CA1129947A - Cell containing an alkali metal anode, a solid cathode, and a closoborane and/or closocarborane electrolyte - Google Patents
Cell containing an alkali metal anode, a solid cathode, and a closoborane and/or closocarborane electrolyteInfo
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- CA1129947A CA1129947A CA333,354A CA333354A CA1129947A CA 1129947 A CA1129947 A CA 1129947A CA 333354 A CA333354 A CA 333354A CA 1129947 A CA1129947 A CA 1129947A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
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- 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
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Abstract
U.S. 956,746 ABSTRACT OF THE DISCLOSURE A novel electrochemical cell is disclosed which contains an alkali metal anode, a solid cathode, and an electrolyte containing one or more closoborane and/or closocarborane compounds in aprotic solvent. Preferred cells are those containing lithium anodes, chalcogenide cathodes and electrolytes containing one or more closoborane compounds in aprotic solvent with a chelating agent.
Description
39~7 _
2 1. Field of the Invention
3 This invention relates to a novel electric current
4 producing cell. More particularly, this invention relates to improvements in electric current producing cells having 6 alkali metal-containing anodes, solid cathodes, and electro-7 lytes, wherein the electrolytes contain closoborane and/or 8 closocarborane compounds in aprotic solvent with chelating 9 agent.
2. Description of the Prior Art 11 There has been considerable interest in recent 12 years in developing high energy density batteries or volt-13 aic cells. Among the systems being investigated are those 14 employing nonaqueous liquid, ~used or solid electrolytes, with lightweight metals, such as alkali metals, as anodes, 16 and with cathodes co~taining metal chalcogenide compounds.
17 Such systems are described, ~or example, in U.S. Patent 18 Nos. 3,988,164; 3,925,098; 3,864,167 and 3,791,867.
19 Various efforts have been made to develop new electrolytes for these and similar secondary cell systems.
21 For example, U.S. Patent NoO 4,060,674 (Klemann et al) de-22 scribed alkali metal anode/solid cathode cells having elec-23 trolytes of organometallic alkali metal salts and organic 24 solvents. Also, the use of clovoboranes as additives to electrolytes in certain cells has been taught in U.S.
26 Patent Nos. 4,020,240 (Schlaikjer) and 4,071,664 ~Dey). How-27 ever, these patents teach the use of clovoboranes as elec-28 trolyte additives in cell systems containing a liquid 29 cathode-electrolyte salt compo~ition. No sugges~ion is made that clovoboranes may be used with aprotic organic solvents 31 or that th~y may be used in cells having solid cathodes.
33 The present invention is directed to a novel elec-34 trochemical cell which contains an al~ali metal anode, a solid cathodeJ and an electrolyte containing one or more 36 closoborane and/or closocarborane compounds in aprotic or-37 ganic solvent with a chelating agent.
, . ..
3~4~
2 The present invention is directed to electrochemi-3 cal cells having alkali metal anodes, solid cathodes, and 4 electrolytes containing one or more compounds selected from the group consisting of:
6 (i) closoborane compounds of the formula:
7 Z2BnXn (1) 8 wherein Z is an alkali metal, B is boron, X is one or more 9 substituents selected from the group consisting of hydrogen and the halogens and n is an integer from 6 to 12; and 11 (ii) closocarborane compounds of the formula:
12 ZCRBmXm (2) 13 wherein Z is an alkali metal, C is carbon, R is a radical 14 selected from the group consisting o~ organic radicals, hy-drogen and the halogens, B is boron, X is one or more sub-1~ stituents selected from the group consisting of hydrogen and 17 the halogens, and m is an integer from 5 to 11. These clo-18 soborane and closocarborane compounds are employed in apro-19 tic organic solvent with a chelating agent.
The anode employed in the cell of the present in-21 vention i5, as mentioned, one which contains an alkali metal 22 as its anode-active material. Desirably, thi anode-active 23 material is sodium, potassium, lithium, or alloys containing 24 these. It should be noted, therefore, that when the speci-fic alkali metal~ are recited herein with respect to the 26 anode, such recitations are meant to include alloys of such 27 ~lkali metals. The anode-active material used in the anode ~8 o~ the present invention is preferably sodium or lithium, 29 and is most preferably lithium. These anode-active materi-als may, for Pxample, be in contact with other metal struc-31 stures, e.g., nickel, copper or silver screen, which serve 32 as urrent collectors and are well known in `the art.
33 The cathode used in the cell of the present in-34 vention may be any cathode which produces electric current when coupled with an alkali metal anode and which will func-36 tion using the specific solid electrolyte described herein.
37 A useul cathode for the cell of the present invention is ,, :
lZ9947 1 one which contains as its cathode-active material one or 2 more chalcogenide compounds selected from the group consist-3 ing of the sulfides, the selenides, and the tellurides of 4 titanium, zirconium, hafnium, niobium, tantalum, molybdenum and vanadium. In general, such chalcogenides contain about 6 1.8 to about 3.2 atoms of the chalcogen per metal atom. Ad-7 vantageously, these chalcogenides are the sulfides, the 8 selenides, and the tellurides of one or more metals selected 9 from the mentioned group and desirably one or more metals selected from titanium, molybdenum and vanadium. Preferred 11 are the titanium chalcogenides. Among the chalcogens em-12 ployed i~ the chalcogenides used as the cathode-active ma-13 terials are, as mentioned, sulfur, selenium, and tellurium.
