EP1431422B1 - Procédé de fabrication de lithium - Google Patents

Procédé de fabrication de lithium Download PDF

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Publication number
EP1431422B1
EP1431422B1 EP03026514A EP03026514A EP1431422B1 EP 1431422 B1 EP1431422 B1 EP 1431422B1 EP 03026514 A EP03026514 A EP 03026514A EP 03026514 A EP03026514 A EP 03026514A EP 1431422 B1 EP1431422 B1 EP 1431422B1
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EP
European Patent Office
Prior art keywords
lithium
amalgam
compounds
powder
lithium ion
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Expired - Lifetime
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EP03026514A
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German (de)
English (en)
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EP1431422A1 (fr
Inventor
Kerstin Dr. Schierle-Arndt
Günther Huber
Werner Prof.Dr. Weppner
Christian Dr. Dietz
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BASF SE
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BASF SE
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/02—Electrolytic production, recovery or refining of metals by electrolysis of melts of alkali or alkaline earth metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10—Obtaining alkali metals
    • C22B26/12—Obtaining lithium
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/04—Diaphragms; Spacing elements

Definitions

  • the present invention relates to a process for recovering lithium.
  • the invention relates to a process for recovering lithium from lithium amalgam by electrolysis on a lithium ion conductive solid electrolyte. It further relates to a process for the preparation of this electrolyte.
  • Lithium is an important basic inorganic chemical and is used in a number of different technical applications.
  • lithium is used to produce organolithium compounds, which in turn serve as strong bases or starting materials for specific syntheses, as alloying additives, or in lithium batteries.
  • Ullmann's Encyclopedia of Industrial Chemistry, 6th Edition, 2000 Electronic Release, keyword “Lithium and Lithium Compounds", in particular sections 5.1 “Production of Lithium Metal” and 5.2 “Uses of Lithium Metal” gives an overview of the state of the art the production and use of lithium.
  • the technically common way to produce lithium is the fused-salt electrolysis of a eutectic mixture of lithium chloride with potassium chloride at 400 to 460 ° C. This method requires comparatively much energy (28 - 32 kWh / kg lithium), besides, only anhydrous lithium chloride can be used. Since lithium chloride is hygroscopic, the necessary drying additionally stresses the economy of this process.
  • lithium ion-conducting solid electrolyte namely a) Li- ⁇ "-Al 2 O 3 or Li- ⁇ -Al 2 O 3 , b) lithium analogues of so-called NASICON ceramics of specific structure and composition, c) so-called LISICONS with specific structure and composition, d) lithium ionic conductors with perovskite structure and a specific composition, and e) sulphidic glasses.
  • lithium ion conductors are derived from lithium silicate, with silicon partially replaced by aluminum, phosphorus and / or sulfur.
  • U.S. 4,042,482 teaches monoclinic compounds of the formula Li 4 + wxy Si 1-wxy Al w P x S y O 4 where w is from 0 to 0.45, x is from 0 to 0.5, and y is from 0 to 0.35, and wherein at least one of w or (x + 2y) is 0.1 or more.
  • RA Huggins, Electrochimica Acta 22 (1977) 773-781 teaches the preparation of solid solutions of LiSiO 4 with Li 3 PO 4 by hot pressing a stoichiometric mixture of lithium hydroxide, silica and ammonium dihydrogen phosphate.
  • Y.-W Hu, ID Raistrick and RA Huggins disclose in Mat. Res. Bull. 11 (1976) 1227-1230 as well as in J. Electrochem. Soc. 124 (1977) 1240-1242 Process for the preparation of such compounds by hot pressing a mixture of lithium phosphate and lithium silicate.
  • DE 199 48 548 A1 discloses pasty masses for electrochemical components, with nanocrystalline materials and a matrix, inter alia, also Li 0.5 Si 0.5 P 0.5 O 4 , which is pasty at particle sizes below 10 microns even without a matrix.
  • Suitable ion conductors for the production of lithium must meet a number of requirements.
  • suitable electrochemical properties for example, good conductivity for lithium ions under the process conditions used, stability to liquid lithium and lithium amalgam and negligible electron conductivity
  • a particular problem is the formation of microcracks, which form or enlarge under electrochemical stress and lead to leaks of mercury in the recovered lithium.
  • the ion conductors known for lithium production do not meet all of these requirements in a completely satisfactory manner.
  • Li- ⁇ "-Al 2 O 3 , Li- ⁇ -Al 2 O 3 or lithium analogs of NASICON ceramics preferred for their electrochemical properties are comparatively expensive and, due to their hygroscopicity, are only handled and stored with special precautions. so as not to impair their efficiency in the process.
  • a process for recovering lithium from lithium amalgam by electrolysis has been found on a lithium ionic solid conductor characterized by using a lithium ion conductor obtained by deforming and calcining Li 4-x Si 1-x P x O 4 1 where x has a value of at least 0.3 and at most 0.7 is prepared using the Li 4-x Si 1-x P x O 4 and / or the compounds in the form of powder having an average particle size of at most 5 microns.
  • the invention is based on the finding that the lithium phosphate silicates to be used according to the invention are good lithium-ion conductors for obtaining lithium from lithium amalgam.
  • it is based on the finding that, when using the comparatively finely divided lithium salts, it is possible to produce particularly dense lithium phosphate silicates which are particularly resistant to the formation of cracks and are therefore dense and very stable.
  • the process according to the invention for obtaining lithium from lithium amalgam by electrolysis on a solid lithium ion conductor is carried out in an electrolysis cell whose anode and cathode spaces are separated by a lithium ion-conducting solid electrolyte having the composition Li 4-x Si 1-x P x O 4 .
