CN117976986A - Fluorine-containing rechargeable magnesium battery electrolyte and preparation method and application thereof - Google Patents
Fluorine-containing rechargeable magnesium battery electrolyte and preparation method and application thereof Download PDFInfo
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- CN117976986A CN117976986A CN202410112360.4A CN202410112360A CN117976986A CN 117976986 A CN117976986 A CN 117976986A CN 202410112360 A CN202410112360 A CN 202410112360A CN 117976986 A CN117976986 A CN 117976986A
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- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 97
- 239000011737 fluorine Substances 0.000 title claims abstract description 97
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 239000011777 magnesium Substances 0.000 title claims abstract description 85
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 239000003792 electrolyte Substances 0.000 title claims abstract description 81
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000002841 Lewis acid Substances 0.000 claims abstract description 29
- 239000002879 Lewis base Substances 0.000 claims abstract description 27
- 150000007517 lewis acids Chemical class 0.000 claims abstract description 24
- 150000007527 lewis bases Chemical class 0.000 claims abstract description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 14
- 159000000003 magnesium salts Chemical class 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 239000002798 polar solvent Substances 0.000 claims abstract description 11
- 150000001412 amines Chemical class 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 125000003118 aryl group Chemical group 0.000 claims abstract description 6
- 125000003709 fluoroalkyl group Chemical group 0.000 claims abstract description 6
- 125000004407 fluoroaryl group Chemical group 0.000 claims abstract description 6
- 239000012046 mixed solvent Substances 0.000 claims abstract description 5
- 125000001033 ether group Chemical group 0.000 claims abstract description 4
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 3
- 125000004429 atom Chemical group 0.000 claims abstract description 3
- 229910052796 boron Inorganic materials 0.000 claims abstract description 3
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 3
- 150000002367 halogens Chemical group 0.000 claims abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 32
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 16
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 8
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 8
- ASUDFOJKTJLAIK-UHFFFAOYSA-N 2-methoxyethanamine Chemical compound COCCN ASUDFOJKTJLAIK-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- IWCVDCOJSPWGRW-UHFFFAOYSA-M magnesium;benzene;chloride Chemical compound [Mg+2].[Cl-].C1=CC=[C-]C=C1 IWCVDCOJSPWGRW-UHFFFAOYSA-M 0.000 claims description 5
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 4
- 229910001623 magnesium bromide Inorganic materials 0.000 claims description 4
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 claims description 4
- BLQJIBCZHWBKSL-UHFFFAOYSA-L magnesium iodide Chemical compound [Mg+2].[I-].[I-] BLQJIBCZHWBKSL-UHFFFAOYSA-L 0.000 claims description 4
- 229910001641 magnesium iodide Inorganic materials 0.000 claims description 4
- FRIJBUGBVQZNTB-UHFFFAOYSA-M magnesium;ethane;bromide Chemical compound [Mg+2].[Br-].[CH2-]C FRIJBUGBVQZNTB-UHFFFAOYSA-M 0.000 claims description 4
- YCCXQARVHOPWFJ-UHFFFAOYSA-M magnesium;ethane;chloride Chemical compound [Mg+2].[Cl-].[CH2-]C YCCXQARVHOPWFJ-UHFFFAOYSA-M 0.000 claims description 4
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims description 4
- VDFVNEFVBPFDSB-UHFFFAOYSA-N 1,3-dioxane Chemical compound C1COCOC1 VDFVNEFVBPFDSB-UHFFFAOYSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 2
- NXMXETCTWNXSFG-UHFFFAOYSA-N 1-methoxypropan-2-amine Chemical compound COCC(C)N NXMXETCTWNXSFG-UHFFFAOYSA-N 0.000 claims description 2
- IBZKBSXREAQDTO-UHFFFAOYSA-N 2-methoxy-n-(2-methoxyethyl)ethanamine Chemical compound COCCNCCOC IBZKBSXREAQDTO-UHFFFAOYSA-N 0.000 claims description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 2
- FAXDZWQIWUSWJH-UHFFFAOYSA-N 3-methoxypropan-1-amine Chemical compound COCCCN FAXDZWQIWUSWJH-UHFFFAOYSA-N 0.000 claims description 2
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 claims description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims 1
- 229910052785 arsenic Inorganic materials 0.000 claims 1
- 150000002148 esters Chemical group 0.000 claims 1
