ES2546604T3 - Batería de metal-aire con un dispositivo de protección del electrodo de aire - Google Patents

Batería de metal-aire con un dispositivo de protección del electrodo de aire Download PDF

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Publication number
ES2546604T3
ES2546604T3 ES12728689.6T ES12728689T ES2546604T3 ES 2546604 T3 ES2546604 T3 ES 2546604T3 ES 12728689 T ES12728689 T ES 12728689T ES 2546604 T3 ES2546604 T3 ES 2546604T3
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air
electrode
terminal
metal
air electrode
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Gwenaëlle TOUSSAINT
Philippe Stevens
Bernard TOUSSAINT
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Electricite de France SA
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Electricite de France SA
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/425—Structural combination with electronic components, e.g. electronic circuits integrated to the outside of the casing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/44—Methods for charging or discharging
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/48—Accumulators combined with arrangements for measuring, testing or indicating the condition of cells, e.g. the level or density of the electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/572—Means for preventing undesired use or discharge
    • H01M50/574—Devices or arrangements for the interruption of current
    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02J—ELECTRIC POWER NETWORKS; CIRCUIT ARRANGEMENTS OR SYSTEMS FOR SUPPLYING OR DISTRIBUTING ELECTRIC POWER; SYSTEMS FOR STORING ELECTRIC ENERGY
    • H02J7/00—Circuit arrangements for charging or discharging batteries or for supplying loads from batteries
    • H02J7/865—Battery or charger load switching, e.g. concurrent charging and load supply
    • 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
    • Y02E60/10—Energy storage using batteries

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Hybrid Cells (AREA)
  • Inert Electrodes (AREA)
  • Secondary Cells (AREA)

Abstract

Batería recargable que comprende una o más celdas metal-aire, comprendiendo cada celda - un primer terminal (1) y un segundo terminal (2), - un electrodo negativo (3) metálico para la celda metal-aire, conectado al primer terminal (1), - un primer electrodo positivo (4) de evolución de oxígeno, - un segundo electrodo positivo (5) que es un electrodo de aire poroso que contiene al menos un catalizador de reducción de oxígeno, y - un electrolito, caracterizada por que comprende además - medios de control (6) adaptados para comparar de modo continuo la tensión medida (Vm) entre el terminal (2) y el terminal (1) con un valor de referencia (Vr) y para enviar una señal de conmutación a los medios de conmutación (7) cuando la tensión medida (Vm) llega a ser más baja que el valor de referencia (Vr), - medios de conmutación (7) adaptados para recibir una señal de conmutación que proviene de los medios de control (6) y para conectar y desconectar el electrodo de aire (5) del segundo terminal (2).

