ES2533760A1 - Membrana polimérica de litio basada en una matriz polimérica fluorada semicristalina y un surfactante no iónico - Google Patents

Membrana polimérica de litio basada en una matriz polimérica fluorada semicristalina y un surfactante no iónico Download PDF

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ES2533760A1
ES2533760A1 ES201331499A ES201331499A ES2533760A1 ES 2533760 A1 ES2533760 A1 ES 2533760A1 ES 201331499 A ES201331499 A ES 201331499A ES 201331499 A ES201331499 A ES 201331499A ES 2533760 A1 ES2533760 A1 ES 2533760A1
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lithium
polymeric
ionic surfactant
semi
polymeric membrane
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ES2533760B1 (es
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Leire ZUBIZARRETA SÁENZ DE ZAITEGUI
María Teresa GIL AGUSTÍ
Alfredo Quijano López
Marta GARCÍA PELLICER
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INST TECNOLOGICO de la EN ITE
Instituto Tecnologico de la Energia-Ite
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INST TECNOLOGICO de la EN ITE
Instituto Tecnologico de la Energia-Ite
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Priority to EP14183036.4A priority patent/EP2860790B1/en
Priority to ES14183036.4T priority patent/ES2642922T3/es
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409Separators, membranes or diaphragms characterised by the material
    • H01M50/411Organic material
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    • H01M50/417Polyolefins
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    • C08K3/32Phosphorus-containing compounds
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/16Homopolymers or copolymers or vinylidene fluoride
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02Polyalkylene oxides
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    • C09D127/00Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C09D127/16Homopolymers or copolymers of vinylidene fluoride
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/056Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565Polymeric materials, e.g. gel-type or solid-type
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    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/497Ionic conductivity
    • CCHEMISTRY; METALLURGY
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    • C08K3/32Phosphorus-containing compounds
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    • C08K2003/324Alkali metal phosphate
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    • H01M2300/0082Organic polymers
    • YGENERAL 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
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Abstract

Membrana polimérica de litio basada en una matriz polimerica fluorada semicristalina y un surfactante no iónico. Membrana polimérica de litio caracterizada porque comprende una matriz polimérica fluorada y semicristalina una sal de litio y un surfactante no iónico como plastificante. Preferiblemente, comprende poli(vinilideno fluoruro-co-hexafluoropropileno), polietilenglicol tert-octilfenil éter y hexafluorofosfato de litio. Así como el uso de esta membrana polimérica como electrolito y/o aislante eléctrico en baterías poliméricas de litio.

