EP1431422A1 - Procédé de fabrication de lithium - Google Patents

Procédé de fabrication de lithium Download PDF

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Publication number
EP1431422A1
EP1431422A1 EP03026514A EP03026514A EP1431422A1 EP 1431422 A1 EP1431422 A1 EP 1431422A1 EP 03026514 A EP03026514 A EP 03026514A EP 03026514 A EP03026514 A EP 03026514A EP 1431422 A1 EP1431422 A1 EP 1431422A1
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EP
European Patent Office
Prior art keywords
lithium
amalgam
ion conductor
lithium ion
value
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EP03026514A
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German (de)
English (en)
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EP1431422B1 (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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    • 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 method for obtaining lithium.
  • the invention a process for the production of lithium from lithium amalgam by electrolysis on a lithium ion conductive solid electrolyte. It also concerns a procedure for Production of this electrolyte.
  • Lithium is an important inorganic basic chemical and is used in a number of different ways technical applications.
  • lithium is used to create organolithium compounds, which in turn are strong bases or starting materials for special syntheses serve as an alloy additive or used 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 in production and use of lithium.
  • the technically common way to produce lithium is by melt flow electrolysis a eutectic mixture of lithium chloride with potassium chloride at 400 to 460 ° C.
  • This process requires a comparatively large amount of energy (28 - 32 kWh / kg lithium), and can also only anhydrous lithium chloride can be used. Since lithium chloride is hygroscopic, it is contaminated the necessary drying the economy of this process in addition.
  • lithium ion-conducting solid electrolytes Some types of suitable lithium ion-conducting solid electrolytes are named, namely a) Li- ⁇ "-Al 2 O 3 or Li- ⁇ -Al 2 O 3 , b) lithium analogs of so-called NASICON ceramics with a specific structure and composition, c) so-called LISICONS with a certain structure and composition, d) lithium ion conductor with a perovskite structure and a certain composition, and e) sulfidic glasses.
  • lithium silicate silicon being partially replaced by aluminum, phosphorus and / or sulfur.
  • US 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 at least one of the two values w or (x + 2y) being 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, silicon dioxide and ammonium dihydrogen phosphate.
  • Y.-W Hu, ID Raistrick and RA Huggins disclose in Mat. Res. Bull. 11 (1976) 1227-1230 and 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.
  • Suitable ion conductors for the production of lithium have to meet a number of requirements.
  • suitable electrochemical properties for example good conductivity for lithium ions under the process conditions used, stability towards liquid lithium and lithium amalgam and negligible low electron conductivity
  • they should also be simple and inexpensive to produce, easy to store and easy to handle, and the highest possible stability and therefore long service life exhibit.
  • a particular problem is the formation of microcracks, which form or enlarge under electrochemical stress and lead to leakages of mercury into the lithium obtained.
  • 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 analogues of NASICON ceramics are comparatively expensive and, due to their hygroscopicity, can only be handled and stored with special precautions, so as not to impair their performance in the process.
  • the object is to find improved processes for the production of lithium and in particular other lithium ion conductors for use in this method, those mentioned above Meet requirements. There is also the task of processes for producing such to find ionic conductors.
  • a process has been found for obtaining lithium from lithium amalgam by electrolysis on a solid lithium ion conductor, which is characterized in that a lithium ion conductor of the composition Li 4-x Si 1-x P x O 4 is used, where x has a value of at least 0 , 3 and at most 0.7.
