Organoaluminum electrolytes for the electrolytic deposition of high-purity aluminum

Abstract: The invention relates to organoaluminum electro­ lytes for the electrolytic deposition of high-purity aluminum, which are characterized in that they contain mixtures of organoaluminum complex compounds of the type MF . 2 AlR₃ ( A ), wherein M represents potassium or mixtures of K with a maximum of about 15% by mole of sodium, as well as trialkylaluminum AlR₃ ( B ) which has not been complexed to an alkali metal fluoride in a molar ratio of A : B of from 4:0.6 to 4:2, as well as a polyfunctional Lewis base of the type R′-OCH₂CH₂-OR″ ( C ) in a molar ratio of B : C of from 1:0.5 to 1:1. The organyl radicals R in A are ethyl groups (Et), methyl groups (Me) and iso-butyl groups (iBu) in a molar ratio of Et:Me:iBu as 3:m:n, wherein m and n are numerical values of between 1.1 and 0 and the sum (m+n) is from 0.75 to 1.4. As the solvent for said electrolytes there are used from 3 to 4.5 moles, relative to the amount of alkali metal fluoride employed, of an aromatic hydro­ carbon which is liquid at 0 °C or a mixture of such hydrocarbons. The invention further relates to a process for the electrolytic deposition of high-purity aluminum by using said electrolytes.

Description: The invention relates to organoaluminum electrolytes for the electrolytic deposition of high-purity aluminum by using soluble anodes made of the aluminum to be refined, and to a process therefor. Organoaluminum complex compounds have been used for the electrolytic deposition of aluminum for a long time. {Lit. 1: Dissertation H. Lehmkuhl, TH Aachen 1954; Lit. 2: Angew. Chem. 67 (1955) 424; Lit. 3: DE-PS 1 047 450; Lit. 4: Z. anorg. Chem. 283 (1956) 414; Lit. 5: Chem. Ber. 92 (1959) 2320; Lit. 6: Chem. Ing. Tech. 36 (1964) 616; Lit. 7: DE-PS 1 056 377}. As the electrolytes there have been proposed complexes of the general type MX . 2 AlR₃ which are employed either as molten salts or in the form of their solutions in liquid aromatic hydrocarbons. MX are either alkali metal halides or onium halides, preferably fluorides. R are alkyl groups or hydrogen. Superhigh-purity aluminum is a very important starting material for electronic components. The most important application so far is the use for conductive and contacting layers on microprocessors and memory chips. The organoaluminum electrolytes that are electrolyzed in closed systems at moderate temperatures between 60 °C and 150 °C, due to the particular selectivity of these compounds in the dissolution reaction of the metal anodes, are of great technical importance in refining aluminum to produce superhigh-purity grades of at least 99.999 % and even higher purity (Lit. 1; Lit. 4). Due to the chemistry of the anode reaction in these organoaluminum electrolytes, the transition metals present as impurities in the aluminum to be refined as well as Si, Ge, As are depleted in the refined metal and accordingly much accumulated in the anode slime (Lit. 6). So far there have been investigated in greater detail as electrolytes for the organometal refining of aluminum: 1. Melts of NaF . 2 AlEt₃ (Lit. 1-4, 6). With this electrolyte, current densities of 2.3 A/dm² may be employed (Lit. 6). One drawback is that it auto-ignites upon contact with air or oxygen. The degree of purity of the refined aluminum cathodically deposited has been reported to be ≧ 99.999%, based on the analytical methods available at that time (Lit. 1, 2, 4, 6). The cathodic and anodic current yields were 98-100% at current densities up to 1.1 A/dm² (Lit. 1). 2. Solutions of NaF . 1.25 AlEt₃ to NaF . 