14 Of these, sulfur and selenium are desired, and sulfur is preferred. Also, among the chalcogenides, those which con-16 tain about 1.8 to about 2.1 atoms of chalcogen per metal 17 atom, commonLy referred to as dichalcogenides, are preferred.
18 Examples of cathode-active materials which may be 19 useful, and which are selected from the above-mentioned chalcogenides are titanium disulfide, zirconium disulfide, 21 hafnium disulfide, niobium triselenide, tantalum disulfide, 22 molybdenu~ trisulfide, vanadium disulfide, vanadium di-23 selenide, and vanadium ditelluride. Also included are the 24 chalcogenides ha~ing more than one of the mentioned metals, e.g., V0.25 Tio.75 S2.0 26 The cathode-active material used in the cathode of 27 the cells of the presen~ invention, as men~ioned, is prefer-28 ably a chalcogenide selected from those described above.
29 However, any functional cathode-active material may be used which will function with the alkali metal anode and the elec-31 trolyte described herein. For example, such chalcogenide 32 catho~e-active materials as iron sulfide, FeOCl, MoO3, V2O5, 33 VOCl, VS4, FePS3 or even the non-chalcogenide cathode ma-34 terials such as CFX, e.g., CYo 5, which are known in the art, may be used.
36 The cathode structure itself need not necessarily 37 consist of the cathode-active material alone, but may be a . . , 1 structure such as carbon, nickel, zinc, etc., upon which 2 the cathode-active material is deposited. In one preferred 3 embodiment, however, the cathode structure consists entirely 4 of the cathode-active material. Thus, the cathode-active S material is typically a good electronic conductor and may 6 often serve as its own current collector. Also, the 7 cathode-active material may be admi~ed or diluted with a 8 minor amount of any other electrochemically active material, 9 and alloys (i.e., solid solutions) of the individual cathode-active materials may be used. The ca~hode may be readily 11 fabricated from the individual or alloyed cathode~active 12 materials using materials and methods well known in the 13 prior art. For example, when the chalcogenides are used, 14 polytetrafluoroethylene bonding agents or support structures such as nickel or copper mesh may be included.
16 The electrolyte of the cell of the present inven-17 tion is one which contains one or more closoborane and/or 18 closocarborane compounds in aprotic organic solvent.
19 The closoboranes are those of Formula (1) above with the specified variables. The variable Z is any alkali 21 metal. Desirably, Z is sodium, potassium or lithium, with 22 lithium and sodium being advantageous and with lithium be-23 ing preferred. The variable X is, as m ntioned, selected 24 from the group consisting of hydrogen and the halogens, e.g., F, Cl, Br and I. Of these, H, F and Cl are desired, with H
26 and Cl preferred. The variable n is an integer from 6 to 27 12, desirably 8 to 12, and preferably 10 to 12.
28 The closocarboranes are those of Formula (2) above 29 with the specified variables. The comments made with respect to Formula (1) variables Z and X are applicable here. The 31 variable m is an integer from 5 to 11 and is desirably 7 to 32 11 and preferably 9 to lI. The variable R is selec~ed from 33 the group consisting of organic radicals and X, i.e., hydro-34 gen and the halogens. Of hydrogen and the halogens, the com-ments above concerning X in Formula (1) are applicable. Con-36 cerning the organic radicals represented by R, these include 37 organic radicals selected from the group consisting of . , .
- , , ' : , ' ., : -, , 2~
1 inertly substituted and unsubstituted alkyls, aryls, alk-2 aryls and aralkyls. By "inertly substituted" is meantradi-3 cals containing substituents which have no detrimental ef-4 fect on the electrolyte compositions in the context of their effectiveness in electrochemical cells. Such inert substi-6 tuents include halogens, cyanoradical, etc. In general, 7 the alkyl radicals have 1 to 8 car~on atoms, the aryls have 8 6 to 18 carbon atoms and the aralkyl and alkaryl radicals 9 have 7 to 50 carbon atoms. Desirably, the organic radicals are those selected from alkyls having 2 to 6 carbon atoms, ll aryls having 6 to 12 carbon atoms and alkaryls and aralkyls 12 having 7 to 25 carbon atoms. Preferably, the organic radi-13 cals are those selected from alkyls having 2 to 4 carbon 14 atoms and the phenyl radical.
Among the closoborane and closocarborane compounds 16 used in the electrolyte of the cell of the present in~ention 17 are:
18 Li2B10Cl10 19 Li2B12C112 Li2B8Br8 21 Li2BloCl8H2 (6) 22 Li2B8H8 (7) 23 Li2BllIl0H (8) 24 LiC(CH3)BllClll LiC(C2~5)B7Cl7 (10) 26 Lic(c2H4cl)B8cl8 (11) 27 LiC(C6Hs)BloBrl0 (12) 28 and the like.
29 Other embodiments of the closoboranes and closo-carboranes should now become apparent in view of the fore-31 going. Of course, the analogs and homologs as well as the 32 corresponding other alkali metal based compounds are in-33 cluded, e.g., Na2~10C110 and NaC(C3H7)BgIg.
34 The closoboranes and closocarboranes used in the present invention electrolyte systems are employed in apro-36 tic solvent. In addition, it is necessary to include an 37 amount of a chela~ing agent, e.g., a chelating ether.
. . " . . .
1 The aprotic solvent used in the electrolyte of the 2 present invention is any aprotic organic solvent which ena-3 bles ions to migrate between anode and cathode in the pre-4 sence of the above-mentioned closoborane and/or closocar-borane compounds, when used in conjunction with a chelating 6 agent. Among the aprotic organic solvents which may be em-7 ployed are dioxolane, tetrahydrofuran, propylene carbonate, 8 methyl sulfoxide, mixtures thereof and the like. The ethers, 9 e.g., dioxolane, are preferred.