  • x has a value of generally at least 0.3, and preferably at least 0.4, and generally at most 0.7, and more preferably at most 0.6.
  • a preferred solid electrolyte is Li 4-x Si 1-x P x O 4 having a value x of about 0.5
  • a particularly preferred solid electrolyte is Li 4-x Si 1-x P x O 4 having a value x of 0 ; 5.
  • a method of recovering lithium from lithium amalgam by electrolysis on a solid lithium ion conductor separating the anode and cathode compartments of an electrolytic cell is known.
  • the inventive method is carried out as the known methods, with the difference that the lithium ion conductor to be used according to the invention Li 4-x Si 1-x P x O 4 , wherein the value of x in the range of 0.3 to 0.7 as cathodes - And Anondenraum separating wall ("membrane") is used.
  • the process according to the invention for recovering lithium from lithium amalgam is carried out in exactly the same way as the process known from DE 199 14 221 A1 (or from its equivalents EP 1 041 177 and US Pat. No.
  • the lithium amalgam used in the lithium recovery process of the invention is a solution of lithium in mercury that is liquid at the reaction temperature used. It generally contains at least 0.02 wt.% Lithium (about 0.5 atomic%), and preferably at least 0.04 wt.% Lithium (about 1 atomic%), and generally at most 0.19 wt. % Lithium (5 at.%) And preferably at most 0.1% by weight. is liquid. It generally contains at least 0.02 wt.% Lithium (about 0.5 atomic%), and preferably at least 0.04 wt.% Lithium (about 1 atomic%), and generally at most 0.19 wt.
  • -% lithium 5 atomic%) and preferably at most 0.1 wt.% Lithium (about 3 atomic%), balance mercury.
  • It may be prepared in any manner, for example from an aqueous lithium salt solution in an electrolytic cell by the amalgam process.
  • a lithium chloride solution with a lithium chloride content of 220 to 350 g / l used and next Lithiumamalgam (at the cathode) chlorine (at the anode) produced, completely analogous to the known amalgam process for Chloralkalielektrolyse, after the world on a large scale, for example, chlorine and sodium amalgam are prepared, the latter is often decomposed to produce sodium hydroxide with water.
  • lithium waste from batteries and reaction solutions such as in the implementation of organolithium compounds with halogen-substituted compounds and subsequent aqueous workup resulting lithium salt solutions.
  • aqueous lithium chloride solutions are usually formed, but other lithium halides can also be used, and other lithium salts such as lithium sulfate, lithium sulfonates or lithium salts of organic acids.
  • lithium chloride anodic chlorine is produced in lithium amalgam production, which is processed as usual, if other lithium salts are used, it may be necessary to resort to other process engineering measures (for example, when lithium sulfate is used, oxygen is generated anodically, and lithium-containing bases must be added pH of the brine can be adjusted and maintained in the range of 2 to 4). These measures are known.
  • the lithium amalgam is used as a liquid, preferably agitated anode in an electrolytic cell.
  • the Litthiumamalgam anode is separated by a lithium ion conductive and otherwise as dense partition from the cathode compartment in which liquid lithium is.
  • the lithium is transferred from the amalgam in the form of lithium ions through the lithium-ion-conducting membrane in the cathode compartment and reduced there to metal.
  • the anode potential is adjusted so that no more noble metals are oxidized as lithium, in particular no mercury to mercury ions.
  • the recovered lithium metal is withdrawn from the cathode compartment and further processed in the usual way.
  • Fresh lithium amalgam is fed into the anode compartment and lithium-depleted amalgam or mercury is withdrawn.
  • the mercury or depleted amalgam is recycled to lithium amalgam synthesis.
  • the process is carried out at a temperature at which both lithium amalgam and lithium are liquid and the conductivity of the lithium ion conducting partition for lithium ions is sufficiently high.
  • the reaction temperature is typically at least 150 ° C, more preferably at least 180 ° C, and most preferably at least 200 ° C, and generally at most 450 ° C, preferably at most 400 ° C and most preferably at most 350 ° C.
  • a slight overpressure against the anode side is used on the cathode side to prevent leakage of mercury into the recovered lithium. This overpressure is generally at least 0.1 bar, preferably at least 0.5 bar and generally at most 5 bar and preferably at most 1 bar.
  • the lithium ion conducting partition wall (also simply called “membrane”, “ionic conductor” or “solid electrolyte”) separates the anode and cathode compartments from each other.
  • the seal is made “phelium-tight", so that apart from lithium in ionic form, no substances are exchanged between the anode and cathode compartments.
  • the shape of the partition is chosen according to the shape of the electrolytic cell.
  • a convenient and commonly used form of the lithium ion conducting partition is that of a unilaterally closed tube of circular or other cross-section, at the open end of which an electrically insulating gasket, such as an electrically insulating ring with a helium-tight, electrically insulating glass solder connection, is mounted.
  • an electrically insulating gasket such as an electrically insulating ring with a helium-tight, electrically insulating glass solder connection.
  • the thickness of the partition wall is selected to provide mechanical strength (stability and pressure resistance) and tightness, but on the other hand does not unnecessarily hinder the migration of the lithium ions through the partition wall. In general, it is at least 0.3 mm, and preferably at least 1 mm, and generally at most 5 mm, more preferably at most 3 mm, and most preferably at most 2 mm.
  • Li 4-x Si 1 -x P x O 4 is brought into the desired shape of the dividing wall. This can be done in any way, for example by shaping a powder of Li 4-x Si 1-x P x O 4 or by synthesis of the compound in the desired form.