1.50 AlEt₃ in 1 mole of toluene per mole of NaF {Lit. 8: Aluminium 37 (1961) 267}. The advantage of these electrolytes is a reduced tendency to auto-ignite. Disadvantages are reduced conductivities and current density limitations to values of ≦ 0.5 A/dm². 3. Solutions of NaF . 2 AlEt₃ in 1 mole of toluene per mole of NaF {Lit. 9: Raffinationsverfahren in der Metallurgie, Verlag Chemie 1983, pages 55-68}. As the most beneficial operational conditions there are indicated 100 °C and current densities of 0.35 A/dm². 4. Solutions of KF (m-n)AlEt₃ . n AlR₃ m wherein m = 1.8 - 2.2, preferably 2.0 n = 0.2 - 0.5, preferably 0.4 and R = CH₃ oder C₄H₉ (Lit, 9a: EP 0 084 816, Siemens AG). This electrolyte is applied in form of a solution of 1-10 mole, preferably 1-5 mole in liquid aromatic hydrocarbons, preferably toluene. As specific example a complex of KF 1.6 AlEt₃ . 0.4 Al(i-C₄H₉)₃ . 0.4 toluene (Lit 9a) is mentioned. In the electrolyte systems quoted under the items 2. and 3. the reduced tendency to auto-ignite has been attained by reducing the concentration of trialkylaluminum and/or diluting with toluene at the expense of compromising the applicable current density load. However, the use of a current density as high as possible is of great importance for assessing an electrolyte system, since the space-time yield will depend thereon. Further important criteria of assessment are the thermal stability of the electrolyte, the electrolytic conductivity, the formation of aluminum deposits which are as compact as possible without any co-deposition of alkali metal, and the retention of homogeneous liquid phases even upon cooling to from 20 °C to 0 °C, because otherwise malfunctions would occur due to crystallization in cases of discontinuation of the operation or troubles in the course thereof in unheated pipe conduits or pumps. It has been known that potassium fluoride . 2 trialkylaluminum complexes are better electrolytic conductors than are the analogous respective sodium fluoride compounds (Lit. 1). It is a disadvantage inherent in these complexes containing potassium fluoride that in general they have melting points higher than those of the corresponding sodium compounds and, therefore, have a higher tendency to crystallize from solution in aromatic hydrocarbons when cooled. It has further been known that known 1:2 complexes of the type MF . 2 AlR₃ comprising alkyl moieties of low carbon number (e.g. Me, Et) are virtually not miscible with excessive trialkyl aluminum AlR₃. Thus, NaF . 2 AlEt₃ which is liquid at 35 °C forms two non-miscible phases with AlEt₃ {Lit. 1, Lit. 10: Liebigs Ann. Chem. 629 (1960) 33}. Therefrom ensues the object to provide electrolytes for the deposition of high-purity aluminum which in an optimal manner combine the properties required for a technical application in aluminum refining such as a conductivity as high as possible and an applicable current density load up to in excess of 6 A/dm², an aluminum deposit formed as compact as possible, a high selectivity in dissolving the aluminum anode and a homogeneous solubility down to temperatures of from 20 °C to 0 °C. Now it was unexpectedly found that mixtures comprising certain organoaluminum complexes together with organoaluminum, certain bifunctional Lewis bases of the type of the 1,2-dialkoxyalkane and aromatic hydrocarbons which are liquid at room temperature such as toluene and/or a liquid xylene within certain narrow mixing ratios have optimum electrolyte properties for refining aluminum, despite the unfavourable properties of their individual components. Thus, the non-complexed aluminum alkyls {Lit. 11: Angew. Chem. 67 (1955) 525}, 1,2-dialkoxyalkane and toluene or xylene are virtually electrolytic non-conductors. The inherent conductivity of triethylaluminum in hydrocarbons, e.g., is about 10⁻⁸ S.cm⁻¹ (Lit. 11). KF . 