US20040118700A1 - Isolation of lithium - Google Patents
Isolation of lithium Download PDFInfo
- Publication number
- US20040118700A1 US20040118700A1 US10/731,166 US73116603A US2004118700A1 US 20040118700 A1 US20040118700 A1 US 20040118700A1 US 73116603 A US73116603 A US 73116603A US 2004118700 A1 US2004118700 A1 US 2004118700A1
- Authority
- US
- United States
- Prior art keywords
- lithium
- amalgam
- ion conductor
- compounds
- powder
- 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.)
- Abandoned
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 71
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 238000002955 isolation Methods 0.000 title description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 36
- 239000010416 ion conductor Substances 0.000 claims abstract description 32
- 229910000497 Amalgam Inorganic materials 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 18
- 239000007787 solid Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 30
- 150000001875 compounds Chemical class 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 18
- 238000007493 shaping process Methods 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 5
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 9
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 9
- 229910001386 lithium phosphate Inorganic materials 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 229910052753 mercury Inorganic materials 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 238000005245 sintering Methods 0.000 description 8
- 239000007784 solid electrolyte Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- -1 lithium phosphate silicates Chemical class 0.000 description 7
- 229910003002 lithium salt Inorganic materials 0.000 description 7
- 159000000002 lithium salts Chemical class 0.000 description 7
- 238000003801 milling Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000009694 cold isostatic pressing Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Chemical compound [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 3
- 229910052912 lithium silicate Inorganic materials 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000002228 NASICON Substances 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 239000011362 coarse particle Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001513 hot isostatic pressing Methods 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 150000002641 lithium Chemical class 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- MJGFBOZCAJSGQW-UHFFFAOYSA-N mercury sodium Chemical compound [Na].[Hg] MJGFBOZCAJSGQW-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000002900 organolithium compounds Chemical class 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 229910001023 sodium amalgam Inorganic materials 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 229910006587 β-Al2O3 Inorganic materials 0.000 description 2
- 229910003155 β′′-Al2O3 Inorganic materials 0.000 description 2
- 229910007562 Li2SiO3 Inorganic materials 0.000 description 1
- 229910010951 LiH2 Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910006937 Si0.5P0.5 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical compound [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000374 eutectic mixture Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 238000002356 laser light scattering Methods 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229940008718 metallic mercury Drugs 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000010327 methods by industry Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 239000002707 nanocrystalline material Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000003921 particle size analysis Methods 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- LFGREXWGYUGZLY-UHFFFAOYSA-N phosphoryl Chemical class [P]=O LFGREXWGYUGZLY-UHFFFAOYSA-N 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000007569 slipcasting Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002203 sulfidic glass Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 230000001550 time effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
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 producing lithium.
- the invention relates to a process for isolating lithium from lithium amalgam by electrolysis over a solid electrolyte which conducts lithium ions. It also relates to a process for preparing this electrolyte.
- Lithium is an important basic inorganic chemical and is required in a variety of industrial applications.
- lithium is used for producing organolithium compounds which in turn serve as strong bases or starting materials for specific syntheses, as alloying additives or in lithium batteries.
- the usual industrial method of producing lithium is melt electrolysis of a eutectic mixture of lithium chloride with potassium chloride at from 400 to 460° C.
- This process requires a comparatively large quantity of energy (28-32 kWh/kg of lithium) and, in addition, only anhydrous lithium chloride can be used. Since lithium chloride is hygroscopic, the necessity of drying has an additional adverse effect on the economics of this process.
- DE 199 14 221 A1 discloses a comparatively economical process for preparing lithium from aqueous solutions, in which a lithium amalgam is firstly produced from an aqueous lithium salt solution and, in a second step, lithium is isolated from this amalgam by connecting the amalgam as anode in an electrolysis cell having a solid electrolyte which conducts lithium ions and a lithium cathode.
- the solid electrolyte viz. a ceramic material or a glass, separates the anode and cathode spaces in a “helium-type” manner but is permeable to lithium ions.
- a number of types of suitable solid electrolytes which conduct lithium ions are mentioned, namely a) Li- ⁇ ′′-Al 2 O 3 or Li- ⁇ -Al 2 O 3 , b) lithium analogues of NASICON ceramics having a particular structure and composition, c) LISICONS having a particular structure and composition, d) lithium ion conductors having a perovskite structure and a particular composition and e) sulfidic glasses.
- Another class of known lithium ion conductors is derived from lithium silicate in which silicon is partly replaced by aluminum, phosphorus and/or sulfur.
- U.S. Pat. No. 4,042,482 discloses monoclinic compounds of the formula Li 4+w ⁇ x ⁇ y Si 1 ⁇ w ⁇ x ⁇ y 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 and (x+2y) is 0.1 or more.
