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WO1999067844A1 - Purification of battery electrolytes by means of physical adsorption - Google Patents

Purification of battery electrolytes by means of physical adsorption Download PDF

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Publication number
WO1999067844A1
WO1999067844A1 PCT/EP1999/003938 EP9903938W WO9967844A1 WO 1999067844 A1 WO1999067844 A1 WO 1999067844A1 EP 9903938 W EP9903938 W EP 9903938W WO 9967844 A1 WO9967844 A1 WO 9967844A1
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Prior art keywords
carbonate
adsorbent
added
methyl
ethyl
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PCT/EP1999/003938
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German (de)
French (fr)
Inventor
Michael Jungnitz
Original Assignee
Merck Patent Gmbh
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Publication date
Application filed by Merck Patent Gmbh filed Critical Merck Patent Gmbh
Priority to AU43741/99A priority Critical patent/AU4374199A/en
Publication of WO1999067844A1 publication Critical patent/WO1999067844A1/en

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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
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
    • H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte

Definitions

  • the present invention relates to a method for removing protic impurities from battery electrolytes by means of physical adsorption.
  • the commonly used lithium batteries (secondary and primary battery cells) generally use electrolytes that consist of conductive salts such as LiPF 6 , LiBF 4 , LiCIO 4 , LiAsF 6 , Li methide, Li imide or Li triflate and a mixture consist of solvents, mainly organic carbonates, such as propylene carbonate, ethylene carbonate or butylene carbonate, ethers, such as dimethyl ether, and propionates, such as methyl propionate or ethyl propionate.
  • conductive salts such as LiPF 6 , LiBF 4 , LiCIO 4 , LiAsF 6 , Li methide, Li imide or Li triflate
  • solvents mainly organic carbonates, such as propylene carbonate, ethylene carbonate or butylene carbonate, ethers, such as dimethyl ether, and propionates, such as methyl propionate or ethyl propionate.
  • these electrolyte solutions normally contain protic impurities such as water, alcohols, peroxides.
  • the conductive salts in the electrolyte solutions are extremely sensitive to these impurities and, in the case of LiPF 6 , decompose, for example, to HF, LiF or POF 3 and to various oxyfluorophosphoric acids (H a P b O c F d ).
  • These decomposition products are very harmful to the battery cells because they attack the cell components, i.e. the cathode and anode, and the
  • HF in particular is very aggressive in this regard, it is necessary to significantly reduce the HF content in the electrolyte mixtures, which is normally 50-80 ppm. An HF content of less than 30 ppm is desired for most applications.
  • the water content of the electrolyte mixture should also be as low as possible so that these decomposition products cannot occur to the extent that existed up to now.
  • the lowest possible water content (for example less than 20 ppm) is therefore desirable.
  • the previously used methods of reducing the water content in a conventional way are not effective enough.
  • the invention therefore relates to a process for the purification of electrolyte solutions for lithium cells, characterized by the following steps: a) addition of an adsorbent which contains the protic impurities
  • the electrolyte solutions according to the invention essentially consist of conductive salts such as LiPF 6 , LiBF 4 , LiCIO 4 , LiAsF 6 , Li methides, Li imides or Li triflates, preferably in a concentration of 0.7 to 1.8 mol / l, and
  • organic solvents such as propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, Methyl propyl carbonate, ethyl propyl carbonate and other organic carbonates, and propionates such as methyl propionate or ethyl propionate, formates such as ethyl formate or methyl formate, acetates such as methyl acetate, ethyl acetate, halogenated carbonates such as chlorinated ethylene carbonate, fluorinated ethylene carbonate, fluorinated propylene carbonate or fluorinated
  • Ethylene carbonate but also ethers such as dimethoxyethane.
  • Suitable substances are all substances which can adsorb protic substances in a physical way, such as silica gel, calcium carbonate, calcium oxide or aluminum oxide such as Al 2 0 3 , 0, but particularly preferably Al 2 O 3 is used as the adsorbent.