2 AlEt₃ and KF . 2 AlMe₃, although they are good electrolytic conductors, have relatively high melting points of 127-129 °C and at 151-152 °C, respectively, and, thus, are not highly soluble in toluene so that for dissolving relatively large amounts of toluene are necessary. On the other hand, KF . 2 Al(iBu)₃, although it melts at already 51-53 °C, exhibits a poor utilizable current density load. Even during electrolysis at 0.4 A/dm² gray potassium-containing deposits are formed at the cathode (Lit. 1). The invention relates to organoaluminum electrolytes for the electrolytic deposition of high-purity aluminum which are characterized in that they contain mixtures of organoaluminum complex compounds of the type MF . 2 AlR₃ ( ), wherein M represents potassium or mixtures of K with a maximum of about 15% by mole of sodium, as well as trialkylaluminum AlR₃ ( ) which has not been complexed to an alkali metal fluoride in a molar ratio of : of from 4:0.6 to 4:2, as well as a polyfunctional Lewis base of the type R'-OCH₂CH₂-OR'' ( ) in a molar ratio of : of from 1:0.5 to 1:1. The organyl radicals R in are ethyl (Et), methyl (Me) and iso-butyl (iBu) groups in a molar ratio of Et:Me:iBu as 3:m:n, wherein m and n are numerical values of between 1.1 and 0 and the sum (m+n) is to amount to from 0.75 to 1.4, and preferably from 0.9 to 1.1. The trialkylaluminum AlR₃ ( ) which has not been complexed to an alkali metal fluoride (e.g. KF) preferably is AlEt₃ or Al(iBu)₃ or a mixture of these two components. The molar mixing ratios of the sum of the alkali metal fluoride . 2 AlR₃ complexes (e.g. KF . 2 AlR₃) to AlR₃ which has not been bonded to an alkali metal fluoride (e.g. KF) preferably are from 4:1.0 to 4:1.6. The molar ratio of the aluminum trialkyls AlR₃ which have not been coordinated to an alkali metal fluoride (e.g. KF) to the polyfunctional Lewis base preferably is between 1:0.5 and 1:0.8. Therein, R′ and R″ may be alkyl, aryl or OCH₂CH₂OR‴ groups, wherein R‴ represents R′ or R″. Bifunctional Lewis bases of the type of the 1,2-dialkoxyalkane R′OCH₂CH₂OR″ with R′ = R″ = Me or Et or R′ = Me and R″ = Et are preferred. The multi-component electrolytes defined according to the invention form homogeneous liquid systems with toluene, meta- or orthoxylene or other hydrocarbons which are liquid at 0 °C, which systems are especially suitable for the electrolytic refining of aluminum. The amount of aromatic hydrocarbon should be from 3 to 4.5 moles, and preferably from 3 to 3.5 moles, per 1 mole of the alkali metal fluoride (e.g. KF). Any further dilution with the solvent is inexpedient because of the reduction in the conductivity associated therewith. At substantially lower solvent contents the systems tend to undergo partially crystallization upon cooling. In the multi-component electrolytes, the alkali metal fluoride . 2 AlR₃ complexes (e.g. KF . 2 AlR₃) impart good electrolytic conductivity. The addition of AlR₃ which has not been complexed to an alkali metal fluoride (e.g. KF) permits the application of high current densities up to more than 6 A/dm², and the presence of the bifunctional Lewis base of the 1,2-dialkoxyalkane type results in the formation of very compact aluminum deposits. In contrast thereto, in the absence of said Lewis bases a highly dendritic growth of the aluminum on the cathode is observed which will readily produce a short circuit between cathode and anode. Preferred