The chelating agent is one which enhances the solu-11 bility of the closoborane and/or closocarborane in the apro-12 tic oxganic solvent. Among these chelating agents are di-13 methoxyethane, diglyme, triglyme, tetraglyme, TMED, PMDT, 14 other chelating tertiary amines, mixtures thereof, and the like. Of these, the ethers, e.g., dimethoxyethane, are 16 preferred.
17 In general, about 2 to about 50 grams of closo-18 borane and/or closocarborane compound are used per 100 grams 19 of aprotic organic solvent (excluding chelating agent). De-sirably, about 5 to about 30 grams of compound per 100 grams 21 of aprotic organic solvent, preferably about 12 to about 18 22 grams per 100 grams of aprotic organic solvent, are used.
23 As to the chelating agen~, in general about 2 to about 50 ~4 grams of chelating agent are used per 100 grams of aprotic organic solvent. Desirably, about 5 to about 30, and pref-26 erably about 12 to about 18 grams of chelating agent per 27 100 grams of aprotic organic solvent are employed.
28 It has thus been discovered that cells having al-29 kali metal anodes, solid cathodes and electrolytes as de-scribed are obtained which have high cell capacities and 31 advantageous utility.
32 The present invention is more fully understood by 33 the following examples, presented for illustrative purposes 34 only.
EXA~PLE 1 36 A cell was prepared with lithium anode material, 37 titanium disulfide cathode material and a DME chelated closo-.
:^ , . , , :
'- .
- , . . .
, - ` -1 borane in dioxolane. The anode was lithium sheet and the 2 cathode was made up of 90 weight percent TiS2 and 10 weight 3 percent Teflon~which was hot pressed at 300C. onto an ex-4 panded stainless steel metal grid. The electrolyte was 39 weight percent Li2BloBllo-5DME, remainder dioxolane.
6 The cell was constructed by surrounding the ca-7 thode with polypropylene separators and a sheet of lithium 8 and the above as electrolyte. The steady voltage of this 9 cell was 2.68 volts which on discharge at 2 ma fell to 2.40 volts. The discharge rate was increased to 4 ma after 1 hour, 11 and the total utilization of the cell was greater than 85~
12 based on the reaction Li + TiS2~ LiTiS2. On decreasing 13 the rate to 2 mz, 92~ of the theoretical capacity was ob-14 tained. The cell was then charged at 2 ma, followed by a discharge at 2 ma; more than 90~ of the first discharge ca-16 pacity was obtained on this second discharge. This charge/
17 discharge cycling was then repeated more than 20 times, thus 18 indicating the intrinsic reversibility of the electrolyte.
A cell having a lithium sheet anode, a 0.079 molar 21 Li2BloCllo in a 30~ DME, -70% by weight dioxolane electro-22 lyte and a cathode having a 90 weight percent TiS2, 10 23 weight percent Teflon~hot pressed at 300C. into an expended 24 metal grid, was constructed as in Example 1. This cell had a very low capacity on initial discharge (~ 2~ theoretical 26 capacity), but on cycling the cell the capacity increased 27 significantly; thus, on the 10th cycle the capacity was over 28 74~ of the theoretical expected for the reaction Li + TiS2 29 LiTiS2. This again shows the intrinsic reversibility of this electrolyte. It is beli~ved that the observed behavior 31 is probably associated with an initial electrolyte of very 32 10W concentration. This concentration increased on cycling 33 as the electrolyte solvent volatilized, rendering the in-34 creased capacity.
36 A cell was made up as in above examples except 37 that, as electrolyte, Li2B12C112 was dissolved to saturation " ~ rfacle ~nnrk ..... . .
-.
~2~
1 (0.15 molar) in acetonitrile. The cell emf was just below 2 2.5 volts on discharge at 4 ma, but considerable gassing of 3 the cell occurred at the lithium anode. Little recharge-4 ability was observed and no capacity on the second discharge.
The cell was warm to the touch at this point and clearly 6 there was spontaneous reaction between the electrolyte sol-7 vent and the lithium. This was confirmed in a blank reac-8 tion. This example shows that even though the salt may be 9 dissolved in highly polar solvents such as water and aceto-nitrile, such systems are not compatible with alkali such 11 as lithium metal anodes.
,...... . . .
2. Description of the Prior Art 11 There has been considerable interest in recent 12 years in developing high energy density batteries or volt-13 aic cells. Among the systems being investigated are those 14 employing nonaqueous liquid, ~used or solid electrolytes, with lightweight metals, such as alkali metals, as anodes, 16 and with cathodes co~taining metal chalcogenide compounds.
17 Such systems are described, ~or example, in U.S. Patent 18 Nos. 3,988,164; 3,925,098; 3,864,167 and 3,791,867.
19 Various efforts have been made to develop new electrolytes for these and similar secondary cell systems.
21 For example, U.S. Patent NoO 4,060,674 (Klemann et al) de-22 scribed alkali metal anode/solid cathode cells having elec-23 trolytes of organometallic alkali metal salts and organic 24 solvents. Also, the use of clovoboranes as additives to electrolytes in certain cells has been taught in U.S.
