US20160181662A1 - Functionalized carboranyl magnesium electrolyte for magnesium battery - Google Patents
Functionalized carboranyl magnesium electrolyte for magnesium battery Download PDFInfo
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- US20160181662A1 US20160181662A1 US14/581,768 US201414581768A US2016181662A1 US 20160181662 A1 US20160181662 A1 US 20160181662A1 US 201414581768 A US201414581768 A US 201414581768A US 2016181662 A1 US2016181662 A1 US 2016181662A1
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- carboranyl
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- 239000011777 magnesium Substances 0.000 title claims abstract description 71
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 51
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000003792 electrolyte Substances 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 14
- 230000008569 process Effects 0.000 claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- 150000001450 anions Chemical class 0.000 claims abstract description 10
- 125000003118 aryl group Chemical group 0.000 claims abstract description 9
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 8
- 125000004104 aryloxy group Chemical group 0.000 claims abstract description 8
- 159000000003 magnesium salts Chemical class 0.000 claims description 39
- -1 magnesium halide Chemical class 0.000 claims description 10
- 239000010406 cathode material Substances 0.000 claims description 8
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 239000000460 chlorine Substances 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 5
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 5
- 229910052740 iodine Inorganic materials 0.000 claims description 5
- 239000011630 iodine Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 abstract description 5
- 229910000510 noble metal Inorganic materials 0.000 abstract description 3
- 150000004820 halides Chemical class 0.000 abstract 1
- 239000002904 solvent Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 239000004020 conductor Substances 0.000 description 7
- 239000002243 precursor Substances 0.000 description 7
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000005649 metathesis reaction Methods 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical class [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 4
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000004891 communication Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910017699 MgY2 Inorganic materials 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 2
- ANOOTOPTCJRUPK-UHFFFAOYSA-N 1-iodohexane Chemical compound CCCCCCI ANOOTOPTCJRUPK-UHFFFAOYSA-N 0.000 description 1
- RTYCZCFQHXCMGC-UHFFFAOYSA-N 1-methoxy-2-[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]ethane Chemical compound COCCOCCOCCOCCOC.COCCOCCOCCOCCOC RTYCZCFQHXCMGC-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- QYHKLBKLFBZGAI-UHFFFAOYSA-N boron magnesium Chemical class [B].[Mg] QYHKLBKLFBZGAI-UHFFFAOYSA-N 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical group II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 1
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 1
- 229910001623 magnesium bromide Inorganic materials 0.000 description 1
- 229940096405 magnesium cation Drugs 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Images
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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
- H01M10/0568—Liquid materials characterised by the solutes
-
- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M10/058—Construction or manufacture
-
- 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
- H01M4/134—Electrodes based on metals, Si or alloys
-
- 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
- H01M4/137—Electrodes based on electro-active polymers
-
- 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
-
- 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
- H01M4/466—Magnesium 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
- 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
-
- 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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present disclosure is directed in part to an electrochemical device having a functionalized carboranyl magnesium electrolyte.
- the present disclosure is also directed to a method for making such an electrolytic cell.
- Magnesium batteries have received significant attention as potential replacements for lithium batteries due to their high volumetric capacity, lack of dendrite formation, and the relative inexpensiveness of magnesium.
- Discovery and development of suitable electrolytes for magnesium batteries has proven challenging however.
- Conventional inorganic magnesium salts have typically been found incompatible with reversible magnesium deposition as they tend to form an ion-blocking layer at the magnesium electrode during their electrochemical reduction.
- organic magnesium salts such as those derived from Grignard reagents have been found to be highly corrosive, particularly toward non-noble cathodes, possibly due to the presence of chloride co-anions.
- electrochemical devices having a carboranyl magnesium electrolyte and a process of forming these electrochemical devices.
- An electrochemical device having a magnesium-containing anode, a cathode, and an electrolyte.
- the electrolyte includes a functionalized carboranyl magnesium salt having a formula of:
- i is an integer within a range of 5 through 11, inclusive
- j is an integer within a range of 0 through i inclusive
- k is an integer between 0 and i inclusive
- each X independently of each other X, is fluorine, chlorine, bromine, or iodine
- each R independently of each other R, is an alkyl, aryl, alkoxy, aryloxy, their partially or completely fluorinated analogues, or a moiety combining the aforementioned functionalities.
- a process for preparing an electrochemical device includes a step of connecting a magnesium-containing anode and a cathode via an external electrically conductive structure.
- the process also includes a step of contacting the anode and cathode with an electrolyte.
- the electrolyte includes a functionalized carboranyl magnesium salt having a formula of:
- i is an integer within a range of 5 through 11, inclusive
- j is an integer within a range of 0 through i inclusive
- k is an integer between 0 and i inclusive
- each X independently of each other X, is fluorine, chlorine, bromine, or iodine
- each R independently of each other R, is an alkyl, aryl, alkoxy, aryloxy, their partially or completely fluorinated analogues, or a moiety combining the aforementioned functionalities.