  • a method for producing a lithium ion conductor of the composition Li 4-x Si 1-x P x O 4 , where x has a value of at least 0.3 and at most 0.7 by deforming and calcining Li 4-x Si 1 -x P x O 4 , where x has a value of at least 0.3 to at most 0.7 and / or of compounds which react during the calcination, which is characterized in that the Li 4-x Si 1-x P x O 4 and / or the compounds are used in the form of powder with an average particle size of at most 5 micrometers.
  • the invention is based on the one hand on the knowledge that those to be used according to the invention Lithium phosphate silicates are good lithium ion conductors for obtaining lithium from lithium amalgam are. On the other hand, it is based on the knowledge that when using the comparatively finely divided lithium salts, particularly dense lithium phosphate silicates can be produced can, which are particularly resistant to the formation of cracks and therefore dense and very stable are.
  • 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, the anodes of which. and cathode spaces are separated by a lithium ion-conducting solid electrolyte which has the composition Li 4-x Si 1-x P x O 4 , where x has a value of generally at least 0.3 and preferably at least 0.4 and generally of at most 0.7 and preferably at most 0.6.
  • a preferred solid electrolyte is Li 4-x Si 1-x P x O 4 with a value x of approximately 0.5
  • a particularly preferred solid electrolyte is Li 4-x Si 1-x P x O 4 with a value x of 0 ; 5.
  • Processes for obtaining lithium from lithium amalgam by electrolysis on a solid lithium ion conductor which separates the anode and cathode spaces of an electrolysis cell are known.
  • the method according to the invention is carried out like the known methods, with the difference that the lithium ion conductor Li 4-x Si 1-x P x O 4 to be used according to the invention, the value of x being in the range from 0.3 to 0.7 as cathode - Wall and separating anon chamber ("membrane") is used.
  • the process according to the invention for obtaining 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 process according to the invention for the production of lithium is a solution of lithium in mercury that is applied at the reaction temperature is liquid. It generally contains at least 0.02% by weight lithium (around 0.5 atom%) and in preferably at least 0.04% by weight of lithium (around 1 atomic%) and in general at most 0.19% by weight lithium (5 atomic%) and preferably at most 0.1% by weight Lithium (around 3 atom%), the rest mercury. It can be made in any way for example from an aqueous lithium salt solution in an electrolytic cell after Amalgam process.
  • a lithium chloride solution is usually treated with a lithium chloride from 220 to 350 g / l and in addition to lithium amalgam (on the cathode) chlorine (on the anode) generated, completely analogous to the known amalgam process for chlor-alkali electrolysis which produces chlorine and sodium amalgam on a large scale worldwide, the latter often being decomposed with water to produce sodium hydroxide solution. That ⁇ s how it is possible to use other lithium sources, such as lithium waste from batteries and reaction solutions such as that in the implementation of organolithium compounds with halogen-substituted Compounds and subsequent aqueous workup resulting lithium salt solutions.
  • Lithium halides are used, and other lithium salts such as lithium sulfate, lithium sulfonates or lithium salts of organic acids.
  • Lithium amalgam production produces anodic chlorine, which is processed as usual
  • other lithium salts are used, other process engineering may have to be used Measures are taken (for example, when using lithium sulfate anodic oxygen, and by adding lithium-containing bases, a pH value of the brine in the Range from 2 to 4 can be set and held). These measures are known.
  • the lithium amalgam is used to obtain metallic lithium from lithium amalgam liquid, preferably moving anode used in an electrolytic cell.
  • the lithium amalgam anode is due to a lithium ion conductive and otherwise as dense partition separated from the cathode compartment, in which liquid lithium is located.
  • electrolysis in one In such a cell the lithium from the amalgam in the form of lithium ions is replaced by the lithium ions conductive membrane transferred into the cathode compartment and reduced there to the metal.
