CN105047987B - 用于镁蓄电池的不含氯化物的电解质和将镁电解质转化为不含氯化物的电解质的方法 - Google Patents
用于镁蓄电池的不含氯化物的电解质和将镁电解质转化为不含氯化物的电解质的方法 Download PDFInfo
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- CN105047987B CN105047987B CN201510211870.8A CN201510211870A CN105047987B CN 105047987 B CN105047987 B CN 105047987B CN 201510211870 A CN201510211870 A CN 201510211870A CN 105047987 B CN105047987 B CN 105047987B
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- magnesium
- formula
- salt
- borate
- anion
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- 239000011777 magnesium Substances 0.000 title claims abstract description 176
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 99
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 239000003792 electrolyte Substances 0.000 title claims abstract description 41
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 37
- 150000003839 salts Chemical class 0.000 claims abstract description 43
- 238000005342 ion exchange Methods 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- JSJVLOHJGMWSOG-UHFFFAOYSA-N B([O-])([O-])[O-].[C+4].B([O-])([O-])[O-].B([O-])([O-])[O-].B([O-])([O-])[O-].[C+4].[C+4] Chemical compound B([O-])([O-])[O-].[C+4].B([O-])([O-])[O-].B([O-])([O-])[O-].B([O-])([O-])[O-].[C+4].[C+4] JSJVLOHJGMWSOG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 159000000003 magnesium salts Chemical class 0.000 claims abstract description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 70
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 50
- 239000002904 solvent Substances 0.000 claims description 48
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 33
- 150000001450 anions Chemical class 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 26
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 claims description 24
- -1 Mo6S8 Inorganic materials 0.000 claims description 21
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 19
- 229910006400 μ-Cl Inorganic materials 0.000 claims description 19
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 17
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 15
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 15
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 229910001623 magnesium bromide Inorganic materials 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 125000005037 alkyl phenyl group Chemical group 0.000 claims description 8
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 7
- 230000005611 electricity Effects 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 239000007818 Grignard reagent Substances 0.000 claims description 5
- 150000001721 carbon Chemical group 0.000 claims description 5
- 150000004795 grignard reagents Chemical class 0.000 claims description 5
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 5
- 229910021645 metal ion Inorganic materials 0.000 claims description 5
- 229910000085 borane Inorganic materials 0.000 claims description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 4
- 239000011736 potassium bicarbonate Substances 0.000 claims description 4
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 4
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 claims description 4
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 4
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 3