- DE 199 48 548 A1 discloses paste-like compositions for electrochemical components, which comprise nanocrystalline materials and a matrix, including Li 0.5 Si 0.5 P 0.5 O 4 which at particle sizes below 10 microns is paste-like even without a matrix.
- Ion conductors for the preparation of lithium have to satisfy a number of requirements in order to be suitable. Apart from suitable electrochemical properties (for example good conductivity for lithium ions under the process conditions employed, stability to liquid lithium and lithium amalgam and a negligibly low electron conductivity), they should also be simple and inexpensive to produce, be stable on storage and easy to handle and have a very high stability and thus a long life. A particular problem is the formation of microcracks which form under electrochemical stress or grow larger and lead to leakages of mercury into the lithium produced. The ion conductors known for the isolation of lithium do not fulfill all these requirements in a fully satisfactory manner.
- Li- ⁇ ′′-Al 2 O 3 , Li- ⁇ -Al 2 O 3 or lithium analogues of NASICON ceramics which are preferred from the point of view of their electrochemical properties, are comparatively expensive and, owing to their hygroscopic nature, special precautions have to be taken when handling and storing them to ensure that their performance in the process is not impaired.
- a further object is to find a process for preparing such ion conductors.
- Li 4 ⁇ x Si 1 ⁇ x P x O 4 having the composition Li 4 ⁇ x Si 1 ⁇ x P x O 4 , where x is at least 0.3 and not more than 0.7, by shaping and calcining Li 4 ⁇ x Si 1 ⁇ x P x O 4 , where x is at least 0.3 and not more than 0.7 and/or compounds which are converted into this during calcination, wherein the Li 4 ⁇ x Si 1 ⁇ x P x O 4 and/or the compounds is/are used in the form of powder having a mean particle size of not more than 5 microns.
- the invention is firstly based on the recognition that the lithium phosphate silicates to be used according to the present invention are good lithium ion conductors for the recovery of lithium from lithium amalgam. Secondly, it is based on the recognition that the use of comparatively finely divided lithium salts makes it possible to produce particularly impermeable lithium phosphate silicates which are particularly resistant to crack formation and are therefore impermeable and very stable.
- the process of the present invention for isolating lithium from lithium amalgam by electrolysis over a solid lithium ion conductor is carried out in an electrolysis cell whose anode and cathode spaces are separated by a solid electrolyte which conducts lithium ions and has the composition Li 4 ⁇ x Si 1 ⁇ x P x O 4 , where x is generally at least 0.3 and preferably at least 0.4 and is generally not more than 0.7 and preferably not more than 0.6.
- a preferred solid electrolyte is Li 4 ⁇ x Si 1 ⁇ x P x O 4 in which x is about 0.5
- a particularly preferred solid electrolyte is Li 4 ⁇ x Si 1 ⁇ x P x O 4 in which x is 0.5.
- Processes for isolating lithium from lithium amalgam by electrolysis over a solid lithium ion conductor which separates the anode and cathode spaces of an electrolysis cell are known.
- the process of the present invention is carried out like the known processes except that the lithium ion conductor Li 4 ⁇ x Si 1 ⁇ x P x O 4 to be used according to the present invention, in which x is in the range from 0.3 to 0.7, is used as wall (“membrane”) separating cathode and anode spaces.
- the process of the present invention for isolating lithium from lithium amalgam is carried out precisely like the process known from DE 199 14 221 A1 (or from its equivalents EP 1 041 177 and U.S. Pat. No.
- lithium ion conductor Li 4 ⁇ x Si 1 ⁇ x P x O 4 to be used here according to the present invention in which x is in the range from 0.3 to 0.7, is employed as wall (“membrane”) separating the cathode and anode spaces of the electrolysis cell. Its teachings are hereby expressly incorporated by reference.
- the lithium amalgam used in the process of the present invention for the isolation of lithium is a solution of lithium in mercury which is liquid at the reaction temperature employed. It generally contains at least 0.02% by weight of lithium (about 0.5 atom %) and preferably contains at least 0.04% by weight of lithium (about 1 atom %) and generally not more than 0.19% by weight of lithium (5 atom %) and preferably not more than 0.1% by weight of lithium (about 3 atom %), balance mercury. It can be prepared in any way, for example from an aqueous lithium salt solution in an electrolysis cell by the amalgam process.
- a lithium chloride solution having a lithium chloride content of from 220 to 350 g/l is fed in and lithium amalgam is produced at the cathode and chlorine is produced at the anode, completely analogous to the known amalgam process for chloralkali electrolysis by means of which chlorine and sodium amalgam, for example, are produced worldwide on a large scale.
- the sodium amalgam is often decomposed by means of water to produce sodium hydroxide. It is likewise possible to use other sources of lithium, for instance lithium waste from batteries and reaction solutions like the lithium salt solutions formed in the reaction of organolithium compounds with halogen-substituted compounds and subsequent aqueous work-up.