Description

E12728689
02-09-2015
DESCRIPCIÓN
Batería de metal-aire con un dispositivo de protección del electrodo de aire
5 Sector de la técnica
La presente invención se refiere a una batería de metal-aire recargable que comprende un electrodo de aire, un electrodo de evolución de oxígeno y un dispositivo automático de protección del electrodo de aire en fase de carga y de descarga de la batería. La invención se refiere a igualmente un procedimiento de almacenamiento y de liberación de la energía eléctrica utilizando dicha batería.
Estado de la técnica
Las baterías de metal-aire utilizan un electrodo negativo a base de un metal tal como el zinc, el hierro o el litio,
15 acoplado a un electrodo de aire. Durante la descarga de dicha batería, el oxígeno molecular se reduce en el electrodo positivo y el metal se oxida en el electrodo negativo:
imagen1
Los dos electrodos normalmente están en contacto con un electrolito acuoso alcalino.
25 Las pilas zinc-aire se comercializan, por ejemplo, para su utilización en prótesis auditivas.
Se han efectuado numerosos trabajos desde hace varias décadas para la puesta a punto y la optimización de electrodos de aire que permiten realizar generadores electroquímicos del tipo metal-aire, conocidos por sus elevadas energías másicas, que pueden alcanzar varios cientos de Wh/kg.
Los electrodos de aire presentan la ventaja de poder utilizar como agente oxidante para la reducción electroquímical oxígeno del aire, disponible en cantidad ilimitada en cualquier lugar y en todo momento. No obstante es necesaria una gran superficie de reacción ya que la densidad del oxígeno en el aire es baja (0,03 mol/l). La estructura sólida porosa de los electrodos de aire proporciona esta gran superficie de reacción. Un
35 electrodo de aire es una estructura sólida porosa en contacto con el electrolito líquido, generalmente una solución acuosa alcalina. La interfaz entre el electrodo de aire y el electrolito líquido es una interfaz denominada de «triple contacto» donde están presentes simultáneamente la materia activa del electrodo, el oxidante gaseoso y el electrolito líquido.
Se puede hacer referencia, por ejemplo, al artículo de V. Neburchilov y al. «A review on air cathodes for zinc-air fuel cells» Journal of Power Sources 195 (2010), páginas 1271 - 1291 para una descripción de los diferentes tipos de electrodos de aire utilizables en las baterías zinc-aire.
Los electrodos de aire, no obstante, presentan un inconveniente considerable que es su gran fragilidad cuando se
45 utilizan durante la recarga de la batería. En efecto, el electrodo de aire tiene una estructura porosa y funciona como un electrodo volumétrico en el que la reacción electroquímica se produce en todo el volumen del electrodo, en la interfaz entre el oxidante gaseoso, el electrolito líquido y la materia activa sólida (triple contacto). En fase de carga, el oxígeno molecular gaseoso se forma en el seno de la estructura del electrodo de aire. Este oxígeno gaseoso conduce rápidamente a la destrucción mecánica de la estructura porosa del electrodo de aire rompiendo los enlaces entre las partículas de carbono y el polímero aglutinante utilizado.
Por otro lado, la corrosión del carbono en presencia del oxígeno por oxidación del carbono se acelera igualmente a potenciales elevados (véase el artículo de Kim J., Lee J. Tak Y., «Relationship between carbon corrosion and positive electrode potential in a proton-exchange membrane fuel-cell during star/stop operation» (2009), Journal of
55 Power Sources, 192 (2), páginas 674 - 678, y el capítulo «Carbon» de Kinishita, K. (2007), en el Handbook of Battery Materials (director de la publicación J.O. Besenhard), Wiley-VCH Verlag GmbH, Weinheim, Alemania.).
Los inventores han observado también que los catalizadores de reducción del oxígeno incorporados en el electrodo de aire, en la superficie de las partículas de carbono, no son estables a potenciales elevados, necesarios para la reacción de oxidación inversa. Ciertos autores han utilizado catalizadores de reducción del oxígeno más resistentes, acoplados a un catalizador de evolución de oxígeno en un electrodo bifuncional compuesto por dos capas eléctricamente acopladas (véase el documento US 5 306 579). Esta configuración, sin embargo, produce electrodos que tienen una vida útil baja y un número de ciclos limitado.
65 Otra solución conocida para ese problema de la degradación del electrodo de aire durante la fase de recarga de la batería es el uso de un electrodo de evolución de oxígeno, es decir, de un segundo electrodo positivo que no
2
imagen2
imagen3
imagen4
imagen5

Claims (1)

  1. imagen1
ES12728689.6T 2011-05-19 2012-05-15 Batería de metal-aire con un dispositivo de protección del electrodo de aire Active ES2546604T3 (es)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR1154356A FR2975534B1 (fr) 2011-05-19 2011-05-19 Accumulateur metal-air avec dispositif de protection de l'electrode a air
FR1154356 2011-05-19
PCT/FR2012/051080 WO2012156639A1 (fr) 2011-05-19 2012-05-15 Accumulateur métal-air avec dispositif de protection de l'électrode à air

Publications (1)

Publication Number Publication Date
ES2546604T3 true ES2546604T3 (es) 2015-09-25

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Country Status (11)

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US (1) US9293757B2 (es)
EP (1) EP2710663B1 (es)
JP (2) JP6198720B2 (es)
KR (2) KR101674628B1 (es)
CN (2) CN105514517B (es)
DK (1) DK2710663T3 (es)
ES (1) ES2546604T3 (es)
FR (1) FR2975534B1 (es)
PT (1) PT2710663E (es)
SG (1) SG195019A1 (es)
WO (1) WO2012156639A1 (es)

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US20140191727A1 (en) 2014-07-10
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WO2012156639A1 (fr) 2012-11-22
FR2975534B1 (fr) 2013-06-28
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