  • a simple and preferred method is to deform a compound or mixture of compounds that ultimately reacts in sum to form Li 4-x Si 1-x P x O 4 , in powder form and in the desired stoichiometry, and the subsequent Reacting the powder or powder mixture in the molding to Li 4-x Si 1-x P x O 4 , wherein x has a value of at least 0.3 and at most 0.7.
  • Li 4-x Si 1 -x P x O 4 it is possible to use all compounds and compound mixtures which, in the production of the ionic conductor, in total convert to Li 4-x Si 1 -x P x O 4 .
  • lithium phosphate and lithium silicate are used as the anhydrous ortho compounds Li 3 PO 4 and Li 4 SiO 4 .
  • compounds which convert into these substances in the course of the production of the ionic conductor It is also possible to use compounds containing hydrated water or hydrates, such as Li 3 O 4 . 1 ⁇ 2 H 2 O, meta compounds such as Li 2 SiO 3 or LiPO 3 or hydrogen salts such as Li 2 HPO 4 or LiH 2 PO 4 are used.
  • the stoichiometry can also be adjusted by addition of phosphorus oxides such as P 2 O 5 or P 2 O 3 , silica, also in hydrated or partially hydrated form (“silica gel”) lithium oxide and / or lithium hydroxide.
  • powdery starting materials are used which have a certain average grain size.
  • the mean grain size (often referred to simply as "d50") states that 50% by weight of the powder is in the form of particles having a particle size of at most this average grain size.
  • the mean grain size is measured with sieves, with finer particles in the range of only a few micrometers, laser light diffraction (according to the ISO / DIS 13320 Particle Size Analysis Guide to Laser Diffraction) is used Diameter, for non-spherical particles the measuring method necessarily measures an effective diameter of the particles corresponding to the diameter of spherical particles of the same volume, Similarly, the powders have so-called d90 values, ie this value indicates that 90% by weight. of the powder in the form of particles having an effective diameter of at most this value.
  • the average particle size of the powdery starting materials used is generally at most 5 micrometers. In preferred form, it is at most 3 microns, and more preferably at most 1 micrometer.
  • the powder used contain little or no comparatively coarse particles.
  • the d90 value is not much higher than the d50 value.
  • the d90 value is at most five times the d50, and most preferably at least three times.
  • the powder used if it does not have this grain size, adjusted to this grain size before deformation.
  • Any known comminution method can be used for this purpose.
  • Particularly suitable for this purpose are ball mills or attritor mills, into which the powder is usually introduced as a suspension in an inert suspending agent (for example water, alcohols, ethers or hydrocarbons).
  • an inert suspending agent for example water, alcohols, ethers or hydrocarbons.
  • alcohols in particular C 1 -C 4 -alcohols (methanol, ethanol, propanol, isopropanol, butanol, sec-butanol, isobutanol, tert-butanol) as suspending agent.
  • d50 values of about 0.5 microns can be achieved.
  • the most important parameter when using ball or attritor mills is the grinding time. It is always ground until the desired fineness is achieved. If a mixture of compounds is used, the intensive mixing necessary before the deformation
  • the deformation of the ionic conductor or a mixture of substances from which it is prepared, in the desired shape is carried out by known deformation methods, such as cold isostatic pressing, hot isostatic pressing, slip casting, or tape casting.
  • the powder if necessary, after the milling step, and if necessary, after removal of suspending agent, subjected to the corresponding process.
  • a preferred shaping method is cold isostatic pressing.
  • the powder is pressed in a mold, wherein a pressure of generally at least 1000 bar, preferably at least 2000 bar and most preferably at least 3000 bar is used.
  • the ion conductor is densely fired by heating ("annealing", “calcining” or “sintering") to produce the final partition wall of the electrolytic cell, unless Li 4-x Si 1-x P x O 4 is itself deformed with a value x of at least 0.3 and at most 0.7, this ionic conductor is also produced from the powder mixture used in the sintering process
  • the sintering takes place by heating the shaped bodies to a temperature of generally at least 700 ° C., preferably at least 800 ° C. and more preferably at least 900 ° C. The sintering is carried out until an ionic conductor of the desired density is obtained at the temperature set in.
  • the sintering temperature preferably at least 30 minutes and more preferably at least one hour after not more than 10 hours, preferably no more than 6 hours sintering and more preferably not more than 4 hours.
  • the heating or cooling rate does not become larger chosen as 20 ° C / min, preferably not greater than 10 ° C / min and in a particularly preferred form not greater than 5 ° C / min.
  • lithium ion conductors with excellent tightness and crack resistance which are ideal for lithium production, can be produced.
  • the powder was formed into a crucible shape by cold isostatic pressing at a pressure of 3500 bar, heated to 1000 ° C at a heating rate of 1 ° C / min, sintered at that temperature for 2 hours, and then cooled at a cooling rate of 1 ° C / min ,
  • the powder was formed into a crucible shape by cold isostatic pressing at a pressure of 3500 bar, heated to 1000 ° C at a heating rate of 1 ° C / min, sintered at that temperature for 2 hours, and then cooled at a cooling rate of 1 ° C / min ,
  • Example 3 Lithium ion conduction in the model system
  • Example 1 The ceramic produced in Example 1 was subjected to a transfer measurement in the lithium-lithium model system at 195 ° C. This corresponds to the procedure for the electrolysis of lithium amalgam, but liquid lithium is used on both sides of the partition wall. The polarity of the electrodes was adjusted so as to be transported from the outside to the inside of the lithium ion conductor crucible. Over a period of 70 hours was one Current of 1 mA applied. The achieved current efficiency was quantitative within the scope of the measurement accuracy. Cracks of the ionic conductor were not observed.