  • the purification according to the invention can be carried out in various ways.
  • the first option is to mix the electrolyte solution, then add the adsorbent to separate the protic impurities' 5 , which is then separated off again.
  • the solvents required for the electrolyte solution are first mixed, then the adsorbent is added.
  • the adsorbent is separated off again and only at the end is the conductive salt mixed in. 0
  • the adsorbent can be introduced into the respective mixture with stirring and then separated off again by filtration.
  • reaction time can be chosen as desired, but is preferably kept as short as possible; experience has shown that a short one is sufficient
  • the adsorbent can be filled into a column.
  • the solution to be cleaned is passed through the adsorbent column by means of a pump.
  • the adsorbent to be anhydrous, preferably it is before
  • the anhydrous Al 2 O 3 is preferably dried for a few days or weeks at about 400 ° C. in a stream of nitrogen, cooled and then stored in the absence of moisture or better used immediately.
  • adsorbent Preferably, 0.3 to 3% by weight of adsorbent is added to the electrolyte solutions to be cleaned. A content of 0.5 to 1% by weight of adsorbent is particularly preferred.
  • the adsorbent is separated off by filtration or the like. These conventional methods are known to the person skilled in the art.
  • the battery solvents purified according to the invention have values for the water content of less than 10 ppm and for the HF content of less than 30 ppm.
  • the electrolyte solutions according to the invention therefore show improved properties, such as higher cycle efficiency and longer service life, when used in lithium-ion and lithium batteries.
  • the invention thus also relates to electrolyte solutions which are suitable for lithium cells (primary or secondary) and which are characterized in that they are purified by the method described here.
  • Al 2 O 3 is dried anhydrous in a nitrogen stream at 400 ° C. for 4 weeks. After drying, the Al 2 0 3 is cooled and stored in the glove box.
  • the electrolytic solution is prepared as follows:
  • 440 g of ethylene carbonate and 440 g of dimethyl carbonate are mixed and cooled to 10 ° C. Then 120 g of LiPF 6 are added and mixed with stirring.
  • the electrolyte contains 60 ppm HF.
  • the solvents for the electrolyte, 440 g of ethylene carbonate and 440 g of dimethyl carbonate are mixed and the mixture is cooled to 10 ° C. Then 10 g of dried Al 2 O 3 are added, the mixture is stirred for 10 minutes and the adsorbent is filtered off again. Then it is cooled to 10 ° C. and 120 g of LiPF s are added with stirring.
  • the HF and H 2 O content is less than 20 ppm after the treatment.
  • Example 3 Al 2 0 3 is dried and stored as described in Example 1.
  • the adsorbent is then filled into a column.
  • An electrolytic solution is made as follows:
  • 440 g of ethylene carbonate and 440 g of dimethyl carbonate are mixed and the mixture is cooled to 10 ° C. 120 g of LiPF 6 are added and the mixture is mixed with stirring.
  • the electrolyte contains 60 ppm HF.
  • the electrolyte solution is then pumped over the column.
  • Q After purification, the HF and H 2 O content is less than 10 ppm each.
  • the electrolyte solution treated in this way has a water content of less

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Secondary Cells (AREA)

Abstract

The present invention relates to the removal of protic impurities from battery electrodes which are suitable for lithium cells by means of physical adsorption.

Description

Aufreinigung von Batterieelektrolyten mittels physikalischerPurification of battery electrolytes using physical
Adsorptionadsorption
Die vorliegende Erfindung betrifft eine Methode zur Entfernung von protischen Verunreinigungen aus Batterieelektrolyten mittels physikalischer Adsorption.The present invention relates to a method for removing protic impurities from battery electrolytes by means of physical adsorption.