26 Patent Nos. 4,020,240 (Schlaikjer) and 4,071,664 ~Dey). How-27 ever, these patents teach the use of clovoboranes as elec-28 trolyte additives in cell systems containing a liquid 29 cathode-electrolyte salt compo~ition. No sugges~ion is made that clovoboranes may be used with aprotic organic solvents 31 or that th~y may be used in cells having solid cathodes.
33 The present invention is directed to a novel elec-34 trochemical cell which contains an al~ali metal anode, a solid cathodeJ and an electrolyte containing one or more 36 closoborane and/or closocarborane compounds in aprotic or-37 ganic solvent with a chelating agent.
, . ..
3~4~
2 The present invention is directed to electrochemi-3 cal cells having alkali metal anodes, solid cathodes, and 4 electrolytes containing one or more compounds selected from the group consisting of:
6 (i) closoborane compounds of the formula:
7 Z2BnXn (1) 8 wherein Z is an alkali metal, B is boron, X is one or more 9 substituents selected from the group consisting of hydrogen and the halogens and n is an integer from 6 to 12; and 11 (ii) closocarborane compounds of the formula:
12 ZCRBmXm (2) 13 wherein Z is an alkali metal, C is carbon, R is a radical 14 selected from the group consisting o~ organic radicals, hy-drogen and the halogens, B is boron, X is one or more sub-1~ stituents selected from the group consisting of hydrogen and 17 the halogens, and m is an integer from 5 to 11. These clo-18 soborane and closocarborane compounds are employed in apro-19 tic organic solvent with a chelating agent.
The anode employed in the cell of the present in-21 vention i5, as mentioned, one which contains an alkali metal 22 as its anode-active material. Desirably, thi anode-active 23 material is sodium, potassium, lithium, or alloys containing 24 these. It should be noted, therefore, that when the speci-fic alkali metal~ are recited herein with respect to the 26 anode, such recitations are meant to include alloys of such 27 ~lkali metals. The anode-active material used in the anode ~8 o~ the present invention is preferably sodium or lithium, 29 and is most preferably lithium. These anode-active materi-als may, for Pxample, be in contact with other metal struc-31 stures, e.g., nickel, copper or silver screen, which serve 32 as urrent collectors and are well known in `the art.
33 The cathode used in the cell of the present in-34 vention may be any cathode which produces electric current when coupled with an alkali metal anode and which will func-36 tion using the specific solid electrolyte described herein.
37 A useul cathode for the cell of the present invention is ,, :
lZ9947 1 one which contains as its cathode-active material one or 2 more chalcogenide compounds selected from the group consist-3 ing of the sulfides, the selenides, and the tellurides of 4 titanium, zirconium, hafnium, niobium, tantalum, molybdenum and vanadium. In general, such chalcogenides contain about 6 1.8 to about 3.2 atoms of the chalcogen per metal atom. Ad-7 vantageously, these chalcogenides are the sulfides, the 8 selenides, and the tellurides of one or more metals selected 9 from the mentioned group and desirably one or more metals selected from titanium, molybdenum and vanadium. Preferred 11 are the titanium chalcogenides. Among the chalcogens em-12 ployed i~ the chalcogenides used as the cathode-active ma-13 terials are, as mentioned, sulfur, selenium, and tellurium.
14 Of these, sulfur and selenium are desired, and sulfur is preferred. Also, among the chalcogenides, those which con-16 tain about 1.8 to about 2.1 atoms of chalcogen per metal 17 atom, commonLy referred to as dichalcogenides, are preferred.
18 Examples of cathode-active materials which may be 19 useful, and which are selected from the above-mentioned chalcogenides are titanium disulfide, zirconium disulfide, 21 hafnium disulfide, niobium triselenide, tantalum disulfide, 22 molybdenu~ trisulfide, vanadium disulfide, vanadium di-23 selenide, and vanadium ditelluride. Also included are the 24 chalcogenides ha~ing more than one of the mentioned metals, e.g., V0.25 Tio.75 S2.0 26 The cathode-active material used in the cathode of 27 the cells of the presen~ invention, as men~ioned, is prefer-28 ably a chalcogenide selected from those described above.
29 However, any functional cathode-active material may be used which will function with the alkali metal anode and the elec-31 trolyte described herein. For example, such chalcogenide 32 catho~e-active materials as iron sulfide, FeOCl, MoO3, V2O5, 33 VOCl, VS4, FePS3 or even the non-chalcogenide cathode ma-34 terials such as CFX, e.g., CYo 5, which are known in the art, may be used.
36 The cathode structure itself need not necessarily 37 consist of the cathode-active material alone, but may be a . . , 1 structure such as carbon, nickel, zinc, etc., upon which 2 the cathode-active material is deposited. In one preferred 3 embodiment, however, the cathode structure consists entirely 4 of the cathode-active material. Thus, the cathode-active S material is typically a good electronic conductor and may 6 often serve as its own current collector. Also, the 7 cathode-active material may be admi~ed or diluted with a 8 minor amount of any other electrochemically active material, 9 and alloys (i.e., solid solutions) of the individual cathode-active materials may be used. The ca~hode may be readily 11 fabricated from the individual or alloyed cathode~active 12 materials using materials and methods well known in the 13 prior art. For example, when the chalcogenides are used, 14 polytetrafluoroethylene bonding agents or support structures such as nickel or copper mesh may be included.
16 The electrolyte of the cell of the present inven-17 tion is one which contains one or more closoborane and/or 18 closocarborane compounds in aprotic organic solvent.