- FIG. 1 is a cyclic voltammogram of a platinum (Pt) working electrode in contact with 0.2 M Mg(CB 11 H 11 (CH 3 )) 2 in tetraethylene glycol dimethyl ether (tetraglyme) at a scan rate of 5 mV/s; and
- FIG. 2 is a cyclic voltammogram of a Pt working electrode in contact with 0.1 M Mg(CB 11 H 12 ) 2 in tetraglyme at a scan rate of 5 mV/s.
- the present disclosure provides electrochemical devices having electrolytes that include functionalized carboranyl magnesium salts.
- the results described here indicate that the present, functionalized carboranyl magnesium salts are capable of mediating reversible magnesium deposition at a magnesium anode, while being relatively non-corrosive and oxidatively stable at the cathodic current collector in a manner previously shown for non-functionalized carboranyl magnesium containing electrolytes.
- the present electrolytes are functionalized on the carboranyl anion with one or more alkyl or other substantially non-polar moieties in order to increase the electrolyte solubility in ethereal solvent.
- the functionalized carboranyl magnesium salts can thus be particularly beneficial for use as electrolytes in magnesium batteries having a cathodic current collector made of non-noble metals such as stainless steel.
- the presently disclosed functionalized carboranyl magnesium salts combine the properties of electrochemical compatibility with reversible and repeated magnesium deposition at the magnesium anode, lack of corrosiveness at the cathodic current collector, and high solubility for enhanced energy density.
- an electrochemical device that includes an anode; a cathode; and an electrolyte in contact with the anode and the cathode.
- the electrolyte will contain a salt having at least one magnesium cation (Mg 2+ ) and at least one functionalized carboranyl anion per stoichiometric unit.
- the electrolyte will comprise a functionalized carboranyl magnesium salt having a formula of:
- i is an integer within a range of 5 through 11, inclusive
- j is an integer within a range of 0 through i inclusive
- k is an integer between 0 and i inclusive
- each X, independently of each other X is fluorine, chlorine, bromine, or iodine
- each R, independently of each other R is an alkyl, aryl, alkoxy, aryloxy, their partially or completely fluorinated analogues, or a moiety combining the aforementioned functionalities.
- at least one of j and k will be equal to or greater than 1.
- k will be equal to or greater than 1.
- the electrochemical device will include an electrolyte containing a functionalized carboranyl magnesium salt according to Formula I, with or without the other functionalized carboranyl salt according to Formula II.
- alkyl refers to a branched or straight-chain alkyl group having 1 to 18 carbons (C1-C18) which can optionally be partially or completely fluorinated.
- aryl refers to an aromatic hydrocarbon group having 6 to 14 carbons (C6-14), such as phenyl or naphthyl. An aryl can also optionally be partially or completely fluorinated.
- alkoxy refers to group having a formula —R alk where R alk is an alkyl as defined above. An alkoxy group can optionally be partially or completely fluorinated.
- aryloxy refers to a group having a formula —R aryl , where R aryl is an aryl group as defined above. An aryloxy group can optionally be partially or completely fluorinated.
- the functionalized carboranyl anion represented above as [CB i H [(i+1)-j-k] X j R k ] ⁇ or [C 2 B (i ⁇ 1) H (i-j-k) X j R k ] ⁇ will be a functionalized anion of a closo-carborane. In some instances, it will be a functionalized anion of an icosahedral-closo-carborane, wherein the cumulative number of carbon and boron atoms, exclusive of H, X, and R groups, is 12.
- R can be covalently attached to the carbon of the carboranyl anion.
- R can be alkyl. In some such implementations, R can be methyl or hexyl.
- the functionalized carboranyl magnesium salts employed in the electrochemical device described herein are materials that are either soluble or partially soluble in ethereal solvents under normal operating conditions for the associated electrochemical device.
- Suitable ethereal solvents can include, but are not limited to, tetrahydrofuran (THF), 1,2-dimethoxyethane (glyme), bis(2-methoxyethyl) ether (diglyme), triethylene glycol dimethyl ether (triglyme), tetraethylene glycol dimethyl ether (tetraglyme), or any other ethereal solvent capable of solubilizing the functionalized carboranyl magnesium electrolyte employed and suitable to the configuration and requirements of the electrochemical device.
- THF tetrahydrofuran
- glyme 1,2-dimethoxyethane
- diglyme bis(2-methoxyethyl) ether
- triglyme triethylene glycol dimethyl ether
- the functionalized carboranyl magnesium electrolyte will have solubility in any of the aforementioned solvents of at least 0.01 M at 25° C. and atmospheric pressure.
- a functionalized carboranyl magnesium salt of the present disclosure will have higher solubility in a given ethereal solvent than does an analogous carboranyl magnesium salt lacking any functional groups, X or R.
- functionalized carboranyl magnesium salts can be obtained by a salt metathesis reaction between a functionalized carboranyl silver precursor and a magnesium halide.
- a solution of magnesium halide, such as magnesium bromide can be added to a solution of functionalized carboranyl silver salt, such as Ag(CB 11 H 11 (CH 3 )).