working temperatures for the electrolysis are 80-135 °C for systems containing meta-xylene and 90-105 °C for systems containing toluene. Electrolyte systems according to the invention have been set forth in Table 1 by way of example. The compositions need not be accurately as indicated, but an approximate compliance will do as well. The formulae have been written so that it may be recognized from which constituent components the electrolytes have been composed. This does not involve any statement of that in the multi-component mixtures they are actually present unchanged in the same initial forms. Since it has been known (Lit. 1) that the trialkylaluminum compounds AlMe₃ and AlEt₃ will displace the triisobutylaluminum from KF . 2 Al(iBu)₃ from the complex bonding to KF according to KF . 2 Al(iBu)₃ + AlMe₃ → KF . AlMe₃ . Al(iBu)₃ + Al(iBu)₃ , in the electrolytes according to the invention there will also be released triisobutylaluminum from KF . 2 Al(iBu)₃ upon the addition of AlEt₃ or AlMe₃. In the same manner the AlEt₃ complex-bonded in NaF . 2 AlEt₃ will be displaced by AlMe₃ upon addition of AlMe₃, e.g. upon an addition in a molar ratio of 1:1 according to the equation NaF . 2 AlEt₃ + AlMe₃ → NaF . AlMe₃ . AlEt₃ + AlEt₃ . Hence, the tendencies for complex formation of the aluminum trialkyls decrease in the sequence AlMe₃ > AlEt₃ > Al(iBu)₃. Al(iBu)₃ is displaced from the alkali fluoride complexes of the Al(iBu)₃ by AlMe₃ or AlEt₃, and AlEt₃ is displaced from the corresponding AlEt₃ complexes only by AlMe₃. This effect may be utilized in the preparation of the multi-component electrolytes. Thus, absolutely identical electrolytes will be obtained, no matter whether a) a mixture comprising 0.75 moles of KF . 2 AlEt₃ and 0.25 moles of KF . 2 AlMe₃ in 3 moles of toluene is charged and admixed with 0.25 moles of Al(iBu)₃ and 0.25 moles of MeOCH₂CH₂OMe, or b) a mixture comprising 0.75 moles of KF . 2 AlEt₃, 0.125 moles of KF . 2 AlMe₃ and 0.125 moles of KF . 2 Al(iBu)₃ in 3 moles of toluene is charged, and 0.25 moles of AlMe₃ and 0.25 moles of MeOCH₂CH₂OMe are dropwise added thereto, or c) 0.25 moles of AlEt₃ and 0.25 moles of MeOCH₂CH₂OMe are added to a mixture comprising 0.625 moles of KF . 2 AlEt₃, 0.25 moles of KF . 2 AlMe₃ and 0.125 moles of KF . 2 Al(iBu)₃ in 3 moles of toluene, or d) 0.25 moles of the complex Al(iBu)₃ . MeOCH₂CH₂OMe is added to a mixture comprising 0.75 moles of KF . 2 AlEt₃ and 0.25 moles of KF . 2 AlMe₃ in 3 moles of toluene. Example 1 An electrolyte system according to the invention was obtained from 0.51 moles of KF . 2 AlMe₃, 1.53 moles KF . 2 AlEt₃, 647 ml of toluene, 0.59 moles of AlEt₃ and 0.30 moles of MeOCH₂CH₂OMe. Electrolysis was carried out in a closed electrolytic cell at 95-98 °C under a protective gas. A sheet of pure aluminum was arranged as a cathode between two anodes at distances of 30 mm from each of both said anodes made of the aluminum to be refined. Electrolysis was conducted at current densities of 1.5 A/dm² for the cathode and 2.3 dm² for the anodes at a cell voltage of 2.7 V and a current of 3.0 A for 66.2 hours. During this period, 66.69 g of aluminum had been dissolved, which is 99.3% of the theoretical amount. The cathodic current yield was quantitative. Example 2 An electrolyte prepared from KF . 2 AlEt₃, KF . 