19 The closoboranes are those of Formula (1) above with the specified variables. The variable Z is any alkali 21 metal. Desirably, Z is sodium, potassium or lithium, with 22 lithium and sodium being advantageous and with lithium be-23 ing preferred. The variable X is, as m ntioned, selected 24 from the group consisting of hydrogen and the halogens, e.g., F, Cl, Br and I. Of these, H, F and Cl are desired, with H
26 and Cl preferred. The variable n is an integer from 6 to 27 12, desirably 8 to 12, and preferably 10 to 12.
28 The closocarboranes are those of Formula (2) above 29 with the specified variables. The comments made with respect to Formula (1) variables Z and X are applicable here. The 31 variable m is an integer from 5 to 11 and is desirably 7 to 32 11 and preferably 9 to lI. The variable R is selec~ed from 33 the group consisting of organic radicals and X, i.e., hydro-34 gen and the halogens. Of hydrogen and the halogens, the com-ments above concerning X in Formula (1) are applicable. Con-36 cerning the organic radicals represented by R, these include 37 organic radicals selected from the group consisting of . , .
- , , ' : , ' ., : -, , 2~
1 inertly substituted and unsubstituted alkyls, aryls, alk-2 aryls and aralkyls. By "inertly substituted" is meantradi-3 cals containing substituents which have no detrimental ef-4 fect on the electrolyte compositions in the context of their effectiveness in electrochemical cells. Such inert substi-6 tuents include halogens, cyanoradical, etc. In general, 7 the alkyl radicals have 1 to 8 car~on atoms, the aryls have 8 6 to 18 carbon atoms and the aralkyl and alkaryl radicals 9 have 7 to 50 carbon atoms. Desirably, the organic radicals are those selected from alkyls having 2 to 6 carbon atoms, ll aryls having 6 to 12 carbon atoms and alkaryls and aralkyls 12 having 7 to 25 carbon atoms. Preferably, the organic radi-13 cals are those selected from alkyls having 2 to 4 carbon 14 atoms and the phenyl radical.
Among the closoborane and closocarborane compounds 16 used in the electrolyte of the cell of the present in~ention 17 are:
18 Li2B10Cl10 19 Li2B12C112 Li2B8Br8 21 Li2BloCl8H2 (6) 22 Li2B8H8 (7) 23 Li2BllIl0H (8) 24 LiC(CH3)BllClll LiC(C2~5)B7Cl7 (10) 26 Lic(c2H4cl)B8cl8 (11) 27 LiC(C6Hs)BloBrl0 (12) 28 and the like.
29 Other embodiments of the closoboranes and closo-carboranes should now become apparent in view of the fore-31 going. Of course, the analogs and homologs as well as the 32 corresponding other alkali metal based compounds are in-33 cluded, e.g., Na2~10C110 and NaC(C3H7)BgIg.
34 The closoboranes and closocarboranes used in the present invention electrolyte systems are employed in apro-36 tic solvent. In addition, it is necessary to include an 37 amount of a chela~ing agent, e.g., a chelating ether.
. . " . . .
1 The aprotic solvent used in the electrolyte of the 2 present invention is any aprotic organic solvent which ena-3 bles ions to migrate between anode and cathode in the pre-4 sence of the above-mentioned closoborane and/or closocar-borane compounds, when used in conjunction with a chelating 6 agent. Among the aprotic organic solvents which may be em-7 ployed are dioxolane, tetrahydrofuran, propylene carbonate, 8 methyl sulfoxide, mixtures thereof and the like. The ethers, 9 e.g., dioxolane, are preferred.
The chelating agent is one which enhances the solu-11 bility of the closoborane and/or closocarborane in the apro-12 tic oxganic solvent. Among these chelating agents are di-13 methoxyethane, diglyme, triglyme, tetraglyme, TMED, PMDT, 14 other chelating tertiary amines, mixtures thereof, and the like. Of these, the ethers, e.g., dimethoxyethane, are 16 preferred.
17 In general, about 2 to about 50 grams of closo-18 borane and/or closocarborane compound are used per 100 grams 19 of aprotic organic solvent (excluding chelating agent). De-sirably, about 5 to about 30 grams of compound per 100 grams 21 of aprotic organic solvent, preferably about 12 to about 18 22 grams per 100 grams of aprotic organic solvent, are used.
23 As to the chelating agen~, in general about 2 to about 50 ~4 grams of chelating agent are used per 100 grams of aprotic organic solvent. Desirably, about 5 to about 30, and pref-26 erably about 12 to about 18 grams of chelating agent per 27 100 grams of aprotic organic solvent are employed.
28 It has thus been discovered that cells having al-29 kali metal anodes, solid cathodes and electrolytes as de-scribed are obtained which have high cell capacities and 31 advantageous utility.
32 The present invention is more fully understood by 33 the following examples, presented for illustrative purposes 34 only.
EXA~PLE 1 36 A cell was prepared with lithium anode material, 37 titanium disulfide cathode material and a DME chelated closo-.
:^ , . , , :
'- .
- , . . .
, - ` -1 borane in dioxolane. The anode was lithium sheet and the 2 cathode was made up of 90 weight percent TiS2 and 10 weight 3 percent Teflon~which was hot pressed at 300C. onto an ex-4 panded stainless steel metal grid. The electrolyte was 39 weight percent Li2BloBllo-5DME, remainder dioxolane.