- 230000008021 deposition Effects 0.000 abstract description 14
- 238000004090 dissolution Methods 0.000 abstract description 13
- 239000002994 raw material Substances 0.000 abstract description 7
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 abstract description 6
- 229910001425 magnesium ion Inorganic materials 0.000 abstract description 6
- 230000010287 polarization Effects 0.000 abstract description 6
- 230000001351 cycling effect Effects 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 125000004185 ester group Chemical group 0.000 abstract description 2
- 230000006399 behavior Effects 0.000 abstract 1
- 239000003153 chemical reaction reagent Substances 0.000 description 18
- 238000005303 weighing Methods 0.000 description 18
- -1 Lewis base phenyl magnesium chloride Chemical class 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- 239000000243 solution Substances 0.000 description 12
- 229910001220 stainless steel Inorganic materials 0.000 description 9
- 239000010935 stainless steel Substances 0.000 description 9
- 238000002484 cyclic voltammetry Methods 0.000 description 7
- 238000007865 diluting Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- CHNLPLHJUPMEOI-UHFFFAOYSA-N oxolane;trifluoroborane Chemical compound FB(F)F.C1CCOC1 CHNLPLHJUPMEOI-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000002441 reversible effect Effects 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 229940021013 electrolyte solution Drugs 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 238000004502 linear sweep voltammetry Methods 0.000 description 2
- WRYKIHMRDIOPSI-UHFFFAOYSA-N magnesium;benzene Chemical compound [Mg+2].C1=CC=[C-]C=C1.C1=CC=[C-]C=C1 WRYKIHMRDIOPSI-UHFFFAOYSA-N 0.000 description 2
- QCEASURNFXDAGH-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-yloxyboronic acid Chemical compound OB(O)OC(C(F)(F)F)C(F)(F)F QCEASURNFXDAGH-UHFFFAOYSA-N 0.000 description 1
- 229910016569 AlF 3 Inorganic materials 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007922 dissolution test Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 150000002221 fluorine Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- OBCUTHMOOONNBS-UHFFFAOYSA-N phosphorus pentafluoride Chemical compound FP(F)(F)(F)F OBCUTHMOOONNBS-UHFFFAOYSA-N 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method 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
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a fluorine-containing rechargeable magnesium battery electrolyte, and a preparation method and application thereof. The electrolyte consists of fluorine-containing magnesium salt and organic aprotic polar solvent, wherein the fluorine-containing magnesium salt is a complex formed by compositing fluorine-containing Lewis acid R aAFb and magnesium-containing Lewis base R '2‑cMgXc, R is alkyl, alkoxy, ester group, aryl, fluoroalkyl and fluoroaryl, R' is alkyl, aryl, fluoroalkyl and fluoroaryl, X represents halogen, A is B, al, N, P, as atoms, a is a positive integer of 0-4, b is a positive integer of 1-5, and c is a positive integer of 0-2; the organic aprotic polar solvent is an ether solvent, an amine solvent or a mixed solvent thereof. The electrolyte of the fluorine-containing rechargeable magnesium battery has good electrochemical stability, does not passivate a magnesium electrode, can ensure high-efficiency deposition and dissolution behaviors of magnesium ions on the magnesium electrode, can obviously improve the cycling stability of the battery and reduce the polarization of the battery. In addition, the electrolyte has simple preparation process and wide raw material sources, and is beneficial to industrial application.
Description
Technical Field
The invention belongs to the technical field of electrochemistry, and particularly relates to a fluorine-containing rechargeable magnesium battery electrolyte, a preparation method and application thereof.
Background
Development of rechargeable batteries is a key to solving the problem of renewable energy storage. The metal magnesium has the advantages of abundant reserves, low cost, environmental protection, stable physical and chemical properties, high theoretical volume specific capacity (3833 mAh/cm 3) and the like. Therefore, rechargeable magnesium batteries using magnesium metal as a negative electrode have become a new energy storage system with great development prospects. However, magnesium metal is easy to be passivated in electrolyte, and has the problem of poor interface stability, which restricts the development of rechargeable magnesium batteries.
