CA1070760A - Method of preparing lithium-aluminum alloy electrodes - Google Patents
Method of preparing lithium-aluminum alloy electrodesInfo
- Publication number
- CA1070760A CA1070760A CA284,185A CA284185A CA1070760A CA 1070760 A CA1070760 A CA 1070760A CA 284185 A CA284185 A CA 284185A CA 1070760 A CA1070760 A CA 1070760A
- Authority
- CA
- Canada
- Prior art keywords
- lithium
- aluminum
- sheet material
- range
- laminate
- 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.)
- Expired
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/40—Alloys based on alkali metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/72—Grids
- H01M4/74—Meshes or woven material; Expanded metal
- H01M4/742—Meshes or woven material; Expanded metal perforated material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/049—Manufacturing of an active layer by chemical means
- H01M4/0492—Chemical attack of the support material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/40—Alloys based on alkali metals
- H01M4/405—Alloys based on lithium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/46—Alloys based on magnesium or aluminium
- H01M4/463—Aluminium based
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/72—Grids
- H01M4/74—Meshes or woven material; Expanded metal
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49002—Electrical device making
- Y10T29/49108—Electric battery cell making
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A lithium-aluminum alloy electrode is formed by contacting a preformed lithium-aluminum laminate with a solution of a lithium salt in an organic solvent.
A lithium-aluminum alloy electrode is formed by contacting a preformed lithium-aluminum laminate with a solution of a lithium salt in an organic solvent.
Description
~7~ ~ 6
2 l. FieYd of the I~ention .__ ____
3 Th~s invention relates to a method for preparing
4 a lithium~aluminum alloy ele~trode for use in electrochemi-cal cells incorporating su~h eleetrodesO
6 2- Description of the Prior Art ____ 7 Lithium~aluminum all~ys have been suggested as 8 negative electrodes for eleetroehemlcal eells because of 9 the highly electronegati~e nature of the lithium and the low atomic weight of the lithium aluminum alloy. The com~
11 bination of high eleetronegatl~lty plus 1GW atomie weight 12 makes possible the ccnstruction of high energy density cells.
13 Several techniques are known ~or fabrlcating 14 lithium aluminum alloys for use as elec~ro~e ma~erials~
One prior ar~ technique ~or forming a lithium-16 aluminum ele~trode in~olves the electrochemical deposi~ion 17 of lithi~m onto a substantially pure aluminum electrode 18 from a m~lten l~thium salt bathO An example of such a 19 process is set forth in U.S. Patent 3,607,413.
Another technique for preparing lithium-aluminum 21 alloys involves eommon metallurgical practices such as melt-22 ing approprlate pr~portions of li~hium and aluminum in an 23 inert atmosphere and thereafter comminuting the cooled 24 lithium alumInum al1Oy so as to produce a finely divided powder. As an example of this technique see U.S. Patent 26 3,957,532.
27 In yet another technique, a sandwich structure of 28 lithium and al~minum sheets are heat soaked at temperatures ~ close to ~he meltin~ point of lith~um while simultaneously 30 applying pressure to the sandwieh struetureO See, for 31 example~ U.S~ Patent 3,981,743O
32 Eaeh of the foregoing general techniques has some ~ 2 - ~
~ ~7~ 7 ~
1 limitatl~ns and problems associated wlth lt~ In ~ddition 2 thereto, all of the above-mentioned teehniques suffer from 3 the disadvantage that considerable energy input is required 4 in ~he formation of the all~y, in the form of thermal energy, electrlcal energy or both~ Thus, there remains a need for 6 a simple procedure or Eorming lithium-aluminum alloy elec-7 trodes which can be aohieved at lower energy input.
8 SUMMA~Y OF THE INVENTIO~
9 I~ its simplest sense, the present invention relates to an improved technique for forming a lithium-11 aluminum alloy electrode by first fcrming a laminate from 12 sheets of li~hium and aluminum and therea~ter contacting 13 the lamina~e with a solut~on o a lithium salt dissolved 14 in an organic soLvent~ The relative proportion of lithlum and al~min~m sheet materiaL employed in the formation of the 16 laminate will, of course, depend upon the portion of 17 l~thium and al~m~num desired in the resulting alloy, 18 although it is partieularly preferred that in forming the 19 laminate, the lithium will be used in amounts ranging between about 20 weight % and 80 welght-%, the balance 21 being essentially aluminum.
22 BRI~F DESCRIPTION OF THE DRAWINGS
23 Figure 1 is an enlàrged cross-section of a ~ami-24 nate of lithium and aluminum sheet materials empIoyed in the abrication of the lith;um-aluminum alloys in accordance 26 with the present mvention.
27 Figure 2 is an enlarged cross-section o~ a lami-28 nate of lithium and aluminum sheet materials in whlch the aluminum sheet material encloses the lithium sheet material.
~ Figure 3 is an isometric drawing illustrating the 3I preferred technique of preparlng a lithium-aluminum alloy 32 in accordance with the invention.
, 'D
~7~7~ ~
DETAIL~:_DE~SCRIP 1 ION
2 Referring now to Flgure l of the drawings~ a 3 l~th~m-alum~num alloy electrode is prepared by first 4 orming a laminate l0 having one ply of aluminum sheet m~terial ll and one ply o~ lithlum sheet ma~erial 12.