  • the anode potential is set so that, if possible, no nobler metals than lithium oxidize become mercury ions, especially not mercury.
  • the lithium metal obtained is withdrawn from the cathode compartment and processed in the usual way.
  • Fresh lithium amalgam is supplied to the anode compartment and amalgam depleted in lithium or subtracted mercury.
  • the mercury or the depleted amalgam is in the Lithium amalgam synthesis recycled.
  • the process is carried out at a temperature in which both lithium amalgam and lithium are present in liquid form and the conductivity of the lithium ions conductive partition for lithium ions is sufficiently high.
  • the reaction temperature is typically at least 150 ° C, preferably at least 180 ° C and in a particularly preferred manner at at least 200 ° C. and generally at most 450 ° C, preferably at a maximum of 400 ° C and in a particularly preferred manner at at most 350 ° C.
  • a slight excess pressure is preferably applied on the cathode side the anode side to prevent leakage of mercury into the lithium obtained. This excess pressure 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 conductive partition also simply “membrane”, “ion conductor” or “solid electrolyte” separates the anode and cathode compartments from each other.
  • the seal becomes “helium-tight” so that apart from lithium in ionic form no substances between anode and cathode compartment are replaced.
  • the shape of the partition is chosen according to the shape of the electrolytic cell.
  • a expedient and frequently used form of the lithium ion conductive partition is one tube closed on one side with a round or other cross-section, at its open end an electrically insulating seal such as an electrically insulating ring with a helium-tight, electrically insulating glass solder connection is attached.
  • Such constructions are known see. z. B. GB 2 207 5645 A, EP 482 785 A1.
  • the thickness of the partition is chosen so that mechanical strength (stability and pressure resistance) and tightness are achieved, but on the other hand, the migration of the lithium ions through the partition is not unnecessarily complicated becomes. Generally it is at least 0.3 mm and preferably at least 1 mm and generally at most 5 mm, preferably at most 3 mm and in a particularly preferred manner at most 2 mm.
  • Li 4-x Si 1-x P x O 4 is brought into the desired shape of the partition wall. This can be done in any conceivable 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 the shaping of a compound or a mixture of compounds which ultimately convert to Li 4-x Si 1 -x P x O 4 , in powder form and in the desired stoichiometry, and the subsequent conversion of the powder or Powder mixture in the molded part to form Li 4-x Si 1-x P x O 4 , where x has a value of at least 0.3 and at most 0.7.
  • lithium phosphate and lithium silicate are used as 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 ion conductor Compounds or hydrates containing water of crystallization such as Li 3 O 4 can also be used .
  • 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 can be used.
  • the stoichiometry can also be adjusted by adding phosphorus oxides such as P 2 O 5 or P 2 O 3 , silicon dioxide, also in hydrated or partially hydrated form (“silica gel”), lithium oxide and / or lithium hydroxide.
  • Powdery feedstocks which have a certain mean are preferably used Have grain size.
  • the average grain size (often referred to as "d50" for short) states that 50% by weight of the powder in the form of particles with a particle size of at most this average Grain size is available.
  • the average grain size is measured with sieves, In the case of finer particles in the range of only a few micrometers, laser light diffraction is generally used (according to ISO / DIS 13320 "Particle Size Analysis Guide to Laser Diffraction) used.
  • the measured particle size corresponds to the sphere diameter
  • the measurement method makes this necessary an effective diameter of the particles is measured
  • the diameter of the spherical Corresponds to particles of the same volume.
  • the powders have so-called d90 values , i.e. this value means that 90% by weight of the powder in the form of particles with a effective diameter of at most this value.