Studies have demonstrated that most fluorine-containing electrolytes are capable of participating in the formation of an electrode/electrolyte interface, and that the fluorine-containing species generated by its decomposition are critical to ensuring interface stability. The most representative fluorine-containing electrolyte was developed based on magnesium tetrakis (hexafluoroisopropyl) borate Mg (HFIP) 2. The electrolyte can realize efficient magnesium ion deposition and dissolution, and most importantly, the fluorine-containing magnesium salt can react with magnesium metal to generate a fluorine-containing interface (ACS ENERGY LETTERS,2018,3 (8): 2005-2013) with excellent performance. CN102916220B discloses a magnesium battery electrolyte, which consists of fluorine-containing magnesium salt and aprotic polar solvent. The fluorine-containing magnesium salt related to the patent can be obtained through multi-step reaction, which greatly increases the process difficulty of preparing fluorine-containing electrolyte. CN114551999B discloses an electrolyte for a rechargeable magnesium battery, a preparation method thereof, and a rechargeable magnesium battery comprising the same; in the patent, various fluorine-substituted alcohols are used as raw materials to synthesize a series of fluorine-containing magnesium salts, so that fluorine is introduced into electrolyte; however, fluoro substituted alcohols are expensive, which increases the cost of preparing the fluorine-containing electrolyte. In summary, the existing preparation method of the fluorine-containing electrolyte generally has the problems of complex process and high raw material price, so that the fluorine-containing electrolyte is difficult to commercially popularize.
Therefore, it is very urgent and important to develop a fluorine-containing rechargeable magnesium battery electrolyte with low cost and simple process.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide the fluorine-containing rechargeable magnesium battery electrolyte which solves the problems of poor electrochemical stability, high raw material cost, complex preparation process and the like existing in the prior art.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
The fluorine-containing rechargeable magnesium battery electrolyte is characterized in that the raw materials required for preparing the electrolyte comprise the following components: the fluorine-containing magnesium salt and the organic aprotic polar solvent are obtained by the reaction of fluorine-containing Lewis acid R aAFb and magnesium-containing Lewis base R '2-cMgXc, wherein A is B, al, N, P, as atoms, R is alkyl, alkoxy, ester group, aryl, fluoroalkyl and fluoroaryl, R' is alkyl, aryl, fluoroalkyl and fluoroaryl, X represents halogen, a is a positive integer of 0-4, b is a positive integer of 1-5, c is a positive integer of 0-2, and the organic aprotic polar solvent is an ether solvent, an amine solvent or a mixed solvent thereof.
Further:
The above-mentioned fluorine-containing lewis acid R aAFb is a main source of fluorine element in the fluorine-containing electrolyte, where b is not zero, and may be a positive integer of 1 to 5, which means that the lewis acid contains at least one F atom.
The fluorine-containing magnesium salt can be obtained by reacting one fluorine-containing Lewis acid with one magnesium-containing Lewis base, or can be obtained by reacting a plurality of fluorine-containing Lewis acids with a plurality of magnesium-containing Lewis bases.
The concentration of fluorine-containing magnesium salt in the fluorine-containing rechargeable magnesium battery electrolyte is 0.1-10.0 mol/L.
The ratio of the fluorine-containing Lewis acid to the magnesium-containing Lewis base is 5:1-1:5.
The fluorine-containing lewis acid may be selected from compounds represented by any of the following structural formulas:
The above magnesium-containing lewis base may be selected from compounds represented by any one of the following structural formulas: phMgCl, phMgBr, ph 2Mg、EtMgCl、EtMgBr、MgCl2、MgBr2、MgI2 (PhMgCl, phMgBr, ph 2Mg、EtMgCl、EtMgBr、MgCl2、MgBr2、MgI2),
The organic aprotic polar solvent is an ether solvent, an amine solvent or a mixed solvent thereof.
The ether solvent can be one or more of ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1, 3-dioxane, 1, 4-dioxane, diethyl ether and butyl ether.
The amine solvent can be one or more of 2-methoxyethylamine, 3-methoxypropylamine, di (2-methoxyethyl) amine, 2-methoxyisopropyl amine and 1, 4-oxazahexacyclic ring.