6 ~vantageous~y, the llthium and alumin~m sheet material 7 are pressed together ~sing hand pressure with or wit~out 8 the ald of a rollerj or cptlonally by passing the sheets g of material through the n~p of a doub1e roll mechanism.
In any event9 the ~moun~ of pressure exer~ed is not at all 1I cr~tical and merely sufficient press~re to assure oontact 12 between the two sheet materials will sufflce.
l3 In an altern~te embodiment shown ln Figure 2, a-14 lithium-aluminum Lam~nate 20 ~s Eormed from three sheets o material, two of which are alumin~m and the third is 16 li~hium. In the embodiment shown In Figure 2, the bot~om l7 sheet 23 of alumlnum has the same dimensions as the core 18 sheet 22 of lithi~mO However, top sheet 21 of aluminum is 19 of la~ger dImensions~ so as tc completely encase the 7ithium sheet 22 as a central core when sheet 21 is pressed around 21 sheet 22.
22 In yet another and particularly preerred embodi-23 ment of the present invention, the lamlnated structure is 24 fonmed from four sheet materials. As can be seen in Figure 3~ these comprise an open support structure 34, lithium foi1 26 35, and top and bottom alumlnum foll 36 and 37~ respectively.
27 The open structure 34 preferably is metal mesh or screen, 28 such as an iron screen~ Other materials such as nickel, copper3 and stainless steel, wlth or withou~ electropla~ed coatings on them, may be used for the support structure 34.
31 Convenient7y~ the lithium foil sheet material 35 can be 32 pressed onto and embedded into support 34. Thereafter, ~137~76~
l aluminum foil 36 and 37 are pressed so as to cover both 2 sides of the lithium foll 35 embedded in support structure 4 It should be noted that in the Figure 3 embodi- .
6 2- Description of the Prior Art ____ 7 Lithium~aluminum all~ys have been suggested as 8 negative electrodes for eleetroehemlcal eells because of 9 the highly electronegati~e nature of the lithium and the low atomic weight of the lithium aluminum alloy. The com~
11 bination of high eleetronegatl~lty plus 1GW atomie weight 12 makes possible the ccnstruction of high energy density cells.
13 Several techniques are known ~or fabrlcating 14 lithium aluminum alloys for use as elec~ro~e ma~erials~
One prior ar~ technique ~or forming a lithium-16 aluminum ele~trode in~olves the electrochemical deposi~ion 17 of lithi~m onto a substantially pure aluminum electrode 18 from a m~lten l~thium salt bathO An example of such a 19 process is set forth in U.S. Patent 3,607,413.
Another technique for preparing lithium-aluminum 21 alloys involves eommon metallurgical practices such as melt-22 ing approprlate pr~portions of li~hium and aluminum in an 23 inert atmosphere and thereafter comminuting the cooled 24 lithium alumInum al1Oy so as to produce a finely divided powder. As an example of this technique see U.S. Patent 26 3,957,532.
27 In yet another technique, a sandwich structure of 28 lithium and al~minum sheets are heat soaked at temperatures ~ close to ~he meltin~ point of lith~um while simultaneously 30 applying pressure to the sandwieh struetureO See, for 31 example~ U.S~ Patent 3,981,743O
32 Eaeh of the foregoing general techniques has some ~ 2 - ~
~ ~7~ 7 ~
1 limitatl~ns and problems associated wlth lt~ In ~ddition 2 thereto, all of the above-mentioned teehniques suffer from 3 the disadvantage that considerable energy input is required 4 in ~he formation of the all~y, in the form of thermal energy, electrlcal energy or both~ Thus, there remains a need for 6 a simple procedure or Eorming lithium-aluminum alloy elec-7 trodes which can be aohieved at lower energy input.
8 SUMMA~Y OF THE INVENTIO~
9 I~ its simplest sense, the present invention relates to an improved technique for forming a lithium-11 aluminum alloy electrode by first fcrming a laminate from 12 sheets of li~hium and aluminum and therea~ter contacting 13 the lamina~e with a solut~on o a lithium salt dissolved 14 in an organic soLvent~ The relative proportion of lithlum and al~min~m sheet materiaL employed in the formation of the 16 laminate will, of course, depend upon the portion of 17 l~thium and al~m~num desired in the resulting alloy, 18 although it is partieularly preferred that in forming the 19 laminate, the lithium will be used in amounts ranging between about 20 weight % and 80 welght-%, the balance 21 being essentially aluminum.
22 BRI~F DESCRIPTION OF THE DRAWINGS
23 Figure 1 is an enlàrged cross-section of a ~ami-24 nate of lithium and aluminum sheet materials empIoyed in the abrication of the lith;um-aluminum alloys in accordance 26 with the present mvention.
27 Figure 2 is an enlarged cross-section o~ a lami-28 nate of lithium and aluminum sheet materials in whlch the aluminum sheet material encloses the lithium sheet material.
~ Figure 3 is an isometric drawing illustrating the 3I preferred technique of preparlng a lithium-aluminum alloy 32 in accordance with the invention.
, 'D
~7~7~ ~
DETAIL~:_DE~SCRIP 1 ION
2 Referring now to Flgure l of the drawings~ a 3 l~th~m-alum~num alloy electrode is prepared by first 4 orming a laminate l0 having one ply of aluminum sheet m~terial ll and one ply o~ lithlum sheet ma~erial 12.