6 The cell was constructed by surrounding the ca-7 thode with polypropylene separators and a sheet of lithium 8 and the above as electrolyte. The steady voltage of this 9 cell was 2.68 volts which on discharge at 2 ma fell to 2.40 volts. The discharge rate was increased to 4 ma after 1 hour, 11 and the total utilization of the cell was greater than 85~
12 based on the reaction Li + TiS2~ LiTiS2. On decreasing 13 the rate to 2 mz, 92~ of the theoretical capacity was ob-14 tained. The cell was then charged at 2 ma, followed by a discharge at 2 ma; more than 90~ of the first discharge ca-16 pacity was obtained on this second discharge. This charge/
17 discharge cycling was then repeated more than 20 times, thus 18 indicating the intrinsic reversibility of the electrolyte.
A cell having a lithium sheet anode, a 0.079 molar 21 Li2BloCllo in a 30~ DME, -70% by weight dioxolane electro-22 lyte and a cathode having a 90 weight percent TiS2, 10 23 weight percent Teflon~hot pressed at 300C. into an expended 24 metal grid, was constructed as in Example 1. This cell had a very low capacity on initial discharge (~ 2~ theoretical 26 capacity), but on cycling the cell the capacity increased 27 significantly; thus, on the 10th cycle the capacity was over 28 74~ of the theoretical expected for the reaction Li + TiS2 29 LiTiS2. This again shows the intrinsic reversibility of this electrolyte. It is beli~ved that the observed behavior 31 is probably associated with an initial electrolyte of very 32 10W concentration. This concentration increased on cycling 33 as the electrolyte solvent volatilized, rendering the in-34 creased capacity.
36 A cell was made up as in above examples except 37 that, as electrolyte, Li2B12C112 was dissolved to saturation " ~ rfacle ~nnrk ..... . .
-.
~2~
1 (0.15 molar) in acetonitrile. The cell emf was just below 2 2.5 volts on discharge at 4 ma, but considerable gassing of 3 the cell occurred at the lithium anode. Little recharge-4 ability was observed and no capacity on the second discharge.
The cell was warm to the touch at this point and clearly 6 there was spontaneous reaction between the electrolyte sol-7 vent and the lithium. This was confirmed in a blank reac-8 tion. This example shows that even though the salt may be 9 dissolved in highly polar solvents such as water and aceto-nitrile, such systems are not compatible with alkali such 11 as lithium metal anodes.
,...... . . .
Claims (10)
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. An electrochemical cell, comprising:
(a) an alkali metal-containing anode;
(b) a solid cathode; and, (c) an electrolyte containing one or more compounds selected from the group consisting of:
(i) closoborane compounds of the formula:
Z2BnXn wherein Z is an alkali metal, B is boron, X is one or more sub-stituents selected from the group consisting of hydrogen and the hydrogens, and n is an integer from 6 to 12; and, (ii) closocarborane compounds of the formula:
ZCRBmXm wherein Z, B and X are as defined above, C is carbon, and R is selected from the group consisting of inertly substituted and un-substituted alkyls, aryls, alkaryls and aralkyls, hydrogen, and the halogens, and m is an integer from 5 to 11, said compounds being dissolved in aprotic organic solvent in the presence of a chelat-ing agent sufficient to enable the migration of ions between said anode and said cathode.
(a) an alkali metal-containing anode;
(b) a solid cathode; and, (c) an electrolyte containing one or more compounds selected from the group consisting of:
(i) closoborane compounds of the formula:
Z2BnXn wherein Z is an alkali metal, B is boron, X is one or more sub-stituents selected from the group consisting of hydrogen and the hydrogens, and n is an integer from 6 to 12; and, (ii) closocarborane compounds of the formula:
ZCRBmXm wherein Z, B and X are as defined above, C is carbon, and R is selected from the group consisting of inertly substituted and un-substituted alkyls, aryls, alkaryls and aralkyls, hydrogen, and the halogens, and m is an integer from 5 to 11, said compounds being dissolved in aprotic organic solvent in the presence of a chelat-ing agent sufficient to enable the migration of ions between said anode and said cathode.
2. The cell of claim 1 wherein said electrolyte con-tains one or more closoborane compounds.
3. The cell of claim 2 wherein said variable X is selected from the group consisting of H, F and Cl.
4. The cell of claim 1 wherein said alkali metal-con-taining anode contains an alkali metal selected from the group consisting of lithium, sodium and potassium.
5. The cell of claim 4 wherein said solid cathode is a chalcogenide.
6. The cell of claim 1 wherein said electrolyte contains one or more closocarborane compounds.
7. The cell of claim 6 wherein the variable R is select-ed from the group consisting of inertly substituted and unsubstituted organic radicals selected from alkyls having 1 to 8 carbon atoms, aryls having 6 to 18 carbon atoms and alkaryls and aralkyls having 7 to 50 carbon atoms, hydrogen and the halogens.
8. The cell of claim 7 wherein R is selected from the group consisting of hydrogen and the halogens.
9. The cell of claim 7 wherein R is selected from the group consisting of inertly substituted and unsubstituted organic radicals selected from alkyls having 2 to 6 carbon atoms, aryls having 6 to 12 carbon atoms and alkaryls and aralkyls having 7 to 25 carbon atoms.