2 AlMe₃, Al(iBu)₃ and dimethoxyethane in a molar ratio of 3:1:1:1 in 3 moles of xylene per mole of KF was electrolyzed at 120 °C between two aluminum electrodes with 3 A/dm². A thick silvery-lustrous somewhat warty aluminum deposit was obtained. The anodic current yield was 99.7%, the cathodic current yield was quantitative. Example 3 The electrolyte described in Example 2 was electrolyzed at 97-98 °C with 2.8 volt and 0.18 A and current densities up to 6 A/dm². A thick silvery-lustrous warty aluminum deposit was obtained. The electrolyte remains liquid also when cooled at 0 °C for weeks of storage. Example 4 In the same manner as in Example 2 the same components were dissolved in 3 moles of toluene in the place of xylene. The resulting electrolyte also remained a homogeneous liquid down to 0 °C. However, in comparison to the xylene solution, it has a substantially higher conductivity of 25.5 mS.cm⁻¹ at 95 °C. The conductivity of the xylene solution at the same temperature is 16.7 mS.cm⁻¹. Example 5 An electrolyte prepared from KF . 2 AlEt₃, KF . 2 AlMe₃, AlEt₃ and EtOCH₂CH₂OEt or MeOCH₂CH₂OEt in a molar ratio of 3:1:1.6:0.8 in 4 moles of toluene per mole of KF was electrolyzed between two aluminum electrodes at 93-96 °C in three different experiments with 3 A/dm² (3.7 volt; 0.88 A), with 4.5 A/dm² (5.4 volt; 1.32 A), and with 6.0 A/dm² (6.2 volt; 1.78 A). In each case there were obtained bright shiny crystalline aluminum deposits. At 6 A/dm² lump formation was observed at the edges of the cathode. The cathodic and anodic current yields were 100 and 99.4%, 99.6 and 99.6% as well as 99.8 and 99.3%. Example 6 The same electrolyte systems as described in Examples 2 or 4 were obtained by combining 2 moles of K[Et₃AlF], 1 mole of AlEt₃, 1 mole of AlMe₃, 0.5 moles of Al(iBu)₃ and 0.5 moles of dimethoxyethane in 6 moles of meta-xylene or toluene. The electrolyses conducted with these systems produced the same results as described in Examples 2 to 4. Example 7 Electrolyte systems of the Examples 2 and 4 were obtainable also by dropwise adding at 50-60 °C to a suspension of 2 moles of dried potassium fluoride in 6 moles of xylene or toluene first 2 moles of AlEt₃ and then, after cooling to about 30 °C, a mixture of 1 mole of AlEt₃, 1 mole of AlMe₃ and 0.5 moles of Al(iBu)₃. This was followed by the addition of 0.5 moles of MeOCH₂CH₂OMe. Example 8 An electrolyte prepared from 94.7 mmoles of KF . 2 AlEt₃, 30.1 mmoles of KF . 2 AlMe₃, 13.8 mmoles of NaF . 2 Al(iBu)₃, 40.4 mmoles of AlEt₃ and 31.5 mmoles of MeOCH₂CH₂OMe in 416 mmoles of toluene was electrolyzed at 95 °C between two aluminum anodes. With a cathodic current density of 3 A/dm², a coarsely crystalline warty shiny aluminum deposit was obtained. The anodic current yield was 98.4%, the cathodic current yield was quantitative. The purity of the aluminum cathodically deposited was >99.999%. Example 9 An electrolyte identical to that of Example 8 was obtained by mixing 94.7 mmoles of KF . 2 AlEt₃, 30.1 mmoles of KF . 2 AlMe₃, 13.8 mmoles of NaF . 2 AlEt₃, 12.8 mmoles of AlEt₃, 27.6 mmoles of Al(iBu)₃, and 31.5 mmoles of MeOCH₂CH₂OMe with 416 mmoles of toluene. Example 10 An electrolyte prepared by dissolving 96.1 mmoles of KF . 2 AlEt₃, 28.7 mmoles of KF . 2 AlMe₃, 10.0 mmoles of AlEt₃ . MeOCH₂CH₂OMe, and 28.7 mmoles of Al(iBu)₃ . MeOCH₂CH₂OMe in 371 mmoles of toluene at 60-70 °C was electrolyzed at 95 °C between two aluminum anodes. With a cathodic current density of 3 A/dm², a bright grey warty aluminum deposit without dendrite formation was obtained. The anodic and cathodic current yields were quantitative. The purity of the aluminum cathodically deposited was >99.999%. Example 11 An electrolyte identical to that of Example 10 was obtained by dissolving 67.4 mmoles of KF . 2 AlEt₃, 57.4 mmoles of KF . AlMe₃ . AlEt₃, 10.0 mmoles of AlEt₃ . MeOCH₂CH₂OMe, and 28.7 mmoles of Al(iBu)₃ . MeOCH₂CH₂OMe in 371 mmoles of toluene at 60-70 °C.

Claims: Claims for the following Contracting States : AT, BE, CH, DE, DK, FR, GB, IT, LI, LU, NL, SE Organoaluminum electrolytes for the electrolytic deposition of high-purity aluminum, characterized in that they contain mixtures of organoaluminum complex compounds of the type MF . 2 AlR₃ ( ), wherein M represents potassium or mixtures of K with a maximum of about 15% by mole of sodium, as well as trialkylaluminum AlR₃ ( ) which has not been complexed to an alkali metal fluoride in a molar ratio of : of from 4:0.6 to 4:2, as well as a polyfunctional Lewis base of the type R'-OCH₂CH₂-OR'' ( ) in a molar ratio of : of from 1:0.5 to 1:1. The electrolytes according to claim 1, characterized in that the organyl radicals R in the complex compounds MF . 2 AlR₃ ( ) are ethyl groups (Et), methyl groups (Me) and iso-butyl groups (iBu) in a molar ratio of Et:Me:iBu as 3:m:n, wherein m and n are numerical values of between 1.1 and 0 and the sum (m+n) is from 0.75 to 1.4, and preferably from 0.9 to 1.1. The electrolytes according to claim 1, characterized in that the trialkylaluminum AlR₃ ( ) is AlEt₃ or Al(iBu)₃ or consists of a mixture of AlEt₃ and Al(iBu)₃. The electrolytes according to claims 1 to 3, characterized in that the molar ratio of : preferably is from 4:1 to 4:1.6. The electrolytes according to claims 1 to 4, characterized in that in the polyfunctional Lewis bases ( ) there are R' = R'', preferably methyl or ethyl, or R' = methyl and R'' = ethyl, or R' = methyl or ethyl and R'' = OCH₂CH₂OR''', wherein R''' represents R' or R''. The electrolytes according to claims 1 to 5, characterized in that they have been dissolved in from 3 to 4.5 moles, per mole of alkali metal fluoride employed, of an aromatic hydrocarbon which is liquid at 0 °C. The electrolytes according to claim 6, characterized in that the proportion of the solvent is from 3 to 3.5 moles, per mole of alkali metal fluoride employed. The electrolytes according to claims 6 and 7, characterized in that toluene or a liquid xylene is used as the solvent. A process for the electrolytic deposition of highly pure aluminum by using the organoaluminum electrolyte according to claims 6 and 7 at a temperature which is from 90 °C to 105 °C, if toluene solutions are used, and which is from 80 °C to 135 °C, if xylene solutions are used. Claims for the following Contracting State : ES A process for the electrolytic deposition of high-purity aluminum which process is characterized by employing electrolytes which contain mixtures of organoaluminum complex compounds of the type MF . 2 AlR₃ ( ), wherein M represents potassium or mixtures of K with a maximum of about 15% by mole of sodium, as well as trialkylaluminum AlR₃ ( ) which has not been complexed to an alkali metal fluoride in a molar ratio of : of from 4:0.6 to 4:2, as well as a polyfunctional Lewis base of the type R'-OCH₂CH₂-OR'' ( ) in a molar ratio of : of from 1:0.5 to 1:1. The process according to claim 1, characterized in that the organyl radicals R in the complex compounds MF . 2 AlR₃ ( ) are ethyl groups (Et), methyl groups (Me) and iso-butyl groups (iBu) in a molar ratio of Et:Me:iBu as 3:m:n, wherein m and n are numerical values of between 1.1 and 0 and the sum (m+n) is from 0.75 to 1.4, and preferably from 0.9 to 1.1. The process according to claim 1, characterized in that the trialkylaluminum AlR₃ ( ) is AlEt₃ or Al(iBu)₃ or consists of a mixture of AlEt₃ and Al(iBu)₃. The process according to claims 1 to 3, characterized in that the molar ratio of : preferably is from 4:1 to 4:1.6. The process according to claims 1 to 4, characterized in that in the polyfunctional Lewis bases ( ) there are R' = R'', preferably methyl or ethyl, or R' = methyl and R'' = ethyl, or R' = methyl or ethyl and R'' = OCH₂CH₂OR''', wherein R''' represents R' or R''. The process according to claims 1 to 5, characterized in that they have been dissolved in from 3 to 4.5 moles, per mole of alkali metal fluoride employed, of an aromatic hydrocarbon which is liquid at 0 °C. The process according to claim 6, characterized in that the proportion of the solvent is from 3 to 3.5 moles, per mole of alkali metal fluoride employed. The process according to claims 6 and 7, characterized in that toluene or a liquid xylene is used as the solvent. The process according to claims 6 and 7 characterized by a temperature which is from 90 °C to 105 °C, if toluene solutions are used, and which is from 80 °C to 135 °C, if xylene solutions are used.

Inventors: LEHMKUHL HERBERT, MEHLER KLAUS-DIETER, LEHMKUHL, HERBERT, MEHLER, KLAUS-DIETER
Applicants: STUDIENGESELLSCHAFT KOHLE MBH
Application year: 1990
Main classification: C25D3
IPC codes: C25C3, C25D3