Bei den üblich verwendeten Lithium-Batterien (sekundär und primär Batteriezellen) werden im Allgemeinen Elektrolyte eingesetzt, die aus Leitsalzen wie z.B. LiPF6, LiBF4, LiCIO4, LiAsF6, Li-Methiden, Li-Imiden oder Li-Triflaten und einer Mischung aus Lösungsmitteln, hauptsächlich organische Carbonate, wie Propylencarbonat, Ethylencarbonat oder Butylencarbonat, Ether, wie Dimethylethter, und Propionate, wie Methylpropionat oder Ethylpropionat, bestehen.The commonly used lithium batteries (secondary and primary battery cells) generally use electrolytes that consist of conductive salts such as LiPF 6 , LiBF 4 , LiCIO 4 , LiAsF 6 , Li methide, Li imide or Li triflate and a mixture consist of solvents, mainly organic carbonates, such as propylene carbonate, ethylene carbonate or butylene carbonate, ethers, such as dimethyl ether, and propionates, such as methyl propionate or ethyl propionate.
Diese Elektrolytlösungen enthalten normalerweise trotz hoher Reinheit der einzelnen Komponenten protische Verunreinigungen wie z.B. Wasser, Alkohole, Peroxide. Die Leitsalze in den Elektrolytlösungen reagieren jedoch äußerst empfindlich auf diese Verunreinigungen und zersetzen sich im Falle von LiPF6 beispielsweise zu HF, LiF oder POF3 und zu verschiedenen Oxyfluorphosphorsäuren (HaPbOcFd). Diese Zersetzungsprodukte sind für die Batteriezellen sehr schädlich, da sie die Zellkomponenten, also Kathode und Anode, angreifen und dieDespite the high purity of the individual components, these electrolyte solutions normally contain protic impurities such as water, alcohols, peroxides. However, the conductive salts in the electrolyte solutions are extremely sensitive to these impurities and, in the case of LiPF 6 , decompose, for example, to HF, LiF or POF 3 and to various oxyfluorophosphoric acids (H a P b O c F d ). These decomposition products are very harmful to the battery cells because they attack the cell components, i.e. the cathode and anode, and the
Deckschichtbildung an den Elektrolyten massiv beeinflussen. Die Lebenszeit einer Batterie wird dadurch wesentlich verkürzt.Massively influence the formation of cover layers on the electrolytes. This significantly shortens the life of a battery.
Da vor allem HF in dieser Beziehung sehr aggressiv ist, ist es notwendig, den Gehalt an HF in den Elektrolytmischungen, der normalerweise 50 - 80 ppm beträgt, wesentlich zu verringern. Für die meisten Anwendung wird ein HF-Gehalt von weniger als 30 ppm gewünscht.Since HF in particular is very aggressive in this regard, it is necessary to significantly reduce the HF content in the electrolyte mixtures, which is normally 50-80 ppm. An HF content of less than 30 ppm is desired for most applications.
Der Wassergehalt der Elektrolytmischung sollte möglichst ebenfalls sehr gering sein, damit diese Zersetzungsprodukte erst gar nicht in dem bisher bestehenden Umfang auftreten können. Ein möglichst geringer Wassergehalt (z.B. weniger als 20 ppm) ist daher wünschenswert. Die bisher angewandten Methoden, den Wassergehalt auf konventionelle Art zu reduzieren, sind nicht effektiv genug.The water content of the electrolyte mixture should also be as low as possible so that these decomposition products cannot occur to the extent that existed up to now. The lowest possible water content (for example less than 20 ppm) is therefore desirable. The previously used methods of reducing the water content in a conventional way are not effective enough.
