also act on the boundary between two dissimilar metals and determine the contact potential difference between them. / Sivukhin D.V. General course of physics. Tutorial: For universities. In 5 t. T. III. Electricity. - 4th ed., Stereo. - M .: FIZMATLIT; MIPT Publishing House, 2004. - 656 p. - ISBN 5 9221-0227-3; 5-89155-086-5., Pp. 189 - 193 /
  • Hole conductivity is due to the presence of quantum states not occupied by electrons in the valence band. Such quantum states are called holes. In an electric field, the holes move in the same way as a positively charged particle with a certain mass would move under classical consideration. Due to the low concentration to the electrons in the conduction band and to the holes in the valence band, the classical Boltzmann statistics is applicable. / Sivukhin D.V. "General course of physics.” Tutorial: For universities. In 5 t. " D.111.” Electricity ". - 4th ed., Stereo. - M .:” FIZMATLIT “; MIPT Publishing House, 2004. - 656 p. - ISBN 5-9221-0227-3; 5 -89155-086-5., P. 431 - 434 /
  • Polyelectrolytes are polymers capable of dissociating in solution into ions, with a large number of periodically repeating charges arising in one macromolecule.
  • Cross-linked polyelectrolytes ion exchangers, ion exchange resins
  • A.A. Tager Physical Chemistry of Polymers, Chemistry Publishing House, Moscow 1968.
  • the Donnan potential is an equilibrium potential difference arising at the phase boundary between two electrolytes in the case that this boundary is not permeable for all ions.
  • the impermeability of the boundary for some ions may be due, for example, to the presence of a membrane with very narrow pores, which are impassable for particles exceeding a certain size.
  • Selective permeability of the interphase boundary occurs even if some ions are so firmly bound in one of the phases that they cannot leave it at all. This is how ionic, or ion-exchange groups, fixed by homeopolar bonds in a molecular lattice or matrix, behave in ion exchange resins.
  • the solution inside such a matrix forms together with it a single phase; the solution outside it is the second. /TO.
  • Fetter “Electrochemical Kinetics”, translated from German with the author's additions for the Russian edition edited by Corr. USSR Academy of Sciences prof. Kolotyrkina Y.M., Chemistry Publishing House Moscow 1967. - 856 p., Pp. 76 - 79 /
  • the electric double layer is a combination of two oppositely charged layers that appear at the interface between two layers located at some distance from each other. /TO. Fetter "Electrochemical Kinetics”, translated from German with the author's additions for the Russian edition edited by Corr. USSR Academy of Sciences prof. Kolotyrkina Y.M., publishing house "KHIMIYA” Moscow 1967. - 856 s, p. 96 /
  • Intercalated carbon is crystalline carbon, in the interlayer space of the crystal lattice of which molecules of another substance, intercalate, are implanted. Such structures are also called intercalated graphite or graphite embedding compound (hereinafter referred to as CSG).
  • CSG intercalated graphite or graphite embedding compound
  • CSAs are divided into two broad classes: donor and acceptor. The redistribution of the electron density between the intercalate molecules and carbon atoms in the acceptor-type GHGs leads to the appearance of an additional number of delocalized holes in the graphite layers.
  • donor compounds the implanted substances donate their valence electrons, and conductivity is carried out by excess electrons in the carbon layers.
  • Acceptor compounds are formed during the introduction of substances such as halogens, metal halides, acids.
  • Donor compounds are formed when alkali or alkaline earth metals are embedded in a graphite matrix. / Link to the Internet information resource http://www.nanometer.ru/2008/12/21/grafit_54995.html, Nanometer nanotechnological community, publications / Brief Description of the Drawings
  • the external part of the electrode is a graphite rod, which is in electrical contact with the internal part and is intended, inter alia, to connect an external circuit;
  • the inner part of the electrode is a compacted briquette of porous activated carbon intercalated with a donor impurity to increase the concentration of conduction electrons of the coal;
  • the external part of the electrode is a graphite rod, which is in electrical contact with the internal part and is intended, inter alia, for connecting an external circuit;
  • the inner part of the electrode is a compacted briquette of porous activated carbon intercalated with an acceptor impurity in order to reduce the concentration of conduction electrons and create hole conductivity of coal;
  • An aqueous solution contains some amount of inorganic salt to prevent, as a result of dissociation, excessive unfolding of macromolecules of polyelectrolytes and to maintain the preferential conformation of macromolecules in the form of a coil.
  • membrane 6 is permeable for ions to which this salt dissociates into water.
  • an internal CRP arises due to the diffusion of electrons from part 3, made of intercalated graphite donor impurity, into part 1, made of ordinary graphite.
  • a double electric layer appears between the contacting surfaces, with the surface of part 3 being positively charged, and part 1 being negative.
  • the internal CRP associated with the difference in the contacting substances of the concentrations of conduction electrons.
  • an internal ⁇ arises, due to the diffusion of electrons from part 2, made of ordinary graphite, into part 4, made of intercalated acceptor impurity of graphite. Between the contacting surfaces there is a double electric layer, and the surface of part 2 is positively charged, and part 4 - negative.
  • the internal CRP which is related to the difference in the concentrations of conduction electrons from the contacting substances.
  • the dimensions of ions and molecules mean the sizes of their solvation shells, on which the dynamic and geometric characteristics of particles in a solution substantially depend.
  • the internal parts 3 and 4 of the composite electrodes are made of activated carbon, i.e. a material having, among other qualities, a very large surface area.
  • a large surface area of the electrodes is needed, in particular, in order to achieve a practically significant increase in the efficiency of the Element associated with the use of the Donnan potential arising at the interface between the surfaces of the electrodes and the solution.
  • the increase will occur due to the fact that, firstly, when moving through an external circuit from the inside of the anode 4 to the inside of the cathode, 3 fields of double electric layers at the junction of the parts of composite electrodes 4, 2 and 1, 3 for electrons are accelerating; and secondly: when moving through the solution from the inside of the anode 4 to the inside of the cathode 3 fields of double electric layers at the interfaces between the surfaces of electrodes and electrolytes, as well as electrolytes of the cathode and anode spaces between them, are also accelerating for hydrogen ions H + .
  • this also means that the external hydrogen pressure used for the Element operation can be reduced, leaving the quantitative current output in the load at the same level if additional emf is used in the Element operation. E add .
  • the increase will occur due to the fact that firstly: when moving through the external circuit from the inside of the anode 4 to the inside of the cathode, 3 fields of double electric layers at the junction of the parts of composite electrodes 4, 2 and 1, 3 for electrons are accelerating; and secondly: when moving through the solution from the inside of the anode 4 to the inside of the cathode 3 fields of double electric layers at the interfaces between the surfaces of electrodes and electrolytes, as well as electrolytes of the cathode and anode spaces between them, for hydrogen ions H + and hydroxide ions OH "are also accelerated.
  • the Element having design features aimed at using the potential of Donnan and the internal PKK of type I conductors for more emf in the circuit, it allows to increase the efficiency of electrolysis processes and to obtain useful electric power in the load, which, all other things being equal, entails an increase in the efficiency of the Element.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Hybrid Cells (AREA)
  • Primary Cells (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