10. The cell of claim 9 wherein R is selected from the group consisting of inertly substituted and unsubstituted organic radicals selected from the group consisting of alkyls having 2 to 4 carbon atoms and phenyl.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US956,746 | 1978-11-01 | ||
| US05/956,746 US4201839A (en) | 1978-11-01 | 1978-11-01 | Cell containing an alkali metal anode, a solid cathode, and a closoborane and/or closocarborane electrolyte |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1129947A true CA1129947A (en) | 1982-08-17 |
Family
ID=25498648
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA333,354A Expired CA1129947A (en) | 1978-11-01 | 1979-08-08 | Cell containing an alkali metal anode, a solid cathode, and a closoborane and/or closocarborane electrolyte |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US4201839A (en) |
| JP (1) | JPS5566873A (en) |
| BE (1) | BE879756A (en) |
| CA (1) | CA1129947A (en) |
| CH (1) | CH643690A5 (en) |
| DE (1) | DE2944026A1 (en) |
| FR (1) | FR2440625A1 (en) |
| GB (1) | GB2035670B (en) |
| NL (1) | NL188127C (en) |
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| US4329404A (en) * | 1980-09-02 | 1982-05-11 | Duracell International Inc. | Rechargeable non-aqueous cells with complex electrolyte salts |
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| WO1983003322A1 (en) * | 1982-03-18 | 1983-09-29 | Armand, Michel | Electrolytes formed of solid solutions of closoboranes in a plastic macromolecular material and electrochemical generators containing such electrolytes |
| US4619874A (en) * | 1982-05-06 | 1986-10-28 | Medtronic, Inc. | Electrochemical cells with end-of-life indicator |
| JPS59167969A (en) * | 1983-03-11 | 1984-09-21 | Sanyo Electric Co Ltd | Nonaqueous electrolyte cell |
| JPS59189565A (en) * | 1983-04-12 | 1984-10-27 | Sanyo Electric Co Ltd | non-aqueous electrolyte battery |
| US4508800A (en) * | 1983-06-30 | 1985-04-02 | Duracell Inc. | Cell with FeBr3 cathode |
| US4508798A (en) * | 1983-06-30 | 1985-04-02 | Duracell Inc. | Cell with CoCl2 cathode |
| US4510220A (en) * | 1983-06-30 | 1985-04-09 | Duracell Inc. | Cell with PbCl2 cathode |
| FR2548464B1 (en) * | 1983-06-30 | 1987-06-26 | Duracell Int | NON-AQUEOUS ELECTROCHEMICAL CELLS |
| US4508799A (en) * | 1983-06-30 | 1985-04-02 | Duracell Inc. | Cell with NiCl2 cathode |
| US4528254A (en) * | 1983-11-30 | 1985-07-09 | Allied Corporation | Conjugated polymer battery containing organosulfur solvent |
| US4560630A (en) * | 1984-09-27 | 1985-12-24 | The United States Of America As Represented By The Secretary Of The Army | Rechargeable lithium cell having an electrolyte comprising 4-butyrolactone in dimethoxyethane |
| USH452H (en) | 1985-06-27 | 1988-04-05 | The United States Of America As Represented By The Secretary Of The Army | Cathode including a non fluorinated linear chain polymer as the binder, method of making the cathode, and lithium electrochemical cell containing the cathode |
| USH519H (en) | 1985-06-27 | 1988-09-06 | The United States Of America As Represented By The Secretary Of The Army | Cathode including a non fluorinated linear chain polymer as the binder, method of making the cathode, and lithium electrochemical cell containing the cathode |
| FR2641902B1 (en) * | 1988-12-26 | 1993-08-13 | Centre Nat Rech Scient | RECHARGEABLE BATTERY WITH POLYMER SOLID ELECTROLYTE |
| US6022643A (en) * | 1997-12-08 | 2000-02-08 | Brookhaven Science Associates | Boron compounds as anion binding agents for nonaqueous battery electrolytes |
| JP4170712B2 (en) * | 2002-09-05 | 2008-10-22 | パイオニア株式会社 | Spherical aberration corrector |
| CA2479589C (en) * | 2003-09-04 | 2011-05-24 | Air Products And Chemicals, Inc. | Polyfluorinated boron cluster anions for lithium electrolytes |
| US7311993B2 (en) * | 2003-09-04 | 2007-12-25 | Air Products And Chemicals, Inc. | Polyfluorinated boron cluster anions for lithium electrolytes |
| US7785740B2 (en) * | 2004-04-09 | 2010-08-31 | Air Products And Chemicals, Inc. | Overcharge protection for electrochemical cells |
| US7981388B2 (en) * | 2004-08-23 | 2011-07-19 | Air Products And Chemicals, Inc. | Process for the purification of lithium salts |
| US7465517B2 (en) | 2004-08-23 | 2008-12-16 | Air Products And Chemicals, Inc. | High purity lithium polyhalogenated boron cluster salts useful in lithium batteries |
| US20060216612A1 (en) * | 2005-01-11 | 2006-09-28 | Krishnakumar Jambunathan | Electrolytes, cells and methods of forming passivation layers |
| US20080026297A1 (en) * | 2005-01-11 | 2008-01-31 | Air Products And Chemicals, Inc. | Electrolytes, cells and methods of forming passivaton layers |
| US20060204843A1 (en) * | 2005-03-10 | 2006-09-14 | Ivanov Sergei V | Polyfluorinated boron cluster anions for lithium electrolytes |
| US20070048605A1 (en) | 2005-08-23 | 2007-03-01 | Pez Guido P | Stable electrolyte counteranions for electrochemical devices |