In der kanadischen Patentanmeldung 2,193,119 wird eine Methode beschrieben, bei welcher die sauren Verunreinigungen mittels wasserstofffreien Chloriden, Bromiden oder lodiden abgetrennt werden. Jedoch ist diese Methode auch nicht optimal, denn die entstehenden Reaktionsprodukte HCI, HBr und HJ sind während und auch noch in geringem Umfang nach der Abtrennung durch Destillation in den Elektrolytmischungen mitenthalten und könnten daher weitere Reaktionen 1 Q auslösen. Ferner werden die Elektrolyte bei der Destillation erhitzt, was ebenfalls negative Auswirkungen haben kann. Ein weiterer Schritt kann notwendig sein, wenn ein festes Reaktionsprodukt noch anfällt und dieses ebenfalls noch abgetrennt werden soll.Canadian patent application 2,193,119 describes a method in which the acidic impurities are separated off using hydrogen-free chlorides, bromides or iodides. However, this method is also not optimal, because the reaction products formed HCl, HBr and HI are jointly contain by distillation into the electrolyte mixtures during and even to a small extent after the separation and could therefore trigger 1 Q further reactions. Furthermore, the electrolytes are heated during distillation, which can also have negative effects. A further step may be necessary if a solid reaction product still occurs and this should also be separated off.
Aufgabe der vorliegenden Erfindung war es nun, eine Methode zur „ c Abtrennung von protischen Verunreinigungen, insbesondere z.B. vonIt is an object of the present invention, a method for "c separation of protic impurities, in particular, for example, by
Wasser oder HF, zu finden, die einfach, schnell und effektiv durchzuführen ist und welche den Gehalt von Wasser auf weniger als 10 ppm und den von HF auf weniger als 30 ppm reduzieren kann.Find water, or HF, that is easy, quick, and effective to do, and that can reduce the water content to less than 10 ppm and that of HF to less than 30 ppm.
Es wurde nun gefunden, daß eine Abtrennung der protischen Verunreinigungen aus Batterielösungsmitteln einfach und sehr effektivIt has now been found that separation of the protic contaminants from battery solvents is simple and very effective
20 mittels physikalischer Adsorption durchgeführt werden kann.20 can be carried out by means of physical adsorption.
Gegenstand der Erfindung ist daher ein Verfahren zur Aufreinigung von Elektrolytlösungen für Lithium-Zellen, gekennzeichnet durch folgende Schritte: a) Zugabe eines Adsorbens, welches die protischen VerunreinigungenThe invention therefore relates to a process for the purification of electrolyte solutions for lithium cells, characterized by the following steps: a) addition of an adsorbent which contains the protic impurities
25 physikalisch adsorbiert, und b) Abtrennung des Adsorbens.25 physically adsorbed, and b) separation of the adsorbent.
Die erfindungsgemäßen Elektrolytlösungen bestehen im Wesentlichen aus Leitsalzen wie LiPF6, LiBF4, LiCIO4, LiAsF6, Li-Methiden, Li-Imiden oder Li- Triflaten, vorzugsweise in einer Konzentration von 0,7 bis 1 ,8 mol/l, undThe electrolyte solutions according to the invention essentially consist of conductive salts such as LiPF 6 , LiBF 4 , LiCIO 4 , LiAsF 6 , Li methides, Li imides or Li triflates, preferably in a concentration of 0.7 to 1.8 mol / l, and
30 Lösungsmittelgemischen ausgewählt aus den organischen Lösungsmitteln organische Carbonate wie Propylencarbonat, Ethylencarbonat, Butylencarbonat, Dimethylcarbonat, Diethylcarbonat, Ethylmethylcarbonat, Methylpropylcarbonat, Ethylpropylcarbonat und weitere organische Carbonate, und Propionate, wie Methylpropionat oder Ethylpropionat, Formiate, wie Ethylformiat oder Methylformiat, Acetate wie Methyiacetat, Ethylacetat, halogenierte Carbonate, wie chloriertes Ethylencarbonat, fluoriertes Ethylencarbonat, fluoriertes Propylencarbonat oder fluoriertes30 solvent mixtures selected from the organic solvents organic carbonates such as propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, Methyl propyl carbonate, ethyl propyl carbonate and other organic carbonates, and propionates such as methyl propionate or ethyl propionate, formates such as ethyl formate or methyl formate, acetates such as methyl acetate, ethyl acetate, halogenated carbonates such as chlorinated ethylene carbonate, fluorinated ethylene carbonate, fluorinated propylene carbonate or fluorinated
Ethylencarbonat, aber auch Ether wie Dimethoxyethan.Ethylene carbonate, but also ethers such as dimethoxyethane.