- Functionalized carboranyl silver precursor can be prepared fully solvent dry according to published methods. Typically both the magnesium halide and functionalized carboranyl silver reactants would be present in an ethereal solvent such as THF.
- the solid product resulting from reaction of the magnesium halide and the functionalized carboranyl silver salt can be separated from the filtrate by filtration.
- the collected solid is composed of solely silver halide, and the functionalized carboranyl magnesium salt can be obtained by removal of the solvent from the filtrate.
- the collected solid contains the functionalized carboranyl magnesium salt in addition to the silver halide; and the functionalized carboranyl magnesium salt can be purified by extraction with an alkylated glycol, such as tetraglyme.
- the salt metathesis reaction generally proceeds according to Reactions A1 and A2:
- X, R, i, j, and k are as defined above, and Y is fluorine, chlorine, bromine, or iodine, independently of X.
- functionalized carboranyl magnesium salts of the present disclosure can be derived from a wide variety of functionalized carboranyl metal precursor salts using salt metathesis reactions of the type shown in Reactions A1 and A2, and that these reactions are not limited to using silver salts as precursors.
- a functionalized carboranyl cesium salt of the type shown below in Example 1 is a suitable precursor for production of the corresponding functionalized carboranyl magnesium salt via salt metathesis.
- the electrolytes comprising functionalized carboranyl magnesium salts provided herein, when placed under an electric potential in a disclosed electrochemical device, exhibit high oxidative stability of well over 3.0 V (vs. Mg reference). In some instances the oxidative stability of the electrolytes exceeds 3.5 V vs. Mg.
- Mg(CB 11 H 11 (CH 3 )) 2 in tetraglyme has oxidative stability to about 3.5 V vs. Mg on a platinum disk cathode as measured against a magnesium reference electrode, as shown in FIG. 1 .
- the electrolyte containing a functionalized carboranyl magnesium salt supports a similar current density to that of an electrolyte containing an analogous non-functionalized carboranyl magnesium salt, Mg(CB 11 H 12 ) 2 , in an otherwise similarly configured cell.
- the electrolyte containing a functionalized carboranyl magnesium salt has similar oxidative stability compared to that of the electrolyte containing its analogous non-functionalized carboranyl magnesium salt.
- the functionalized and non-functionalized carboranyl magnesium salts are each oxidatively stable in this case at an electrical potential up to about 3.5 V vs. Mg.
- An electrochemical device and having an electrolyte which includes a functionalized carboranyl magnesium salt will, in many implementations, be a magnesium battery wherein a reduction/oxidation reaction according to Reaction B occurs:
- the electrochemical device will be a secondary battery or a subunit of a secondary battery.
- anode refers to an electrode at which magnesium oxidation occurs during device discharge and at which magnesium reduction occurs during device charge.
- cathode refers in such implementations to an electrode at which a cathode material reduction occurs during device discharge and at which a cathode material oxidation occurs during device charge.
- the anode can comprise any material or combination of materials effective to participate in electrochemical oxidation of magnesium during a device discharge.
- the anode can comprise any material or combination of materials effective to participate in electrochemical reduction of magnesium cations and to incorporate reduced magnesium during a device charging event.
- the anode can consist essentially of elemental magnesium (i.e. magnesium atoms having no formal charge) or comprise at least one surface layer of elemental magnesium.
- the anode can comprise a magnesium-containing alloy and/or an insertion-type magnesium electrode such as a tin electrode, containing magnesium in complex or alloy with other materials to the extent the cell is charged.
- the cathode can comprise any material or combination of materials effective to participate in electrochemical insertion of a cathode material during a device discharge.
- the cathode can comprise any material or combination of materials effective to participate in electrochemical extraction of said cathode material during a device charging event.
- the cathode material which is inserted at the cathode during a device discharge and extracted from the cathode during device charging event can comprise magnesium.
- cathode materials can include a Chevrel phase molybdenum composition such as Mo 6 S 8 FeSiO 4 (reversibly MgFeSiO 4 ), MnO 2 , MgFePO 4 , sulfur, organosulfur compounds, an organic cathode material such as poly(2,2,6,6-tetramethyl-piperidinyl-1-oxy-4-yl methacrylate) (PTMA), air or any other suitable materials.
- a Chevrel phase molybdenum composition such as Mo 6 S 8 FeSiO 4 (reversibly MgFeSiO 4 ), MnO 2 , MgFePO 4 , sulfur, organosulfur compounds
- an organic cathode material such as poly(2,2,6,6-tetramethyl-piperidinyl-1-oxy-4-yl methacrylate) (PTMA), air or any other suitable materials.
- PTMA poly(2,2,6,6-tetramethyl-piperidinyl-1-oxy-4
- the electrochemical device can additionally include at least one external conductor, configured to enable electrical communication between the anode and the cathode.
- the at least one external conductor can be a single conductor such as a wire connected at one end to the anode and at an opposite end to the cathode.
- the at least one external conductor can include a plurality of conductors putting the anode and the cathode in electrical communication with a power supply device configured to apply an electric potential to the electrochemical device during a charging event, with other electrical devices situated to receive power from the electrochemical device, or both.