- lithium chloride chlorine is produced anodically in the preparation of lithium amalgam and this is processed further in a customary fashion; if other lithium salts are used, other process engineering measures may have to be employed (the use of lithium sulphate results, for example, in formation of oxygen at the anode and a pH of the liquor of generally from 2 to 4 has to be set and maintained by addition of lithium-containing bases.) These measures are known.
- the lithium amalgam is used as liquid anode which is preferably kept in motion in an electrolysis cell.
- the lithium amalgam anode is separated from the cathode space in which liquor lithium is present by a dividing wall which conducts lithium ions and is otherwise very impermeable.
- the lithium is conveyed from the amalgam in the form of lithium ions through the membrane which conducts lithium ions into the cathode space and is there reduced to the metal.
- the anode potential is set so that virtually no metals which are more noble than lithium are oxidized, in particular no mercury is oxidized to mercury ions.
- the lithium metal obtained is taken off from the cathode space and processed further in a customary fashion.
- Fresh liquid amalgam is fed into the anode space and lithium-depleted amalgam or mercury is taken off from this space.
- the mercury or the depleted amalgam is recirculated to the lithium amalgam synthesis.
- the process is carried out at a temperature at which both lithium amalgam and lithium are liquid and the conductivity for lithium ions of the dividing wall which conducts lithium ions is sufficiently high.
- the reaction temperature is typically at least 150° C., preferably at least 180° C. and particularly preferably at least 200° C. and generally not more than 450° C., preferably not more than 400° C. and particularly preferably not more 350° C.
- a pressure which is slightly above that on the anode side is preferably applied on the cathode side to prevent leakages of mercury into the lithium obtained.
- This overpressure is generally at least 0.1 bar, preferably at least 0.5 bar, and generally not more than 5 bar and preferably not more than 1 bar.
- the dividing wall which conducts lithium ions (also referred to simply as “membrane”, “ion conductor” or “solid electrolyte”) separates the anode space and cathode space from one another.
- the seal is made “helium-tight” so that no substances apart from lithium in ionic form are exchanged between anode space and cathode space.
- the shape chosen for the dividing wall depends on the shape of the electrolysis cell.
- An advantageous and frequently used shape of the dividing wall which conducts lithium ions is that of a tube which is closed at one end and has a circular or other cross s ction and at whose open end there is an electrically insulating seal, for instance an electrically insulating ring with a helium-tight, electrically insulating glass solder connection.
- Such constructions are known, for example from GB 2 207 5645 A, EP 482 785 A1.
- the thickness of the dividing wall is chosen so that sufficient mechanical strength (stability and pressure resistance) and impermeability are achieved but migration of the lithium ions through the dividing wall is not made unnecessarily difficult. It is in general at least 0.3 mm and preferably at least 1 mm and generally not more than 5 mm, preferably not more than 3 mm and particularly preferably not more than 2 mm.
- the impermeability of the dividing wall has to meet high standards in order to avoid leakage of metallic mercury into the lithium which has been obtained. “Helium-tight” dividing walls which have leakage rates of less than 10 ⁇ 9 mbar per liter and second in a helium leakage test are desirable.
- the other seals in the system should also be liquid-tight and gastight in order to prevent diffusion of mercury vapor into the environment or into the lithium obtained.
- Li 4 ⁇ x Si 1 ⁇ x P x O 4 where x is at least 0.3 and not more than 0.7 is brought to the desired shape of the dividing wall. This can be carried out in any conceivable way, for example by shaping an Li 4 ⁇ x Si 1 ⁇ x P x O 4 powder or by synthesis of the compound in the desired shape.
- a simple and preferred method is shaping a compound or a mixture of compounds which finally react to give Li 4 ⁇ x Si 1 ⁇ x P x O 4 in powder form and in the desired stoichiometry and subsequently reacting the powder or powder mixture in the shaped part to form Li 4 ⁇ x Si 1 ⁇ x P x O 4 , where x is at least 0.3 and not more than 0.7.
- the stoichiometry can also be adjusted by addition of phosphorus oxides such as P 2 O 5 or P 2 O 3 , silicon dioxide, including silicon hydroxide in hydrated or partly hydrated form (“silica gel”), lithium oxide and/or lithium hydroxide.
- phosphorus oxides such as P 2 O 5 or P 2 O 3
- silicon dioxide including silicon hydroxide in hydrated or partly hydrated form (“silica gel”), lithium oxide and/or lithium hydroxide.
- the mean particle size (often also referred to as “d50”) is such that 50% by weight of the powder is present in the form of particles having a particle size of not more than this mean particle size.
- d50 the mean particle size is measured by means of sieves, while in the case of finer particles in the size range of only a few microns, use is genrally made of laser light scattering (in accordance with the ISO/DIS standard 13320 “Particle Size Analysis Guide to Laser Diffraction).