The invention also provides a preparation method of the fluorine-containing rechargeable magnesium battery electrolyte, which specifically comprises the following steps:
And mixing the fluorine-containing Lewis acid, the magnesium-containing Lewis base and the organic aprotic polar solvent in proportion at the temperature of between 0 and 80 ℃ and stirring for 2 to 72 hours to obtain the fluorine-containing rechargeable magnesium battery electrolyte.
In yet another aspect, the present invention provides a rechargeable magnesium battery comprising the fluorine-containing rechargeable magnesium battery electrolyte described above.
Preferably:
the concentration of the fluorine-containing magnesium salt is 0.5-1.0 mol/L.
The preparation ratio of the fluorine-containing Lewis acid to the magnesium-containing Lewis base is 2:1-1:2.
The fluorine-containing Lewis acid can be selected from BF 3、PF5 and AlF 3 small molecular compounds, and the fluorine-containing raw materials are all industrial products, and have wide sources and low cost.
The preparation method of the fluorine-containing rechargeable magnesium battery electrolyte has the advantages of mild conditions and simple operation, and the experimental temperature is 25-50 ℃ and the reaction time is 2-48 hours.
Compared with the prior art, the invention has the following beneficial effects:
(1) The fluorine-containing rechargeable magnesium battery electrolyte provided by the invention has the advantages that the fluorine-containing component can endow the electrolyte with good electrochemical stability and compatibility, a magnesium electrode is not passivated, the efficient deposition and dissolution behavior of magnesium ions on the magnesium electrode can be ensured, meanwhile, the cycling stability of the battery can be obviously improved, and the polarization of the battery is reduced.
(2) The fluorine-containing rechargeable magnesium battery electrolyte provided by the invention is prepared from fluorine-containing magnesium salt (which is a complex formed by compositing fluorine-containing Lewis acid and magnesium-containing Lewis base and is used as a solute) and an organic aprotic polar solvent, has the advantages of simple preparation process, low raw material cost and wide source, and is beneficial to industrial application.
Drawings
FIG. 1 is a cyclic voltammogram of a stainless steel electrode scanned over a different number of turns in an electrolyte as described in example 1;
FIG. 2 is a cyclic voltammogram of a stainless steel electrode scanned over a different number of turns in an electrolyte as described in example 2;
FIG. 3 is a cyclic voltammogram of a stainless steel electrode scanned over a different number of turns in the electrolyte described in comparative example 1;
FIG. 4 is a graph showing reversible magnesium deposition/dissolution cycle curves and coulombic efficiencies at a current density of 0.5mA cm -2 in the electrolyte described in example 1 using a stainless steel foil as the working electrode;
FIG. 5 is a graph showing reversible magnesium deposition/dissolution cycle curves and coulombic efficiencies at a current density of 0.5mA cm -2 in the electrolyte described in example 2 using a stainless steel foil as the working electrode;
FIG. 6 is a graph of polarization performance of a Mg symmetric cell assembled using the electrolyte of example 1 at a current density of 0.5mA cm -2;
FIG. 7 is a graph of polarization performance of a Mg symmetric cell assembled with the electrolyte of example 2 at a current density of 0.5mA cm -2;
fig. 8 is a graph of capacity and coulombic efficiency of a Mo 6S8 Mg cell assembled using the electrolyte of example 1.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It should be noted that these examples are only for illustrating the present invention, and not for limiting the present invention, and simple modifications of the method under the premise of the inventive concept are all within the scope of the claimed invention.
1. Preparation of electrolyte
Example 1
Firstly, weighing 0.2798g of fluorine-containing Lewis acid boron trifluoride tetrahydrofuran complex in a reagent bottle, and diluting with 4mL of tetrahydrofuran; second step, weighing 0.2737g of Lewis base phenyl magnesium chloride and 0.5712g of Lewis base magnesium chloride in another reagent bottle, and dissolving the components by using 4mL of tetrahydrofuran; and thirdly, mixing the two solutions, stirring, and reacting for 48 hours at room temperature to obtain the fluorine-containing rechargeable magnesium battery electrolyte.
Example 2
Firstly, weighing 0.2798g of fluorine-containing Lewis acid boron trifluoride tetrahydrofuran complex in a reagent bottle, and diluting with 4mL of tetrahydrofuran; second step, weighing 0.3626g of Lewis base phenylmagnesium bromide and 0.5712g of Lewis base magnesium chloride in another reagent bottle, and dissolving the components by using 4mL of tetrahydrofuran; and thirdly, mixing the two solutions, stirring, and reacting for 24 hours at room temperature to obtain the fluorine-containing rechargeable magnesium battery electrolyte.
Example 3
Firstly, weighing 0.2798g of fluorine-containing Lewis acid boron trifluoride tetrahydrofuran complex in a reagent bottle, and diluting with 3mL of tetrahydrofuran; weighing 0.2737g of Lewis alkali phenyl magnesium chloride in another reagent bottle, and dissolving the Lewis alkali phenyl magnesium chloride in 3mL of tetrahydrofuran; and thirdly, mixing the two solutions, then adding 1mL of 2-methoxyethylamine, stirring, and reacting for 48 hours at room temperature to obtain the fluorine-containing rechargeable magnesium battery electrolyte.
Example 4
Firstly, weighing 0.2798g of fluorine-containing Lewis acid boron trifluoride tetrahydrofuran complex in a reagent bottle, and diluting with 3mL of tetrahydrofuran; step two, weighing 0.3626g of Lewis base phenylmagnesium bromide in another reagent bottle, and dissolving the same by using 3mL of tetrahydrofuran; and thirdly, mixing the two solutions, then adding 1mL of 2-methoxyethylamine, stirring, and reacting for 48 hours at room temperature to obtain the fluorine-containing rechargeable magnesium battery electrolyte.
Example 5
Firstly, weighing 0.2798g of fluorine-containing Lewis acid boron trifluoride tetrahydrofuran complex in a reagent bottle, and diluting with 3mL of tetrahydrofuran; weighing 0.3570g of Lewis base diphenylmagnesium in another reagent bottle, and dissolving by using 3mL of tetrahydrofuran; and thirdly, mixing the two solutions, then adding 1mL of 2-methoxyethylamine, stirring, and reacting for 48 hours at room temperature to obtain the fluorine-containing rechargeable magnesium battery electrolyte.
Example 6
Firstly, weighing 0.2519g of fluorine-containing Lewis acid phosphorus pentafluoride in a reagent bottle, and dissolving by using 4mL of ethylene glycol dimethyl ether; weighing 0.3570g of Lewis base diphenylmagnesium in another reagent bottle, and dissolving by using 4mL of ethylene glycol dimethyl ether; and thirdly, mixing the two solutions, stirring, and reacting for 24 hours at room temperature to obtain the fluorine-containing rechargeable magnesium battery electrolyte.
Example 7
Firstly, weighing 0.1679g of fluorine-containing Lewis acid aluminum trifluoride in a reagent bottle, and dissolving the fluorine-containing Lewis acid aluminum trifluoride in 5mL of diethylene glycol dimethyl ether; weighing 0.4266g of Lewis base 4-fluoro-2-methylphenyl magnesium bromide and 0.5712g of Lewis base magnesium chloride in another reagent bottle, and dissolving the components by using 5mL of diethylene glycol dimethyl ether; and thirdly, mixing the two solutions, stirring, and reacting for 48 hours at 50 ℃ to obtain the fluorine-containing rechargeable magnesium battery electrolyte.
Example 8
Firstly, weighing 0.2798g of fluorine-containing Lewis acid boron trifluoride tetrahydrofuran complex in a reagent bottle, and diluting with 5mL of tetrahydrofuran; step two, weighing 0.4266g of Lewis base 4-fluoro-2-methylphenyl magnesium bromide and 0.5712g of Lewis base magnesium chloride in another reagent bottle, and dissolving the components by using 5mL of tetrahydrofuran; and thirdly, mixing the two solutions, stirring, and reacting for 12 hours at room temperature to obtain the fluorine-containing rechargeable magnesium battery electrolyte.
Comparative example 1
Firstly, weighing 0.2343g of Lewis acid boron trichloride in a reagent bottle, and dissolving the Lewis acid boron trichloride in 4mL of tetrahydrofuran; weighing 0.2737g of Lewis alkali phenyl magnesium chloride in another reagent bottle, and dissolving by using 4mL of tetrahydrofuran; and thirdly, mixing the two solutions, stirring, and reacting for 48 hours at room temperature to obtain the fluorine-free rechargeable magnesium battery electrolyte.
2. Performance detection and evaluation of electrolyte
1. Conductivity test
The conductivity of the electrolyte is tested by using an alternating current impedance technology; stainless steel foil electrodes are used as working electrodes and counter electrodes; the disturbance voltage is 5mV, and the frequency range is 1 MHz-0.01 Hz; the test temperature was 30 ℃.
2. Reversible magnesium deposition dissolution Performance and oxidative stability test
Reversible magnesium deposition dissolution performance and oxidation stability of the electrolyte are respectively obtained through cyclic voltammetry and linear sweep voltammetry tests. The linear sweep voltammetry test adopts a two-electrode system, a magnesium sheet electrode is used as a counter electrode, a stainless steel electrode is used as a working electrode, the test voltage range is scanned from open circuit voltage to 4V, and the sweep speed is 1mV s -1. The cyclic voltammetry test adopts a three-electrode system, a magnesium sheet electrode is used as a reference electrode and a counter electrode, a stainless steel electrode is used as a working electrode, the test voltage range is scanned from-1V to 2V, and the scanning speed is 25mV s -1.
3. Magnesium deposition/dissolution cycle efficiency test
The deposition/dissolution cycle efficiency and the charge-discharge characteristics of magnesium in the electrolyte were tested using a coin cell, using a magnesium sheet electrode as a counter electrode, stainless steel as a working electrode, a test current density of 0.5mA cm -2, a discharge time of 0.5 hours, and a charge cut-off voltage of 1V.
4. Polarization performance test
Long-term cycling stability of magnesium in electrolyte was tested by button cell; the working electrode and the counter electrode are both made of magnesium sheets, the test current density is 0.5mA cm -2, and the charge/discharge time is 0.5 hour.
5. Battery performance test
And a constant current charge and discharge test is carried out by taking a magnesium sheet as a negative electrode and Mo 6S8 as a positive electrode to assemble a button cell, wherein the charge and discharge working voltage range is 0.2-1.8V, and the current is 0.5C.
The electrolytes prepared in examples 1 to 8 and comparative example 1 were tested using the above test methods and analyzed as follows:
As can be seen from Table 1, the various properties of the fluorine-containing rechargeable magnesium battery electrolyte are superior to those of the fluorine-free electrolyte, especially in the magnesium deposition/dissolution test. The fluorine-free electrolyte does not support efficient and stable deposition/dissolution of magnesium, but the deposition/dissolution process of magnesium in the fluorine-containing electrolyte can be stably circulated for a long time, and the average coulombic efficiency is high. This is because the fluorine-containing component can form a protective layer on the surface of the magnesium electrode, which can effectively improve the interfacial stability and give the battery better cycle performance.
TABLE 1 electrochemical Properties of the electrolytes prepared in examples 1 to 8 and comparative example 1
Referring to fig. 1 and 2, which are cyclic voltammetry test curves of the fluorine-containing electrolyte solutions described in examples 1 and 2, respectively, magnesium ions can perform normal deposition and dissolution behavior, and have good reversibility, and as the cycle proceeds, the test curves substantially coincide, which indicates that the electrochemical process of magnesium ions gradually tends to be stable.
Fig. 3 is a cyclic voltammetry test curve of the fluorine-free electrolyte solution of comparative example 1, in which magnesium ions cannot be normally deposited and eluted, indicating passivation of the magnesium electrode. Such comparison further reflects the advantages of the fluorine-containing electrolyte.
Referring to fig. 4 to 7, the fluorine-containing electrolytes described in examples 1 and 2 exhibited good stability in both magnesium deposition dissolution coulombic efficiency and polarization performance tests.
Fig. 8 shows the cycling performance of the fluorine-containing electrolyte described in example 1 in a Mo 6S8 Mg cell with little capacity fade after 600 cycles of cell cycling. In addition, after the battery cycle is stabilized, the coulombic efficiency per charge-discharge cycle is close to 100%, exhibiting very excellent battery performance.
Compared with the examples 1 and 2, the mixed solvents of ethers and amines are used in the examples 3 and 4, so that the oxidation stability of the electrolyte is slightly improved; the fluorine-containing electrolyte prepared in the examples 5 and 6 does not contain corrosive chloride ions and bromide ions, so that the oxidation stability of the electrolyte is greatly improved; examples 7 and 8 use both a fluorine-containing lewis acid and a fluorine-containing lewis base to prepare a fluorine-containing electrolyte, and the molecular structure of the fluorine-containing lewis base is large, and the migration resistance of the corresponding ions in the electrolyte is large, resulting in a slight decrease in conductivity. In general, examples 3 to 8 have comparable electrochemical properties and battery performance as examples 1 and 2, but the average coulombic efficiency is not as good as examples 1 and 2, and the capacity and coulombic efficiency graphs of the electrolyte assembled batteries of examples 3 to 8 and the like are omitted herein.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the technical solution, and those skilled in the art should understand that modifications and equivalents may be made to the technical solution of the present invention without departing from the spirit and scope of the present invention, and all such modifications and equivalents are included in the scope of the claims.
Claims (10)
1. The fluorine-containing rechargeable magnesium battery electrolyte is characterized by being prepared from fluorine-containing magnesium salt serving as a solute and an organic aprotic polar solvent, wherein the concentration of the fluorine-containing magnesium salt is 0.1-10.0 mol/L.
2. The fluorine-containing rechargeable magnesium battery electrolyte according to claim 1, wherein the fluorine-containing magnesium salt is a complex formed by compositing fluorine-containing Lewis acid R aAFb and magnesium-containing Lewis base R' 2-cMgXc, and the preparation ratio of the fluorine-containing Lewis acid to the magnesium-containing Lewis base is 5:1-1:5.
3. The fluorine-containing rechargeable magnesium battery electrolyte of claim 2, wherein the fluorine-containing lewis acid is R aAFb, wherein a is B, al, N, P or As atom, R is alkyl, alkoxy, ester, aryl, fluoroalkyl or fluoroaryl, a is a positive integer from 0 to 4, and b is a positive integer from 1 to 5.
4. A fluorine-containing rechargeable magnesium battery electrolyte according to claim 3, wherein said fluorine-containing lewis acid is selected from compounds represented by any of the following structural formulas:
5. The fluorine-containing rechargeable magnesium battery electrolyte of claim 2, wherein the magnesium-containing lewis base is R '2-cMgXc, wherein R' is an alkyl, aryl, fluoroalkyl or fluoroaryl group, X represents a halogen, and c is a positive integer from 0 to 2.
6. The fluorine-containing rechargeable magnesium battery electrolyte of claim 5, wherein the magnesium-containing lewis base is selected from compounds represented by any of the following structural formulas: phMgCl, phMgBr, ph 2Mg、EtMgCl、EtMgBr、MgCl2、MgBr2、MgI2 (PhMgCl, phMgBr, ph 2Mg、EtMgCl、EtMgBr、MgCl2、MgBr2、MgI2),
7. The fluorine-containing rechargeable magnesium battery electrolyte of claim 1, wherein the organic aprotic polar solvent is an ether solvent, an amine solvent or a mixed solvent thereof.
8. The fluorine-containing rechargeable magnesium battery electrolyte of claim 7, wherein the ether solvent is one or more of ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1, 3-dioxolane, 1, 3-dioxane, 1, 4-dioxane, diethyl ether, butyl ether; the amine solvent is one or more of 2-methoxyethylamine, 3-methoxypropylamine, di (2-methoxyethyl) amine, 2-methoxyisopropyl amine and 1, 4-oxazahexacyclic ring.
9. The preparation method of the fluorine-containing rechargeable magnesium battery electrolyte is characterized by comprising the following steps of: mixing the fluorine-containing Lewis acid, the magnesium-containing Lewis base and the organic aprotic polar solvent according to any one of claims 1 to 8 at the temperature of 0 to 80 ℃ and stirring for 2 to 72 hours to obtain the fluorine-containing rechargeable magnesium battery electrolyte.
10. Use of the electrolyte according to claims 1-9 in rechargeable magnesium batteries.
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