- the process includes a step of contacting an anode and a cathode with an electrolyte comprising a functionalized carboranyl magnesium salt.
- the anode, the cathode, and the electrolyte are all as described above with respect to the disclosed electrochemical device.
- the process can include an additional step of putting the anode and the cathode into electrical communication with one another via at least one external conductor.
- the at least one external conductor when present, is also as described above with reference to the electrochemical device.
- the functionalized carboranyl cesium salt is a suitable precursor for production of the corresponding functionalized carboranyl magnesium salt via salt metathesis.
- Electrochemical testing was conducted in a three-electrode BASi 4 dram shell vial placed inside an MBraun glove box at 25° C. at less than 0.1 ppm O 2 and H 2 O content.
- the electrodes used in all experiments were as follows: working electrode—0.02 cm 2 platinum; counter electrode—magnesium ribbon (BASi); reference electrode—magnesium wire (BASi).
- the working electrode was polished, sonicated, and kept in a dry vacuum oven prior to each experiment. The surfaces of all magnesium electrodes were thoroughly rubbed with a glass slide prior to use to remove any possible oxides.
- Electrochemical testing was conducted using a BioLogic potentiostat operated at a scan rate of 5 mV ⁇ s ⁇ 1 and data were acquired and analyzed with EC-lab Software®.
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Abstract
An electrochemical device is provided having a functionalized carboranyl magnesium electrolyte. Specifically the disclosure relates to an electrochemical device having a magnesium anode, a cathode, a current collector made of non-noble metal, and a functionalized carboranyl magnesium electrolyte. The functionalized carboranyl electrolyte includes a carboranyl anion functionalized with at least one halide, or one alkyl, aryl, alkoxy, aryloxy groups, or their partially or completely fluorinated analogues. In contact with the electrolyte, the non-noble metal cathodic current collector has unusually high oxidative stability >3.0V vs. a magnesium reference. Processes for making the electrochemical device are additionally provided.
Description
- The present disclosure is directed in part to an electrochemical device having a functionalized carboranyl magnesium electrolyte. The present disclosure is also directed to a method for making such an electrolytic cell.
- Magnesium batteries have received significant attention as potential replacements for lithium batteries due to their high volumetric capacity, lack of dendrite formation, and the relative inexpensiveness of magnesium. Discovery and development of suitable electrolytes for magnesium batteries has proven challenging however. Conventional inorganic magnesium salts have typically been found incompatible with reversible magnesium deposition as they tend to form an ion-blocking layer at the magnesium electrode during their electrochemical reduction. On the other hand, organic magnesium salts such as those derived from Grignard reagents have been found to be highly corrosive, particularly toward non-noble cathodes, possibly due to the presence of chloride co-anions.
- Previous studies have shown the electrochemical compatibility and non-corrosiveness of magnesium boron clusters such as MgB12H12 with magnesium electrodes and their use in magnesium batteries. While having comparable electrochemical compatibility and non-corrosiveness in a magnesium cell as compared to the closo-borate containing electrolytes, the carboranyl electrolytes benefit from the inherently superior solubility of carboranyl clusters, relative to closo-borate clusters, in ethereal solvent.
- In order to maximize current density it would be advantageous to develop electrolyte salts for use in magnesium batteries having yet higher solubility in suitable solvents.
- Disclosed, in various non-limiting embodiments, are electrochemical devices having a carboranyl magnesium electrolyte and a process of forming these electrochemical devices.
- An electrochemical device is provided having a magnesium-containing anode, a cathode, and an electrolyte. The electrolyte includes a functionalized carboranyl magnesium salt having a formula of:
-
Mg(CBiH[(i+1)-j-k]XjRk)2, Formula I: -
Mg(C2B(i−1)H(i-j-k)XjRk)2, or Formula II: - a combination of at least two of the foregoing, wherein i is an integer within a range of 5 through 11, inclusive; j is an integer within a range of 0 through i inclusive; k is an integer between 0 and i inclusive; each X, independently of each other X, is fluorine, chlorine, bromine, or iodine; and each R, independently of each other R, is an alkyl, aryl, alkoxy, aryloxy, their partially or completely fluorinated analogues, or a moiety combining the aforementioned functionalities.
- In yet another embodiment, provided herein is a process for preparing an electrochemical device. The process includes a step of connecting a magnesium-containing anode and a cathode via an external electrically conductive structure. The process also includes a step of contacting the anode and cathode with an electrolyte. The electrolyte includes a functionalized carboranyl magnesium salt having a formula of:
-
Mg(CBiH[(i+1)-j-k]XjRk)2, Formula I: -
Mg(C2B(i−1)H(i-j-k)XjRk)2, or Formula II: - a combination of at least two of the foregoing, wherein i is an integer within a range of 5 through 11, inclusive; j is an integer within a range of 0 through i inclusive; k is an integer between 0 and i inclusive; each X, independently of each other X, is fluorine, chlorine, bromine, or iodine; and each R, independently of each other R, is an alkyl, aryl, alkoxy, aryloxy, their partially or completely fluorinated analogues, or a moiety combining the aforementioned functionalities.
- These and other features of the electrochemical device having a functionalized carboranyl magnesium electrolyte, and the process for making the same, will become apparent from the following detailed description when read in conjunction with the figures and examples, which are exemplary, not limiting.
- For a better understanding of the processes and devices having a functionalized carboranyl magnesium electrolyte, with regard to the particular variations and examples discussed herein, reference is made to the accompanying figures, in which:
-
FIG. 1 is a cyclic voltammogram of a platinum (Pt) working electrode in contact with 0.2 M Mg(CB11H11(CH3))2 in tetraethylene glycol dimethyl ether (tetraglyme) at a scan rate of 5 mV/s; and -
FIG. 2 is a cyclic voltammogram of a Pt working electrode in contact with 0.1 M Mg(CB11H12)2 in tetraglyme at a scan rate of 5 mV/s. - The present disclosure provides electrochemical devices having electrolytes that include functionalized carboranyl magnesium salts. The results described here indicate that the present, functionalized carboranyl magnesium salts are capable of mediating reversible magnesium deposition at a magnesium anode, while being relatively non-corrosive and oxidatively stable at the cathodic current collector in a manner previously shown for non-functionalized carboranyl magnesium containing electrolytes. The present electrolytes are functionalized on the carboranyl anion with one or more alkyl or other substantially non-polar moieties in order to increase the electrolyte solubility in ethereal solvent.
- The functionalized carboranyl magnesium salts can thus be particularly beneficial for use as electrolytes in magnesium batteries having a cathodic current collector made of non-noble metals such as stainless steel. The presently disclosed functionalized carboranyl magnesium salts combine the properties of electrochemical compatibility with reversible and repeated magnesium deposition at the magnesium anode, lack of corrosiveness at the cathodic current collector, and high solubility for enhanced energy density.
- Accordingly, provided herein is an electrochemical device that includes an anode; a cathode; and an electrolyte in contact with the anode and the cathode. In general, the electrolyte will contain a salt having at least one magnesium cation (Mg2+) and at least one functionalized carboranyl anion per stoichiometric unit. In some instances, the electrolyte will comprise a functionalized carboranyl magnesium salt having a formula of:
-
Mg(CBiH[(i+1)-j-k]XjRk)2, Formula I: -
Mg(C2B(i−1)H(i-j-k)XjRk)2, or Formula II: - a combination of at least two of the foregoing, wherein i is an integer within a range of 5 through 11, inclusive; j is an integer within a range of 0 through i inclusive; k is an integer between 0 and i inclusive; each X, independently of each other X, is fluorine, chlorine, bromine, or iodine; and each R, independently of each other R, is an alkyl, aryl, alkoxy, aryloxy, their partially or completely fluorinated analogues, or a moiety combining the aforementioned functionalities. In many implementations, at least one of j and k will be equal to or greater than 1. In some implementations, k will be equal to or greater than 1.
- In some implementations, the electrochemical device will include an electrolyte containing a functionalized carboranyl magnesium salt according to Formula I, with or without the other functionalized carboranyl salt according to Formula II.
- As used herein, the term “alkyl” refers to a branched or straight-chain alkyl group having 1 to 18 carbons (C1-C18) which can optionally be partially or completely fluorinated. The term “aryl” as used herein refers to an aromatic hydrocarbon group having 6 to 14 carbons (C6-14), such as phenyl or naphthyl. An aryl can also optionally be partially or completely fluorinated. The term “alkoxy” as used herein refers to group having a formula —Ralk where Ralk is an alkyl as defined above. An alkoxy group can optionally be partially or completely fluorinated. The term “aryloxy” as used herein refers to a group having a formula —Raryl, where Raryl is an aryl group as defined above. An aryloxy group can optionally be partially or completely fluorinated.
- Generally, the functionalized carboranyl anion, represented above as [CBiH[(i+1)-j-k]XjRk]− or [C2B(i−1)H(i-j-k)XjRk]− will be a functionalized anion of a closo-carborane. In some instances, it will be a functionalized anion of an icosahedral-closo-carborane, wherein the cumulative number of carbon and boron atoms, exclusive of H, X, and R groups, is 12.
- In some implementations of the disclosed electrochemical device in which the functionalized carboranyl magnesium salt is a salt according to Formula I, R can be covalently attached to the carbon of the carboranyl anion. In some implementations wherein the functionalized carboranyl magnesium salt is a salt according to Formula I, R can be alkyl. In some such implementations, R can be methyl or hexyl.
- The functionalized carboranyl magnesium salts employed in the electrochemical device described herein are materials that are either soluble or partially soluble in ethereal solvents under normal operating conditions for the associated electrochemical device. Suitable ethereal solvents can include, but are not limited to, tetrahydrofuran (THF), 1,2-dimethoxyethane (glyme), bis(2-methoxyethyl) ether (diglyme), triethylene glycol dimethyl ether (triglyme), tetraethylene glycol dimethyl ether (tetraglyme), or any other ethereal solvent capable of solubilizing the functionalized carboranyl magnesium electrolyte employed and suitable to the configuration and requirements of the electrochemical device. In certain embodiments, the functionalized carboranyl magnesium electrolyte will have solubility in any of the aforementioned solvents of at least 0.01 M at 25° C. and atmospheric pressure. Typically, a functionalized carboranyl magnesium salt of the present disclosure will have higher solubility in a given ethereal solvent than does an analogous carboranyl magnesium salt lacking any functional groups, X or R.
- In some implementations, functionalized carboranyl magnesium salts can be obtained by a salt metathesis reaction between a functionalized carboranyl silver precursor and a magnesium halide. For example, a solution of magnesium halide, such as magnesium bromide can be added to a solution of functionalized carboranyl silver salt, such as Ag(CB11H11(CH3)). Functionalized carboranyl silver precursor can be prepared fully solvent dry according to published methods. Typically both the magnesium halide and functionalized carboranyl silver reactants would be present in an ethereal solvent such as THF. The solid product resulting from reaction of the magnesium halide and the functionalized carboranyl silver salt, can be separated from the filtrate by filtration. In some cases, the collected solid is composed of solely silver halide, and the functionalized carboranyl magnesium salt can be obtained by removal of the solvent from the filtrate. In some instances, the collected solid contains the functionalized carboranyl magnesium salt in addition to the silver halide; and the functionalized carboranyl magnesium salt can be purified by extraction with an alkylated glycol, such as tetraglyme. The salt metathesis reaction generally proceeds according to Reactions A1 and A2:
-
MgY2+2Ag(CBiH[(i+1)-j-k]XjRk)→Mg(CBiH[(i+1)-j-k]XjRk)2+2 AgY, A1, -
MgY2+2Ag(C2B(i−1)H(i-j-k)XjRk)→Mg(C2B(i−1)H(i-j-k)XjRk)2+2AgY, A2, - where X, R, i, j, and k are as defined above, and Y is fluorine, chlorine, bromine, or iodine, independently of X. It is to be understood that functionalized carboranyl magnesium salts of the present disclosure can be derived from a wide variety of functionalized carboranyl metal precursor salts using salt metathesis reactions of the type shown in Reactions A1 and A2, and that these reactions are not limited to using silver salts as precursors. For example, a functionalized carboranyl cesium salt of the type shown below in Example 1 is a suitable precursor for production of the corresponding functionalized carboranyl magnesium salt via salt metathesis.
- The electrolytes comprising functionalized carboranyl magnesium salts provided herein, when placed under an electric potential in a disclosed electrochemical device, exhibit high oxidative stability of well over 3.0 V (vs. Mg reference). In some instances the oxidative stability of the electrolytes exceeds 3.5 V vs. Mg.
- In an example, Mg(CB11H11(CH3))2 in tetraglyme has oxidative stability to about 3.5 V vs. Mg on a platinum disk cathode as measured against a magnesium reference electrode, as shown in
FIG. 1 . ComparingFIG. 1 toFIG. 2 , the electrolyte containing a functionalized carboranyl magnesium salt supports a similar current density to that of an electrolyte containing an analogous non-functionalized carboranyl magnesium salt, Mg(CB11H12)2, in an otherwise similarly configured cell. Additionally, the electrolyte containing a functionalized carboranyl magnesium salt has similar oxidative stability compared to that of the electrolyte containing its analogous non-functionalized carboranyl magnesium salt. The functionalized and non-functionalized carboranyl magnesium salts are each oxidatively stable in this case at an electrical potential up to about 3.5 V vs. Mg. - An electrochemical device according to the present disclosure and having an electrolyte which includes a functionalized carboranyl magnesium salt will, in many implementations, be a magnesium battery wherein a reduction/oxidation reaction according to Reaction B occurs:
- In many implementations, the electrochemical device will be a secondary battery or a subunit of a secondary battery. In such implementations, it is to be understood that the term “anode” as used herein refers to an electrode at which magnesium oxidation occurs during device discharge and at which magnesium reduction occurs during device charge. Similarly, it is to be understood that the term “cathode” refers in such implementations to an electrode at which a cathode material reduction occurs during device discharge and at which a cathode material oxidation occurs during device charge.
- In such implementations, the anode can comprise any material or combination of materials effective to participate in electrochemical oxidation of magnesium during a device discharge. Similarly, the anode can comprise any material or combination of materials effective to participate in electrochemical reduction of magnesium cations and to incorporate reduced magnesium during a device charging event. In some implementations, the anode can consist essentially of elemental magnesium (i.e. magnesium atoms having no formal charge) or comprise at least one surface layer of elemental magnesium. In other implementations, the anode can comprise a magnesium-containing alloy and/or an insertion-type magnesium electrode such as a tin electrode, containing magnesium in complex or alloy with other materials to the extent the cell is charged.