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  • Chemical & Material Sciences (AREA)
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Claims (3)

  1. Procédé d'obtention de lithium à partir d'un amalgame de lithium par électrolyse sur un conducteur d'ions lithium solide, caractérisé en ce qu'on utilise un conducteur d'ions lithium fabriqué par mise en forme et calcination de Li4- xSi1-xPxO4 et/ou de composés qui se transforment en somme en Li4-xSix-1PxO4, x étant une valeur d'au moins 0,3 et de tout au plus 0,7, dans lequel on utilise le Li4-xSi1-xPxO4 et/ou les composés sous forme de poudre avec une grosseur moyenne de particule de tout au plus 5 micromètres.
  2. Procédé selon la revendication 1, caractérisé en ce qu'on utilise un conducteur d'ions lithium de la composition Li4-xSi1-xPxO4, x étant une valeur d'au moins 0,4 et de tout au plus 0,6.
  3. Procédé selon la revendication 2, caractérisé en ce qu'on utilise un conducteur d'ions lithium de la composition Li4-xSi1-xPxO4, x étant une valeur d'environ 0,5.
EP03026514A 2002-12-16 2003-11-18 Procédé de fabrication de lithium Expired - Lifetime EP1431422B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10259020 2002-12-16
DE10259020 2002-12-16

Publications (2)

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EP1431422A1 EP1431422A1 (fr) 2004-06-23
EP1431422B1 true EP1431422B1 (fr) 2006-12-13

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EP03026514A Expired - Lifetime EP1431422B1 (fr) 2002-12-16 2003-11-18 Procédé de fabrication de lithium

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US (1) US20040118700A1 (fr)
EP (1) EP1431422B1 (fr)
JP (1) JP2004218078A (fr)
AT (1) ATE348204T1 (fr)
DE (1) DE50305946D1 (fr)

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US10084168B2 (en) 2012-10-09 2018-09-25 Johnson Battery Technologies, Inc. Solid-state battery separators and methods of fabrication

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US7993773B2 (en) 2002-08-09 2011-08-09 Infinite Power Solutions, Inc. Electrochemical apparatus with barrier layer protected substrate
US8394522B2 (en) 2002-08-09 2013-03-12 Infinite Power Solutions, Inc. Robust metal film encapsulation
US8445130B2 (en) 2002-08-09 2013-05-21 Infinite Power Solutions, Inc. Hybrid thin-film battery
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CN101931097B (zh) 2004-12-08 2012-11-21 希莫菲克斯公司 LiCoO2的沉积
US7959769B2 (en) 2004-12-08 2011-06-14 Infinite Power Solutions, Inc. Deposition of LiCoO2
US8062708B2 (en) 2006-09-29 2011-11-22 Infinite Power Solutions, Inc. Masking of and material constraint for depositing battery layers on flexible substrates
US8197781B2 (en) 2006-11-07 2012-06-12 Infinite Power Solutions, Inc. Sputtering target of Li3PO4 and method for producing same
US8268488B2 (en) 2007-12-21 2012-09-18 Infinite Power Solutions, Inc. Thin film electrolyte for thin film batteries
KR20100102180A (ko) 2007-12-21 2010-09-20 인피니트 파워 솔루션스, 인크. 전해질 막을 위한 표적을 스퍼터링하는 방법
JP5705549B2 (ja) 2008-01-11 2015-04-22 インフィニット パワー ソリューションズ， インコーポレイテッド 薄膜電池および他のデバイスのための薄膜カプセル化
US8350519B2 (en) 2008-04-02 2013-01-08 Infinite Power Solutions, Inc Passive over/under voltage control and protection for energy storage devices associated with energy harvesting
US8906523B2 (en) 2008-08-11 2014-12-09 Infinite Power Solutions, Inc. Energy device with integral collector surface for electromagnetic energy harvesting and method thereof
EP2332127A4 (fr) 2008-09-12 2011-11-09 Infinite Power Solutions Inc Dispositif d'énergie ayant une surface conductrice intégrée pour une communication de données par l'intermédiaire d'une énergie électromagnétique et procédé associé
WO2010042594A1 (fr) * 2008-10-08 2010-04-15 Infinite Power Solutions, Inc. Module de capteurs sans fil alimenté par l’environnement
EP2474056B1 (fr) 2009-09-01 2016-05-04 Sapurast Research LLC Carte de circuit imprimé avec une batterie à film mince intégrée
JP2013528912A (ja) 2010-06-07 2013-07-11 インフィニット パワー ソリューションズ， インコーポレイテッド 再充電可能高密度電気化学素子
WO2012017448A2 (fr) * 2010-08-03 2012-02-09 Hetero Research Foundation Sels de la lapatinib
AR082684A1 (es) 2010-08-12 2012-12-26 Res Inst Ind Science & Tech Un metodo para extraer litio de alta pureza desde una solucion portadora de litio por electrolisis
WO2013131005A2 (fr) 2012-03-01 2013-09-06 Excellatron Solid State, Llc Cathode composite à semi-conducteur à haute capacité, séparateur composite à semi-conducteur, pile au lithium rechargeable à semi-conducteur et procédés de fabrication associés
US20150014184A1 (en) * 2013-07-10 2015-01-15 Lawence Ralph Swonger Producing lithium
US10450660B2 (en) 2014-11-04 2019-10-22 Savannah River Nuclear Solutions, Llc Recovery of tritium from molten lithium blanket
JP6763965B2 (ja) 2015-12-21 2020-09-30 ジョンソン・アイピー・ホールディング・エルエルシー 固体電池、セパレータ、電極および製造方法
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CN110106526B (zh) * 2019-05-07 2021-05-14 清华大学 基于固态电解质制备金属锂的方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10084168B2 (en) 2012-10-09 2018-09-25 Johnson Battery Technologies, Inc. Solid-state battery separators and methods of fabrication

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ATE348204T1 (de) 2007-01-15
JP2004218078A (ja) 2004-08-05
US20040118700A1 (en) 2004-06-24
EP1431422A1 (fr) 2004-06-23
DE50305946D1 (de) 2007-01-25

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