Description

imagen1
imagen2
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En otra realización preferida, la matriz polimérica fluorada y semicristalina es poli(vinilideno fluoruro-co-hexafluoropropileno) (PVdF-HFP). Preferiblemente, con un punto de fusión entre 110 y 160 ºC, más preferiblemente 140ºC. Esta matriz polimérica es estable en la ventana de potencial típica de las baterías de litio, es decir, entre 2-4 V.
En otra realización preferida, la membrana polimérica de litio tal como se describe en esta solicitud de patente comprende una sal de litio soluble en disolventes orgánicos, estable química y electroquímicamente. Preferiblemente se selecciona del grupo que consiste en triflato de litio, bis(oxalato)borato de litio, perclorato de litio y hexafluorofosfato de litio. Más preferiblemente, la sal de litio es hexafluorofosfato de litio.
En otra realización preferida, la membrana polimérica de litio tal como se describe en esta solicitud de patente, preferiblemente cuando comprende PVdF-HFP, hexafluorofosfato de litio y polietilenglicol tert-octilfenil éter, presenta una conductividad entre 2.4 10-8 y 1.20-5 S cm-1 a 25 ºC; y entre 1.6 10-5 y 3.4 10-4 en el rango de temperaturas de 40-100ºC.
En otra realización preferida, la membrana polimérica de litio de la presente invención comprende entre 35 y 55% de PVdF-HFP, entre 15 y 30 % de hexafluorofosfato de litio y entre 30 y 50% de polietilenglicol tert-octilfenil éter.
Tal como se muestra en el apartado de los ejemplos, la membrana polimérica de la presente invención permite obtener un valor de conductividad similar al de otras membranas de carbonato obtenidas por el mismo procedimiento, con la misma proporción de reactivos, siendo la sal de litio y matriz polimérica idénticas, y la utilización de un carbonato, en los ejemplos EC (carbonato de etileno) o DEC (carbonato de dietilo), como plastificante la única diferencia entre ambas.
Así la presente invención proporciona una membrana polimérica de litio mejorada respecto a las conocidas que comprenden carbonato ya que presenta conductividades del mismo orden de magnitud a éstas, siendo el resto de componentes y el procedimiento de obtención iguales, con la ventaja adicional de que la membrana de la invención es más estable térmica y electroquímicamente, y utiliza plastificantes no inflamables. Además, tal como se ha mencionado anteriormente, la presente invención proporciona una membrana polimérica con hasta un 30 % en peso de sal de litio respecto al peso total de la membrana, con
7
imagen6
En una realización preferida, la presente invención se refiere al uso de la membrana polimérica que comprende PVdF-HFP, hexafluorofosfato de litio y polietilenglicol tertoctilfenil éter, como electrolito y/o aislante eléctrico en baterías poliméricas de litio.
BREVE DESCRIPCIÓN DE LAS FIGURAS
Figura 1. Voltametria lineal de barrido para P72 (carbonatos líquidos)
Figura 2. Voltametria lineal de barrido para S2 (surfactante no iónico).
Figura 3. Termograma de las membranas S2 y P72.
Figura 4. Curvas de tensión-deformación de las membranas S3 y P73.
EJEMPLOS
Ejemplo 1: Membrana polimérica que comprende surfactante no iónico (muestra S2 y S3)
Se preparó en primer lugar, bajo atmosfera inerte, una suspensión polimérica que contenía PVdF-HFP, hexafluorofosfato de litio y polietilenglicol tert-octilfenil éter. La mezcla de los tres componentes se disolvió en tetrahidrofurano a 60 ºC durante 1 hora. Una vez obtenida la disolución polimérica se llevó a cabo el proceso de casting que consiste en depositar sobre un sustrato plano una película de polímero con el espesor deseado. Una vez realizada la deposición se dejó evaporar el disolvente a 22-25ºC y bajo una corriente de nitrógeno hasta que el contenido de disolventes residuales sea menor del 1%.
Las proporciones de los componentes de la membrana estudiadas fueron 35-55% de PVdF-HFP, 15-30 % de hexafluorofosfato de litio y 30-50% de polietilenglicol tert-octilfenil éter.
Ejemplo 2: Membrana polimérica que comprende surfactante basado en carbonatos (muestra P72 y P73)
La membrana polimérica que contiene carbonato líquido se sintetizó utilizando exactamente el mismo procedimiento descrito en el ejemplo 1, con la salvedad de utilizar como
9
plastificante una mezcla 1/1 en volumen de EC/DEC que da lugar a los valores de conductividad de la tabla 2.
Tabla 1. Composición de membranas poliméricas desarrolladas utilizando surfactante no iónico (S2 y S3) y membranas poliméricas con carbonatos líquidos (P72 y P73) utilizadas para la medición de la conductividad iónica en la tabla 2
Muestra
Plastificante %Polímero (PVdF-HFP) %Sal (LiPF6) %Plastificante
S2
Surfactante no iónico (polietilenglicol tertoctilfenil éter) 55 15 30
P72
Carbonatos líquidos 55 15 30
S3
Surfactante no iónico (polietilenglicol tertoctilfenil éter) 40 30 30
P73
Carbonatos líquidos 40 30 30
10 Tabla 2. Conductividad iónica a temperatura ambiente de S2, P72, S3 y P73
MEMBRANA
CONDUCTIVIDAD T=25ºC (S cm-1)
S2 (surfactante no iónico)
2.8 10-7
P72 (carbonatos líquidos)
9.5 10-7
S3 (surfactante no iónico)
4.6 10-6
P73 (carbonatos líquidos)
1.0 10-5
10
imagen7

Claims (1)

  1. imagen1
ES201331499A 2013-10-11 2013-10-11 Membrana polimérica de litio basada en una matriz polimérica fluorada semicristalina y un surfactante no iónico Active ES2533760B1 (es)

Priority Applications (3)

Application Number Priority Date Filing Date Title
ES201331499A ES2533760B1 (es) 2013-10-11 2013-10-11 Membrana polimérica de litio basada en una matriz polimérica fluorada semicristalina y un surfactante no iónico
EP14183036.4A EP2860790B1 (en) 2013-10-11 2014-09-01 Lithium polymeric membrane based on a semi-crystalline fluorinated polymeric matrix and a non-ionic surfactant
ES14183036.4T ES2642922T3 (es) 2013-10-11 2014-09-01 Membrana polimérica de litio basada en una matriz polimérica fluorada semicristalina y un tensioactivo no iónico

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ES201331499A ES2533760B1 (es) 2013-10-11 2013-10-11 Membrana polimérica de litio basada en una matriz polimérica fluorada semicristalina y un surfactante no iónico

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ES14183036.4T Active ES2642922T3 (es) 2013-10-11 2014-09-01 Membrana polimérica de litio basada en una matriz polimérica fluorada semicristalina y un tensioactivo no iónico

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20160036105A (ko) * 2007-12-21 2016-04-01 바티움 캐나다 인크. 리튬 폴리머 배터리용 전해질
JP5412937B2 (ja) * 2009-04-27 2014-02-12 ソニー株式会社 非水電解質組成物及び非水電解質二次電池

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ES2533760B1 (es) 2016-02-05
EP2860790B1 (en) 2017-09-27
EP2860790A1 (en) 2015-04-15

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