Als geeignete Adsorbentien kommen alle Substanzen in Frage, die auf physikalische Art protische Substanzen adsorbieren können, wie z.B. Silicagel, Calciumcarbonat, Calciumoxid oder Aluminiumoxid wie Al203, 0 insbesondere bevorzugt wird jedoch AI2O3 als Adsorbens verwendet.Suitable substances are all substances which can adsorb protic substances in a physical way, such as silica gel, calcium carbonate, calcium oxide or aluminum oxide such as Al 2 0 3 , 0, but particularly preferably Al 2 O 3 is used as the adsorbent.
Die Durchführung der erfindungsgemäßen Aufreinigung kann auf verschiedene Art und Weise geschehen.The purification according to the invention can be carried out in various ways.
Die erste Möglichkeit besteht darin, die Elektrolytlösung fertig zu mischen, dann das Adsorbens zur Abtrennung der protischen Verunreinigungen ' 5 zuzugegeben, welches dann anschließend wieder abgetrennt wird.The first option is to mix the electrolyte solution, then add the adsorbent to separate the protic impurities' 5 , which is then separated off again.
Bei der zweiten Möglichkeit werden zunächst die für die Elektrolytlösung benötigten Lösungsmittel gemischt, dann wird das Adsorbens zugegeben.In the second option, the solvents required for the electrolyte solution are first mixed, then the adsorbent is added.
Nach beendeter Adsoprtion wird das Adsorbens wieder abgetrennt und zum Schluß erst wird das Leitsalz zugemischt. 0After the adsorption has ended, the adsorbent is separated off again and only at the end is the conductive salt mixed in. 0
Das Adsorbens kann einerseits unter Rühren in die jeweilige Mischung eingebracht und anschließend durch Filtration wieder abgetrennt werden.On the one hand, the adsorbent can be introduced into the respective mixture with stirring and then separated off again by filtration.
Die Reaktionszeit kann beliebig gewählt werden, vorzugsweise wird sie jedoch so kurz wie möglich gehalten; erfahrungsgemäß reicht ein kurzesThe reaction time can be chosen as desired, but is preferably kept as short as possible; experience has shown that a short one is sufficient
Rühren von bis zu 10 Minuten aus, um die Adsorption vollständig 5 durchzuführen.Stir for up to 10 minutes to complete adsorption.
Andererseits kann das Adsorbens in eine Säule gefüllt werden. Die zu reinigende Lösung wird wie üblich mittels einer Pumpe über die Adsorbenssäule gegeben.On the other hand, the adsorbent can be filled into a column. As usual, the solution to be cleaned is passed through the adsorbent column by means of a pump.
3Q Das Adsorbens ums wasserfrei sein, vorzugsweise wird es vor dem3Q The adsorbent to be anhydrous, preferably it is before
Einsatz gut getrocknet. Vorzugsweise wird das wasserfreie AI2O3 über einige Tage oder Wochen bei ca. 400 °C im Stickstoffstrom getrocknet, abgekühlt und anschließend unter Ausschluß von Feuchtigkeit aufbewahrt oder besser sofort verwendet.Use well dried. The anhydrous Al 2 O 3 is preferably dried for a few days or weeks at about 400 ° C. in a stream of nitrogen, cooled and then stored in the absence of moisture or better used immediately.
Vorzugsweise gibt man 0,3 bis 3 Gew.-% an Adsorbens zu den zu reinigenden Elektrolytlösungen. Insbesondere bevorzugt ist ein Gehalt von 0,5 bis 1 Gew.-% an Adsorbens.Preferably, 0.3 to 3% by weight of adsorbent is added to the electrolyte solutions to be cleaned. A content of 0.5 to 1% by weight of adsorbent is particularly preferred.
Die Abtrennung des Adsorbens erfolgt durch Filtration oder Ähnliches. Diese konventionellen Methoden sind dem Fachmann bekannt.The adsorbent is separated off by filtration or the like. These conventional methods are known to the person skilled in the art.