- the particle size measured corresponds to the sphere diameter, while in the case of nonspherical particles, the measurement method necessarily gives an effective diameter of the particles which corresponds to the diameter of spherical particles having the same volume.
- the powders have d90 values, at which 90% by weight of the powder is present in the form of particles having an effective diameter of not more than this value.
- the mean particle size of the pulverulent starting materials used is generally not more than 5 microns. It is preferably not more than 3 microns and particularly preferably not more than 1 micron.
- the powder used it is not absolutely necessary but is preferred for the powder used to contain few or no comparatively coarse particles.
- the d90 is preferably not very much higher than the d50.
- the d90 is preferably not more than five times the d50 and particularly preferably not more than three times the d50.
- the powder used does not have this particle size, it is brought to this particle size prior to shaping.
- Particularly useful apparatuses for this purpose are ball mills or attritor mills into which the powder is usually introduced as a suspension in an inert suspension medium (for example water, alcohols, ethers or hydrocarbons).
- an inert suspension medium for example water, alcohols, ethers or hydrocarbons.
- Attritor mills can achieve d50 values of about 0.5 microns.
- the most important parameter when using ball or attritor mills is the milling time. Milling is always continued until the desired fineness has been reached. If a mixture of compounds is used, joint milling can conveniently at the same time effect the intensive
- Shaping of the ion conductor or a mixture of substances from which it is prepared to produce the desired shape is carried out using known shaping methods, for example cold isostatic pressing, hot isostatic pressing, slip casting or tape casting.
- the powder is, if necessary after milling and if necessary after removal of suspension medium, subjected to the appropriate process.
- a preferred shaping process is cold isostatic pressing.
- the powder is pressed in a mold under a pressure of generally at least 1000 bar, preferably at least 2000 bar and particularly preferably at least 3000 bar.
- the ion conductor is fired to full density by heating (“heat treatment”, “calcination” or “sintering”) so as to produce the finished dividing wall of the electrolysis cell.
- heat treatment “calcination” or “sintering”
- sintering is carried out by heating the shaped bodies to a temperature of generally at least 700° C., preferably at least 800° C. and particularly preferably at least 900° C.
- Sintering is continued until an ion conductor of the desired density is obtained at the temperature set.
- the sintering temperature is held for at least 15 minutes, preferably at least 30 minutes and particularly preferably at least 1 hour.
- Sintering is generally complete after no more than 10 hours; sintering is preferably carried out for not more than 6 hours and particularly preferably for not more than 4 hours.
- the heating or cooling rate is therefore generally not more than 20° C./min, preferably not more than 10° C./min and particularly preferably not more than 5° C./min.
- Lithium ion conductors which have a high density and cracking resistance and are very suitable for lithium production can be produced in this way.
- the powder was shaped into a crucible shape by cold isostatic pressing at a pressure of 3500 bar, heated at a heating rate of 1° C./min to 1000° C., sintered at this temperature for 2 hours and subsequently cooled at a cooling rate of 1° C./min.
- the powder was shaped into a crucible shape by cold isostatic pressing at a pressure of 3500 bar, heated at a heating rate of 1° C./min to 1000° C., sintered at this temperature for 2 hours and subsequently cooled at a cooling rate of 1° C./min.
- the ceramic produced in example 1 was subjected to a transport measurement in the model system lithium-lithium at 195° C. This corresponds to the procedure in the electrolysis of lithium amalgam, but liquid lithium is used on both sides of the dividing wall.
- the polarity of the electrodes was set so that transport occurred from the exterior into the interior of the lithium ion conductor crucible.
- a current of 1 mA was applied for a period of 70 hours.
- the current yield achieved was quantitative within the measurement accuracy. Cracks in the ion conductor were not observed.
Abstract
Lithium is isolated from lithium amalgam by electrolysis over a solid lithium ion conductor having the composition Li4−xSi1−xPxO4, where x is at least 0.3 and not more than 0.7.
Description
- The present invention relates to a process for producing lithium. In particular, the invention relates to a process for isolating lithium from lithium amalgam by electrolysis over a solid electrolyte which conducts lithium ions. It also relates to a process for preparing this electrolyte.
- Lithium is an important basic inorganic chemical and is required in a variety of industrial applications. For example, lithium is used for producing 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 prior art relating to the production and use of lithium. The usual industrial method of producing lithium is melt electrolysis of a eutectic mixture of lithium chloride with potassium chloride at from 400 to 460° C. This process requires a comparatively large quantity of energy (28-32 kWh/kg of lithium) and, in addition, only anhydrous lithium chloride can be used. Since lithium chloride is hygroscopic, the necessity of drying has an additional adverse effect on the economics of this process.