6 ~vantageous~y, the llthium and alumin~m sheet material 7 are pressed together ~sing hand pressure with or wit~out 8 the ald of a rollerj or cptlonally by passing the sheets g of material through the n~p of a doub1e roll mechanism.
In any event9 the ~moun~ of pressure exer~ed is not at all 1I cr~tical and merely sufficient press~re to assure oontact 12 between the two sheet materials will sufflce.
l3 In an altern~te embodiment shown ln Figure 2, a-14 lithium-aluminum Lam~nate 20 ~s Eormed from three sheets o material, two of which are alumin~m and the third is 16 li~hium. In the embodiment shown In Figure 2, the bot~om l7 sheet 23 of alumlnum has the same dimensions as the core 18 sheet 22 of lithi~mO However, top sheet 21 of aluminum is 19 of la~ger dImensions~ so as tc completely encase the 7ithium sheet 22 as a central core when sheet 21 is pressed around 21 sheet 22.
22 In yet another and particularly preerred embodi-23 ment of the present invention, the lamlnated structure is 24 fonmed from four sheet materials. As can be seen in Figure 3~ these comprise an open support structure 34, lithium foi1 26 35, and top and bottom alumlnum foll 36 and 37~ respectively.
27 The open structure 34 preferably is metal mesh or screen, 28 such as an iron screen~ Other materials such as nickel, copper3 and stainless steel, wlth or withou~ electropla~ed coatings on them, may be used for the support structure 34.
31 Convenient7y~ the lithium foil sheet material 35 can be 32 pressed onto and embedded into support 34. Thereafter, ~137~76~
l aluminum foil 36 and 37 are pressed so as to cover both 2 sides of the lithium foll 35 embedded in support structure 4 It should be noted that in the Figure 3 embodi- .
5 ment~ the aluminum foil 36 and 37 are shown as having per- :
6 forations 39. This ~s par~icularly deslrable in order to
7 insure formation o ~he alloy in practlcal time periods.
8 Indeed3 when lith~um is used as the ceTltral core material
9 such that it ~ompletely is surrounded by aluminum, as is shown in Figure 2~ it is essential that the aluminum foil ll be perforated. The slze of the perforations are not criti-12 cal~ so lcng as they are suffislen~ly large ~o permit the l3 lithium ion con~ain~ng solution hereinafter described to l4 come into conta¢t wlth the l~thlum and the aluminum.
lS The rel.ative amounts of lithium and aluminum sheet l6 material used will depPnd upon the composition of the 17 lithium-aluminum alloy electrode belng prepared. The rela-18 tive proportions of lithium and alumlnum m~y range, for 19 ~xample9 from as l~w as 10 we~ght % lithium to as much as about 95 weight % lithium, the balance being aluminum.
21 However, lithium~alumin~m weight ratlos generally between 22 about 20 welght % and ab~ut 80 welght % are very desirable 23 and indeed it is especially preferred to use in the range 24 of ab~ut 20 weight % to about 80 welght % of lithium~ the balance of alumin~m, in the formation of laminate sheet 26 ma~eriaL.
27 Af~er formlng a laminate from the lithium and 28 aluminum, the laminate is then contacted with a solution ~ of a lithium salt dissolved in a nonaqueous organic sol-vent. Examples of nonaqueous organic solvents that can be 31 used in the formation of a lithium-alumlnum alloy electrode 32 include dloxolane, tetrahydrofuran, dimethoxy ethane and -- 5 --.
~7~
l propylene ~arbonate, to mention a few Dio~olane has been ~ found to be a particularly preferred solvent 3 As indicated~ the organic solvent contains a dis-4 solved lithium salt. Advantageously thlose lithl~m salts that display the highest solubility in the particular organ-6 ic solvent are used~ Examples of useful lithium salts 7 lnclude lithium perchlorate9 lithium hexafluorophosphate~
8 lithium tetrafluoroborate, lithium aluminum tetrachloride 9 and lithium thio¢yanate. Lithium perchlora~e i.8 particu-larly preferred.
ll The concentr~tion of salt in thP organic solvent 12 will range generally from about 1 to 3 molar. However7 it 13 is part~cularly preerred tha~ the salt solution be in the 14 range of 2.5 to 3 mo~ar.
While not wishing to be bound by any ~heory, it 16 appears that when lithium is in contact with aluminum in a 17 nonaqueous solution con~aining 1ithium icns9 corrosion o 18 lithium ~ccurs leading to the formation of lithium-aluminum 19 alloy.
In general, alloy formativn o¢curs at ambient 21 temperatures. Consequen~ly, the aluminum and lithium lami-22 nate is contaeted with an organie solu~on o~ a lithium salt 23 for a time sufficient for the laminate to be converted into 24 a lithium aluminum alloy, such contacting being made in the form of a half~cell and/or part of a galvanic cell. In ~he 26 lat~er oase, in situ formation of ~he alloy occurs.
27 The process o alloy fcrmation may take anywhere 28 frcm several hours to greater than 24 hours depending on the ~ areas of con~act of lithium~aluminum-eleetrolyte ln~erface, and also depending upon the composition of the alloy desired.
31 The area of contact will, of course, depencl on the porosity 32 and pore size distribution of the perforation in the aluminum ~ ~ 7~ 7 ~
1 oil. It is preferred that the perforations in the aluminum 2 foil provide an open area whlch is greater than about 35%
3 of the total area cE the foil sheet as determined from the 4 length and width of the sheet, for example. Typically the 5 perforations in the aluminum sheet will provide an open area 6 less than about 75% of th~ total area of the foil sheet.