  • the average grain size of the powdery feedstocks used is generally included 5 microns at most. In a preferred form it is at most 3 micrometers and in particular preferred form at a maximum of 1 micrometer.
  • the powder used be none or contain only a little comparatively coarse particles, in other words, in a preferred manner
  • the d90 value is not very much higher than the d50 value.
  • the d90 value is at most five times the d50 value and, more preferably, Way three times at most.
  • the powder used is adjusted to this grain size before shaping. Any known comminution process can be used for this.
  • Ball mills or attritor mills in which the powder is usually introduced as a suspension in an inert suspension medium (for example water, alcohols, ethers or hydrocarbons), are particularly suitable for this purpose. It is preferred to use alcohols, in particular C 1 -C 4 alcohols (methanol, ethanol, propanol, isopropanol, butanol, sec-butanol, isobutanol, tert-butanol) as suspending agents.
  • d50 values of around 0.5 micrometers can be achieved. The most important parameter when using ball or attritor mills is the milling time. It is always ground until the desired fineness is achieved. If a mixture of compounds is used, the intensive mixing necessary before the shaping can be carried out conveniently at the same time by grinding together.
  • the deformation of the ion conductor or a mixture of substances from which it is made, in the desired shape is carried out using known deformation processes, for example cold isostatic Pressing, hot isostatic pressing, slip casting, or tape casting.
  • This will be Powder if necessary after the milling step and if necessary after removal of Suspension agent, subjected to the corresponding process.
  • a preferred deformation process is cold isostatic pressing, the powder is pressed in a press mold, whereby a pressure of generally at least 1000 bar, preferably at least 2000 bar and in at least 3000 bar is particularly preferably used.
  • the ion conductor is fired tightly by heating ("tempering", calcining "or” sintering ") and the finished partition of the electrolysis cell is produced.
  • the powder mixture used of this ion conductor which is sintered by heating the moldings to a temperature of generally at least 700 ° C., preferably at least 800 ° C. and particularly preferably at least 900 ° C.
  • Sintering is carried out so long that an ion conductor of the desired density is obtained at the set temperature the sintering temperature is maintained, preferably at least 30 minutes and particularly preferably at least one hour after a maximum of 10 hours, in a preferred form the sintering does not take longer than 6 hours and in a particularly preferred form does not last more than 4 hours.
  • the heating or cooling rate is therefore chosen to be no greater than 20 ° C / min, preferably no greater than 10 ° C / min, and in a particularly preferred form no greater than 5 ° C / min.
  • lithium ion conductors which are particularly suitable for lithium extraction can be obtained produce with high tightness and crack resistance.
  • the powder was cold isostatic Presses shaped into a crucible shape with a pressure of 3500 bar, with a heating rate of 1 ° C / min heated to 1000 ° C, sintered at this temperature for 2 hours, and then with cooled at a cooling rate of 1 ° C / min.
  • the powder was deformed in crucible shape by cold isostatic pressing with a pressure of 3500 bar, with a Heating rate from 1 ° C / min to 1000 ° C, sintered at this temperature for 2 hours, and then cooled at a cooling rate of 1 ° C / min.
  • Example 3 Lithium ion line in the model system
  • Example 1 The ceramic produced in Example 1 became one in the lithium-lithium model system at 195 ° C Subjected to transfer measurement. This corresponds to the procedure for the electrolysis of lithium amalgam, however, liquid lithium is used on both sides of the partition becomes.
  • the polarity of the electrodes was set so that the transport from outside into the Inside of the lithium ion conductor crucible. Over a period of 70 hours, a Current of 1 mA applied. The current yield achieved was within the measurement accuracy quantitatively. No cracks in the ion conductor were observed.