Auf diese Weise erhält man aufgereinigte Elektrolytlösungen, die die hohen Anforderungen nach geringem Wassergehalt und bei Elektrolyten mit fluorierten Leitsalzen geringen HF-Gehalt erfüllen. Die erfindungsgemäß aufgereinigten Batterielösungsmittel weisen Werte für den Wassergehalt von kleiner als 10 ppm und für den HF-Gehalt von kleiner als 30 ppm auf.In this way, purified electrolyte solutions are obtained that meet the high requirements for low water content and low HF content for electrolytes with fluorinated conductive salts. The battery solvents purified according to the invention have values for the water content of less than 10 ppm and for the HF content of less than 30 ppm.
Die erfindungsgemäßen Elektrolytlösungen zeigen daher bei der Verwendung in Lithium-Ionen und Lithiumbatterien verbesserte Eigenschaften wie höhere Zykieneffizienz und längere Lebenszeit.The electrolyte solutions according to the invention therefore show improved properties, such as higher cycle efficiency and longer service life, when used in lithium-ion and lithium batteries.
Gegenstand der Erfindung sind somit auch Elektrolytlösungen, die geeignet sind für Lithium-Zellen (primär oder sekundär), die dadurch gekennzeichnet sind, daß sie nach der hier beschriebenen Methode aufgereinigt werden.The invention thus also relates to electrolyte solutions which are suitable for lithium cells (primary or secondary) and which are characterized in that they are purified by the method described here.
Auch ohne weitere Ausführungen wird davon ausgegangen, daß ein Fachmann die obige Beschreibung in weitesten Umfang nutzen kann. Die bevorzugten Ausführungsformen sind deswegen lediglich als beschreibende, keineswegs als in irgendeine Weise limitierende Offenbarung aufzufassen.Even without further explanations, it is assumed that a person skilled in the art can use the above description in the broadest scope. The preferred embodiments are therefore only to be understood as a descriptive disclosure, and in no way as a limitation in any way.
Die vollständige Offenbarung aller vor- und nachstehend aufgeführten Anmeldungen, Patente und Veröffentlichungen sind durch Bezugnahme in diese Anmeldung eingeführt.The full disclosure of all applications, patents, and publications listed above and below are incorporated by reference into this application.
Die folgenden Beispiele sollen die Erfindung näher erläutern. Beispiel 1The following examples are intended to explain the invention in more detail. example 1
Man trocknet AI2O3 wasserfrei im 400 °C heißen Stickstoffstrom über 4 Wochen. Nach der Trocknung wird das Al203 abgekühlt und in der Glove- Box gelagert.Al 2 O 3 is dried anhydrous in a nitrogen stream at 400 ° C. for 4 weeks. After drying, the Al 2 0 3 is cooled and stored in the glove box.
Die Elektrolytlösung wird folgendermaßen hergestellt:The electrolytic solution is prepared as follows:
440 g Ethylencarbonat und 440 g Dimethylcarbonat werden gemischt und auf 10 °C gekühlt. Danach werden 120 g LiPF6 hinzugegeben und unter Rühren gemischt. Der Elektrolyt enthält 60 ppm HF.440 g of ethylene carbonate and 440 g of dimethyl carbonate are mixed and cooled to 10 ° C. Then 120 g of LiPF 6 are added and mixed with stirring. The electrolyte contains 60 ppm HF.
Danach werden 10 g getrocknetes Al203 hinzugegeben. Nach 10 Minuten Rühren wird das AI2O3 abfiltriert.Then 10 g of dried Al 2 0 3 are added. After stirring for 10 minutes, the Al 2 O 3 is filtered off.