- DE 199 14 221 A1 (US equivalent: U.S. Pat. No. 6,287,448) discloses a comparatively economical process for preparing lithium from aqueous solutions, in which a lithium amalgam is firstly produced from an aqueous lithium salt solution and, in a second step, lithium is isolated from this amalgam by connecting the amalgam as anode in an electrolysis cell having a solid electrolyte which conducts lithium ions and a lithium cathode. The solid electrolyte, viz. a ceramic material or a glass, separates the anode and cathode spaces in a “helium-type” manner but is permeable to lithium ions. A number of types of suitable solid electrolytes which conduct lithium ions are mentioned, namely a) Li-β″-Al2O3 or Li-β-Al2O3, b) lithium analogues of NASICON ceramics having a particular structure and composition, c) LISICONS having a particular structure and composition, d) lithium ion conductors having a perovskite structure and a particular composition and e) sulfidic glasses.
- Another class of known lithium ion conductors is derived from lithium silicate in which silicon is partly replaced by aluminum, phosphorus and/or sulfur. For example, U.S. Pat. No. 4,042,482 discloses monoclinic compounds of the formula Li4+w−x−ySi1−w−x−yAlwPxSyO4, 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 and (x+2y) is 0.1 or more. R. A. Huggins, Electrochimica Acta 22 (1977) 773-781 teaches the preparation of solid solutions of LiSiO4 and Li3PO4 by hot pressing a stoichiometric mixture of lithium hydroxide, silicon dioxide and ammonium dihydrogen phosphate. In Mat. Res. Bull. 11 (1976) 1227-1230 and in J. Electrochem. Soc. 124 (1977) 1240-1242, Y.-W Hu, I. D. Raistrick and R. A. Huggins disclose processes for preparing such compounds by hot pressing a mixture of lithium phosphate and lithium silicate. R. D. Shannon, B. E. Taylor, A. D. English and T. Berzins, Electrochimica Acta 22 (1977) 783-796, teach the preparation of such compounds by mixing lithium hydroxide, silicon dioxide and aluminum hydroxide at 850° C. Although these disclosures mention the possibility of using these compounds as ion conductors in lithium batteries, they have not been employed in practice for this purpose.
- DE 199 48 548 A1 discloses paste-like compositions for electrochemical components, which comprise nanocrystalline materials and a matrix, including Li0.5Si0.5P0.5O4 which at particle sizes below 10 microns is paste-like even without a matrix.
- Ion conductors for the preparation of lithium have to satisfy a number of requirements in order to be suitable. Apart from suitable electrochemical properties (for example good conductivity for lithium ions under the process conditions employed, stability to liquid lithium and lithium amalgam and a negligibly low electron conductivity), they should also be simple and inexpensive to produce, be stable on storage and easy to handle and have a very high stability and thus a long life. A particular problem is the formation of microcracks which form under electrochemical stress or grow larger and lead to leakages of mercury into the lithium produced. The ion conductors known for the isolation of lithium do not fulfill all these requirements in a fully satisfactory manner. For example, Li-β″-Al2O3, Li-β-Al2O3 or lithium analogues of NASICON ceramics, which are preferred from the point of view of their electrochemical properties, are comparatively expensive and, owing to their hygroscopic nature, special precautions have to be taken when handling and storing them to ensure that their performance in the process is not impaired.
- It is an object of the present invention to find an improved process for the isolation of lithium and, in particular, further lithium ion conductors which can be used in this process and satisfy the abovementioned requirements. A further object is to find a process for preparing such ion conductors.
- We have found that this object is achieved by a process for isolating lithium from lithium amalgam by electrolysis over a solid lithium ion conductor which has the composition Li4−xSi1−xPxO4, where x is at least 0.3 and not more than 0.7. We have also found a process for preparing a lithium ion conductor having the composition Li4−xSi1−xPxO4, where x is at least 0.3 and not more than 0.7, by shaping and calcining Li4−xSi1−xPxO4, where x is at least 0.3 and not more than 0.7 and/or compounds which are converted into this during calcination, wherein the Li4−xSi1−xPxO4 and/or the compounds is/are used in the form of powder having a mean particle size of not more than 5 microns.
- The invention is firstly based on the recognition that the lithium phosphate silicates to be used according to the present invention are good lithium ion conductors for the recovery of lithium from lithium amalgam. Secondly, it is based on the recognition that the use of comparatively finely divided lithium salts makes it possible to produce particularly impermeable lithium phosphate silicates which are particularly resistant to crack formation and are therefore impermeable and very stable.
- The process of the present invention for isolating lithium from lithium amalgam by electrolysis over a solid lithium ion conductor is carried out in an electrolysis cell whose anode and cathode spaces are separated by a solid electrolyte which conducts lithium ions and has the composition Li4−xSi1−xPxO4, where x is generally at least 0.3 and preferably at least 0.4 and is generally not more than 0.7 and preferably not more than 0.6. A preferred solid electrolyte is Li4−xSi1−xPxO4 in which x is about 0.5, and a particularly preferred solid electrolyte is Li4−xSi1−xPxO4 in which x is 0.5.