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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

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

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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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US9793525B2 (en) 2012-10-09 2017-10-17 Johnson Battery Technologies, Inc. Solid-state battery electrodes
US10333123B2 (en) 2012-03-01 2019-06-25 Johnson Ip Holding, Llc High capacity solid state composite cathode, solid state composite separator, solid-state rechargeable lithium battery and methods of making same
US10566611B2 (en) 2015-12-21 2020-02-18 Johnson Ip Holding, Llc Solid-state batteries, separators, electrodes, and methods of fabrication
USRE49205E1 (en) 2016-01-22 2022-09-06 Johnson Ip Holding, Llc Johnson lithium oxygen electrochemical engine

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US8404376B2 (en) 2002-08-09 2013-03-26 Infinite Power Solutions, Inc. Metal film encapsulation
US8236443B2 (en) 2002-08-09 2012-08-07 Infinite Power Solutions, Inc. Metal film encapsulation
US8431264B2 (en) 2002-08-09 2013-04-30 Infinite Power Solutions, Inc. Hybrid thin-film battery
US20070264564A1 (en) 2006-03-16 2007-11-15 Infinite Power Solutions, Inc. Thin film battery on an integrated circuit or circuit board and method thereof
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
US8728285B2 (en) 2003-05-23 2014-05-20 Demaray, Llc Transparent conductive oxides
US7959769B2 (en) 2004-12-08 2011-06-14 Infinite Power Solutions, Inc. Deposition of LiCoO2
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US8197781B2 (en) * 2006-11-07 2012-06-12 Infinite Power Solutions, Inc. Sputtering target of Li3PO4 and method for producing same
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US8268488B2 (en) 2007-12-21 2012-09-18 Infinite Power Solutions, Inc. Thin film electrolyte for thin film batteries
US8518581B2 (en) 2008-01-11 2013-08-27 Inifinite Power Solutions, Inc. Thin film encapsulation for thin film batteries and other devices
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JP2012500610A (ja) 2008-08-11 2012-01-05 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 電磁エネルギー獲得ための統合コレクタ表面を有するエネルギーデバイスおよびその方法
CN102150185B (zh) 2008-09-12 2014-05-28 无穷动力解决方案股份有限公司 具有经由电磁能进行数据通信的组成导电表面的能量装置及其方法
WO2010042594A1 (fr) * 2008-10-08 2010-04-15 Infinite Power Solutions, Inc. Module de capteurs sans fil alimenté par l’environnement
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EP2577777B1 (fr) 2010-06-07 2016-12-28 Sapurast Research LLC Dispositif électrochimique à haute densité rechargeable
US20130131090A1 (en) * 2010-08-03 2013-05-23 Bandi Parthasaradhi Reddy Salts of 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
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
WO2020058967A1 (fr) * 2018-09-21 2020-03-26 King Abdullah University Of Science And Technology Détection de ligand par aptamères avec un rapporteur intégré
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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US4042482A (en) * 1976-01-22 1977-08-16 E. I. Du Pont De Nemours And Company Substituted lithium orthosilicates and solid electrolytes therefrom
US4390460A (en) * 1980-09-29 1983-06-28 Hitachi, Ltd. Lithium oxide based amorphous material and process for preparation thereof
GB2167867A (en) * 1984-11-30 1986-06-04 Nat Res Dev Probe for determining lithium content
EP0482785A2 (fr) * 1990-10-25 1992-04-29 Ngk Insulators, Ltd. Pile sodium-soufre et procédé pour solidariser un électrolyte solide tubulaire et un anneau isolant
DE19914221A1 (de) * 1999-03-29 2000-10-05 Basf Ag Verbessertes Verfahren zur elektrochemischen Herstellung von Lithium

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Patent Citations (5)

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Publication number Priority date Publication date Assignee Title
US4042482A (en) * 1976-01-22 1977-08-16 E. I. Du Pont De Nemours And Company Substituted lithium orthosilicates and solid electrolytes therefrom
US4390460A (en) * 1980-09-29 1983-06-28 Hitachi, Ltd. Lithium oxide based amorphous material and process for preparation thereof
GB2167867A (en) * 1984-11-30 1986-06-04 Nat Res Dev Probe for determining lithium content
EP0482785A2 (fr) * 1990-10-25 1992-04-29 Ngk Insulators, Ltd. Pile sodium-soufre et procédé pour solidariser un électrolyte solide tubulaire et un anneau isolant
DE19914221A1 (de) * 1999-03-29 2000-10-05 Basf Ag Verbessertes Verfahren zur elektrochemischen Herstellung von Lithium

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10333123B2 (en) 2012-03-01 2019-06-25 Johnson Ip Holding, Llc High capacity solid state composite cathode, solid state composite separator, solid-state rechargeable lithium battery and methods of making same
US9793525B2 (en) 2012-10-09 2017-10-17 Johnson Battery Technologies, Inc. Solid-state battery electrodes
US12315873B2 (en) 2012-10-09 2025-05-27 Johnson IP Holding, LLC. Solid-state battery separator including low melt temperature inorganic electrolyte and method of fabricating the same
US10566611B2 (en) 2015-12-21 2020-02-18 Johnson Ip Holding, Llc Solid-state batteries, separators, electrodes, and methods of fabrication
US11417873B2 (en) 2015-12-21 2022-08-16 Johnson Ip Holding, Llc Solid-state batteries, separators, electrodes, and methods of fabrication
USRE49205E1 (en) 2016-01-22 2022-09-06 Johnson Ip Holding, Llc Johnson lithium oxygen electrochemical engine

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Publication number Publication date
ATE348204T1 (de) 2007-01-15
JP2004218078A (ja) 2004-08-05
US20040118700A1 (en) 2004-06-24
EP1431422B1 (fr) 2006-12-13
DE50305946D1 (de) 2007-01-25

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