7 The weight ratios of 17 th~um and aluminum foils also will 8 afect ~he rate of ormation of the alloyO In general, 9 li~hium-rich alloys form more rapldly than the alumin~m-
lS The rel.ative amounts of lithium and aluminum sheet l6 material used will depPnd upon the composition of the 17 lithium-aluminum alloy electrode belng prepared. The rela-18 tive proportions of lithium and alumlnum m~y range, for 19 ~xample9 from as l~w as 10 we~ght % lithium to as much as about 95 weight % lithium, the balance being aluminum.
21 However, lithium~alumin~m weight ratlos generally between 22 about 20 welght % and ab~ut 80 welght % are very desirable 23 and indeed it is especially preferred to use in the range 24 of ab~ut 20 weight % to about 80 welght % of lithium~ the balance of alumin~m, in the formation of laminate sheet 26 ma~eriaL.
27 Af~er formlng a laminate from the lithium and 28 aluminum, the laminate is then contacted with a solution ~ of a lithium salt dissolved in a nonaqueous organic sol-vent. Examples of nonaqueous organic solvents that can be 31 used in the formation of a lithium-alumlnum alloy electrode 32 include dloxolane, tetrahydrofuran, dimethoxy ethane and -- 5 --.
~7~
l propylene ~arbonate, to mention a few Dio~olane has been ~ found to be a particularly preferred solvent 3 As indicated~ the organic solvent contains a dis-4 solved lithium salt. Advantageously thlose lithl~m salts that display the highest solubility in the particular organ-6 ic solvent are used~ Examples of useful lithium salts 7 lnclude lithium perchlorate9 lithium hexafluorophosphate~
8 lithium tetrafluoroborate, lithium aluminum tetrachloride 9 and lithium thio¢yanate. Lithium perchlora~e i.8 particu-larly preferred.
ll The concentr~tion of salt in thP organic solvent 12 will range generally from about 1 to 3 molar. However7 it 13 is part~cularly preerred tha~ the salt solution be in the 14 range of 2.5 to 3 mo~ar.
While not wishing to be bound by any ~heory, it 16 appears that when lithium is in contact with aluminum in a 17 nonaqueous solution con~aining 1ithium icns9 corrosion o 18 lithium ~ccurs leading to the formation of lithium-aluminum 19 alloy.
In general, alloy formativn o¢curs at ambient 21 temperatures. Consequen~ly, the aluminum and lithium lami-22 nate is contaeted with an organie solu~on o~ a lithium salt 23 for a time sufficient for the laminate to be converted into 24 a lithium aluminum alloy, such contacting being made in the form of a half~cell and/or part of a galvanic cell. In ~he 26 lat~er oase, in situ formation of ~he alloy occurs.
27 The process o alloy fcrmation may take anywhere 28 frcm several hours to greater than 24 hours depending on the ~ areas of con~act of lithium~aluminum-eleetrolyte ln~erface, and also depending upon the composition of the alloy desired.
31 The area of contact will, of course, depencl on the porosity 32 and pore size distribution of the perforation in the aluminum ~ ~ 7~ 7 ~
1 oil. It is preferred that the perforations in the aluminum 2 foil provide an open area whlch is greater than about 35%
3 of the total area cE the foil sheet as determined from the 4 length and width of the sheet, for example. Typically the 5 perforations in the aluminum sheet will provide an open area 6 less than about 75% of th~ total area of the foil sheet.
7 The weight ratios of 17 th~um and aluminum foils also will 8 afect ~he rate of ormation of the alloyO In general, 9 li~hium-rich alloys form more rapldly than the alumin~m-
10 rich alloys.
ll In order to give those skilled in the art a better 12 understanding, the ollowing example is given~
13 ~ æ~
14 A lithi~m foil 1" x 1" x 0.01" thick was pressed ?
15 ~n~o a 1" x 1" galvaniæed iron mesh and3 thereafter, a per-16 forated a~uminum o11 of 1" x 2" dimension was laminated 17 to the lithium foil by pressing such as to cover both sides l~ of li~hium.. For the purpose of exemplifying the invention, 19 ~he laminated lithlum~alumlnum foil was ineorporated as one ~ electrode ~n a cell having a reference lithlum electrode 21 and a pressed fiber polypropylene separat3r therebetween.
22 Thereafter a 2.5 molar LiC10~ solution in dioxolane was .
23 added to the cell, contac~ing the aluminum-lithium laminate.
24 Thereafter, the open circuit voltage of the laminated elec-25 trode vsO the lithi~m reference electrode was m~asured.
26 A change in open circuit v~l~age was ~ndicative of alloy 27 forma~ion 28 The procedure outli~ed hereinabove was repeated :
29 numerous times using various we~ght ratios of lithium and aluminum~ The open circuit voltages of lithium-aluminum 31 alloy electrodes are given in Table 1 (Column A~ below.
32 Also given in Table 1 (Column B) below for comparative - .
. .
-~ ~7 ~ 7 6~
1 purposes is the open circuit voltage of thenmally formed 2 lithium~aluminum alloy ~le¢trodes vs. lithium reference 3 electrodes.
