[go: up one dir, main page]

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

Info

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
Authority
WO
WIPO (PCT)
Prior art keywords
carbonate
adsorbent
added
methyl
ethyl
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/EP1999/003938
Other languages
German (de)
English (en)
Inventor
Michael Jungnitz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Merck Patent GmbH
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
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

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 Ceased 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

ID=7871576

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1999/003938 Ceased 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
EP2607315A1 (fr) 2011-12-23 2013-06-26 LANXESS Deutschland GmbH Solutions LiPF6
EP2607306A1 (fr) 2011-12-23 2013-06-26 LANXESS Deutschland GmbH Solutions de lipf6
EP2607305A1 (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
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

Similar Documents

Publication Publication Date Title
DE112019005761B4 (de) Prozesse zur Entfernung von reaktivem Lösungsmittel aus Lithium Bis(fluorosulfonyl)imid (LiFSI) unter Verwendung organischer Lösungsmittel, die stabil gegenüber Anoden in Lithium-Ionen- und Lithium-Metall-Batterien sind
EP3818579B1 (fr) L&#39;électrolyte comprenant phosphite comme un additif ou un co-solvant, une batterie secondaire de lithium comprenant l&#39;électrolyte et la méthode pour fabriquer le phosphite
DE112022001347B4 (de) VERFAHREN ZUR HERSTELLUNG EINES POSITIVEN ELEKTRODENMATERIALS FÜR EINE PREUßISCH-BLAU-NATRIUM-IONEN-BATTERIE
DE102005012116B3 (de) Verfahren und Vorrichtung zur Herstellung von 4-Fluorethylencarbonat
EP1097485A1 (fr) Purification d&#39;electrolytes pour accumulateurs a l&#39;aide de l&#39;adsorption chimique
DE1917907B2 (de) Galvanisches primaerelement mit einer negativen leichtmetall elektrode einem nicht waessrigen elektrolyten und einer positiven elektrode aus festem kohlenstoffluorid und verfahren zur herstellung der positiven elektrode
EP2185569B1 (fr) Procédé pour produire des borates de lithium, à faible teneur en acide, et mélanges de borates de lithium à faible teneur en acide et d&#39;hydrures de lithium
DE19963399A1 (de) Herstellungsverfahren für Hexafluorphosphat
DE2834485A1 (de) Wiederaufladbares galvanisches lithium-element
DE112019005762T5 (de) Gereinigte lithiumbis(fluorosulfonyl)imid (lifsi) produkte, verfahren zum reinigen von roh-lifsi, und verwendungen von gereinigten lifsi-produkten
WO1999067844A1 (fr) Purification d&#39;electrolytes pour accumulateurs a l&#39;aide de l&#39;adsorption physique
EP1147569B1 (fr) Systeme d&#39;electrolyte pour piles au lithium et son utilisation, ainsi que procede pour accroitre la securite des piles au lithium
DE10008955A1 (de) Lithiumfluoralkylphosphate und deren Verwendung als Leitsalze
DE102019132622A1 (de) Binderlösung für Festkörperbatterie, Elektrodenaufschlämmung für eine Festkörperbatterie, die selbige aufweist, und ein Herstellungsverfahren einer Festkörperbatterie, die selbige verwendet
DE19732658A1 (de) Elektrolytische Zelle mit einer kontrollierten Elektrodenoberflächengrenzfläche
JPS5981869A (ja) リチウム電池の製造方法
JP3087956B2 (ja) リチウム二次電池用電解液及びその製造方法、並びにその電解液を用いたリチウム二次電池
EP1107930B1 (fr) PROCEDE POUR LA PRODUCTION DE LiBF 4? DE GRANDE PURETE
DE3525475C1 (de) Verfahren zur Aufbereitung von Titandisulfid fuer den Einsatz in Batterien
WO2013092990A1 (fr) Solutions de lipf6
DE102016013809A1 (de) Additiv-Zusammensetzung, Elektrolyt mit der Additiv-Zusammensetzung und wiederaufladbare Batteriezelle mit dem Elektrolyt
DE102023112154A1 (de) Natriumionenbatterie, Verfahren zum Herstellen einer Natriumionenbatterie und Verwendung einer Natriumionenbatterie
DE19824984A1 (de) Verfahren zur Kristallisation von hochreinem LiPF¶6¶ aus organischen Lösungsmitteln
DE19915056A1 (de) Verfahren zur Dehydratisierung Li-Ionen enthaltender Elektrolyte
DE3411258A1 (de) Nichtgasender sicherheitselektrolyt fuer wasserfreie elektrochemische zellen

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AL AM AT AU AZ BA BB BG BR BY CA CH CN CU CZ DE DK EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT UA UG US UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW SD SL SZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: CA