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 claims description 3
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 3
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 3
- 239000013543 active substance Substances 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical group 0.000 claims description 3
- 125000001891 dimethoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 3
- 238000006467 substitution reaction Methods 0.000 claims description 3
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 claims description 3
- 229910016511 CuCr2S4 Inorganic materials 0.000 claims description 2
- 229910019373 Mg0.5VPO4F Inorganic materials 0.000 claims description 2
- 229910020111 MgCr2S4 Inorganic materials 0.000 claims description 2
- 229910017839 MgFe2(PO4)3 Inorganic materials 0.000 claims description 2
- 229910017925 MgMn2O4 Inorganic materials 0.000 claims description 2
- 229910017896 MgMnSiO4 Inorganic materials 0.000 claims description 2
- 229910017678 MgV2(PO4)3 Inorganic materials 0.000 claims description 2
- 229910017686 MgV2O5 Inorganic materials 0.000 claims description 2
- 229910017666 MgVO3 Inorganic materials 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims description 2
- 229910001310 TiP2O7 Inorganic materials 0.000 claims description 2
- 229910003092 TiS2 Inorganic materials 0.000 claims description 2
- 229910000540 VOPO4 Inorganic materials 0.000 claims description 2
- 229910052946 acanthite Inorganic materials 0.000 claims description 2
- 235000009508 confectionery Nutrition 0.000 claims description 2
- 239000000284 extract Substances 0.000 claims description 2
- 229910052961 molybdenite Inorganic materials 0.000 claims description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- FSJWWSXPIWGYKC-UHFFFAOYSA-M silver;silver;sulfanide Chemical compound [SH-].[Ag].[Ag+] FSJWWSXPIWGYKC-UHFFFAOYSA-M 0.000 claims description 2
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 claims description 2
- MXSVLWZRHLXFKH-UHFFFAOYSA-N triphenylborane Chemical compound C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1 MXSVLWZRHLXFKH-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims 3
- 230000001376 precipitating effect Effects 0.000 claims 3
- 239000011521 glass Substances 0.000 claims 2
- 239000012266 salt solution Substances 0.000 claims 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims 1
- 229910003481 amorphous carbon Inorganic materials 0.000 claims 1
- 239000004917 carbon fiber Substances 0.000 claims 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims 1
- 239000002296 pyrolytic carbon Substances 0.000 claims 1
- 125000000547 substituted alkyl group Chemical group 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 14
- 239000002184 metal Substances 0.000 abstract description 14
- 150000002500 ions Chemical group 0.000 abstract description 6
- 150000001642 boronic acid derivatives Chemical class 0.000 abstract description 3
- 229910052783 alkali metal Inorganic materials 0.000 abstract 1
- 150000001340 alkali metals Chemical class 0.000 abstract 1
- 229940091250 magnesium supplement Drugs 0.000 description 68
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 210000004027 cell Anatomy 0.000 description 11
- 229910001220 stainless steel Inorganic materials 0.000 description 10
- 239000010935 stainless steel Substances 0.000 description 10