L'invention se rapporte au domaine de l'industrie électrotechnique et peut être utilisée pour l'électrolyse d'électrolytes et/ou pour la production d'énergie électrique. L'invention concerne un élément électrochimique permettant d'utiliser le potentiel de Donnan et/ou le potentiel de Volta interne de ses parties constituantes afin d'augmenter l'économicité de fonctionnement dans les modes d'électrolyseur et de source de courant. Le potentiel de Donnan des électrodes et le potentiel de Volta interne des conducteurs d'un premier type sont suffisamment bas, ce qui permet d'envisager une augmentation sensible du coefficient d'efficacité de l'élément, par exemple lors d'une diminution de sa rentabilité en diminuant la tension envoyée à l'élément depuis une source d'alimentation externe en mode électrolyseur, ou d'une diminution de la différence des potentiels d'électrode standards en mode source de courant.
PCT/RU2012/000628 2012-06-18 2012-08-01 Élément électrochimique économique WO2013191578A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
RU2012125242/07A RU2012125242A (ru) 2012-06-18 2012-06-18 Экономичный электрохимический элемент
RU2012125242 2012-06-18

Publications (1)

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WO2013191578A1 true WO2013191578A1 (fr) 2013-12-27

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4836992A (en) * 1986-04-25 1989-06-06 Vereinigte Elektrizitatswerke Westfalen Ag Process for desulfurizing waste gases
RU2170468C1 (ru) * 2000-04-10 2001-07-10 Мирзоев Рустам Аминович Электрохимический накопитель энергии высокой удельной мощности и электрод для него
US20050227135A1 (en) * 2004-04-12 2005-10-13 Elena Chalkova Composite membrane for fuel cell and fuel cells incorporating said membranes
RU93804U1 (ru) * 2009-12-14 2010-05-10 Учреждение Российской академии наук Государственный научный центр Российской Федерации-Институт медико-биологических проблем Электрохимическая ячейка для получения водорода
RU2405864C1 (ru) * 2009-06-08 2010-12-10 Учреждение Российской академии наук Институт физической химии и электрохимии им. А.Н. Фрумкина Способ изготовления электрода для электрохимических процессов

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4836992A (en) * 1986-04-25 1989-06-06 Vereinigte Elektrizitatswerke Westfalen Ag Process for desulfurizing waste gases
RU2170468C1 (ru) * 2000-04-10 2001-07-10 Мирзоев Рустам Аминович Электрохимический накопитель энергии высокой удельной мощности и электрод для него
US20050227135A1 (en) * 2004-04-12 2005-10-13 Elena Chalkova Composite membrane for fuel cell and fuel cells incorporating said membranes
RU2405864C1 (ru) * 2009-06-08 2010-12-10 Учреждение Российской академии наук Институт физической химии и электрохимии им. А.Н. Фрумкина Способ изготовления электрода для электрохимических процессов
RU93804U1 (ru) * 2009-12-14 2010-05-10 Учреждение Российской академии наук Государственный научный центр Российской Федерации-Институт медико-биологических проблем Электрохимическая ячейка для получения водорода

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