4 Table 1 5Open Circuit Voltage of LiAl Alloy Electrodes 6Formed Uslng Porous Alumlnum Laminated 7LithiuM ~lectrodes 8~ElectrolYte 2.5 M LiC10/ Dioxolane~
_ 9 ~2e~Ref.
10Colu~ A Co umn ~
11_ ComDos ition Thermall.y 12 ~ 3 Al Lam nate of Ll Formed Allo~s 13 94.3 S.7 O.OQl 0.000 14 89.2 9.8 0.001 0.000 80.4 1906 0.001 ~.000 16 ~9.3 80.7 0.413 0.385 17 ~1.2 88.8 0.414 0.440 18 As can be seen from the foregoing, the lithium~
19 aluminum alloys prepared in a¢cordance with the method dis-closed herein have substantially the same open c~rcuit 21 voltages as ~hose prepared by prior art thermal techniques.
22 Indeed, the lithium aluminum alloy electrodes prepared by 23 ~he present ~nventicn are particularly useful anodes in 24 electrochemica1 cells having electrolytes comprising non-aqueous organic solvents and lithium salts dissolved there-26 in.
,
ll In order to give those skilled in the art a better 12 understanding, the ollowing example is given~
13 ~ æ~
14 A lithi~m foil 1" x 1" x 0.01" thick was pressed ?
15 ~n~o a 1" x 1" galvaniæed iron mesh and3 thereafter, a per-16 forated a~uminum o11 of 1" x 2" dimension was laminated 17 to the lithium foil by pressing such as to cover both sides l~ of li~hium.. For the purpose of exemplifying the invention, 19 ~he laminated lithlum~alumlnum foil was ineorporated as one ~ electrode ~n a cell having a reference lithlum electrode 21 and a pressed fiber polypropylene separat3r therebetween.
22 Thereafter a 2.5 molar LiC10~ solution in dioxolane was .
23 added to the cell, contac~ing the aluminum-lithium laminate.
24 Thereafter, the open circuit voltage of the laminated elec-25 trode vsO the lithi~m reference electrode was m~asured.
26 A change in open circuit v~l~age was ~ndicative of alloy 27 forma~ion 28 The procedure outli~ed hereinabove was repeated :
29 numerous times using various we~ght ratios of lithium and aluminum~ The open circuit voltages of lithium-aluminum 31 alloy electrodes are given in Table 1 (Column A~ below.
32 Also given in Table 1 (Column B) below for comparative - .
. .
-~ ~7 ~ 7 6~
1 purposes is the open circuit voltage of thenmally formed 2 lithium~aluminum alloy ~le¢trodes vs. lithium reference 3 electrodes.
4 Table 1 5Open Circuit Voltage of LiAl Alloy Electrodes 6Formed Uslng Porous Alumlnum Laminated 7LithiuM ~lectrodes 8~ElectrolYte 2.5 M LiC10/ Dioxolane~
_ 9 ~2e~Ref.
10Colu~ A Co umn ~
11_ ComDos ition Thermall.y 12 ~ 3 Al Lam nate of Ll Formed Allo~s 13 94.3 S.7 O.OQl 0.000 14 89.2 9.8 0.001 0.000 80.4 1906 0.001 ~.000 16 ~9.3 80.7 0.413 0.385 17 ~1.2 88.8 0.414 0.440 18 As can be seen from the foregoing, the lithium~
19 aluminum alloys prepared in a¢cordance with the method dis-closed herein have substantially the same open c~rcuit 21 voltages as ~hose prepared by prior art thermal techniques.
22 Indeed, the lithium aluminum alloy electrodes prepared by 23 ~he present ~nventicn are particularly useful anodes in 24 electrochemica1 cells having electrolytes comprising non-aqueous organic solvents and lithium salts dissolved there-26 in.
,
Claims (13)
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A method of making a lithium-aluminum alloy electrode comprising:
(a) forming a laminate having at least one ply of aluminum sheet material and one ply of lithium sheet material;
(b) contacting the laminate with a solution of a lithium salt dissolved in an organic solvent for a time sufficient for allow formation to occur.
(a) forming a laminate having at least one ply of aluminum sheet material and one ply of lithium sheet material;
(b) contacting the laminate with a solution of a lithium salt dissolved in an organic solvent for a time sufficient for allow formation to occur.
2. The method of claim 1 wherein said laminate has two plies of aluminum enclosing one ply of lithium.
3. The method of claim 2 wherein the laminate is supported on a metal mesh support structure.
4. The method of claim 3 wherein the weight ratio of aluminum to lithium is in the range of 10% to 95%
by weight.
by weight.
5. The method of claim 4 wherein the weight ratio of aluminum to lithium is in the range of 20% to 80% by weight.
6. The method of claim 4 wherein the concentra-tion of lithium salt dissolved in an organic solvent is in the range of from about 1 to 3 molar.
7. The method of claim 6 wherein the solution of the salt is lithium perchlorate dissolved in dioxolane.
8. The method of claim 7 wherein the concentration of lithium perchlorate in dioxolane is in the range of from about 2.5 to 3 molar.