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 239000001103 potassium chloride Substances 0.000 description 8
- 235000011164 potassium chloride Nutrition 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 239000004210 ether based solvent Substances 0.000 description 7
- 230000026030 halogenation Effects 0.000 description 7
- 238000005658 halogenation reaction Methods 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 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 description 7
- 238000001819 mass spectrum Methods 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- 239000002841 Lewis acid Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 210000001787 dendrite Anatomy 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000012259 ether extract Substances 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 150000007517 lewis acids Chemical class 0.000 description 3
- 150000002680 magnesium Chemical class 0.000 description 3
- IWCVDCOJSPWGRW-UHFFFAOYSA-M magnesium;benzene;chloride Chemical compound [Mg+2].[Cl-].C1=CC=[C-]C=C1 IWCVDCOJSPWGRW-UHFFFAOYSA-M 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- 125000006850 spacer group Chemical group 0.000 description 3
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 2
- LEEANUDEDHYDTG-UHFFFAOYSA-N 1,2-dimethoxypropane Chemical compound COCC(C)OC LEEANUDEDHYDTG-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229920006370 Kynar Polymers 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000005030 aluminium foil Substances 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 229910021397 glassy carbon Inorganic materials 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229940096405 magnesium cation Drugs 0.000 description 2
- QUXHCILOWRXCEO-UHFFFAOYSA-M magnesium;butane;chloride Chemical compound [Mg+2].[Cl-].CCC[CH2-] QUXHCILOWRXCEO-UHFFFAOYSA-M 0.000 description 2
- CCERQOYLJJULMD-UHFFFAOYSA-M magnesium;carbanide;chloride Chemical compound [CH3-].[Mg+2].[Cl-] CCERQOYLJJULMD-UHFFFAOYSA-M 0.000 description 2
- FRIJBUGBVQZNTB-UHFFFAOYSA-M magnesium;ethane;bromide Chemical compound [Mg+2].[Br-].[CH2-]C FRIJBUGBVQZNTB-UHFFFAOYSA-M 0.000 description 2
- YCCXQARVHOPWFJ-UHFFFAOYSA-M magnesium;ethane;chloride Chemical compound [Mg+2].[Cl-].[CH2-]C YCCXQARVHOPWFJ-UHFFFAOYSA-M 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920005596 polymer binder Polymers 0.000 description 2
- 239000002491 polymer binding agent Substances 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- 238000004293 19F NMR spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical class CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- FVIGODVHAVLZOO-UHFFFAOYSA-N Dixanthogen Chemical compound CCOC(=S)SSC(=S)OCC FVIGODVHAVLZOO-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229920007859 Kynar® HSV 900 Polymers 0.000 description 1
- 239000012448 Lithium borohydride Substances 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 229910017836 MgFe2(PO4)2 Inorganic materials 0.000 description 1
- 239000002228 NASICON Substances 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 240000007817 Olea europaea Species 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- CHBCHAGCVIMDKI-UHFFFAOYSA-N [F].C=C Chemical group [F].C=C CHBCHAGCVIMDKI-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 150000001638 boron Chemical class 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Substances FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910001914 chlorine tetroxide Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical class O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000012500 ion exchange media Substances 0.000 description 1
- SHXXPRJOPFJRHA-UHFFFAOYSA-K iron(iii) fluoride Chemical compound F[Fe](F)F SHXXPRJOPFJRHA-UHFFFAOYSA-K 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- DMFBPGIDUUNBRU-UHFFFAOYSA-N magnesium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Mg+2].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F DMFBPGIDUUNBRU-UHFFFAOYSA-N 0.000 description 1
- KJJBSBKRXUVBMX-UHFFFAOYSA-N magnesium;butane Chemical compound [Mg+2].CCC[CH2-].CCC[CH2-] KJJBSBKRXUVBMX-UHFFFAOYSA-N 0.000 description 1
- LWLPYZUDBNFNAH-UHFFFAOYSA-M magnesium;butane;bromide Chemical compound [Mg+2].[Br-].CCC[CH2-] LWLPYZUDBNFNAH-UHFFFAOYSA-M 0.000 description 1
- 229910000473 manganese(VI) oxide Inorganic materials 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
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- 230000001590 oxidative effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 125000005062 perfluorophenyl group Chemical group FC1=C(C(=C(C(=C1F)F)F)F)* 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 1
- 210000002706 plastid Anatomy 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
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- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
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- 230000002441 reversible effect Effects 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
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- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
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Abstract
本发明提供了用于镁蓄电池的不含氯化物的电解质和将镁电解质转化为不含氯化物的电解质的方法。具体地,提供了制备不含氯化物的镁电解质盐的方法。根据该方法将水稳定的硼酸根类或碳硼酸根类阴离子通过离子交换转化为碱金属或银的金属盐并且随后通过另一次离子交换转化为不含氯化物的镁盐。还提供了适合作为用于镁蓄电池的电解质的不含氯化物的镁盐和含有该不含氯化物的镁电解质的镁蓄电池。
Description
发明背景
发明领域
本发明涉及制备不含氯化物的镁电解质的方法和含有该不含氯化物的活性物质的镁电解质。
背景讨论
镁蓄电池已经成为高度关注和重要的研究和开发工作的主题,以便提供更经济、更安全和更高容量的蓄电池来替代或补充常规锂蓄电池。与锂相比,Mg潜在地具有3832mAhcm-3的体积容量,这明显大于Li的2062mAh cm-3。另外,Mg具有相对于NHE为-2.356V的负还原电势。作为地壳中最丰富元素的第七位,Mg具有较低的来源成本和较低的环境影响程度(参见Aurbach:Nature,第407卷,第724-727页,2000,)。
明显地,Mg不会经受枝晶形成,枝晶形成使得Li金属对于作为高容量阳极材料的商业化是不安全的(West:Journal of Electrochemical Communications,第155卷,第A806-A811页,2008)。
蓄电池研究中持续的目标是增加能量密度超过由锂离子蓄电池所提供的能量密度。这可需要向含有纯金属阳极的蓄电池转移。然而,在锂的情况下,沉积发生不均匀,形成枝晶,这导致在循环期间的安全问题。与锂金属相比,镁金属沉积不受枝晶形成所困扰。另外,当暴露于空气时,镁比锂稳定。然而,镁具有相对于NHE为-2.36V的还原电势并且具有独特的电化学,这排除了镁电解质的使用,该镁电解质为锂电解质的类似物。镁类似物例如Mg(PF6)2、Mg(ClO4)2和Mg(TFSI)2的还原导致在镁阳极表面上形成烫印膜,通过该烫印膜没有观察到成功的镁沉积。(Feng,Z:Surface Coating Technologies,第201卷,第3783-3787页,2006)
由醚类溶液中的格氏试剂的有效镁电沉积的报道远追溯回到1927年并且从那时起定期地出现在文献中。在增强基于格氏剂的电镀浴的稳定性的尝试中,1957年Connor等人调查了由通过MgBr2和LiBH4的反应原位产生的硼氢化镁Mg(BH4)2电沉积镁。遗憾的是,硼与镁以1:9的比例共沉积。近来Mohtadi等人展示了使用硼氢化镁作为用于镁蓄电池的电解质。报道Mg(BH4)2的氧化稳定性与格氏溶液相似。然而,在开发高电压可再充电的镁蓄电池中的一个障碍是超越格氏剂例如溴化乙基镁(EtMgBr)和氯化丁基镁(BuMgCl)的氧化稳定性,格氏剂具有相对于Mg为1.3V的氧化稳定性。格氏溶液的低氧化稳定性限制了可用阴极的选择。1990年Gregory等人由二丁基镁与路易斯酸三正丁基硼烷的反应合成了电解质Mg(B(C4H9)4)2,其显示了相对于BuMgBr增强的氧化稳定性。认为路易斯酸的特点可能为改进电压稳定性的一个因素。通过用三氯化铝(AlCl3)强化烷基格氏剂例如氯化乙基镁(EtMgCl)和氯化甲基镁(MeMgCl)以增强电化学镀覆,Gregory还评价了镁沉积物品质。
Aurbach等人推广了一种新型的电解质,称为有机卤化铝酸镁。这样的一种称为APC的电解质通过三氯化铝(AlCl3)与格氏氯化苯基镁(PhMgCl)以1:2的比例反应而原位产生并且具有相对于Mg超过3.2V的氧化稳定性,并且可以以高库伦效率沉积/溶解镁。所有结晶的有机卤化铝酸镁具有通用阳离子
(Mg2(μ-Cl)3·6THF)+
并且它们的氧化还原稳定性由它们独特的阴离子确定。有机卤化铝酸镁电解质在惰性电极(相对于Mg高于3.0V)例如Pt或玻璃碳上具有高氧化稳定性并且在高电流下能够沉积和提取镁。然而,报道它们对于不太贵重的金属例如铝、镍和不锈钢为腐蚀性的,由于在壳体和集流体材料中利用这样的金属,这限制了硬币式蓄电池组电池结构中低于2.2V充电。由于电解质的氧化稳定性控制阴极的选择,开发将可探索高电压阴极的非腐蚀性镁电解质具有至高的重要性。改进镁电解质在不锈钢上的电压稳定性是关键的,因为不锈钢是广泛使用的集流体和各种蓄电池例如硬币式电池中的主要部件。目前现有技术的有机卤化铝酸镁电解质限制了Mg蓄电池硬币式电池在低于相对于Mg为2.3V下工作的使用。已经很好地证明氯离子是一些最严重的腐蚀离子,其不均匀地侵蚀金属表面,形成点蚀。然而,在本发明之前,没有发现确定镁电解质的氯离子含量的问题和描述尝试制备不含氯化物的镁电解质的报道。
Yamamoto等人(U.S.2013/0337328)描述了镁电化学电池,其含有镁金属或金属合金作为负电极、石墨氟化物/铜正电极和电解质,该电解质为处于醚溶剂(1,2二甲氧基乙烷)中的络合镁金属离子、烷基三氟甲烷磺酸酯和/或盐、季铵盐和/或甲基咪唑盐的混合物。该混合物还包含卤化铝(AlCl3)并且在溶解镁和氯化铝之后添加三氟化硼的醚络合物。将一些硼盐描述为可能的组分。然而,这篇参考文献没有任何地方确定了由电解质的氯化物含量所致的问题或者公开或建议了制备不含氯化物的镁络合物盐作为电解质。
本发明人(U.S.2013/0034780)(U.S.8,318,354)描述了镁络合物盐的合成和结构鉴定,该镁络合物盐可为用于本发明的基本起始材料。然而,没有公开或建议转化为不含氯化物的络合物。
Singh等人(U.S.2013/0266851)描述了具有负电极的镁电化学电池,该负电极含有锡作为活性组分。采用了常规已知的电解质例如基于格氏的体系和双(三氟甲烷磺酰基)酰亚胺镁。然而,这篇文献没有任何地方确定了由电解质的氯化物含量所致的问题或者公开或建议了制备不含氯化物的镁络合物盐作为电解质。
Itaya等人(U.S.2004/0137324)描述了用于镁蓄电池的电解质,其由处于非水有机溶剂例如碳酸酯、醚或熔融盐中的双三氟甲烷磺酰亚胺镁组成。然而,这篇文献没有任何地方确定了由电解质的氯化物含量所致的问题或者公开或建议了制备不含氯化物的镁络合物盐作为电解质。
发明人的初始假设是有机卤化铝酸镁电解质的腐蚀性特点的一个可能原因是镁盐的阳离子(Mg2(μ-Cl)3·6THF)+中的氯离子的存在。因此本发明的一个目的是发现制备不含氯化物的镁电解质的方法,该不含氯化物的镁电解质与用于镁蓄电池中的非贵金属例如Al、Cu和不锈钢为兼容的。
本发明的另一个目的是制备用于镁蓄电池的不含氯化物的电解质。
本发明的另一个目的是提供采用该不含氯化物的镁电解质的镁电化学电池和含有该电化学电池的镁蓄电池。
发明概述
通过本发明实现了这些和其它的目的,本发明的第一实施方案包括制备式(I)的镁盐的方法:
[A]2Mg(Solvent)y (I)
其中Solvent是包含醚氧的非水溶剂并且y为2到6的整数,且A为水稳定的硼酸根类阴离子或碳硼酸根类阴离子。该方法包括根据反应式(c)在非水溶剂(溶剂)中Mg2+对金属离子M+的至少一种离子交换操作:
2(A-M+)+MgBr2→A2Mg(溶剂)y+2MBr(s) (c)
其中M+为选自Li+、Na+、K+、Rb+、Cs+和Ag+中的至少一种。
在本发明选择的实施方案中,金属M可为钾(K)或银(Ag)并且在该方法的另一种实施方案中二次交换,其中首先制备KA并且随后通过离子交换将KA转化为AgA,进而根据反应式(c)将AgA转化为镁电解质。
在一个特定的实施方案中,阴离子A为式(II)的硼酸根类阴离子:
(BR4)- (II)
其中R基团每个独立地为任选用F取代的1-6个碳原子的烷基、任选用F取代的芳基和任选用F取代的烷基苯基。
在特别的实施方案中,式(II)的硼酸根类阴离子为式(IV)的阴离子:
[BPh4]- (IV)
其中每个Ph基团独立地为任选用F取代的芳基和任选用F取代的烷基苯基。
在另一个实施方案中,阴离子A为式(III)的碳硼酸根类阴离子:
(C2B10H11)- (III)
其中碳硼酸根类离子为邻碳硼烷(ortho-carborane)、间碳硼烷(meta-carborane)或对碳硼烷(para-carborane)的阴离子。
在又一个实施方案中,本发明包括式(I)的镁电解质:
[A]2Mg(Solvent)y (I)
其中Solvent是包含醚氧的非水溶剂并且y为2到6的整数,A为水稳定的硼酸根类阴离子或碳硼酸根类阴离子中的至少一种,并且镁电解质盐不含氯化物。
在特殊的实施方案中,电解质包含式(V)的硼酸根类阴离子和/或式(VI)的硼酸根类阴离子作为阴离子A:
[(C6F5)3BPh]- (V)
[(Mes)3BPh]- (VI)
其中Mes为3,5-二甲基苯基。
本发明还包括镁蓄电池,其包含:包含镁的负电极;正电极;溶剂;和式(I)的镁电解质:
[A]2Mg(Solvent)y (I)
其中式(I)的Solvent为包含醚氧的非水溶剂并且y为2到6的整数,A为水稳定和空气稳定的硼酸根类阴离子或碳硼酸根类阴离子中的至少一种,并且镁电解质不含氯化物。
前述描述旨在提供本发明的整体介绍和概述,并不旨在限制于其公开内容,除非另有明确说明。参考结合附图的以下详细描述将最好地理解目前优选的实施方案连同进一步的优点。
附图简要描述
图1显示了在实施例中制备的(PhB(C6F5)3)K的ORTEP曲线(25%热概率椭圆体)。为清楚起见,省略了氢原子。
图2显示了在实施例中制备的钾盐((PhB(C6F5)3)K2)+的质谱。
图3显示了在实施例中制备的银盐((PhB(C6F5)3)Ag2)+的质谱。
图4显示了在实施例中制备的(PhB(C6F5)3)2Mg的ORTEP曲线(25%热概率椭圆体)。为清楚起见,省略了氢原子。
发明详细描述
在本发明的描述中,通过引用将在作者、合作者名下或归于受让人成员的所有引用的参考文献、专利、申请、出版物和文章并入本文。在说明数目限制或范围时,包括端点。此外,如同明确书写出的那样,具体包括了在数目限制或范围内的所有值和子范围。如本文中使用的,词语“一个”和“一种”等带有“一个(种)或多个(种)”的含义。短语“选自由…组成的组”、“选自”等包括指定材料的混合物。术语例如“包含”等为意指“至少包括”的开放性术语,除非另有具体说明。
如上所述,在调查特别适合用于镁电化学电池和/或可逆的镁蓄电池的电解质体系的过程中本发明人认识到所关注的特定电解质的基本组分为下式的镁二聚物:
(Mg2(μ-Cl)3·6THF)+。
由结合的阴离子确定该特定电解质的氧化还原稳定性。有机卤化铝酸镁电解质在惰性电极例如Pt或玻璃碳上具有高氧化稳定性(相对于Mg高于3.0V)并且能够在高电流下沉积和提取镁。然而,报道它们对于较不贵重的金属例如铝、镍和不锈钢为腐蚀性的,由于在壳体和集流体材料中利用这样的金属,这限制了在硬币式蓄电池组结构中的充电低于2.2V。由于电解质的氧化稳定性控制阴极的选择,开发与高电压阴极结合的非腐蚀性镁电解质对于开发具有经济上有吸引力的较高容量和稳定性的高效镁蓄电池为必要的。这样的经济上有吸引力的蓄电池将采用金属例如铝、铜和不锈钢,所有这些在氯离子的存在下经受腐蚀和点蚀。
为了解决这个问题,本发明提供了制备不含氯化物的镁电解质的方法,其中在镁离子由溶剂分子配位并且没有如在有机卤化铝酸盐电解质中常规形成的络合物二聚物中显示的那样与氯化物络合的意义上说镁离子是“裸露的”。
因此,在第一实施方案中,本发明提供了制备式(I)的镁盐的方法:
[A]2Mg(Solvent)y (I)
其中Solvent是包含醚氧的非水溶剂,y为2到6的整数,并且A为空气稳定和水稳定的硼酸根类阴离子或碳硼酸根类阴离子中的至少一种。该方法包括根据反应式(c)在非水溶剂(溶剂)中Mg2+对金属离子M+的至少一种离子交换操作:
2(A-M+)+MgBr2→A2Mg(溶剂)y+2MBr(s) (c)
其中M+为选自Li+、Na+、K+、Rb+、Cs+和Ag+中的至少一种。
本发明的方法的总体效果是将镁二聚物[(Mg2(μ-Cl)3·6THF)+][A-]的盐转化为不与氯离子配位的非二聚物镁阳离子。
可以通过格氏试剂与合适的三取代的硼路易斯酸或与碳硼烷反应来获得为空气稳定和水稳定的硼酸根类或碳硼酸根类的阴离子A-。在两者之一的情况下,获得了含有阴离子与(Mg2(μ-Cl)3·6THF)+的络合物盐。可将该络合物盐从混合物分离和隔离。随后,经由含水离子交换反应A-可转化为金属(M)离子的盐,其中M为选自Li、Na、K、Rb、Cs和Ag中的至少一种。该离子交换可由反应式描述:
[Mg2(μ-Cl)3·6THF]+A-+M2CO3+MHCO3→MA+[Mg2(μ-Cl)3·6THF]+
因为在含水介质中进行离子交换,所以本领域技术人员将认识到所述的离子交换可仅为有效的,只要阴离子A-对于在含水离子交换介质中的分解或降解是稳定的。
根据一个实施方案,M为K并且该离子交换由反应式(a)描述:
[Mg2(μ-Cl)3·6THF]+A-+K2CO3+KHCO3→KA+[Mg2(μ-Cl)3·6THF]+ (a)
根据另一个实施方案,M为Ag并且可以书写类似于(a)的反应式来描述该离子交换。
阴离子A-可为式(II)的硼酸根类阴离子:
(BR4)- (II)
其中R基团每个独立地为任选用F取代的1-6个碳原子的烷基、任选用F取代的芳基和任选用F取代的烷基芳基。
根据本发明的实施方案,式(II)的硼酸根类阴离子为式(IV)的阴离子:
[BPh4]- (IV)
其中每个Ph基团独立地为任选用F取代的芳基和任选用F取代的烷基苯基。这个实施方案的明确的阴离子包括式(V)的阴离子:
[(C6F5)3B(C6H5)]- (V);或
式(VI)的阴离子:
[(Mes)3B(C6H5)]- (VI)
其中Mes为3,5-二甲基苯基。
在完成离子交换以形成MA时,可通过醚提取从离子交换反应介质中提取MA。MA溶解在醚中并且可将醚提取物从水相分离并在减小的压力下蒸发醚以获得固体形式的MA盐。
根据本发明的方法,如在以下段落中描述的由醚提取物获得的MA可直接转化为A2Mg(Solvent)y电解质盐,或者在MA盐为其中M为Li+、Na+、K+、Rb+或Cs+的盐的情况下,可以根据以下反应式使该盐在乙腈中的第二离子交换反应中进一步反应:
MA+AgNO3→AgA+MNO3(s)。
在优选实施方案中,首先在如上所述的离子交换中制备并且如所述的由醚提取物获得钾盐(KA)。随后根据以下反应式经由在乙腈中的离子交换KA可转化为Ag盐:
KA+AgNO3→AgA+KNO3(s)。
促进了这种交换,因为AgA盐在乙腈中为可溶的,而硝酸钾沉淀为固体。
或者,根据反应式(c)通过2当量的MA与1当量的溴化镁在非水醚溶剂中的离子交换反应,MA盐可转化为镁盐:
2(A-M+)+MgBr2→A2Mg(Solvent)y+2MBr(s) (c)
非水醚溶剂为含有醚氧的任何溶剂并且包括例如四氢呋喃(THF)、二甲氧基乙烷(DME)和二乙二醇二甲醚(二甘醇二甲醚)(DGM)。这些实例并不旨在限制并且任何单配位基、双配位基或三配位基醚可为合适的,只要不存在对于阴离子A-为反应性的其它基团。四氢呋喃可为用于进行反应式(c)的离子交换的优选醚溶剂。在THF中进行的反应式(c)的示例性实例由以下反应式表示:
2((C6H5)B(C6F5)3)Ag+MgBr2→((C6H5)B(C6F5)3)2Mg(THF)6+2AgBr
式(VII)
2((C6H5)B(Mes)3)Ag+MgBr2→((C6H5)B(C6H5)3)2Mg(THF)6+2AgBr
式(VIII)
AgBr沉淀物是离子交换反应发生的指示。可由醚溶剂通过用烃溶剂例如己烷、环己烷或石油醚进行分层来获得不含氯化物的镁电解质盐的晶体。可以使所获得的晶体从芳族溶剂例如甲苯或二甲苯中结晶。
在另一个实施方案中,本发明提供不含氯化物的镁电解质盐,该镁电解质盐通过上述的离子交换方法获得。所述的方法可为普遍用于制备为不含氯化物并且在此方面被描述为“裸露的”镁盐。如实施例的描述中所指出的,镁由溶剂分子配位。当溶剂为THF时,单配位基配体,总共六个分子可以存在。然而,如果使该盐从溶剂例如甲苯中结晶,那么甲苯可部分替代镁离子附近的溶剂球中的THF。
在又一个实施方案中,本发明提供了镁蓄电池,其包含:
包含镁的负电极;
正电极;
溶剂;和
式(I)的电解质盐:
[A]2Mg(溶剂)y (I)
其中
溶剂为包含醚氧的非水溶剂并且y为2到6的整数。
在本发明的又一个实施方案中,镁蓄电池包含至少一个不锈钢部件,并且在一个优选实施方案中,用于镁蓄电池的集流体为不锈钢。
这种式(I)的电解质在醚溶剂例如四氢呋喃、聚醚、2-甲基四氢呋喃、二甲氧基乙烷、二甲基乙二醇、甘醇二甲醚、单甘醇二甲醚、乙二醇、甲醚、乙醚、乙基甘醇二甲醚、二甘醇二甲醚、丙二醇二甲醚(proglyme)、乙基二甘醇二甲醚、三甘醇二甲醚、丁基二甘醇二甲醚、四甘醇二甲醚、聚甘醇二甲醚、higlyme或其组合。还可以将这种盐[A]2Mg(Solvent)y溶解在含醚溶剂中并且将它浸渍在聚合物膜中以形成聚合物基电解质。
Mg蓄电池的正电极可包含对于式(I)的Mg电解质为稳定的任何正电极活性物质。这样的正电极活性物质的实例可包括硫,Chevrel相Mo6S8、MnO2、CuS、Cu2S、Ag2S、CrS2、VOPO4,层状结构化合物例如TiS2、V2O5、MgVO3、MoS2、MgV2O5、MoO3,尖晶石结构化合物例如CuCr2S4、MgCr2S4、MgMn2O4、Mg2MnO4,NASICON结构化合物例如MgFe2(PO4)3和MgV2(PO4)3,橄榄石结构化合物例如MgMnSiO4和MgFe2(PO4)2,Tavori te结构化合物例如Mg0.5VPO4F,焦磷酸盐例如TiP2O7和VP2O7,以及氟化物例如FeF3。
根据常规实践,正电极还可包含导电性添加剂,例如炭黑,Super P,Super C65,Ensaco黑,科琴黑,乙炔黑,合成石墨例如Timrex SFG-6、Timrex SFG-15、Timrex SFG-44、Timrex KS-6、Timrex KS-15、Timrex KS-44,天然片状石墨、碳纳米管、富勒烯、硬碳和中间碳微球。
另外,正电极还可包含聚合物黏结剂。聚合物黏结剂的非限制性实例包括聚偏氟乙烯(PVdF)、聚(偏氟乙烯-共-六氟丙烯)(PVdF-HFP)、聚四氟乙烯(PTFE)、Kynar Flex2801、Kynar Powerflex LBG和Kynar HSV 900以及Teflon。聚偏氟乙烯(PVdF)是优选的粘合剂。
Mg蓄电池中合适的溶剂可为对于镁和蓄电池的其它组分(包括式(I)的镁盐)为相容的任何非质子溶剂。在所要求保护的Mg蓄电池中可包括选自四氢呋喃、2-甲基四氢呋喃、二甲氧基乙烷、甘醇二甲醚、单甘醇二甲醚、二甲基乙二醇、甲醚、乙醚、乙基甘醇二甲醚、二甘醇二甲醚、丙二醇二甲醚、乙基二甘醇二甲醚、三甘醇二甲醚、丁基二甘醇二甲醚、四甘醇二甲醚、聚甘醇二甲醚、higlyme或其组合的常规溶剂。
将含有卤化物的溶剂和卤化物盐从如上所述的Mg蓄电池中排除。
根据本发明的Mg蓄电池可通过常规已知的方法构造并且可为由在罐基底(在其上卷有罐盖)中的负电极、多孔聚丙烯或玻璃纤维分隔体和正电极盘的堆叠体组成的纽扣或硬币式蓄电池组。或者,Mg蓄电池可为堆叠的蓄电池组。在其它实施方案中,Mg蓄电池可为由如上所述的负电极、多孔聚丙烯或玻璃纤维分隔体和夹在集流体之间的正电极的一个或多个堆叠体组成的棱柱或袋状电池。可将(一个或多个)堆叠体在经聚合物涂覆的铝箔袋中折叠,真空和热干燥,用电解质进行填充,并且真空和热密封。在其它实施方案中,Mg蓄电池可为由在两侧上涂覆有活性物质并且卷绕在多孔聚丙烯或玻璃纤维分隔体中的正电极和围绕正电极折叠的负电极的一个或多个堆叠体组成的棱柱或袋状双电池。将(一个或多个)堆叠体在经聚合物涂覆的铝箔袋中折叠,在热和/或真空下干燥,用电解质进行填充,并且真空和热密封。在本文中描述的棱柱或袋状电池的一些实施方案中,可通过激光或超声波焊接、胶黏剂或机械接触将由金属箔或碳质材料组成的额外的接线片固定于集流体,以便连接电极与包装外的装置。在其它实施方案中,本文公开的Mg蓄电池为卷绕或柱状电池,其由夹在多孔聚丙烯或玻璃纤维分隔体层之间的在其一侧或两侧上涂覆有活性物质的正电极和负电极的一个或多个堆叠体的卷绕层组成。将(一个或多个)堆叠体卷绕成柱状卷,插入罐中,在热和/或真空下干燥,用电解质进行填充,并且真空和焊接封闭。在本文描述的柱状电池的一些实施方案中,可以通过激光或超声波焊接、胶黏剂或机械接触将由金属箔或碳质材料组成的额外的接线片固定于集流体,以便连接电极与封装外的装置。
不锈钢部件(包括集流体)可由任何常规已知的包括302、304、305、316和384不锈钢类型构造。
已经整体上描述本发明,可参考一些特定实施例来获得进一步的理解,在本文中提供一些特定实施例仅出于说明的目的而不旨在限制,除非另外指明。本领域技术人员将认识到本发明的装置作为蓄电池的用途以及本文中描述的电解质体系的通常用途。
实施例
((C6H5)B(C6F5)3)K的制备:
将2g路易斯酸B(C6F5)3溶解在10ml THF中。快速添加5.5714ml处于THF中的PhMgCl(2.0M溶液)。搅拌3天以进行该反应,此后将gen3的原位产生的电解质添加到100ml的K2CO3和KHCO3的1M的水溶液。搅拌4小时以进行该反应,此后用醚提取钾盐。在无水硫酸镁上干燥该醚提取物并且将其放置在高真空下过夜。钾盐的产量为2.5g。钾盐的NMR在附图中。基于19F和1H NMR来区别gen3电解质与(PhB(C6F5)3)K是不可能的。(钾盐的结构仅可通过质谱来证实,在质谱中同位素图案和666.9487的精确质量与((PhB(C6F5)3)K2)+。)一致)。图1中的X射线结构。C32H23BF15KO3的晶体数据;Mr=790.41;单斜晶系;空间群P21/c; α=90°;β=117.094(3)°;γ=90°; Z=4;T=120(2)K;μ(Mo-Kα)=0.292mm-1;dcalc=1.657g.cm-3;收集了66367次反射;7938次唯一(Rint=0.0403);对于具有[I>2σ(I)]的6173个数据给出R1=0.0485,wR2=0.1234,对于所有7938个数据给出R1=0.0667,wR2=0.1364。残余电子密度()最大值/最小值:2.498/-0.755。在使用0.5°的ω-扫描和-扫描的组合的Kappa X8-APEX-II衍射仪上在无色的块状晶体(近似尺度为0.128×0.119×0.106mm)上收集任意的数据球[1]。对于吸收和极化效应矫正了数据并且对于空间群确定对数据进行分析。通过固有定相方法解释该结构并且按惯例将其展开[2]。通过对所有反射的F2全矩阵最小二乘法分析来细化模型。用各向异性热位移参数细化所有非氢原子。在计算位置中包括氢原子,除非另有说明。氢的热参数受它们所结合的原子的各向同性热参数束缚(对于甲基为1.5×,对于所有其它为1.2×)。
((C6H5)B(C6F5)3)Ag的制备:
基于Buschmann等人的参考文献(Chem.Eur.J 1998,4,no 9 1731)制备了银盐。概括地说,通过与乙腈中的硝酸银反应将钾盐转化为银盐。在反应期间添加醚以帮助沉淀硝酸钾。通过过滤移除沉淀物并且通过蒸发乙腈获得银盐。遗憾的是,银盐是非常有反应性的并且在光中快速分解。通过质谱确认了转化为银盐,在该质谱中同位素图案和1284.9523的精确质量与阳离子((C6H5)B(C6F5)3)Ag2)+一致。
(C6H5)B(C6F5)3)2Mg的制备:
通过银盐与半当量的无水溴化镁在THF中的反应获得镁盐。在反应过程中,溴化银沉淀并且该沉淀物是转化的指示。通过用己烷将含有镁盐的THF溶液分层来获得产物晶体。
使((C6H5)B(C6F5)3)2Mg从甲苯溶液中作为无色的片状晶体结晶。ORTEP曲线(参见图4)显示了原始的中心对称的三斜晶系空间群P-1的晶胞中的一个Mg阳离子分子,两个三全氟苯基分子、苯基硼酸根类阴离子和一个甲苯分子。镁以八面体的方式由六个THF分子配位。其位于晶胞起源的对称中心。非对称单元仅显示三个THF分子和半个Mg原子。三个独立的THF分子中的两个表现出在THF部分中的一个碳原子中的位置无序。在两个位点上对这些碳原子进行建模并且将每个无序中的主要组分和次要组分的占有率细化归于1,对于两个位点产生约0.66:0.34和0.75:0.25比例(参见X射线数据的附录)。分子内的键长和键角是普通的。
还可直接由处于甘醇二甲醚中的钾盐通过与MgBr2反应来获得((C6H5)B(C6F5)3)2Mg。
((C6H5)B(C6F5)3)2Mg的X射线结构:
C39.50H33BF15Mg0.50O3的晶体数据;Mr=863.62;三斜晶系;空间群P-1;α=102.5881(16)°;β=90.2857(17)°;γ=115.1883(15)°; Z=2;T=120(2)K;μ(Mo-Kα)=0.158mm-1;dcalc=1.578g.cm-3;收集了42372次反射;7303次唯一(Rint=0.0479);对于具有[I>2σ(I)]的5451个数据给出R1=0.0514,wR2=0.1098,对于所有7303个数据给出R1=0.0757,wR2=0.1209。残余电子密度()最大值/最小值:1.313/-0.576。在使用0.5°的ω-扫描和-扫描的组合的BrukerAPEX-II衍射仪上在无色的片状晶体(近似尺度为0.146×0.103×0.057mm)上收集任意的数据球。对于吸收和极化效应矫正了数据并且对于空间群确定对数据进行分析[1]。通过Patterson方法解释该结构并且按惯例将其展开[2]。通过对所有反射的F2全矩阵最小二乘法分析来细化该模型。用各向异性热位移参数细化所有非氢原子。在计算位置中包括氢原子,除非另有说明。氢的热参数受它们所结合的原子的各向同性热参数束缚(对于甲基为1.5×,对于所有其它为1.2×)。
Claims (21)
1.一种制备非水镁电解质的方法,该非水镁电解质包含:
包含醚氧的非水溶剂;和
式(I)的镁盐:
[A]2Mg(Solvent)y (I)
其中
该电解质不包含氯离子,
Solvent是包含该醚氧的非水溶剂并且y为2到6的整数,并且
A是水稳定的硼酸根类阴离子或水稳定的碳硼酸根类阴离子中的至少一种,
该方法包括:
使式RMgCl的格氏试剂与在四氢呋喃中的i)式BR3的硼烷,其中R每个独立地选自任选用F取代的1-6个碳原子的烷基、任选用F取代的芳基和任选用F取代的烷基苯基;或ii)式C2B10H12的碳硼烷反应,以获得下式的镁盐:
[Mg2(μ-Cl)3·6THF]A
其中A为:i)式BR4 -(II)的硼酸根类阴离子,其中R每个独立地选自任选用F取代的1-6个碳原子的烷基、任选用F取代的芳基和任选用F取代的烷基苯基;或ii)式C2B10H11 -(III)的碳硼酸根类阴离子;
根据以下反应式在含水介质中形成阴离子A的M+盐:
3[Mg2(μ-Cl)3·6THF]A+M2CO3/MHCO3(aq)→3MA+[Mg2(μ-Cl)3·6THF](CO3)+[Mg2(μ-Cl)3·6THF](HCO3);
从该含水介质中提取MA盐;
将游离的MA盐从提取物分离;和
用Mg2+离子交换MA盐的金属离子M+以获得式(I)的Mg盐,其中该金属离子(M+)是选自Li+、Na+、K+、Rb+、Cs+和Ag+中的至少一种。
2.根据权利要求1的方法,其中M+为Ag+。
3.根据权利要求1的方法,其中M+为K+。
4.根据权利要求3的方法,其中
在醚中提取KA盐;和
通过在真空下移除醚来分离KA盐。
5.根据权利要求4的方法,其还包括:
根据在其中KNO3为不可溶的介质中的交换(b)形成阴离子A-的Ag+盐:
KA+AgNO3→AgA+KNO3(s) (b);
和
从AgA盐的溶液中移除沉淀的KNO3(s)。
6.根据权利要求1的方法,其中式BR4 -(II)的硼酸根类阴离子是式(IV)的阴离子:
[BPh4]- (IV)
其中每个Ph基团独立地为任选用F取代的芳基和任选用F取代的烷基苯基。
7.根据权利要求6的方法,其中式(IV)的硼酸根类阴离子为式(V)的阴离子:
[(C6F5)3B(C6H5)]- (V)。
8.根据权利要求6的方法,其中式(IV)的硼酸根类阴离子为式(VI)的阴离子:
[(Mes)3B(C6H5)]- (VI)
其中Mes为3,5-二甲基苯基。
9.根据权利要求1的方法,其中A是式(III)的碳硼酸根类阴离子:
(C2B10H11)- (III)
其中碳硼酸根类是邻碳硼烷的阴离子、间碳硼烷的阴离子或对碳硼烷的阴离子。
10.根据权利要求1的方法,其中包含醚氧的非水溶剂是四氢呋喃(THF)、二甲氧基乙烷(DME)和二乙二醇二甲醚(二甘醇二甲醚)(DGM)中的至少一种。
11.制备镁电解质的方法,该镁电解质包含:
四氢呋喃;和
式(VII)的盐:
[(C6F5)3B(C6H5)]2Mg(THF)6 (VII)
其中THF是四氢呋喃分子,
该方法包括:
使式C6H5MgCl的格氏试剂与在四氢呋喃中的式B(C6F5)3的硼烷反应,以获得下式的镁盐:
[Mg2(μ-Cl)3·6THF][(C6H5)B(C6F5)3]
根据以下反应式在含水介质中形成阴离子(C6H5)B(C6F5)3的K+盐:
3[Mg2(μ-Cl)3·6THF][(C6H5)B(C6F5)3]+K2CO3/KHCO3(aq)→3K[(C6H5)B(C6F5)3+[Mg2(μ-Cl)3·6THF](CO3)+[Mg2(μ-Cl)3·6THF](HCO3);
根据在其中KNO3为不可溶的介质中的交换(b)形成阴离子(C6H5)B(C6F5)3 -的Ag+盐:
K[(C6H5)B(C6F5)3]+AgNO3→Ag[(C6H5)B(C6F5)3]+KNO3(s)(b);
和
从Ag[(C6H5)B(C6F5)3]盐的溶液移除沉淀的KNO3(s)
根据以下反应式Mg对THF中的Ag的离子交换:
2((C6H5)B(C6F5)3)Ag+MgBr2→((C6H5)B(C6F5)3)2Mg(THF)6+2AgBr
和从镁电解质移除AgBr,
其中该镁电解质不包含氯离子。
12.制备镁电解质的方法,该镁电解质包含:
四氢呋喃;和
式(VIII)的盐:
[(Mes)3B(C6H5)]2Mg(THF)6 (VIII)
其中
THF是四氢呋喃分子,并且
Mes为3,5-二甲基苯基基团,
该方法包括:
使式C6H5MgCl的格氏试剂与在四氢呋喃中的式B(Mes)3的硼烷反应,以获得下式的镁盐:
[Mg2(μ-Cl)3·6THF][(C6H5)B(Mes)3]
根据以下反应式在含水介质中形成阴离子(C6H5)B(Mes)3的K+盐:
3[Mg2(μ-Cl)3·6THF]((C6H5)B(Mes)3+K2CO3/KHCO3(aq)→3K[(C6H5)B(Mes)3]+[Mg2(μ-Cl)3·6THF](CO3)+[Mg2(μ-Cl)3·6THF](HCO3);
根据在其中KNO3为不可溶的介质中的交换(b)形成阴离子(C6H5)B(Mes)3 -的Ag+盐:
K((C6H5)B(Mes)3+AgNO3→Ag[(C6H5)B(C6F5)3]+KNO3(s)(b);
和
从Ag[(C6H5)B(Mes)3]盐的溶液移除沉淀的KNO3(s)
根据以下反应式Mg对THF中的Ag的离子交换:
2((C6H5)B(Mes)3)Ag+MgBr2→((C6H5)B(C6H5)3)2Mg(THF)6+2AgBr
和从镁电解质移除AgBr,
其中该镁电解质不包含氯离子。
13.根据权利要求1的方法所获得的镁电解质,包含:
包含醚氧的非水溶剂;和
式(I)的盐:
[A]2Mg(Solvent)y (I)
其中
Solvent是包含醚氧的非水溶剂并且是选自四氢呋喃、2-甲基四氢呋喃、二甲氧基乙烷、甘醇二甲醚、单甘醇二甲醚、二甲基乙二醇、乙二醇二甲醚、乙醚、乙基甘醇二甲醚、二甘醇二甲醚、二丙二醇二甲醚、乙基二甘醇二甲醚、三甘醇二甲醚、丁基二甘醇二甲醚、四甘醇二甲醚、聚甘醇二甲醚和higlyme中的至少一种,
y为2到6的整数,
A是水稳定的硼酸根类阴离子或水稳定的碳硼酸根类阴离子,其选自:(BR4)-(II),其中R基团每个独立地选自任选用F取代的1-6个碳原子的烷基、任选用F取代的芳基和任选用F取代的烷基苯基;和(C2B10H11)-(III)
并且
镁电解质盐不含氯化物。
14.镁蓄电池,其包含:
包含镁的负电极;
正电极;
溶剂;和
根据权利要求13的镁电解质。
15.根据权利要求14的镁蓄电池,其中负电极为镁。
16.根据权利要求14的镁蓄电池,其中正电极活性物质包含选自硫、石墨碳、碳纤维、玻璃碳、热解碳、无定形碳、Mo6S8、MnO2、CuS、Cu2S、Ag2S、CrS2、VOPO4、TiS2、V2O5、MgVO3、MoS2、MgV2O5、MoO3、CuCr2S4、MgCr2S4、MgMn2O4、Mg2MnO4、MgFe2(PO4)3、MgV2(PO4)3、MgMnSiO4、MgFe2(PO4)2、Mg0.5VPO4F、TiP2O7、VP2O7和FeF3的至少一种组分。
17.根据权利要求14的镁蓄电池,
其中A为式(II)的硼酸根类阴离子:
(BR4)- (II)
其中R基团每个独立地为任选用F取代的1-6个碳原子的烷基、任选用F取代的芳基和任选用F取代的烷基苯基。
18.根据权利要求17的镁蓄电池,
其中式(II)的硼酸根类阴离子为式(IV)的阴离子:
[BPh4]- (IV)
其中每个Ph基团独立地为任选用F取代的芳基和任选用F取代的烷基苯基。
19.根据权利要求18的镁蓄电池,
其中式(IV)的硼酸根类阴离子是式(V)的阴离子:
[(C6F5)3B(C6H5)]- (V)。
20.根据权利要求18的镁蓄电池,
其中式(II)的硼酸根类阴离子为式(VI)的阴离子:
[(Mes)3B(C6H5)]- (VI)
其中Mes为3,5-二甲基苯基。
21.根据权利要求14的镁蓄电池,其中A为式(III)的碳硼酸根类阴离子:
(C2B10H11)- (III)
其中碳硼酸根类是邻碳硼烷、间碳硼烷或对碳硼烷的阴离子。
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US10147970B2 (en) | 2018-12-04 |
DE102015106453A1 (de) | 2015-10-29 |
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US20150311565A1 (en) | 2015-10-29 |
CN105047987A (zh) | 2015-11-11 |
JP6752552B2 (ja) | 2020-09-09 |
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