CN117457970A - Asymmetric heterogeneous boron center anion magnesium electrolyte salt, electrolyte, and preparation method and application thereof - Google Patents
Asymmetric heterogeneous boron center anion magnesium electrolyte salt, electrolyte, and preparation method and application thereof Download PDFInfo
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- CN117457970A CN117457970A CN202311445751.XA CN202311445751A CN117457970A CN 117457970 A CN117457970 A CN 117457970A CN 202311445751 A CN202311445751 A CN 202311445751A CN 117457970 A CN117457970 A CN 117457970A
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- magnesium
- borate
- electrolyte
- salt
- asymmetric
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 150
- 239000011777 magnesium Substances 0.000 title claims abstract description 125
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 99
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 81
- 150000003839 salts Chemical class 0.000 title claims abstract description 60
- 150000001450 anions Chemical class 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- -1 boric acid ester Chemical class 0.000 claims abstract description 63
- 159000000003 magnesium salts Chemical class 0.000 claims abstract description 60
- 239000003960 organic solvent Substances 0.000 claims abstract description 40
- 125000000129 anionic group Chemical group 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 12
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 25
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 24
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- 150000001642 boronic acid derivatives Chemical class 0.000 claims description 12
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 12
- 239000007983 Tris buffer Substances 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 10
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims description 10
- BZQRBEVTLZHKEA-UHFFFAOYSA-L magnesium;trifluoromethanesulfonate Chemical compound [Mg+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F BZQRBEVTLZHKEA-UHFFFAOYSA-L 0.000 claims description 9
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 8
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 8
- 239000012266 salt solution Substances 0.000 claims description 8
- VDFVNEFVBPFDSB-UHFFFAOYSA-N 1,3-dioxane Chemical compound C1COCOC1 VDFVNEFVBPFDSB-UHFFFAOYSA-N 0.000 claims description 7
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 7
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 7
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- IBZKBSXREAQDTO-UHFFFAOYSA-N 2-methoxy-n-(2-methoxyethyl)ethanamine Chemical compound COCCNCCOC IBZKBSXREAQDTO-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- QWDJLDTYWNBUKE-UHFFFAOYSA-L magnesium bicarbonate Chemical compound [Mg+2].OC([O-])=O.OC([O-])=O QWDJLDTYWNBUKE-UHFFFAOYSA-L 0.000 claims description 6
- 238000003760 magnetic stirring Methods 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 5
- UUAMLBIYJDPGFU-UHFFFAOYSA-N 1,3-dimethoxypropane Chemical compound COCCCOC UUAMLBIYJDPGFU-UHFFFAOYSA-N 0.000 claims description 5
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 5
- QAFODUGVXFNLBE-UHFFFAOYSA-N 1-methoxybutan-2-amine Chemical compound CCC(N)COC QAFODUGVXFNLBE-UHFFFAOYSA-N 0.000 claims description 5
- NXMXETCTWNXSFG-UHFFFAOYSA-N 1-methoxypropan-2-amine Chemical compound COCC(C)N NXMXETCTWNXSFG-UHFFFAOYSA-N 0.000 claims description 5
- IJAQSERNJJEFFD-UHFFFAOYSA-N 2-(trifluoromethoxy)ethanamine Chemical compound NCCOC(F)(F)F IJAQSERNJJEFFD-UHFFFAOYSA-N 0.000 claims description 5
- BPGIOCZAQDIBPI-UHFFFAOYSA-N 2-ethoxyethanamine Chemical compound CCOCCN BPGIOCZAQDIBPI-UHFFFAOYSA-N 0.000 claims description 5
- KOHBEDRJXKOYHL-UHFFFAOYSA-N 2-methoxy-n-methylethanamine Chemical compound CNCCOC KOHBEDRJXKOYHL-UHFFFAOYSA-N 0.000 claims description 5
- ASUDFOJKTJLAIK-UHFFFAOYSA-N 2-methoxyethanamine Chemical compound COCCN ASUDFOJKTJLAIK-UHFFFAOYSA-N 0.000 claims description 5
- USECIYVEPXUVHT-UHFFFAOYSA-N 2-propan-2-yloxyethanamine Chemical compound CC(C)OCCN USECIYVEPXUVHT-UHFFFAOYSA-N 0.000 claims description 5
- HMWXCSCBUXKXSA-UHFFFAOYSA-N 2-propoxyethanamine Chemical compound CCCOCCN HMWXCSCBUXKXSA-UHFFFAOYSA-N 0.000 claims description 5
- FAXDZWQIWUSWJH-UHFFFAOYSA-N 3-methoxypropan-1-amine Chemical compound COCCCN FAXDZWQIWUSWJH-UHFFFAOYSA-N 0.000 claims description 5
- VHYUNSUGCNKWSO-UHFFFAOYSA-N 3-propan-2-yloxypropan-1-amine Chemical compound CC(C)OCCCN VHYUNSUGCNKWSO-UHFFFAOYSA-N 0.000 claims description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 5
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 claims description 5
- 229910000085 borane Inorganic materials 0.000 claims description 4
- 229940043279 diisopropylamine Drugs 0.000 claims description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- NHDIQVFFNDKAQU-UHFFFAOYSA-N tripropan-2-yl borate Chemical compound CC(C)OB(OC(C)C)OC(C)C NHDIQVFFNDKAQU-UHFFFAOYSA-N 0.000 claims description 4
- GCMBIWYUVPAPEG-UHFFFAOYSA-N tris(1,1,1,3,3,3-hexafluoropropan-2-yl) borate Chemical compound FC(F)(F)C(C(F)(F)F)OB(OC(C(F)(F)F)C(F)(F)F)OC(C(F)(F)F)C(F)(F)F GCMBIWYUVPAPEG-UHFFFAOYSA-N 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 2
- MPCRDALPQLDDFX-UHFFFAOYSA-L Magnesium perchlorate Chemical compound [Mg+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O MPCRDALPQLDDFX-UHFFFAOYSA-L 0.000 claims description 2
- 150000004703 alkoxides Chemical class 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 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 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- AJSTXXYNEIHPMD-UHFFFAOYSA-N triethyl borate Chemical compound CCOB(OCC)OCC AJSTXXYNEIHPMD-UHFFFAOYSA-N 0.000 claims description 2
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 claims description 2
- QIIPFRVUQAVEFJ-UHFFFAOYSA-N tris(2,2-difluoroethyl) borate Chemical compound FC(F)COB(OCC(F)F)OCC(F)F QIIPFRVUQAVEFJ-UHFFFAOYSA-N 0.000 claims description 2
- ZWTOJDDJAARGAE-UHFFFAOYSA-N tris[1,1,1,3,3,3-hexafluoro-2-(trifluoromethyl)propan-2-yl] borate Chemical compound FC(F)(F)C(C(F)(F)F)(C(F)(F)F)OB(OC(C(F)(F)F)(C(F)(F)F)C(F)(F)F)OC(C(F)(F)F)(C(F)(F)F)C(F)(F)F ZWTOJDDJAARGAE-UHFFFAOYSA-N 0.000 claims description 2
- ZMCWFMOZBTXGKI-UHFFFAOYSA-N tritert-butyl borate Chemical compound CC(C)(C)OB(OC(C)(C)C)OC(C)(C)C ZMCWFMOZBTXGKI-UHFFFAOYSA-N 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 abstract description 23
- 230000008021 deposition Effects 0.000 abstract description 13