9. The method of forming a lithium-aluminum alloy electrode comprising:
pressing a sheet of lithium metal onto a metal mesh support structure;
pressing aluminum sheet material on each major surface of said lithium pressed on said wire mesh, thereby forming a laminated structure, said aluminum sheet material being perforated, the weight ratio of aluminum sheet materi-al to lithium sheet material being in the range of from about 10% to about 95% by weight;
contacting said laminated structure with a nona-queous organic solution of a lithium salt for a time suffi-cient for alloy formation to occur.
pressing a sheet of lithium metal onto a metal mesh support structure;
pressing aluminum sheet material on each major surface of said lithium pressed on said wire mesh, thereby forming a laminated structure, said aluminum sheet material being perforated, the weight ratio of aluminum sheet materi-al to lithium sheet material being in the range of from about 10% to about 95% by weight;
contacting said laminated structure with a nona-queous organic solution of a lithium salt for a time suffi-cient for alloy formation to occur.
10. The method of claim 9 wherein the weight ratio of aluminum to lithium sheet material is in the range from about 20% to about 80% by weight.
11. The method of claim 10 wherein the perfora-tions in said aluminum sheet comprise greater than 35% of the total area of said aluminum sheet.
12. The method of claim 11 wherein the concentra-tion of lithium salt solution is between about 1.0 and 3.0 molar.
13. The method of claim 12 wherein the lithium salt is lithium perchlorate and wherein the nonaqueous or-ganic solvent is dioxolane.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/750,965 US4056885A (en) | 1976-12-15 | 1976-12-15 | Method of preparing lithium-aluminum alloy electrodes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1070760A true CA1070760A (en) | 1980-01-29 |
Family
ID=25019877
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA284,185A Expired CA1070760A (en) | 1976-12-15 | 1977-08-05 | Method of preparing lithium-aluminum alloy electrodes |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US4056885A (en) |
| JP (1) | JPS5375434A (en) |
| BE (1) | BE858665A (en) |
| CA (1) | CA1070760A (en) |
| CH (1) | CH634953A5 (en) |
| DE (1) | DE2737895C2 (en) |
| FR (1) | FR2374750A1 (en) |
| GB (1) | GB1583783A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5278005A (en) * | 1992-04-06 | 1994-01-11 | Advanced Energy Technologies Inc. | Electrochemical cell comprising dispersion alloy anode |
Families Citing this family (49)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4434213A (en) | 1982-05-13 | 1984-02-28 | Rayovac Corporation | Lithium anode |
| DE3230410A1 (en) * | 1982-08-16 | 1984-02-16 | Varta Batterie Ag, 3000 Hannover | SUPPORT AND DISCHARGE DEVICES WITH INTERMETALLIC ADMINISTRATORS FOR LITHIUM-CONTAINING BATTERY ELECTRODES |
| JPS59186274A (en) * | 1983-04-07 | 1984-10-23 | Matsushita Electric Ind Co Ltd | Manufacturing method of non-aqueous electrolyte secondary battery |
| US4448861A (en) * | 1983-06-24 | 1984-05-15 | Rayovac Corporation | Lithium-thionyl chloride cell with lithium surface alloys to reduce voltage delay |
| GB8329207D0 (en) * | 1983-11-02 | 1983-12-07 | Raychem Ltd | Making electrical device |
| CA1244301A (en) * | 1984-04-11 | 1988-11-08 | Hydro-Quebec | Process for the preparation of alloyed negative electrodes, and devices making use of said electrodes |
| US4780380A (en) * | 1984-06-07 | 1988-10-25 | Standard Oil Company (Indiana) | Porous lithium electrodes and their use in nonaqueous electrochemical cells |
| JPH0746602B2 (en) * | 1985-03-12 | 1995-05-17 | 日立マクセル株式会社 | Method for manufacturing lithium organic secondary battery |
| JPH0630246B2 (en) * | 1985-03-12 | 1994-04-20 | 日立マクセル株式会社 | Button type lithium organic secondary battery |
| JPH0763016B2 (en) * | 1985-03-22 | 1995-07-05 | ソニー株式会社 | Organic electrolyte battery |
| DE3688533T2 (en) * | 1985-03-22 | 1994-01-20 | Sony Eveready Inc | Cell with organic electrolyte. |
| US4632889A (en) * | 1985-07-02 | 1986-12-30 | The United States Of America As Represented By The Secretary Of The Navy | Lithium composite anode |
| US4610081A (en) * | 1985-08-05 | 1986-09-09 | Gould, Inc. | Method of fabricating battery plates for electrochemical cells |
| JPS62119877A (en) * | 1985-11-19 | 1987-06-01 | Fuji Elelctrochem Co Ltd | Manufacture of negative electrode for secondary cell of nonaqueous electrolytic solution |
| JPS62123663A (en) * | 1985-11-25 | 1987-06-04 | Hitachi Maxell Ltd | Manufacture of lithium secondary cell |
| JPH0646578B2 (en) * | 1986-04-14 | 1994-06-15 | 三洋電機株式会社 | Non-aqueous secondary battery |
| JPS6373232U (en) * | 1986-10-30 | 1988-05-16 | ||
| JPS63181274A (en) * | 1987-01-22 | 1988-07-26 | Hitachi Maxell Ltd | Manufacture of lithium secondary battery |