- Processes for isolating lithium from lithium amalgam by electrolysis over a solid lithium ion conductor which separates the anode and cathode spaces of an electrolysis cell are known. The process of the present invention is carried out like the known processes except that the lithium ion conductor Li4−xSi1−xPxO4 to be used according to the present invention, in which x is in the range from 0.3 to 0.7, is used as wall (“membrane”) separating cathode and anode spaces. In particular, the process of the present invention for isolating lithium from lithium amalgam is carried out precisely like the process known from DE 199 14 221 A1 (or from its equivalents EP 1 041 177 and U.S. Pat. No. 6,287,448), except that the lithium ion conductor Li4−xSi1−xPxO4 to be used here according to the present invention, in which x is in the range from 0.3 to 0.7, is employed as wall (“membrane”) separating the cathode and anode spaces of the electrolysis cell. Its teachings are hereby expressly incorporated by reference.
- The lithium amalgam used in the process of the present invention for the isolation of lithium is a solution of lithium in mercury which is liquid at the reaction temperature employed. It generally contains at least 0.02% by weight of lithium (about 0.5 atom %) and preferably contains at least 0.04% by weight of lithium (about 1 atom %) and generally not more than 0.19% by weight of lithium (5 atom %) and preferably not more than 0.1% by weight of lithium (about 3 atom %), balance mercury. It can be prepared in any way, for example from an aqueous lithium salt solution in an electrolysis cell by the amalgam process. For this purpose, a lithium chloride solution having a lithium chloride content of from 220 to 350 g/l is fed in and lithium amalgam is produced at the cathode and chlorine is produced at the anode, completely analogous to the known amalgam process for chloralkali electrolysis by means of which chlorine and sodium amalgam, for example, are produced worldwide on a large scale. The sodium amalgam is often decomposed by means of water to produce sodium hydroxide. It is likewise possible to use other sources of lithium, for instance lithium waste from batteries and reaction solutions like the lithium salt solutions formed in the reaction of organolithium compounds with halogen-substituted compounds and subsequent aqueous work-up. This usually gives aqueous lithium chloride solutions, but it is also possible to use other lithium halides and other lithium salts such as lithium sulphate, lithium sulphonates or lithium salts of organic acids. If lithium chloride is used, chlorine is produced anodically in the preparation of lithium amalgam and this is processed further in a customary fashion; if other lithium salts are used, other process engineering measures may have to be employed (the use of lithium sulphate results, for example, in formation of oxygen at the anode and a pH of the liquor of generally from 2 to 4 has to be set and maintained by addition of lithium-containing bases.) These measures are known.
- To isolate metallic lithium from lithium amalgam, the lithium amalgam is used as liquid anode which is preferably kept in motion in an electrolysis cell. The lithium amalgam anode is separated from the cathode space in which liquor lithium is present by a dividing wall which conducts lithium ions and is otherwise very impermeable. During electrolysis in such a cell, the lithium is conveyed from the amalgam in the form of lithium ions through the membrane which conducts lithium ions into the cathode space and is there reduced to the metal. The anode potential is set so that virtually no metals which are more noble than lithium are oxidized, in particular no mercury is oxidized to mercury ions. The lithium metal obtained is taken off from the cathode space and processed further in a customary fashion. Fresh liquid amalgam is fed into the anode space and lithium-depleted amalgam or mercury is taken off from this space. The mercury or the depleted amalgam is recirculated to the lithium amalgam synthesis. The process is carried out at a temperature at which both lithium amalgam and lithium are liquid and the conductivity for lithium ions of the dividing wall which conducts lithium ions is sufficiently high. The reaction temperature is typically at least 150° C., preferably at least 180° C. and particularly preferably at least 200° C. and generally not more than 450° C., preferably not more than 400° C. and particularly preferably not more 350° C. A pressure which is slightly above that on the anode side is preferably applied on the cathode side to prevent leakages of mercury into the lithium obtained. This overpressure is generally at least 0.1 bar, preferably at least 0.5 bar, and generally not more than 5 bar and preferably not more than 1 bar.
- The dividing wall which conducts lithium ions (also referred to simply as “membrane”, “ion conductor” or “solid electrolyte”) separates the anode space and cathode space from one another. The seal is made “helium-tight” so that no substances apart from lithium in ionic form are exchanged between anode space and cathode space.
- The shape chosen for the dividing wall depends on the shape of the electrolysis cell. An advantageous and frequently used shape of the dividing wall which conducts lithium ions is that of a tube which is closed at one end and has a circular or other cross s ction and at whose open end there is an electrically insulating seal, for instance an electrically insulating ring with a helium-tight, electrically insulating glass solder connection. Such constructions are known, for example from GB 2 207 5645 A, EP 482 785 A1. The thickness of the dividing wall is chosen so that sufficient mechanical strength (stability and pressure resistance) and impermeability are achieved but migration of the lithium ions through the dividing wall is not made unnecessarily difficult. It is in general at least 0.3 mm and preferably at least 1 mm and generally not more than 5 mm, preferably not more than 3 mm and particularly preferably not more than 2 mm.