- 230000003647 oxidation Effects 0.000 abstract description 10
- 238000007254 oxidation reaction Methods 0.000 abstract description 10
- 239000004327 boric acid Substances 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 16
- 230000002441 reversible effect Effects 0.000 description 13
- 210000004027 cell Anatomy 0.000 description 12
- 238000000151 deposition Methods 0.000 description 12
- 239000011888 foil Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000002484 cyclic voltammetry Methods 0.000 description 5
- 230000007774 longterm Effects 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 230000010287 polarization Effects 0.000 description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000004070 electrodeposition Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 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
- 150000001298 alcohols Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- DBDNZCBRIPTLJF-UHFFFAOYSA-N boron(1-) monohydride Chemical compound [BH-] DBDNZCBRIPTLJF-UHFFFAOYSA-N 0.000 description 2
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000004502 linear sweep voltammetry Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006864 oxidative decomposition reaction Methods 0.000 description 2
- 239000012453 solvate Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 1
- TXOZSRCVHASUCW-UHFFFAOYSA-N 1,3,3,3-tetrafluoropropan-1-ol Chemical compound OC(F)CC(F)(F)F TXOZSRCVHASUCW-UHFFFAOYSA-N 0.000 description 1
- XBVURNWWURAQSY-UHFFFAOYSA-N 2,2,2-trifluoroethoxyboronic acid Chemical compound OB(O)OCC(F)(F)F XBVURNWWURAQSY-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 229910017267 Mo 6 S 8 Inorganic materials 0.000 description 1
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
-
- 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
- H01M2300/0088—Composites
- H01M2300/0091—Composites in the form of mixtures
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
Abstract
The invention belongs to the technical field of new energy battery preparation, and particularly relates to an asymmetric heterogeneous boron center anion magnesium electrolyte salt, an electrolyte, and a preparation method and application thereof. The asymmetric heterogeneous boron center anion magnesium electrolyte salt is characterized by comprising anions shown in a structural formula (1),wherein the-OR group is an alkoxy group OR a fluorinated alkoxy group and the-OR' group is an anionic group of a magnesium salt. The magnesium electrolyte salt adopts magnesium salt, anhydrous anaerobic organic solvent and boric acid ester/boric acid ester derivative as raw materials; raw materials are easy to obtain and the price is low; in addition, the electrolyte based on the magnesium electrolyte salt has high conductivity, high oxidation stability potential, high coulomb efficiency of magnesium deposition/dissolution up to more than 98%, and good cycle stability.
Description
Technical Field
The invention belongs to the technical field of new energy battery preparation, and particularly relates to an asymmetric heterogeneous boron center anion magnesium electrolyte salt, an electrolyte, and a preparation method and application thereof.
Background
High energy storage systems composed of rechargeable metal batteries will play a key role in the fields of electric automobiles, large-scale energy storage, and the like. Among them, the rechargeable magnesium battery has been considered as a very promising energy storage system, and development of the rechargeable magnesium battery has potential advantages for large-scale energy storage, mainly because magnesium metal has the following characteristics: (1) the reduction potential of magnesium is low (-2.37V vs. SHE); (2) Since magnesium metal has +2 valence, the volume specific capacity is up to 3833mAhcm -3 Is higher than the lithium metal cathode (2026 mAhcm) -3 ) The realization of high energy density is facilitated; (3) Magnesium is a metal with mild chemical properties and rich reserves; (4) More importantly, unlike lithium metal, magnesium metal is not prone to dendrite formation during reversible electrochemical deposition/dissolution, so that the use of magnesium metal as a battery anode material does not create serious safety hazards.
But at present, the lack of a suitable electrolyte becomes a significant impediment to the development of rechargeable magnesium metal batteries. The method specifically comprises the following steps: because of the chemical activity of Mg, solutions that provide neither protons nor accept protons are suitable as electrolytes, but these solutions generally lead to the growth of passive films, inhibit the dissolution of reversible magnesium deposits, and thus limit the full play of the high volumetric energy density of rechargeable magnesium batteries, affecting the electrochemical performance of magnesium electrolytes. Conventional organometallic grignard reagents proved to have good electrochemical properties (higher Coulombic Efficiency (CE) and lower overpotential during magnesium deposition/dissolution); however, almost all organometallic grignard reagents are easily oxidized, often limiting the electrochemical stability window of the electrolyte, affecting the match with the positive electrode material.
Currently, more and more research is focused on single-salt electrolyte salts and electrolytes having high voltage and high ionic conductivity, such as Mg (TFSI) 2 、Mg(OTf) 2 Tool and method for manufacturing the sameMagnesium electrolyte salts having a bulky weakly coordinating boron anion. In particular magnesium electrolyte salts (electrolytes) of bulky weakly coordinating boron anions, e.g. Mg [ B (hfip) 4 ] 2 DME, such electrolyte salts (electrolytes) are based on the presence of symmetrical bulky boron anions B (hfip) 4 - Reduced anionic and cationic Mg 2+ The interaction between the two components realizes a weak coordination effect, thereby obviously increasing the solubility and the ion conductivity of the electrolyte, and simultaneously the electrolyte does not contain Cl - And the stability of the structure of the electrolyte improves the oxidation stability to 4.0V vs. Mg/Mg 2+ Left and right. However, the traditional magnesium electrolyte salt (electrolyte) of the symmetrical large-volume weak-coordination boron anion has the problems of complex preparation process, high raw material price and the like, and seriously hinders the large-scale commercial application process.