| JPS63202851A (en) * | 1987-02-17 | 1988-08-22 | Fuji Elelctrochem Co Ltd | Manufacture of negative electrode for nonaqueous electrolyte secondary battery |
| DE3816199A1 (en) * | 1987-05-12 | 1988-11-24 | Bridgestone Corp | Electrical cell and method for its production |
| US4865932A (en) * | 1987-05-12 | 1989-09-12 | Bridgestone Corporation | Electric cells and process for making the same |
| JPH01124956A (en) * | 1987-11-09 | 1989-05-17 | Nippon Denso Co Ltd | Lithium secondary battery |
| DE3838329A1 (en) * | 1987-11-11 | 1989-05-24 | Ricoh Kk | Negative electrode for a secondary battery |
| SE463536B (en) * | 1988-04-19 | 1990-12-03 | Inclusion Ab | PROVIDED TO MAKE AN AGREEMENT OF ANNEX UNITS AND SUBJECT BEFORE IMPLEMENTING THE SET |
| JPH01317927A (en) * | 1988-06-16 | 1989-12-22 | Nec Corp | Sheet supply device |
| JP2934449B2 (en) * | 1989-03-23 | 1999-08-16 | 株式会社リコー | Rechargeable battery |
| JP3364968B2 (en) * | 1992-09-01 | 2003-01-08 | 株式会社デンソー | Battery |
| US5494762A (en) * | 1992-01-16 | 1996-02-27 | Nippondenso Co., Ltd. | Non-aqueous electrolyte lithium secondary cell |
| JPH06231755A (en) * | 1993-06-08 | 1994-08-19 | Hitachi Maxell Ltd | Button type lithium organic secondary battery and method of manufacturing the same |
| KR200150028Y1 (en) * | 1996-07-02 | 1999-07-01 | 손욱 | Electrode plate |
| US5932375A (en) * | 1997-02-18 | 1999-08-03 | Aluminum Company Of America | Form charging aluminum-lithium battery cells |
| JP4423699B2 (en) | 1999-05-27 | 2010-03-03 | ソニー株式会社 | Semiconductor laser device and manufacturing method thereof |
| IL135981A0 (en) * | 2000-05-04 | 2001-05-20 | Israel State | A new fe-li-al anode composite and thermal battery containing same |
| US6670071B2 (en) | 2002-01-15 | 2003-12-30 | Quallion Llc | Electric storage battery construction and method of manufacture |
| US6677076B2 (en) | 2002-01-15 | 2004-01-13 | Quallion Llc | Electric storage battery construction and method of manufacture |
| US10629947B2 (en) | 2008-08-05 | 2020-04-21 | Sion Power Corporation | Electrochemical cell |
| US8080329B1 (en) | 2004-03-25 | 2011-12-20 | Quallion Llc | Uniformly wound battery |
| US20080318128A1 (en) * | 2007-06-22 | 2008-12-25 | Sion Power Corporation | Lithium alloy/sulfur batteries |
| JP2012022972A (en) * | 2010-07-16 | 2012-02-02 | Kobelco Kaken:Kk | Material for negative electrode active material, and secondary battery and capacitor using negative electrode active material formed by alloying the same |
| EP2721665B1 (en) | 2011-06-17 | 2021-10-27 | Sion Power Corporation | Plating technique for electrode |
| CN102881862B (en) | 2011-07-12 | 2015-03-25 | 中国科学院上海硅酸盐研究所 | Protective metal anode structure and preparation method thereof |
| CN103947027B (en) | 2011-10-13 | 2016-12-21 | 赛昂能源有限公司 | Electrode structure and manufacture method thereof |
| JP6344859B2 (en) * | 2015-04-08 | 2018-06-20 | マクセルホールディングス株式会社 | Non-aqueous electrolyte primary battery and manufacturing method thereof |
| EP3886221A4 (en) * | 2018-11-22 | 2022-08-03 | Sumitomo Chemical Company Limited | NEGATIVE ELECTRODE ACTIVE MATERIAL FOR NON-AQUEOUS ELECTROLYTE BATTERY, NEGATIVE ELECTRODE, CELL AND LAMINATE |
| CN111640915B (en) | 2019-03-01 | 2024-12-31 | 麻省固能控股有限公司 | Negative electrode, secondary battery including the same, and method for manufacturing the negative electrode |
| US11444277B2 (en) | 2019-03-01 | 2022-09-13 | Ses Holdings Pte. Ltd. | Anodes, secondary batteries including the same, and methods of making anodes |
| CN110364686B (en) * | 2019-07-15 | 2023-01-20 | 湖北锂诺新能源科技有限公司 | Method for manufacturing negative electrode of rechargeable button lithium-manganese battery |
| CN114421069A (en) * | 2020-10-13 | 2022-04-29 | 宜昌力佳科技有限公司 | A method for making a wide temperature type button battery with a lithium-aluminum alloy as the negative electrode |
| CN114361401A (en) * | 2020-10-13 | 2022-04-15 | 宜昌力佳科技有限公司 | A method for making a lithium-aluminum alloy negative electrode of a button-type primary battery |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3607413A (en) * | 1968-09-10 | 1971-09-21 | Standard Oil Co Ohio | Method for electrochemical alloying of aluminum and lithium |
| US3756789A (en) * | 1971-03-03 | 1973-09-04 | Du Pont | Metallurgically bonded lithium conductive metal electrode |
| NL174508C (en) * | 1972-08-04 | 1984-01-16 | Du Pont | METHOD OF MANUFACTURING A COMPOSITE ELECTRICAL CONDUCTIVE COATING, CONTAINING A METALLIC BASIS AND AN ELECTRICALLY CONDUCTIVE COATING ON THIS, AND A GALVANIC CELL IN WHICH ONE OR MORE OF THESE ELECTRODES ARE PLACED. |
| US3957532A (en) * | 1974-06-20 | 1976-05-18 | The United States Of America As Represented By The United States Energy Research And Development Administration | Method of preparing an electrode material of lithium-aluminum alloy |
| US3981743A (en) * | 1975-06-06 | 1976-09-21 | Esb Incorporated | Method of preparing a lithium-aluminum electrode |