- The cathode can comprise any material or combination of materials effective to participate in electrochemical insertion of a cathode material during a device discharge. Similarly, the cathode can comprise any material or combination of materials effective to participate in electrochemical extraction of said cathode material during a device charging event. In some variations, the cathode material which is inserted at the cathode during a device discharge and extracted from the cathode during device charging event can comprise magnesium. Suitable but non-exclusive examples of cathode materials can include a Chevrel phase molybdenum composition such as Mo6S8 FeSiO4 (reversibly MgFeSiO4), MnO2, MgFePO4, sulfur, organosulfur compounds, an organic cathode material such as poly(2,2,6,6-tetramethyl-piperidinyl-1-oxy-4-yl methacrylate) (PTMA), air or any other suitable materials.
- The electrochemical device can additionally include at least one external conductor, configured to enable electrical communication between the anode and the cathode. In a simple implementation, the at least one external conductor can be a single conductor such as a wire connected at one end to the anode and at an opposite end to the cathode. In other implementations, the at least one external conductor can include a plurality of conductors putting the anode and the cathode in electrical communication with a power supply device configured to apply an electric potential to the electrochemical device during a charging event, with other electrical devices situated to receive power from the electrochemical device, or both.
- Also provided herein is a process for preparing an electrochemical device. The process includes a step of contacting an anode and a cathode with an electrolyte comprising a functionalized carboranyl magnesium salt. The anode, the cathode, and the electrolyte are all as described above with respect to the disclosed electrochemical device. The process can include an additional step of putting the anode and the cathode into electrical communication with one another via at least one external conductor. The at least one external conductor, when present, is also as described above with reference to the electrochemical device.
- Various aspects of the present disclosure are further illustrated with respect to the following Examples. It is to be understood that these Examples are provided to illustrate specific embodiments of the present disclosure and should not be construed as limiting the scope of the present disclosure in or to any particular aspect.
- To a solution of Cs(CB11H12) (1.38 g, 5 mmol) in dry THF (40 mL) under argon, n-BuLi solution in hexane (1.6 M, 6.4 mL, 10.24 mmol) was added drop-wise with stirring at −78° C. The reaction mixture was stirred for 15 min at −78° C., then warmed to 0° C. and further stirred for 1 h. The resulting white suspension was added hexyl iodide (1.9 ml, 12.9 mmol) at 0° C., then the mixture was allowed to warm to room temperature and stirred for 5 h. Water was added slowly and the solvent was removed under vacuum. The residue was extracted with Et2O (3×50 mL), and the resulting solution was washed with a 20% aqueous solution of CsCl (2×50 mL). The combined CsCl wash was extracted with Et2O (3×50 mL). The combined organic phase was dried over Cs2CO3 and evaporated to dryness. The residue was recrystallized from hot water, washed with water and pentane, and dried at under vacuum at 120° C. to obtain Cs(1-Hex-CB11H11) as a white solid. It is to be understood that an analogous route can be employed for the synthesis of Cesium 1-methyl-1-carba-closo-dodecaborate, the precursor to the functionalized carboranyl magnesium salt employed in the electrochemical device of
FIG. 1 . As noted above, the functionalized carboranyl cesium salt is a suitable precursor for production of the corresponding functionalized carboranyl magnesium salt via salt metathesis. - Electrochemical testing was conducted in a three-
electrode BASi 4 dram shell vial placed inside an MBraun glove box at 25° C. at less than 0.1 ppm O2 and H2O content. The electrodes used in all experiments were as follows: working electrode—0.02 cm2 platinum; counter electrode—magnesium ribbon (BASi); reference electrode—magnesium wire (BASi). The working electrode was polished, sonicated, and kept in a dry vacuum oven prior to each experiment. The surfaces of all magnesium electrodes were thoroughly rubbed with a glass slide prior to use to remove any possible oxides. - Electrochemical testing was conducted using a BioLogic potentiostat operated at a scan rate of 5 mV·s−1 and data were acquired and analyzed with EC-lab Software®.
- While particular embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents that are or may be presently unforeseen may arise to applicants or others skilled in the art. Accordingly, the appended claims as filed and as they may be amended, are intended to embrace all such alternatives, modifications variations, improvements, and substantial equivalents.
Claims (11)
1. An electrochemical device, comprising:
an anode comprising magnesium;
a cathode; and
an electrolyte in contact with the anode and the cathode, the electrolyte comprising a functionalized carboranyl magnesium salt having a formula of:
Mg(CBiH[(i+1)-j-k]XjRk)2, Formula I:
Mg(C2B(i−1)H(i-j-k)XjRk)2, or Formula II:
Mg(CBiH[(i+1)-j-k]XjRk)2, Formula I:
Mg(C2B(i−1)H(i-j-k)XjRk)2, or Formula II:
a combination of at least two of the foregoing, wherein i is an integer within a range of 5 through 11, inclusive; j is an integer within a range of 0 through i inclusive; k is an integer between 0 and i inclusive; each X, independently of each other X, is fluorine, chlorine, bromine, or iodine; and each R, independently of each other R, is an alkyl, aryl, alkoxy, aryloxy, their partially or completely fluorinated analogues, or a moiety combining the aforementioned functionalities.
2. The electrochemical device as recited in claim 1 , wherein the electrolyte comprises a functionalized carboranyl magnesium salt having a formula according to Formula I.
3. The electrochemical device as recited in claim 1 , wherein an anion of the functionalized carboranyl magnesium salt of any of formulae I-II is an icosahedral closo-carboranyl anion.
4. The electrochemical device as recited in claim 1 , wherein the functionalized carboranyl magnesium salt is obtained by contacting functionalized carboranyl silver salt with a magnesium halide.
5. The electrochemical device as recited in claim 1 , wherein the electrolyte is stable at an electrical potential greater than 3.0 V.
6. The electrochemical device as recited in claim 1 , wherein the cathode comprises an organic cathode material.
7. A process for preparing an electrochemical device, comprising:
contacting an anode and a cathode with an electrolyte comprising a functionalized carboranyl magnesium salt having a formula of:
Mg(CBiH[(i+1)-j-k]XjRk)2, Formula I:
Mg(C2B(i−1)H(i-j-k)XjRk)2, or Formula II:
Mg(CBiH[(i+1)-j-k]XjRk)2, Formula I:
Mg(C2B(i−1)H(i-j-k)XjRk)2, or Formula II:
a combination of at least two of the foregoing, wherein i is an integer within a range of 5 through 11, inclusive; j is an integer within a range of 0 through i inclusive; k is an integer between 0 and i inclusive; each X, independently of each other X, is fluorine, chlorine, bromine, or iodine; and each R, independently of each other R, is an alkyl, aryl, alkoxy, aryloxy, their partially or completely fluorinated analogues, or a moiety combining the aforementioned functionalities.
8. The process as recited in claim 7 , wherein the electrolyte comprises a functionalized carboranyl magnesium salt having a formula according to Formula I.
9. The process as recited in claim 7 , wherein the functionalized carboranyl magnesium salt comprises an icosahedral closo-carboranyl anion.
10. The process as recited in claim 7 , wherein the functionalized carboranyl magnesium salt is obtained by contacting functionalized carboranyl silver salt with a magnesium halide.
11. The process as recited in claim 7 , wherein the electrolyte is stable at an electrical potential greater than 3.0V.
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US9240613B2 (en) | 2013-05-25 | 2016-01-19 | Toyota Motor Engineering & Manufacturing North America, Inc. | Carboranyl magnesium electrolyte for magnesium battery |
US9252458B2 (en) * | 2013-05-25 | 2016-02-02 | Toyota Motor Engineering & Manufacturing North America, Inc. | Carboranyl magnesium electrolyte for magnesium battery |
JP2015041572A (en) * | 2013-08-23 | 2015-03-02 | 株式会社豊田中央研究所 | Inorganic magnesium solid electrolyte, magnesium battery, electrochemical device and method for producing inorganic magnesium solid electrolyte |
JP6287649B2 (en) * | 2014-07-08 | 2018-03-07 | 株式会社村田製作所 | Electrolytic solution and electrochemical device |
-
2014
- 2014-12-23 US US14/581,768 patent/US20160181662A1/en not_active Abandoned
-
2015
- 2015-08-14 US US14/826,488 patent/US9431678B2/en active Active
- 2015-12-21 CN CN201510962133.1A patent/CN105720299B/en active Active
- 2015-12-22 JP JP2015249514A patent/JP6101337B2/en active Active
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
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CN108123170A (en) * | 2016-11-28 | 2018-06-05 | 丰田自动车工程及制造北美公司 | There is the high concentration electrolyte for magnesium accumulator of carbon boronation magnesium salts in ether solvents are mixed |
DE102017125383B4 (en) | 2016-11-28 | 2022-12-15 | Toyota Jidosha Kabushiki Kaisha | ELECTROCHEMICAL DEVICE AND METHOD OF MANUFACTURE THE SAME |
EP3422457A1 (en) * | 2017-06-28 | 2019-01-02 | Panasonic Intellectual Property Management Co., Ltd. | Lithium secondary battery |
US10680280B2 (en) | 2017-09-26 | 2020-06-09 | Toyota Jidosha Kabushiki Kaisha | 3D magnesium battery and method of making the same |
US11777135B2 (en) | 2017-09-26 | 2023-10-03 | Toyota Motor Engineering & Manufacturing North America, Inc. | 3D magnesium battery and method of making the same |
US20200091553A1 (en) * | 2018-09-13 | 2020-03-19 | Toyota Motor Engineering & Manufacturing North America, Inc. | Gel electrolyte for use in a magnesium battery |
US10840550B2 (en) * | 2018-09-13 | 2020-11-17 | Toyota Motor Engineering & Manufacturing North America, Inc. | Gel electrolyte for use in a magnesium battery |
Also Published As
Publication number | Publication date |
---|---|
US20160181663A1 (en) | 2016-06-23 |
JP6101337B2 (en) | 2017-03-22 |
JP2016119307A (en) | 2016-06-30 |
CN105720299A (en) | 2016-06-29 |
US9431678B2 (en) | 2016-08-30 |
CN105720299B (en) | 2019-10-29 |
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