Therefore, the development of the magnesium electrolyte salt and the electrolyte of the large-volume weak-coordination boron anions, which are simple to prepare and easy to obtain raw materials, has great significance.
Disclosure of Invention
In order to solve the problems, one of the purposes of the invention is to provide an asymmetric heterogeneous boron center anion magnesium electrolyte salt and an electrolyte, wherein the electrolyte salt is an asymmetric boron center anion magnesium electrolyte salt, and the preparation raw materials only comprise magnesium salt, anhydrous and anaerobic organic solvent and borate/boric acid ester derivative, and are easy to obtain; the preparation method is simple, and the prepared electrolyte salt and electrolyte have the advantages of high conductivity, high oxidation stability, low overpotential, good cycle stability, good compatibility with the positive electrode of the magnesium battery and the like.
In order to achieve the above purpose, the present invention may adopt the following technical scheme:
in one aspect, the invention provides an asymmetric isomerism boron center anion magnesium electrolyte salt which comprises anions shown in a structural formula (1),
wherein the-OR group is an alkoxy group OR a fluorinated alkoxy group and the-OR' group is an anionic group of a magnesium salt.
In another aspect, the present invention provides a method for preparing the asymmetric heterogeneous boron center anionic magnesium electrolyte salt, which comprises: (1) mixing magnesium salt and organic solvent to obtain magnesium salt solution; (2) Mixing magnesium salt solution with borate compound to react and obtain the mixture containing asymmetric heterogeneous boron center anion magnesium electrolyte salt.
In yet another aspect, the present invention provides an asymmetric isomerism boron center anion magnesium salt electrolyte comprising the asymmetric isomerism boron center anion magnesium electrolyte salt and an organic solvent; the organic solvent comprises one or more combinations of 1, 3-dioxolane, 1, 3-dioxane, 1, 4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diethyl cellosolve, 1, 3-dimethoxypropane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-methoxyethylamine, 1-methoxy-2-propylamine, 3-methoxypropylamine, 2-ethoxyethylamine, N- (2-methoxyethyl) methylamine, bis (2-methoxyethyl) amine, 2 '-oxybis (ethylamine), 2-amino-1-methoxybutane, 2-propoxyethylamine, (1, 1-dimethyl-2-methoxyethyl) amine, 2-aminoethyl isopropyl ether, 3-isopropoxypropylamine, N' -dimethylethylenediamine, N '-diethylethylenediamine, ethylenediamine, N' -diisopropylethylenediamine, and 2- (trifluoromethoxy) ethane-1-amine.
In still another aspect, the invention provides an application of the asymmetric heterogeneous boron center anion magnesium salt electrolyte in preparing a magnesium battery.
The beneficial effects of the invention at least comprise:
(1) The asymmetric heterogeneous boron center anion magnesium electrolyte salt provided by the invention adopts magnesium salt, organic solvent and borate compound as raw materials, and the raw materials are easy to obtain; and the price is low; in addition, the electrolyte is obtained by simply mixing raw materials to react, and the preparation method is simple; is beneficial to realizing large-scale commercial application.
(2) The asymmetric heterogeneous boron center anion magnesium salt electrolyte provided by the invention has the advantages of high conductivity, low oxidation stability potential, high coulomb efficiency of reversible deposition-dissolution of magnesium (on a Mo foil substrate) and good cycle stability.
Drawings
FIG. 1 is a mass spectrum of an electrolyte of a sample 1 prepared by the invention;
FIG. 2 is a cyclic voltammogram of sample 1 electrolyte prepared in accordance with the present invention using stainless steel as the working electrode;
FIG. 3 is a graph showing the linear sweep voltammogram of electrolyte of sample 1 prepared in accordance with the present invention over different working electrodes;
FIG. 4 shows the sample 1 electrolyte prepared according to the present invention at 0.1 mA.cm using molybdenum foil as working electrode -2 Reversible magnesium deposition/dissolution cycling curves and coulombic efficiencies at current densities;
FIG. 5 shows a sample 1 electrolyte prepared according to the present invention assembled Mg/Mg symmetrical cell at 0.1mA cm -2 A long-term polarization performance curve at current density;
FIG. 6 is a graph showing the rate polarization performance of an assembled Mg/Mg symmetric battery at different current densities using electrolyte sample 1 prepared in accordance with the present invention.
FIG. 7 is an assembled Mg/Mo sample 1 of the electrolyte prepared by the present invention 6 S 8 Rate performance curves of full cells at different current densities.
FIG. 8 is an assembled Mg/Mo sample 1 of the electrolyte prepared by the present invention 6 S 8 Full cell at 1C (128 mAg -1 ) A long-term cycling stability performance curve;
FIG. 9 is a cyclic voltammogram of sample 2 electrolyte prepared according to the present invention using stainless steel as the working electrode.
Detailed Description
The examples are presented for better illustration of the invention, but the invention is not limited to the examples. Those skilled in the art will appreciate that various modifications and adaptations of the embodiments described above are possible in light of the above teachings and are intended to be within the scope of the invention.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the disclosure. Unless the context clearly differs, singular forms of expression include plural forms of expression. As used herein, it is understood that terms such as "comprising," "having," "including," and the like are intended to indicate the presence of features, numbers, operations, materials, or combinations. The terms of the present invention are disclosed in the specification and are not intended to exclude the possibility that one or more other features, numbers, operations, materials or combinations thereof may be present or may be added. As used herein, "/" may be interpreted as "and" or "as appropriate.
The embodiment of the invention provides an asymmetric heterogeneous boron center anion magnesium electrolyte salt which comprises anions shown in a structural formula (1) and solvated Mg 2+ The complex is used as a catalyst in the preparation of a complex,wherein the-OR group is an alkoxy group OR a fluorinated alkoxy group and the-OR' group is an anionic group of a magnesium salt.
Solvated Mg 2+ The complex refers to a complex solvate (also called an ionic solvate), and an alkoxy group or a fluorinated alkoxy group is known in the art and is an alkoxy group or a fluorinated alkoxy group of a borate compound; the anionic groups of magnesium salts are also known in the art, for example, when the magnesium salt is magnesium triflate, the anionic groups of the magnesium salt are triflate anions.
In some embodiments, the preparation raw materials of the asymmetric heterogeneous boron center anion magnesium electrolyte salt may include magnesium salts, organic solvents and borate compounds, wherein the borate compounds are borate esters and/or borate derivatives.
In the embodiment of the invention, magnesium triflate is taken as a magnesium salt and trifluoroethyl borate is taken as a borate compound, and cations (solvated Mg 2+ Complexes) are [ Mg (OTf) (DME) ] 2 ] + The anions are [ B (OTf) (TFE) ] 3 ]-。
It should also be noted that in the embodiment of the present invention, the magnesium salt is Mg in the electrolyte 2+ (and solvated Mg) 2+ Complex) is a provider of electrolyte to achieve reversible magnesium deposition/dissolution processKey components of (2); the added borate compound (borate or derivative thereof) reacts with magnesium salt to form highly reversible cations with magnesium deposition solubility and asymmetric large-volume weak coordination boron anions, so that the solubility of electrolyte magnesium salt in organic solvent and the conductivity of electrolyte are improved, and the overpotential is reduced; by Mg (OTf) 2 (magnesium triflate) as magnesium salt and tris (2, 2-trifluoroethyl) borate as borate compound, in the organic solvent ethylene glycol dimethyl ether as an example, the action mechanism is as follows: in the electrolyte, electrolyte magnesium salt and solvent ethylene glycol dimethyl ether form dimer cation complex [ Mg (OTf) (DME) ] 2 ] + (solvated Mg2+ complex), tris (2, 2-trifluoroethyl) borate (B (TFE) 3 ) With triflate anions (OTf) - ) Formation of asymmetric isomerically bulky weakly coordinating boron anions [ B (OTf) (TFE) ] 3 ] - The two generated anions and cations can interact with each other to finally reach equilibrium and form electrolyte salt [ Mg (OTf) (DME) ] 2 ][B(OTf)(TFE) 3 ]The solubility of the electrolyte magnesium salt in the organic solvent is increased and the active species providing reversible deposition dissolution are provided, thereby achieving a reversible magnesium deposition dissolution cycle. Specifically, electrolyte salt [ Mg (OTf) (DME) ] 2 ][B(OTf)(TFE) 3 ]The structural formula is as follows:
in some embodiments, the magnesium salt may be selected from all magnesium salts in the art, including, for example, one or more of magnesium chloride, magnesium alkoxide fluoride, magnesium nitrate, magnesium perchlorate, magnesium bis (diisopropylamine), magnesium bis (trifluoromethylsulfonyl) imide, and magnesium trifluoromethylsulfonate. Preferably, the magnesium salt is magnesium triflate, magnesium bis (diisopropylamine), magnesium chloride and magnesium bis (trifluoromethanesulfonyl) imide, and the magnesium salt has wide sources and easy obtainment, and the prepared electrolyte has excellent performance and is superior to other magnesium salts.
In some embodiments, the borate compound may be selected from all borates or derivatives thereof in the art, examples include trimethyl borate, triethyl borate, triisopropyl borate, tri-t-butyl borate, tris (2, 2-trifluoroethyl) borate, tris (2, 3-tetrafluoropropyl) borate, tris (2, 2-difluoroethyl) borate tris (2, 3-pentafluoropropyl) borate, tris (hexafluoroisopropyl) borate one or more of tris (2, 3, 4-hexafluorobutyl) borate and tris (perfluoro-t-butyl) borate. Preferred are triisopropyl borate, tri (2, 2-trifluoroethyl) borate, tri (hexafluoroisopropyl) borate and tri (2, 3-tetrafluoropropyl) borate, which are widely available and easily obtained, and the prepared electrolyte has excellent properties superior to other borates.
In some embodiments, the organic solvent may be selected from any organic solvent known in the art, including, for example, one or more of 1, 3-dioxolane, 1, 3-dioxane, 1, 4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diethyl cellosolve, 1, 3-dimethoxypropane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-methoxyethylamine, 1-methoxy-2-propylamine, 3-methoxypropylamine, 2-ethoxyethylamine, N- (2-methoxyethyl) methylamine, bis (2-methoxyethyl) amine, 2 '-oxybis (ethylamine), 2-amino-1-methoxybutane, 2-propoxyethylamine, (1, 1-dimethyl-2-methoxyethyl) amine, 2-aminoethyl isopropyl ether, 3-isopropoxypropylamine, N' -dimethylethylenediamine, N '-diethylethylenediamine, ethylenediamine, N' -diisopropylethylenediamine, and 2- (trifluoromethoxy) ethane-1-amine. Among them, ethylene glycol dimethyl ether and bis (2-methoxyethyl) amine, and a combination solvent of 1, 3-dioxane, tetrahydrofuran and ethylene glycol dimethyl ether (1:1:3) and a combination solvent of ethylene glycol dimethyl ether and diethylene glycol dimethyl ether (1:1) are preferable, and the electrolyte prepared from the above solvents is excellent in performance, and is superior to other organic solvents.
The synergistic effect among the magnesium salt, the borate compound and the anhydrous and anaerobic organic solvent can endow the electrolyte with the advantages of high oxidation stability, low overpotential, good cycle stability, good compatibility with the positive electrode of the magnesium battery and the like; wherein the magnesium salt and borate/boric acid are containedReaction of ester derivatives to form solvated magnesium cations and asymmetric isomerically bulky weakly coordinating boron anions [ B (OTf) (TFE) ] 3 ]The concentration of the electrolyte magnesium salt in the organic solvent can reach more than 1mol/L, the conductivity of the electrolyte is improved, and the electrochemical properties such as overpotential and the like are reduced. Different magnesium salts, boric acid esters and anhydrous and anaerobic organic solvents are matched to prepare electrolyte with different performances. In the present invention, the combination of magnesium salt, borate and anhydrous oxygen-free organic solvent may be preferably selected from the following: (a) magnesium salt: magnesium triflate, borate or derivatives thereof: b (TFE) 3 Anhydrous and anaerobic organic solvent: ethylene glycol dimethyl ether; (b) magnesium salt: magnesium triflate, borate or derivatives thereof: tris (hexafluoroisopropyl) borate, anhydrous and oxygen-free organic solvent: ethylene glycol dimethyl ether; (c) magnesium salt: magnesium triflate and magnesium chloride in combination, boric acid esters or derivatives thereof: triisopropyl borate, anhydrous and anaerobic organic solvent: 1, 3-dioxane, tetrahydrofuran and ethylene glycol dimethyl ether (3:3:4); (d) magnesium salt: magnesium bis (diisopropylamine), borate or derivative thereof: tris (2, 3-tetrafluoropropyl) boronic acid, anhydrous and anaerobic organic solvent: ethylene glycol dimethyl ether and diethylene glycol dimethyl ether (1:1); (e) magnesium salt: magnesium bis (trifluoromethanesulfonyl) imide, a borate or derivative thereof: tris (2, 3-tetrafluoropropyl) boronic acid, anhydrous and anaerobic organic solvent: the electrolyte prepared by the combination has excellent performance and is superior to other combinations.
In some embodiments, the molar mass ratio of the magnesium salt to the borate compound may be 1 (0.5-2.2), for example, may be 1:0.8, 1:1.2, 1:1.6, 1:1.8, or 1:2, etc. It should be noted that the molar mass ratio of the magnesium salt to the borate compound affects the prepared electrolyte, and too many (molar ratio is less than 1:2.2) or too many (molar ratio is greater than 1:0.5) borate compounds can cause the change of ionic structure in the electrolyte, so that the magnesium salt cannot be completely dissolved, and the magnesium deposition/dissolution performance is poor.
In some embodiments, the molar concentration of magnesium ions may be 0.1mol L -1 ～2.0molL -1 For example, it may be 0.5mol L -1 、1molL -1 Or 1.5mol L -1 Etc. The concentration of magnesium ions is calculated as the anhydrous oxygen-free organic solvent, for example, the molar concentration of magnesium ions may be 0.1mol L -1 In the case of this, 0.1mol of magnesium ion was contained in 1L of the anhydrous oxygen-free organic solvent. In addition, the molar concentration of magnesium ions has an influence on the electrolyte prepared, the solubility of magnesium salt in the solvent provided above is limited, and excessive magnesium salt cannot be dissolved to participate in the reaction, so 0.1mol L is selected in the present invention -1 ～2.0molL -1 。
In some embodiments, the organic solvent has a water and oxygen content of less than 50ppm. It should be noted that, water and air in the organic solvent may cause deterioration, even oxidative decomposition, of the magnesium salt, the borate and the solvent; at the same time, water and air can cause passivation films to be generated on the metal magnesium negative electrode, thereby affecting reversible magnesium deposition/dissolution.
In some embodiments, the above-described borate/borate derivatives may be prepared by simple mixing reactions of borane solutions with various types of fluorine-containing alcohols (2, 2-trifluoroethanol, hexafluoroisopropanol and 2, 3-tetrafluoropropanol) at-2 ℃ to 2 ℃. The reaction of alcohol with borane to produce hydrogen is relatively severe, and therefore, the reaction needs to be carried out in a low-temperature environment.
Another embodiment of the present invention provides a method for preparing the asymmetric heterogeneous boron center anionic magnesium electrolyte salt, which includes: (1) Mixing magnesium salt and anhydrous anaerobic organic solvent to obtain magnesium salt solution; (2) Mixing magnesium salt solution with borate/borate derivative to react and obtain the mixture containing asymmetric heterogeneous boron center anion magnesium electrolyte salt.
In some embodiments, in the step (1), the mixing may include: reacting for 2-12 h under magnetic stirring at normal temperature; and/or in the step (2), the mixing may include: reacting for 12-48 h under magnetic stirring at normal temperature.
In the step (1), the magnesium salt is uniformly dissolved in the anhydrous anaerobic organic solvent, and the dissolution rate of different magnesium salts in different anhydrous anaerobic organic solvents is different, so that the magnesium salt can be stirred to accelerate the dissolution rate, and the stirring mode can be all stirring modes known in the art, preferably magnetic stirring; and the preparation method can be dissolved at normal temperature, is generally stirred at normal temperature, can be basically and completely dissolved for 2-12 hours, and has mild and simple preparation conditions. In addition, in the step (2), different raw materials are selected, the reaction time is also different, and in order to accelerate the reaction, stirring can be performed at the same time of the reaction, and the stirring mode can be all stirring modes known in the art, preferably magnetic stirring; and the reaction can be carried out at normal temperature, the reaction is generally carried out under stirring at normal temperature, the basic reaction can be finished after 12-48 hours, and the preparation conditions are mild and simple.
In some embodiments, the above preparation method may further include: further comprises: and adding a poor solvent into the mixture containing the asymmetric heterogeneous boron center anion magnesium electrolyte salt under the anhydrous and anaerobic condition, performing suction filtration, and drying to obtain the asymmetric heterogeneous boron center anion magnesium electrolyte salt.
It should be noted that the poor solvent may be effective in removing unreacted borane and alcohols, which are known in the art, such as n-hexane, toluene, heptane, or the like. It should be noted that the term "anhydrous anaerobic condition" in the present invention does not mean absolute anhydrous anaerobic conditions, but means relatively anhydrous anaerobic conditions which are achieved within the allowable range of the prior art or future technologies. In addition, it should be understood that the mixture containing the asymmetric heterogeneous boron center anion magnesium electrolyte salt is subjected to suction filtration after the poor solvent is added under the anhydrous and anaerobic condition, and the drying is performed so as to make the purity of the asymmetric heterogeneous boron center anion magnesium electrolyte salt higher, but in some cases, the mixture containing the asymmetric heterogeneous boron center anion magnesium electrolyte salt prepared as described above can also be directly used as an electrolyte solution.
The method is characterized in that the mixture containing the asymmetric heterogeneous boron center anion magnesium electrolyte salt is added with the poor solvent under the anhydrous and anaerobic condition and then subjected to suction filtration, and the drying can be that the mixture containing the asymmetric heterogeneous boron center anion magnesium electrolyte salt is firstly subjected to suction filtration and drying, and then the poor solvent is added under the anhydrous and anaerobic condition and then subjected to suction filtration and drying; or directly adding a poor solvent into the mixture of the asymmetric heterogeneous boron center anion magnesium electrolyte salt under the anhydrous and anaerobic condition, and then carrying out suction filtration and drying; the selection may be made according to the specific circumstances.
In some embodiments, the reaction in step (1) and/or step (2) is performed under inert atmosphere, and the water and oxygen content are less than 0.01ppm. The reaction is preferably carried out in an inert atmosphere and in an environment with water and oxygen content lower than 0.01ppm, so that the deterioration of medicines or oxidative decomposition caused by water and oxygen are avoided, or the magnesium metal cathode is passivated, and the electrochemical performance of the electrolyte or the prepared battery is influenced.
In another embodiment, the present invention provides an electrolyte of an asymmetric heterogeneous boron center anion magnesium salt, comprising the above-mentioned asymmetric heterogeneous boron center anion magnesium electrolyte salt and an organic solvent; the organic solvent comprises one or more combinations of 1, 3-dioxolane, 1, 3-dioxane, 1, 4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diethyl cellosolve, 1, 3-dimethoxypropane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-methoxyethylamine, 1-methoxy-2-propylamine, 3-methoxypropylamine, 2-ethoxyethylamine, N- (2-methoxyethyl) methylamine, bis (2-methoxyethyl) amine, 2 '-oxybis (ethylamine), 2-amino-1-methoxybutane, 2-propoxyethylamine, (1, 1-dimethyl-2-methoxyethyl) amine, 2-aminoethyl isopropyl ether, 3-isopropoxypropylamine, N' -dimethylethylenediamine, N '-diethylethylenediamine, ethylenediamine, N' -diisopropylethylenediamine, and 2- (trifluoromethoxy) ethane-1-amine.
Besides directly using the prepared mixture containing the asymmetric isomerism boron center anion magnesium electrolyte salt as an electrolyte, the purified asymmetric isomerism boron center anion magnesium electrolyte salt can be added with the organic solvent to prepare the asymmetric isomerism boron center anion magnesium electrolyte solution for use.
The invention further provides an application of the asymmetric heterogeneous boron center anion magnesium electrolyte salt or the asymmetric heterogeneous boron center anion magnesium salt electrolyte in preparing a magnesium battery. It should be noted that the above-mentioned asymmetric heterogeneous boron center anion magnesium salt electrolyte may be assembled into a magnesium battery, and the negative electrode of the magnesium battery is a magnesium battery negative electrode known in the art, such as a magnesium foil or a magnesium alloy; the positive electrode of the magnesium battery is known in the art as a magnesium battery positive electrode such as magnesium oxide or cobalt oxide.
For a better understanding of the present invention, the content of the present invention is further elucidated below in connection with the specific examples, but the content of the present invention is not limited to the examples below.
1. Preparation of asymmetric heterogeneous boron center anion magnesium salt electrolyte
In the examples of the present invention, an asymmetric isomerism boron center anion magnesium salt electrolyte was prepared as follows (all the operating steps were performed in an argon filled glove box (water, oxygen content were all below 0.01 ppm):
(1) Dissolving a certain amount of magnesium salt in a reagent bottle containing an organic solvent with a certain amount of water and oxygen content of less than 50ppm, and magnetically stirring at normal temperature of 25 ℃ for reaction (400 r/min) until the magnesium salt is dissolved to obtain a magnesium salt solution;
(2) Slowly adding a certain amount of borate or derivatives thereof into the magnesium salt solution, and magnetically stirring (400 r/min) at the normal temperature of 25 ℃ for reacting for 24 hours to obtain a mixture containing asymmetric heterogeneous boron center anionic magnesium electrolyte salt;
(3) Vacuum-filtering and drying a mixture containing the asymmetric heterogeneous boron center anion magnesium electrolyte salt, then adding a poor solvent (such as n-hexane, toluene or heptane), vacuum-filtering and drying to obtain the asymmetric heterogeneous boron center anion magnesium electrolyte salt;
(4) And adding the asymmetric heterogeneous boron center anion magnesium electrolyte salt into the organic solvent with the water oxygen content of less than 50ppm for dissolution to prepare the asymmetric heterogeneous boron center anion magnesium electrolyte (the concentration of the magnesium electrolyte salt is equal to that of the magnesium salt).
Different raw materials are used for preparing different asymmetric heterogeneous boron center anion magnesium salt electrolyte samples according to the preparation method of the asymmetric heterogeneous boron center anion magnesium salt electrolyte, and specific conditions are shown in table 1.
TABLE 1 preparation of different asymmetric heterogeneous boron center anionic magnesium salt electrolyte samples from different raw materials
2. Asymmetric heterogeneous boron center anion magnesium salt electrolyte structure and performance test
In the embodiment of the invention, the structural test of the asymmetric heterogeneous boron center anion magnesium salt electrolyte is carried out according to the following method:
the electrolyte of the embodiment of the invention is taken 500 microliters to be placed in a centrifuge tube, and the centrifuge tube is placed in a glove box for natural volatilization and drying to obtain the corresponding electrolyte salt. And then a proper amount of dry electrolyte salt is taken and dissolved in anhydrous acetonitrile, and after being uniformly mixed, the mixture is added into a trace reagent bottle for mass spectrometry.
In the embodiment of the invention, the conductivity test of the asymmetric heterogeneous boron center anion magnesium salt electrolyte is carried out according to the following method: the conductivity of the electrolyte was tested using electrochemical impedance spectroscopy (CHI 660E electrochemical workstation); stainless steel foil (12 mm) electrodes are used as reference electrodes, working electrodes and counter electrodes; the voltage during the test is 10mV, and the frequency range is set to be 1MHz-0.1Hz; the test temperature was 25 ℃.
In the embodiment of the invention, the reversible magnesium deposition dissolution performance and oxidation stability test of the asymmetric heterogeneous boron center anion magnesium salt electrolyte are carried out according to the following method: reversible magnesium deposition dissolution performance and oxidation stability of the electrolyte are respectively obtained through cyclic voltammetry and linear sweep voltammetry tests; a two-electrode system is adopted, a magnesium sheet (12 mm) electrode is used as a reference electrode, a counter electrode and electrodes with different current collectors (16 mm) are used as working electrodes; for cyclic voltammetry, the potential range during the test is-1V-2.0V, the sweep speed is 25mV/s, and the scanning is performed from the open circuit voltage negative direction; for the linear sweep voltammetry, the potential range during the test is open-circuit voltage-3.5V, and the sweep speed is 1mV/s; all electrodes are sequentially cleaned by ethanol, deionized water and ethanol, so that impurities on the surface of the whole electrode are thoroughly removed; and (5) drying the cleaned electrode in vacuum for 6 hours, and putting the electrode into a glove box for standby.
In the embodiment of the invention, the magnesium reversible deposition-dissolution coulombic efficiency test of the asymmetric heterogeneous boron center anion magnesium salt electrolyte is carried out according to the following method: the deposition-dissolution cycle efficiency, charge-discharge characteristics, etc. of magnesium in the electrolyte were tested by assembling CR2032 button cell. Assembling in an inert atmosphere glove box, wherein the water and oxygen content is less than 0.01ppm; the working electrode is stainless steel SS, graphite foil GF, molybdenum foil Mo and the like, the counter electrode and the reference electrode adopt polished bright magnesium sheets, the diaphragm adopts GF/A films, and the cathode magnesium salt electrolyte of the asymmetric heterogeneous boron center is assembled together to form a CR2032 button cell; after the battery is assembled, standing for 12 hours at room temperature, and then measuring; the whole test process is carried out on a Wuhan New Wei (new) charge-discharge test system; the electrochemical deposition reaction of magnesium occurs on the working electrode during discharge, and the current density is 0.1mA-0.5mA cm -2 Time control (discharge for 1 hour) was used; the charging process is corresponding to the dissolution reaction of magnesium deposited on the working electrode, and the current density is 0.1mAcm -2 -0.5mAcm -2 Voltage control (charging to 1.2vvs. Mg RE) was used.
In the embodiment of the invention, the polarization performance test of the asymmetric heterogeneous boron center anion magnesium salt electrolyte is carried out according to the following method: long-term and rate polarization performance of magnesium in electrolyte was tested by assembling CR2032 button cell; assembling in an inert atmosphere glove box, wherein the water and oxygen content is less than 0.01ppm; the counter electrode and the reference electrode are made of polished magnesium sheets (14 mm), the diaphragm is made of GF/A film and an asymmetric heterogeneous boron center anion magnesium salt electrolyte to be assembled into a CR2032 button cell; after the battery is assembled, standing for 12 hours at room temperature, and then measuring; the whole test process is carried out on a Wuhan New Wei (New) charge-discharge test system. The electrochemical deposition reaction of magnesium occurs on the working electrode during discharge, and the current density is 0.05mAcm -2 -1mAcm -2 Using time control (discharge 30min); the charging process is corresponding to the dissolution reaction of magnesium deposited on the working electrode, and the current density is 0.05mAcm -2 -1mAcm -2 Time control (charging for 30 min) was used.
In the embodiment of the invention, the full-cell performance test of the asymmetric heterogeneous boron center anion magnesium salt electrolyte is carried out according to the following method: long-term and rate performance of the full cell and the like were tested by assembling CR2032 button cell; assembling in an inert atmosphere glove box, wherein the water and oxygen content is less than 0.01ppm; the negative electrode adopts polished magnesium sheet (14 mm), and the positive electrode is Mo 6 S 8 The diaphragm adopts GF/A film and is assembled with asymmetric heterogeneous boron center anion magnesium salt electrolyte to form a CR2032 button cell; after the battery is assembled, standing for 12 hours at room temperature, and then measuring; the whole test process is carried out on a Wuhan New Wei (New) charge-discharge test system. At different current densities (0.1 c,0.5c,1c,2c,5c,10 c), discharge to 0.2V and then charge to 2V.
The structure and performance of the prepared asymmetric heterogeneous boron center anion magnesium salt electrolyte sample 1 are tested by the method, and the test results are as follows:
(1) Cationic complexes [ Mg (OTf) (DME) ] 2 ] + Is consistent with the test result of mass spectrum m/z= 353.07; asymmetric isomerism bulky weakly coordinated boron anions [ B (OTf) (TFE) ] 3 ] - Is consistent with the spectral m/z= 456.98 test results (see fig. 1);
(2) The conductivity of the electrolyte was 1.72 mS.cm -1 ；
(3) Stainless steel is used as a working electrode, and the deposition overpotential is 270mV after the electrolyte circulates for 30 circles (see FIG. 2);
(4) Oxidation stability potential (vs. Mg/Mg of electrolyte on stainless steel, graphite foil and molybdenum foil electrodes 2+ ) Are all 3.0
(see fig. 3);
(5) The coulombic efficiency of the electrolyte in the reversible deposition-dissolution of magnesium (on Mo foil substrate) in the long-term cycle (1000 turns) was always kept at 98.20% (see fig. 4);
(6) At a current density of 0.1 mA.cm -2 At this time, the initial overpotential was 386mV,with increasing cycle time, the overpotential was 195mV and the polarization potential did not increase with steady cycling for 1000 hours (see fig. 5); at a current density of from 0.1mA cm -2 Gradually increase to 1.0mAcm -2 During the process of (1), the deposition overpotential value increases from 109mV to 208mV; when the current density is recovered to 0.5mAcm - And 0.1mAcm -2 At this time, the overpotential was slightly decreased compared to the previous one, because it was at 0.1mA cm -2 There is an electrochemical conditioning process (see fig. 6).
(7) The full cell can be reversibly cycled between charge and discharge at current densities of 0.1C,0.5C,1C,2C,5C, and 10C (see fig. 7).
(8) The full cell can be cycled stably for over 900 cycles at high current densities (see fig. 8).
The performance test results show that the prepared asymmetric heterogeneous boron center anion magnesium salt electrolyte sample 1 has the excellent performances of high conductivity, small overpotential, electrochemical window, high magnesium deposition-dissolution efficiency, good cycling stability, good compatibility with positive electrodes and the like.
In addition, performance tests were performed on the above-prepared asymmetric heterogeneous boron center anion magnesium salt electrolyte samples 2,3,4 and 5, respectively, by the above-described method, wherein cyclic voltammograms of the sample 2 using stainless steel as a working electrode are shown in fig. 9.
In addition, the test results of the above-mentioned different samples were tabulated as shown in table 2 below.
TABLE 2 Performance of asymmetric heterogeneous boron centered anionic magnesium salt electrolyte samples
As can be seen from fig. 2 to 9 and table 2, the asymmetric heterogeneous boron center anion magnesium salt electrolyte of the present invention has excellent performances of good oxidation stability, high conductivity, small overpotential, wide electrochemical window, high magnesium deposition-dissolution efficiency, good cycle stability, good compatibility with positive electrode, etc.;
in conclusion, the asymmetric heterogeneous boron center anion magnesium salt electrolyte is synthesized by adopting a one-step in-situ method, the raw material cost is low, the mutual synergistic effect among the components can endow the electrolyte with the performance advantages of high oxidation stability, low overpotential, good cycle stability, good compatibility with the positive electrode of a magnesium battery and the like, and the electrolyte has good commercial application prospect. In addition, the invention has the characteristics of simple preparation process and easy large-scale industrial production.
Finally, it is noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered by the scope of the claims of the present invention.
Claims (10)
1. The asymmetric heterogeneous boron center anion magnesium electrolyte salt is characterized by comprising anions shown in a structural formula (1),
wherein the-OR groups are each independently an alkoxy group OR a fluorinated alkoxy group and the-OR' groups are anionic groups of magnesium salts.