| US4002492A (en) * | 1975-07-01 | 1977-01-11 | Exxon Research And Engineering Company | Rechargeable lithium-aluminum anode |
-
1976
- 1976-12-15 US US05/750,965 patent/US4056885A/en not_active Expired - Lifetime
-
1977
- 1977-08-05 CA CA284,185A patent/CA1070760A/en not_active Expired
- 1977-08-08 GB GB33152/77A patent/GB1583783A/en not_active Expired
- 1977-08-22 JP JP10039377A patent/JPS5375434A/en active Granted
- 1977-08-23 DE DE2737895A patent/DE2737895C2/en not_active Expired
- 1977-09-13 BE BE180882A patent/BE858665A/en not_active IP Right Cessation
- 1977-09-16 FR FR7728026A patent/FR2374750A1/en active Granted
- 1977-11-01 CH CH1331477A patent/CH634953A5/en not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5278005A (en) * | 1992-04-06 | 1994-01-11 | Advanced Energy Technologies Inc. | Electrochemical cell comprising dispersion alloy anode |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2374750A1 (en) | 1978-07-13 |
| JPS6146947B2 (en) | 1986-10-16 |
| GB1583783A (en) | 1981-02-04 |
| DE2737895A1 (en) | 1978-06-22 |
| US4056885A (en) | 1977-11-08 |
| DE2737895C2 (en) | 1986-10-23 |
| FR2374750B1 (en) | 1982-02-05 |
| CH634953A5 (en) | 1983-02-28 |
| JPS5375434A (en) | 1978-07-04 |
| BE858665A (en) | 1978-03-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1070760A (en) | Method of preparing lithium-aluminum alloy electrodes | |
| US5350645A (en) | Polymer-lithium batteries and improved methods for manufacturing batteries | |
| US5965298A (en) | Electrode plate for battery and process for producing the same | |
| KR101766292B1 (en) | Three-dimensional net-like aluminum porous material, electrode comprising the aluminum porous material, non-aqueous electrolyte battery equipped with the electrode, and non-aqueous electrolytic solution capacitor equipped with the electrode | |
| DE112012000901B4 (en) | A current collector using an aluminum porous body having a three-dimensional network, an electrode using the current collector and non-aqueous electrolyte battery, capacitor and lithium ion capacitor with non-aqueous electrolytic solution each using the electrode, and method for producing the electrode | |
| CN102666887B (en) | Manufacturing method of aluminum structure and aluminum structure | |
| JPH0658864B2 (en) | Electric double layer capacitor | |
| DE112012000887T5 (en) | Three-dimensional aluminum porous body for a current collector, current collector using the aluminum porous body, electrode using the current collector, and non-aqueous electrolyte battery, capacitor, and lithium-ion capacitor each using the electrode | |
| US4748542A (en) | Solid state electrochemical device | |
| DE2531274A1 (en) | THIN, FLAT CELL CONSTRUCTION WITH A GAS-PERMEABLED COVERED, PERFORATED ANODE | |
| DE112012000851T5 (en) | Three-dimensional network aluminum porous body, electrode using the aluminum porous body, and nonaqueous electrolyte battery, capacitor using a nonaqueous electrolytic solution, and lithium ion capacitor using a nonaqueous electrolytic solution, respectively use the electrode | |
| DE112012000877T5 (en) | Three-dimensional network aluminum porous body for a current collector, electrode using the aluminum porous body, and non-aqueous electrolyte battery, capacitor and non-aqueous electrolytic solution lithium-ion capacitor using the electrode | |
| DE112012000861T5 (en) | Three-dimensional aluminum porous body for a current collector, electrode using the aluminum porous body, non-aqueous electrolyte battery, capacitor and lithium-ion capacitor | |
| US5498495A (en) | Alloy for negative electrode of lithium secondary battery and lithium secondary battery | |
| DE112012000859T5 (en) | An electrode using a three-dimensional network aluminum porous body and a nonaqueous-electrolyte battery, a capacitor and a lithium-ion capacitor with a non-aqueous electrolytic solution, each using the electrode | |
| US4687716A (en) | Organic electrolyte cell | |
| WO2015087948A1 (en) | Carbon material-coated metal porous body, collector, electrode, and power storage device | |
| US6865071B2 (en) | Electrolytic capacitors and method for making them | |
| DE112012000880T5 (en) | Three-dimensional aluminum porous body for a current collector and current collector, electrode, non-aqueous electrolyte battery, capacitor and lithium-ion capacitor, each using the aluminum porous body | |
| JP2010080858A (en) | Electric double layer capacitor and method of manufacturing the same | |
| US4828738A (en) | Solid electrolytic capacitor | |
| JP2015001011A (en) | Aluminum porous body, air electrode collector for air cell, air cell and method of producing aluminum porous body | |
| JP2003077482A (en) | Battery | |
| JP2007067285A (en) | Electric double-layer capacitor | |
| US4844998A (en) | Bipolar silver oxide-aluminum electrode |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |