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 PDFInfo
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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
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- polymeric membrane
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- 239000012528 membrane Substances 0.000 title abstract description 21
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title abstract description 9
- 229910052744 lithium Inorganic materials 0.000 title abstract description 9
- 239000002736 nonionic surfactant Substances 0.000 title abstract description 9
- 239000011159 matrix material Substances 0.000 title abstract description 5
- 239000002202 Polyethylene glycol Substances 0.000 abstract description 8
- -1 lithium hexafluorophosphate Chemical compound 0.000 abstract description 8
- 229920001223 polyethylene glycol Polymers 0.000 abstract description 8
- 239000004014 plasticizer Substances 0.000 abstract description 6
- ODWNBAWYDSWOAF-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-yloxybenzene Chemical compound CC(C)(C)CC(C)(C)OC1=CC=CC=C1 ODWNBAWYDSWOAF-UHFFFAOYSA-N 0.000 abstract description 5
- 229910003002 lithium salt Inorganic materials 0.000 abstract description 5
- 159000000002 lithium salts Chemical class 0.000 abstract description 5
- 239000003792 electrolyte Substances 0.000 abstract description 2
- 239000000615 nonconductor Substances 0.000 abstract description 2
- 229920000131 polyvinylidene Polymers 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000004832 voltammetry Methods 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006126 semicrystalline polymer Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
Classifications
-
- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- 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
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/417—Polyolefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions 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
- C08L27/02—Compositions 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
- C08L27/12—Compositions 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
- C08L27/16—Homopolymers or copolymers or vinylidene fluoride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D127/00—Coating 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
- C09D127/02—Coating 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
- C09D127/12—Coating 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
- C09D127/16—Homopolymers or copolymers of vinylidene fluoride
-
- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators 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
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-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
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/497—Ionic conductivity
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/324—Alkali metal phosphate
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
-
- 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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- Chemical Kinetics & Catalysis (AREA)
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- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
- Compositions Of Macromolecular Compounds (AREA)
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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
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
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.
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
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.
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
Claims (1)
-
imagen1
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 |
Applications Claiming Priority (1)
| 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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| ES2533760A1 true ES2533760A1 (es) | 2015-04-14 |
| ES2533760B1 ES2533760B1 (es) | 2016-02-05 |
Family
ID=51483232
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| ES201331499A Active ES2533760B1 (es) | 2013-10-11 | 2013-10-11 | Membrana polimérica de litio basada en una matriz polimérica fluorada semicristalina y un surfactante no iónico |
| 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 |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| 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 |
Country Status (2)
| Country | Link |
|---|---|
| EP (1) | EP2860790B1 (es) |
| ES (2) | ES2533760B1 (es) |
Family Cites Families (2)
| 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 |
-
2013
- 2013-10-11 ES ES201331499A patent/ES2533760B1/es active Active
-
2014
- 2014-09-01 ES ES14183036.4T patent/ES2642922T3/es active Active
- 2014-09-01 EP EP14183036.4A patent/EP2860790B1/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| ES2642922T3 (es) | 2017-11-20 |
| ES2533760B1 (es) | 2016-02-05 |
| EP2860790B1 (en) | 2017-09-27 |
| EP2860790A1 (en) | 2015-04-15 |
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