- The impermeability of the dividing wall has to meet high standards in order to avoid leakage of metallic mercury into the lithium which has been obtained. “Helium-tight” dividing walls which have leakage rates of less than 10−9 mbar per liter and second in a helium leakage test are desirable. The other seals in the system should also be liquid-tight and gastight in order to prevent diffusion of mercury vapor into the environment or into the lithium obtained.
- To produce dividing walls which conduct lithium ions and are to be used according to the present invention, Li4−xSi1−xPxO4 where x is at least 0.3 and not more than 0.7, is brought to the desired shape of the dividing wall. This can be carried out in any conceivable way, for example by shaping an Li4−xSi1−xPxO4 powder or by synthesis of the compound in the desired shape. A simple and preferred method is shaping a compound or a mixture of compounds which finally react to give Li4−xSi1−xPxO4 in powder form and in the desired stoichiometry and subsequently reacting the powder or powder mixture in the shaped part to form Li4−xSi1−xPxO4, where x is at least 0.3 and not more than 0.7.
- In principle, it is possible to use all compounds and mixtures of compounds which during the preparation of the ion conductor react to give Li4−xSi1−xPxO4 as final product. It is convenient and preferred to use lithium phosphate and lithium silicate as anhydrous ortho compounds Li3PO4 and Li4SiO4. However, it is likewise possible to use compounds which are converted into these substances during the course of the preparation of the ion conductor. It is likewise possible to use compounds containing water of crystallization or hydrates such as Li3O4. ½ H2O, meta compounds such as Li2SiO3 or LiPO3 or hydrogen salts such as Li2HPO4 or LiH2PO4. The stoichiometry can also be adjusted by addition of phosphorus oxides such as P2O5 or P2O3, silicon dioxide, including silicon hydroxide in hydrated or partly hydrated form (“silica gel”), lithium oxide and/or lithium hydroxide.
- Preference is given to using pulverulent starting materials which have a particular mean particle size. The mean particle size (often also referred to as “d50”) is such that 50% by weight of the powder is present in the form of particles having a particle size of not more than this mean particle size. In the case of relatively coarse particles, the mean particle size is measured by means of sieves, while in the case of finer particles in the size range of only a few microns, use is genrally made of laser light scattering (in accordance with the ISO/DIS standard 13320 “Particle Size Analysis Guide to Laser Diffraction). In the case of spherical particles, the particle size measured corresponds to the sphere diameter, while in the case of nonspherical particles, the measurement method necessarily gives an effective diameter of the particles which corresponds to the diameter of spherical particles having the same volume. Analogously, the powders have d90 values, at which 90% by weight of the powder is present in the form of particles having an effective diameter of not more than this value.
- The mean particle size of the pulverulent starting materials used is generally not more than 5 microns. It is preferably not more than 3 microns and particularly preferably not more than 1 micron.
- It is not absolutely necessary but is preferred for the powder used to contain few or no comparatively coarse particles. In other words, the d90 is preferably not very much higher than the d50. The d90 is preferably not more than five times the d50 and particularly preferably not more than three times the d50.
- If the powder used does not have this particle size, it is brought to this particle size prior to shaping. This can be carried out using any known comminution process. Particularly useful apparatuses for this purpose are ball mills or attritor mills into which the powder is usually introduced as a suspension in an inert suspension medium (for example water, alcohols, ethers or hydrocarbons). Preference is given to using alcohols, in particular C1-C4-alcohols (methanol, ethanol, propanol, isopropanol, butanol, sec-butanol, isobutanol, tert-butanol) as suspension medium. Attritor mills can achieve d50 values of about 0.5 microns. The most important parameter when using ball or attritor mills is the milling time. Milling is always continued until the desired fineness has been reached. If a mixture of compounds is used, joint milling can conveniently at the same time effect the intensive mixing necessary before shaping.
- Shaping of the ion conductor or a mixture of substances from which it is prepared to produce the desired shape is carried out using known shaping methods, for example cold isostatic pressing, hot isostatic pressing, slip casting or tape casting. For this purpose, the powder is, if necessary after milling and if necessary after removal of suspension medium, subjected to the appropriate process. A preferred shaping process is cold isostatic pressing. For this purpose, the powder is pressed in a mold under a pressure of generally at least 1000 bar, preferably at least 2000 bar and particularly preferably at least 3000 bar.