Gehalt an HF :HF content:
Anfangsmischung: 60 ppm Nach Adsorption: < 10 ppmInitial mixture: 60 ppm After adsorption: <10 ppm
Gehalt an H2O nach der Aufreinigung: kleiner 10 ppmH 2 O content after purification: less than 10 ppm
Beispiel 2Example 2
Al203 wird wie in Beispiel 1 getrocknet und gelagert.Al 2 0 3 is dried and stored as in Example 1.
Man mischt die Lösungsmittel für den Elektrolyten, 440 g Ethylencarbonat und 440 g Dimethylcarbonat und kühlt auf 10 °C ab. Dann werden 10 g getrocknetes AI2O3 hinzugegeben, rührt 10 Minuten und filtriert das Adsorbens wieder ab. Danach kühlt man auf 10 °C ab und gibt 120 g LiPFs unter Rühren hinzu.The solvents for the electrolyte, 440 g of ethylene carbonate and 440 g of dimethyl carbonate are mixed and the mixture is cooled to 10 ° C. Then 10 g of dried Al 2 O 3 are added, the mixture is stirred for 10 minutes and the adsorbent is filtered off again. Then it is cooled to 10 ° C. and 120 g of LiPF s are added with stirring.
Der Gehalt an HF und H2O liegt nach der Behandlung jeweils bei kleiner 20 ppm.The HF and H 2 O content is less than 20 ppm after the treatment.
Beispiel 3 Al203 wird wie in Beispiel 1 beschrieben getrocknet und gelagert.Example 3 Al 2 0 3 is dried and stored as described in Example 1.
Das Adsorbens wird dann in eine Säule gefüllt.The adsorbent is then filled into a column.
Eine Elektrolytlösung wird folgendermaßen hergestellt:An electrolytic solution is made as follows:
Man mischt 440 g Ethylencarbonat und 440 g Dimethylcarbonat und kühlt auf 10 °C ab. Dazu gibt man 120 g LiPF6 und mischt unter Rühren. Der Elektrolyt enthält 60 ppm HF.440 g of ethylene carbonate and 440 g of dimethyl carbonate are mixed and the mixture is cooled to 10 ° C. 120 g of LiPF 6 are added and the mixture is mixed with stirring. The electrolyte contains 60 ppm HF.
Die Elektrolytlösung wird dann mittels Pumpe über die Säule gegeben. Q Nach der Aufreinigung liegt der Gehalt an HF und H2O dann jeweils bei kleiner 10 ppm.The electrolyte solution is then pumped over the column. Q After purification, the HF and H 2 O content is less than 10 ppm each.
Beispiel 4Example 4
AI2O3 wird wie in Beispiel 1 beschrieben getrocknet und gelagert.Al 2 O 3 is dried and stored as described in Example 1.
Man mischt 500 g Propylencarbonat und 500 g 1 ,2-Dimethoxyethan.500 g of propylene carbonate and 500 g of 1,2-dimethoxyethane are mixed.
^ Anschließend werden unter Rühren und Kühlung 100 g LiCI04 hinzugegeben. Die Mischung hat einen Wassergehalt von 40 ppm.^ Then 100 g LiCI0 4 are added with stirring and cooling. The mixture has a water content of 40 ppm.
Anschließend werden 10 g getrocknetes AI2O3 hinzugegeben und intensiv vermischt. Nach 30 minütigem Stehen wird das Aluminiumoxid abfiltriert.Then 10 g of dried Al 2 O 3 are added and mixed intensively. After standing for 30 minutes, the aluminum oxide is filtered off.
Die so behandelte Elektrolytlösung weist einen Wassergehalt von kleinerThe electrolyte solution treated in this way has a water content of less
10 ppm auf. 2010 ppm. 20th
2525
30 30

Claims

P A T E N T A N S P R Ü C H E PATENT CLAIMS
1. Verfahren zur Aufreinigung von Elektrolytlösungen für Lithium-Zellen, gekennzeichnet durch folgende Schritte: a) Zugabe eines Adsorbens, welches die protischen Verunreinigungen physikalisch adsorbiert, und b) Abtrennung des Adsorbens.1. A process for the purification of electrolyte solutions for lithium cells, characterized by the following steps: a) addition of an adsorbent which physically adsorbs the protic impurities, and b) separation of the adsorbent.
2. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, daß das Adsorbens der fertig gemischten Elektrolytlösung zugegeben wird. 02. The method according to claim 1, characterized in that the adsorbent is added to the mixed electrolyte solution. 0
3. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, daß das Adsorbens zuerst den Lösungsmitteln zugegeben wird, um die Adsorption der Verunreinigungen durchzuführen, dann abgetrennt wird und anschließend erst das Leitsalz zugemischt wird.3. The method according to claim 1, characterized in that the adsorbent is first added to the solvents in order to carry out the adsorption of the impurities, then is separated off and only then the conductive salt is added.
4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch4. The method according to any one of claims 1 to 3, characterized
' gekennzeichnet, daß als Adsorbens AI2O3 verwendet wird.'characterized that AI 2 O 3 is used as the adsorbent.
5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß 0,3 bis 3 Gew.-%, insbesondere 0,5 bis 1 ,0 Gew.-%, Adsorbens zugesetzt werden. 05. The method according to any one of claims 1 to 4, characterized in that 0.3 to 3 wt .-%, in particular 0.5 to 1, 0 wt .-%, adsorbent are added. 0
6. Elektrolytlösung, geeignet für Lithium-Zellen, dadurch gekennzeichnet, daß sie nach dem in Anspruch 1 beschriebenen Verfahren aufgereinigt wird.6. electrolytic solution, suitable for lithium cells, characterized in that it is purified by the method described in claim 1.
7. Elektrolytlösung nach Anspruch 6, welche als Lösungsmittel organische Carbonate und/oder Propionate und/oder Formiate,7. electrolyte solution according to claim 6, which as a solvent organic carbonates and / or propionates and / or formates,
25 und/oder Acetate und/oder und/oder halogenierte Carbonate und/oder25 and / or acetates and / or and / or halogenated carbonates and / or
Ether enthält.Contains ether.
8. Elektrolytlösung nach Anspruch 6, welche als Lösungsmittel organische Carbonate, ausgewählt aus der Gruppe Propylencarbonat, Ethylencarbonat, Butylencarbonat, Dimethylcarbonat, Diethylcarbonat,8. Electrolyte solution according to claim 6, which as a solvent organic carbonates selected from the group propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate,
3Q Ethylmethylcarbonat, Methylpropylcarbonat, Ethylpropylcarbonat, und/oder Propionate, ausgewählt aus der Gruppe Methylpropionat und Ethylpropionat, und/oder Formiate, ausgewählt aus der Gruppe Ethylformiat und Methylformiat, und/oder Acetate, ausgewählt aus der Gruppe Methylacetat und Ethylacetat und/oder halogenierte Carbonate, ausgewählt aus der Gruppe chloriertes Ethylencarbonat, fluoriertes Ethylencarbonat, und fluoriertes Propylencarbonat, und/oder Ether wie Dimethoxyethan enthält.3 Q ethyl methyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, and / or propionate, selected from the group methyl propionate and ethyl propionate, and / or formate, selected from the group Ethyl formate and methyl formate, and / or acetates, selected from the group consisting of methyl acetate and ethyl acetate and / or halogenated carbonates, selected from the group consisting of chlorinated ethylene carbonate, fluorinated ethylene carbonate, and fluorinated propylene carbonate, and / or ethers such as dimethoxyethane.
Elektrolytlösung nach Anspruch 6, welche als Leitsalz LiPF6, LiBF4l LiCIO4, LiAsF6, Li-Methid, Li-Imid oder Li-Triflat enthält. Electrolytic solution according to claim 6, which contains LiPF 6 , LiBF 4l LiCIO 4 , LiAsF 6 , Li methide, Li imide or Li triflate as the conductive salt.
PCT/EP1999/003938 1998-06-20 1999-06-08 Purification of battery electrolytes by means of physical adsorption WO1999067844A1 (en)

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