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WO1999067844A1 - Purification d'electrolytes pour accumulateurs a l'aide de l'adsorption physique - Google Patents

Purification d'electrolytes pour accumulateurs a l'aide de l'adsorption physique 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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WO
WIPO (PCT)
Prior art keywords
carbonate
adsorbent
added
methyl
ethyl
Prior art date
Application number
PCT/EP1999/003938
Other languages
German (de)
English (en)
Inventor
Michael Jungnitz
Original Assignee
Merck Patent Gmbh
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 Merck Patent Gmbh filed Critical Merck Patent Gmbh
Priority to AU43741/99A priority Critical patent/AU4374199A/en
Publication of WO1999067844A1 publication Critical patent/WO1999067844A1/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
    • 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

Landscapes

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

Abstract

La présente invention concerne l'élimination, par adsorption physique, des impuretés protiques présentes dans des électrolytes d'accumulateurs qui sont appropriés pour des éléments d'accumulateur au lithium.
PCT/EP1999/003938 1998-06-20 1999-06-08 Purification d'electrolytes pour accumulateurs a l'aide de l'adsorption physique WO1999067844A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU43741/99A AU4374199A (en) 1998-06-20 1999-06-08 Purification of battery electrolytes by means of physical adsorption

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19827631.1 1998-06-20
DE1998127631 DE19827631A1 (de) 1998-06-20 1998-06-20 Aufreinigung von Batterieelektrolyten mittels physikalischer Adsorption

Publications (1)

Publication Number Publication Date
WO1999067844A1 true WO1999067844A1 (fr) 1999-12-29

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1999/003938 WO1999067844A1 (fr) 1998-06-20 1999-06-08 Purification d'electrolytes pour accumulateurs a l'aide de l'adsorption physique

Country Status (3)

Country Link
AU (1) AU4374199A (fr)
DE (1) DE19827631A1 (fr)
WO (1) WO1999067844A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7635084B2 (en) 1996-12-04 2009-12-22 Esignx Corporation Electronic transaction systems and methods therefor
US7666310B2 (en) 2000-09-27 2010-02-23 Chemetall Gmbh Method of drying organic liquid electrolytes

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10143171A1 (de) * 2001-09-04 2003-03-20 Solvay Fluor & Derivate Verfahren zur Säureabtrennung
EP2607306A1 (fr) 2011-12-23 2013-06-26 LANXESS Deutschland GmbH Solutions de lipf6
EP2607316A1 (fr) 2011-12-23 2013-06-26 LANXESS Deutschland GmbH Solutions LiPF6
EP2607305A1 (fr) 2011-12-23 2013-06-26 LANXESS Deutschland GmbH Solutions de LiPF6
EP2607315A1 (fr) 2011-12-23 2013-06-26 LANXESS Deutschland GmbH Solutions LiPF6
CN118367221A (zh) * 2023-01-11 2024-07-19 陕西奥林波斯电力能源有限责任公司 一种大容量电池及大容量电池的修复方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS54111633A (en) * 1978-02-20 1979-09-01 Sanyo Electric Co Nonnwater electrolyte cell
JPS55100665A (en) * 1979-01-26 1980-07-31 Nippon Telegr & Teleph Corp <Ntt> Battery
EP0075132A1 (fr) * 1981-09-15 1983-03-30 VARTA Batterie Aktiengesellschaft Elément galvanique à "getter" intégré
JPS5981869A (ja) * 1982-11-01 1984-05-11 Hitachi Maxell Ltd リチウム電池の製造方法
JPS6139464A (ja) * 1984-07-31 1986-02-25 Toyota Motor Corp 有機電解液二次電池
JPH05315006A (ja) * 1992-05-11 1993-11-26 Sony Corp 非水電解液電池及びその製造方法
US5304436A (en) * 1992-10-29 1994-04-19 Valence Technology Inc. Method and apparatus for drying a non-aqueous liquid electrolyte
WO1997034334A1 (fr) * 1996-03-15 1997-09-18 Valence Technology, Inc. Appareil et procede de preparation de piles electrochimiques

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS54111633A (en) * 1978-02-20 1979-09-01 Sanyo Electric Co Nonnwater electrolyte cell
JPS55100665A (en) * 1979-01-26 1980-07-31 Nippon Telegr & Teleph Corp <Ntt> Battery
EP0075132A1 (fr) * 1981-09-15 1983-03-30 VARTA Batterie Aktiengesellschaft Elément galvanique à "getter" intégré
JPS5981869A (ja) * 1982-11-01 1984-05-11 Hitachi Maxell Ltd リチウム電池の製造方法
JPS6139464A (ja) * 1984-07-31 1986-02-25 Toyota Motor Corp 有機電解液二次電池
JPH05315006A (ja) * 1992-05-11 1993-11-26 Sony Corp 非水電解液電池及びその製造方法
US5304436A (en) * 1992-10-29 1994-04-19 Valence Technology Inc. Method and apparatus for drying a non-aqueous liquid electrolyte
WO1997034334A1 (fr) * 1996-03-15 1997-09-18 Valence Technology, Inc. Appareil et procede de preparation de piles electrochimiques

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 7941, Derwent World Patents Index; Class L03, AN 79-74301B, XP002116139 *
DATABASE WPI Section Ch Week 8037, Derwent World Patents Index; Class L03, AN 80-65105C, XP002116140 *
PATENT ABSTRACTS OF JAPAN vol. 008, no. 194 (E - 264) 6 September 1984 (1984-09-06) *
PATENT ABSTRACTS OF JAPAN vol. 010, no. 192 (E - 417) 5 July 1986 (1986-07-05) *
PATENT ABSTRACTS OF JAPAN vol. 018, no. 116 (E - 1515) 24 February 1994 (1994-02-24) *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7635084B2 (en) 1996-12-04 2009-12-22 Esignx Corporation Electronic transaction systems and methods therefor
US7666310B2 (en) 2000-09-27 2010-02-23 Chemetall Gmbh Method of drying organic liquid electrolytes

Also Published As

Publication number Publication date
AU4374199A (en) 2000-01-10
DE19827631A1 (de) 1999-12-23

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