- Subsequent to shaping or at the same time as shaping (for instance in the case of hot isostatic pressing), the ion conductor is fired to full density by heating (“heat treatment”, “calcination” or “sintering”) so as to produce the finished dividing wall of the electrolysis cell. If shaping has not been carried out using Li4−xSi1−xPxO4 in which x is at least 0.3 and not more than 0.7 itself, this ion conductor is also produced from the powder mixture used during sintering. Sintering is carried out by heating the shaped bodies to a temperature of generally at least 700° C., preferably at least 800° C. and particularly preferably at least 900° C. Sintering is continued until an ion conductor of the desired density is obtained at the temperature set. In general, the sintering temperature is held for at least 15 minutes, preferably at least 30 minutes and particularly preferably at least 1 hour. Sintering is generally complete after no more than 10 hours; sintering is preferably carried out for not more than 6 hours and particularly preferably for not more than 4 hours. On heating and cooling the shaped bodies to or from the sintering temperature, care has to be taken to ensure that temperature stresses do not cause cracks. The heating or cooling rate is therefore generally not more than 20° C./min, preferably not more than 10° C./min and particularly preferably not more than 5° C./min.
- Lithium ion conductors which have a high density and cracking resistance and are very suitable for lithium production can be produced in this way.
- Preparation of a Lithium Ion Conductor Having the Composition Li4−xSi1−xPxO4, x=0.5
- 15.0 g (0.125 mol) of LiSiO4 and 14.49 g (0.125 mol) of Li3PO4 were placed in a zirconium dioxide container and slurried in 20 ml of isopropanol. Three spherical milling media having diameters of 0.5 and 2 cm were in each case placed in the container. The closed container was left on a ball mill for 12 hours. The isopropanol was subsequently removed by evaporation and the powder which remained was pressed through a sieve. The powder was shaped into a crucible shape by cold isostatic pressing at a pressure of 3500 bar, heated at a heating rate of 1° C./min to 1000° C., sintered at this temperature for 2 hours and subsequently cooled at a cooling rate of 1° C./min.
- Preparation of a Lithium Ion Conductor Having the Composition Li4−xSi1−xPxO4, x=0.5
- 15.0 g (0.125 mol) of LiSiO4 and 14.49 g (0.125 mol) of Li3PO4 were placed in a zirconium dioxide container and slurried in 20 ml of isopropanol. Three spherical milling media having diameters of 0.5 and 2 cm were in each case placed in the container. The closed container was left on a ball mill for 1 hour, and the slurry was subsequently milled in an attritor mill (1.5 kg of spherical ZrO2 milling m dia having a diameter of 2 mm) for another 30 minutes. The isopropanol was removed by evaporation and the powder which remained was pressed through a sieve. The powder was shaped into a crucible shape by cold isostatic pressing at a pressure of 3500 bar, heated at a heating rate of 1° C./min to 1000° C., sintered at this temperature for 2 hours and subsequently cooled at a cooling rate of 1° C./min.
- Lithium Ion Conduction in a Model System
- The ceramic produced in example 1 was subjected to a transport measurement in the model system lithium-lithium at 195° C. This corresponds to the procedure in the electrolysis of lithium amalgam, but liquid lithium is used on both sides of the dividing wall. The polarity of the electrodes was set so that transport occurred from the exterior into the interior of the lithium ion conductor crucible. A current of 1 mA was applied for a period of 70 hours. The current yield achieved was quantitative within the measurement accuracy. Cracks in the ion conductor were not observed.
Claims (5)
1. A process for isolating lithium from lithium amalgam by electrolysis over a solid lithium ion conductor, wherein a lithium ion conductor used has the composition Li4−xSi1−xPxO4 where x is at least 0.3 and not more than 0.7.
2. A process as claimed in claim 1 , wherein the lithium ion conductor used has the composition Li4−xSi1−xPxO4, where x is at least 0.4 and not more than 0.6.
3. A process as claimed in claim 2 , wherein the lithium ion conductor used has the composition Li4−xSi1−xPxO4, where x is about 0.5.
4. A process as claimed in one of claims 1, 2 or 3, wherein the lithium ion conductor used is prepared by shaping and calcining Li4−xSi1−xPxO4, where x is at least 0.3 and not more than 0.7, and/or compounds which are converted into this during calcination, where the Li4−xSi1−xPxO4 and/or the compounds is/are used in the form of powder having a mean particle size of not more than 5 microns.
5. A process as claimed in claim 4 , wherein the Li4−xSi1−xPxO4 and/or the compounds is/are used in the form of powder having a mean particle size of not more than 3 microns.
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- 2003-11-18 DE DE50305946T patent/DE50305946D1/en not_active Expired - Fee Related
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Also Published As
Publication number | Publication date |
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DE50305946D1 (en) | 2007-01-25 |
EP1431422A1 (en) | 2004-06-23 |
JP2004218078A (en) | 2004-08-05 |
ATE348204T1 (en) | 2007-01-15 |
EP1431422B1 (en) | 2006-12-13 |
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