| US20070072085A1 (en) * | 2005-09-26 | 2007-03-29 | Zonghai Chen | Overcharge protection for electrochemical cells |
| US8367253B2 (en) * | 2006-02-02 | 2013-02-05 | U Chicago Argonne Llc | Lithium-ion batteries with intrinsic pulse overcharge protection |
| JP5034287B2 (en) * | 2006-03-24 | 2012-09-26 | ソニー株式会社 | battery |
| US8283074B2 (en) * | 2008-08-15 | 2012-10-09 | Uchicago Argonne, Llc | Electrolyte salts for nonaqueous electrolytes |
| AU2010266488B2 (en) * | 2009-07-01 | 2014-05-29 | Energizer Brands, Llc | Removal of impurities from lithium-iron disulfide electrochemical cells |
| US8703329B2 (en) | 2011-03-25 | 2014-04-22 | Enerdel, Inc. | Redox shuttle for high voltage lithium battery |
| US9588095B2 (en) * | 2012-07-24 | 2017-03-07 | Massachusetts Institute Of Technology | Reagents for oxidizer-based chemical detection |
| US10345281B2 (en) | 2014-04-04 | 2019-07-09 | Massachusetts Institute Of Technology | Reagents for enhanced detection of low volatility analytes |
| US10816530B2 (en) | 2013-07-23 | 2020-10-27 | Massachusetts Institute Of Technology | Substrate containing latent vaporization reagents |
| CN106299470A (en) * | 2015-05-20 | 2017-01-04 | 宁德时代新能源科技股份有限公司 | Solid polymer electrolyte and all-solid-state lithium ion battery using same |
| CN109148959B (en) | 2017-06-28 | 2023-07-25 | 松下知识产权经营株式会社 | lithium secondary battery |
| WO2019212007A1 (en) | 2018-05-02 | 2019-11-07 | 日本特殊陶業株式会社 | Ionic conductor and electricity storage device |
| US11502333B2 (en) * | 2019-05-29 | 2022-11-15 | Toyota Motor Engineering & Manufacturing North America, Inc. | Method for synthesizing novel soft materials based on boron compounds |
| US11349150B2 (en) | 2019-08-01 | 2022-05-31 | Toyota Motor Engineering & Manufacturing North America, Inc. | Ceramic soft composites for solid-state batteries |
| US11498846B2 (en) | 2020-07-15 | 2022-11-15 | Toyota Motor Engineering & Manufacturing North America, Inc. | Method for synthesis of solvent-free lithium boron cluster based salts |
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|---|---|---|---|---|
| US3415687A (en) * | 1966-03-29 | 1968-12-10 | Honeywell Inc | Electric current producing cell |
| FR2102561A5 (en) * | 1970-08-07 | 1972-04-07 | Accumulateurs Fixes | |
| US3877988A (en) * | 1973-03-21 | 1975-04-15 | Mallory & Co Inc P R | Lithium-metal telluride organic electrolyte cell |
| US3887397A (en) * | 1974-01-02 | 1975-06-03 | Honeywell Inc | Highly conductive stable electrolyte for lithium batteries |
| US3988164A (en) * | 1974-04-25 | 1976-10-26 | P. R. Mallory & Co., Inc. | Cathode material for solid state batteries |
| US4020240A (en) * | 1975-09-03 | 1977-04-26 | P. R. Mallory & Co., Inc. | Electrochemical cell with clovoborate salt in electrolyte and method of operation and composition of matter |
| US4060674A (en) * | 1976-12-14 | 1977-11-29 | Exxon Research And Engineering Company | Alkali metal anode-containing cells having electrolytes of organometallic-alkali metal salts and organic solvents |
| US4071664A (en) * | 1977-04-01 | 1978-01-31 | P. R. Mallory & Co. Inc. | Electrolyte salt additive |
| US4104451A (en) * | 1977-09-26 | 1978-08-01 | Exxon Research & Engineering Co. | Alkali metal anode/chalcogenide cathode reversible batteries having alkali metal polyaryl metallic compound electrolytes |
| US4139681A (en) * | 1978-03-02 | 1979-02-13 | Exxon Research & Engineering Co. | Electrochemical cells having alkali metal anodes and electrolyte salt complex compositions including haloorganometallic alkali metal salt complexes |
-
1978
- 1978-11-01 US US05/956,746 patent/US4201839A/en not_active Expired - Lifetime
-
1979
- 1979-08-08 CA CA333,354A patent/CA1129947A/en not_active Expired
- 1979-10-30 CH CH973779A patent/CH643690A5/en not_active IP Right Cessation
- 1979-10-30 GB GB7937603A patent/GB2035670B/en not_active Expired
- 1979-10-31 FR FR7927042A patent/FR2440625A1/en active Granted
- 1979-10-31 BE BE0/197907A patent/BE879756A/en not_active IP Right Cessation
- 1979-10-31 DE DE19792944026 patent/DE2944026A1/en active Granted
- 1979-11-01 NL NLAANVRAGE7908023,A patent/NL188127C/en not_active IP Right Cessation
- 1979-11-01 JP JP14195379A patent/JPS5566873A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| NL188127B (en) | 1991-11-01 |
| BE879756A (en) | 1980-04-30 |
| NL188127C (en) | 1992-04-01 |
| GB2035670A (en) | 1980-06-18 |
| NL7908023A (en) | 1980-05-06 |
| GB2035670B (en) | 1982-12-22 |
| JPS5566873A (en) | 1980-05-20 |
| CH643690A5 (en) | 1984-06-15 |
| FR2440625A1 (en) | 1980-05-30 |
| DE2944026A1 (en) | 1980-05-08 |
| DE2944026C2 (en) | 1988-06-30 |
| JPS6364034B2 (en) | 1988-12-09 |
| FR2440625B1 (en) | 1983-06-10 |
| US4201839A (en) | 1980-05-06 |
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| MKEX | Expiry | ||
| MKEX | Expiry |
Effective date: 19990817 |