2. The asymmetric isomerism boron center anion magnesium electrolyte salt according to claim 1, wherein the preparation raw materials comprise magnesium salt, organic solvent and borate compound, wherein the borate compound is borate and/or borate derivative.
3. The asymmetric heterogeneous boron centered anionic magnesium electrolyte salt of claim 2, wherein the magnesium salt comprises one or more of magnesium chloride, magnesium alkoxide fluoride, magnesium nitrate, magnesium perchlorate, magnesium bis (diisopropylamine), magnesium bis (trifluoromethylsulfonyl) imide, and magnesium trifluoromethylsulfonate;
and/or the organic solvent comprises one or more combinations of 1, 3-dioxolane, 1, 3-dioxane, 1, 4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diethyl cellosolve, 1, 3-dimethoxypropane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-methoxyethylamine, 1-methoxy-2-propylamine, 3-methoxypropylamine, 2-ethoxyethylamine, N- (2-methoxyethyl) methylamine, bis (2-methoxyethyl) amine, 2 '-oxybis (ethylamine), 2-amino-1-methoxybutane, 2-propoxyethylamine, (1, 1-dimethyl-2-methoxyethyl) amine, 2-aminoethyl isopropyl ether, 3-isopropoxypropylamine, N' -dimethylethylenediamine, N '-diethylethylenediamine, ethylenediamine, N' -diisopropylethylenediamine, and 2- (trifluoromethoxy) ethane-1-amine;
and/or borate compounds including trimethyl borate, triethyl borate, triisopropyl borate, tri-t-butyl borate, tri (2, 2-trifluoroethyl) borate, tri (2, 3-tetrafluoropropyl) borate, tri (2, 2-difluoroethyl) borate tris (2, 3-pentafluoropropyl) borate, tris (hexafluoroisopropyl) borate tris (2, 3, 4-hexafluorobutyl) borate one or more of tris (2, 3, 4-hexafluorobutyl) borate and tris (perfluoro-t-butyl) borate.
4. The asymmetric heterogeneous boron-centered anionic magnesium electrolyte salt according to claim 2 or 3, characterized in that the preparation raw material thereof meets one or more of the following conditions: (a) The molar mass ratio of magnesium salt to borate/borate derivative is 1:
(0.5-2.2); (b) The molar concentration of magnesium ions was 0.1mol L -1 ～2.0molL -1 The method comprises the steps of carrying out a first treatment on the surface of the (c) the organic solvent has a water and oxygen content of less than 50ppm.
5. The asymmetric heterogeneous boron center anion magnesium electrolyte salt according to claim 2 or 3, wherein the borate compound is prepared by mixing a borane solution and a fluorine-containing alcohol at-2 ℃ to 2 ℃.
6. The method for producing an asymmetric heterogeneous boron-centered anionic magnesium electrolyte salt according to any one of claims 1 to 5, comprising: (1) mixing magnesium salt and organic solvent to obtain magnesium salt solution; (2) Mixing magnesium salt solution with borate compound to react and obtain the mixture containing asymmetric heterogeneous boron center anion magnesium electrolyte salt.
7. The method for preparing an asymmetric heterogeneous boron center anionic magnesium electrolyte salt according to claim 6, wherein in the step (1), the mixing may comprise: reacting for 2-12 h under magnetic stirring at normal temperature; and/or in step (2), the mixing may comprise: reacting for 12-48 h under magnetic stirring at normal temperature.
8. The method for preparing an asymmetric heterogeneous boron center anionic magnesium electrolyte salt according to claim 6 or 7, further comprising: and adding a poor solvent into the mixture containing the asymmetric heterogeneous boron center anion magnesium electrolyte salt under the anhydrous and anaerobic condition, performing suction filtration, and drying to obtain the asymmetric heterogeneous boron center anion magnesium electrolyte salt.
9. An asymmetric isomerism boron center anion magnesium salt electrolyte, characterized in that it comprises the asymmetric isomerism boron center anion magnesium electrolyte salt of any one of claims 1 to 5 and an organic solvent; the organic solvent comprises one or more combinations of 1, 3-dioxolane, 1, 3-dioxane, 1, 4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diethyl cellosolve, 1, 3-dimethoxypropane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-methoxyethylamine, 1-methoxy-2-propylamine, 3-methoxypropylamine, 2-ethoxyethylamine, N- (2-methoxyethyl) methylamine, bis (2-methoxyethyl) amine, 2 '-oxybis (ethylamine), 2-amino-1-methoxybutane, 2-propoxyethylamine, (1, 1-dimethyl-2-methoxyethyl) amine, 2-aminoethyl isopropyl ether, 3-isopropoxypropylamine, N' -dimethylethylenediamine, N '-diethylethylenediamine, ethylenediamine, N' -diisopropylethylenediamine, and 2- (trifluoromethoxy) ethane-1-amine.
10. Use of the asymmetric heterogeneous boron center anion magnesium electrolyte salt of any one of claims 1 to 5 or the asymmetric heterogeneous boron center anion magnesium salt electrolyte of claim 9 in the preparation of a magnesium battery.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007257875A (en) * | 2006-03-20 | 2007-10-04 | Central Glass Co Ltd | Electrolyte for nonaqueous electrolyte battery, electrolyte and nonaqueous electrolyte battery |
| CN106450448A (en) * | 2016-10-14 | 2017-02-22 | 中国科学院青岛生物能源与过程研究所 | Nonaqueous electrolyte and magnesium secondary battery of nonaqueous electrolyte |
| CN115954549A (en) * | 2023-01-31 | 2023-04-11 | 重庆长安新能源汽车科技有限公司 | Magnesium battery electrolyte, preparation method and magnesium battery |
-
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007257875A (en) * | 2006-03-20 | 2007-10-04 | Central Glass Co Ltd | Electrolyte for nonaqueous electrolyte battery, electrolyte and nonaqueous electrolyte battery |
| CN106450448A (en) * | 2016-10-14 | 2017-02-22 | 中国科学院青岛生物能源与过程研究所 | Nonaqueous electrolyte and magnesium secondary battery of nonaqueous electrolyte |
| CN115954549A (en) * | 2023-01-31 | 2023-04-11 | 重庆长安新能源汽车科技有限公司 | Magnesium battery electrolyte, preparation method and magnesium battery |
Non-Patent Citations (1)
| Title |
|---|
| 黄雪婷: "有机硼基可充镁电池电解液研究", 重庆大学硕士学位论文, 1 November 2023 (2023-11-01), pages 1 - 75 * |
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