CN106916173B - Monokaryon magnesium cation salt dissolving, preparation method and application - Google Patents
Monokaryon magnesium cation salt dissolving, preparation method and application Download PDFInfo
- Publication number
- CN106916173B CN106916173B CN201510996796.5A CN201510996796A CN106916173B CN 106916173 B CN106916173 B CN 106916173B CN 201510996796 A CN201510996796 A CN 201510996796A CN 106916173 B CN106916173 B CN 106916173B
- Authority
- CN
- China
- Prior art keywords
- magnesium
- electrolyte
- monokaryon
- halide ion
- dimethyl ether
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical class [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000011777 magnesium Substances 0.000 claims abstract description 66
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 45
- -1 halide ion Chemical class 0.000 claims abstract description 42
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 40
- 239000003792 electrolyte Substances 0.000 claims abstract description 35
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 38
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 32
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 239000002608 ionic liquid Substances 0.000 claims description 15
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- 159000000003 magnesium salts Chemical class 0.000 claims description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 6
- 150000007527 lewis bases Chemical class 0.000 claims description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 5
- 239000002841 Lewis acid Substances 0.000 claims description 5
- 239000002879 Lewis base Substances 0.000 claims description 5
- 150000001638 boron Chemical class 0.000 claims description 5
- 229910001387 inorganic aluminate Inorganic materials 0.000 claims description 5
- 150000007517 lewis acids Chemical class 0.000 claims description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical class CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 4
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 claims description 4
- 230000005611 electricity Effects 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000003053 piperidines Chemical class 0.000 claims description 3
- 229910016913 AlY3 Inorganic materials 0.000 claims description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- DUDHRYJQHQPTER-UHFFFAOYSA-N N=NC=NN.N=NC=NN.C(COCCO)O Chemical group N=NC=NN.N=NC=NN.C(COCCO)O DUDHRYJQHQPTER-UHFFFAOYSA-N 0.000 claims 1
- 150000002367 halogens Chemical class 0.000 claims 1
- 238000004090 dissolution Methods 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 6
- 230000002441 reversible effect Effects 0.000 abstract description 6
- 238000007254 oxidation reaction Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000000354 decomposition reaction Methods 0.000 abstract 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 27
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 17
- 239000000243 solution Substances 0.000 description 15
- 150000003839 salts Chemical class 0.000 description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
- 150000001450 anions Chemical group 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 8
- 229910001629 magnesium chloride Inorganic materials 0.000 description 8
- 230000008021 deposition Effects 0.000 description 7
- 238000000921 elemental analysis Methods 0.000 description 7
- 238000004146 energy storage Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- SMDQFHZIWNYSMR-UHFFFAOYSA-N sulfanylidenemagnesium Chemical compound S=[Mg] SMDQFHZIWNYSMR-UHFFFAOYSA-N 0.000 description 6
- XPDWGBQVDMORPB-UHFFFAOYSA-N trifluoromethane acid Natural products FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 6
- 238000001237 Raman spectrum Methods 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 230000018109 developmental process Effects 0.000 description 5
- 229910001425 magnesium ion Inorganic materials 0.000 description 5
- 238000010189 synthetic method Methods 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- RWRDLPDLKQPQOW-UHFFFAOYSA-O Pyrrolidinium ion Chemical compound C1CC[NH2+]C1 RWRDLPDLKQPQOW-UHFFFAOYSA-O 0.000 description 3
- 238000001069 Raman spectroscopy Methods 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000003949 imides Chemical class 0.000 description 3
- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical compound CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 description 2
- 239000007818 Grignard reagent Substances 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000002048 anodisation reaction Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000011712 cell development Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000004795 grignard reagents Chemical class 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 238000004502 linear sweep voltammetry Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229940096405 magnesium cation Drugs 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- HPVKETCOXLFZKK-UHFFFAOYSA-N 2-butyl-1-methylpiperidine Chemical class CCCCC1CCCCN1C HPVKETCOXLFZKK-UHFFFAOYSA-N 0.000 description 1
- ZPOLNCDBPYJDSE-UHFFFAOYSA-N 3-[4-[bis(2-chloroethyl)amino]phenyl]-2-formamidopropanoic acid Chemical class O=CNC(C(=O)O)CC1=CC=C(N(CCCl)CCCl)C=C1 ZPOLNCDBPYJDSE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229910019389 Mg(CF3SO3)2 Inorganic materials 0.000 description 1
- LPEBZWCCILEKJA-UHFFFAOYSA-N N=NC=NN.N=NC=NN.C(COCCOCCO)O Chemical compound N=NC=NN.N=NC=NN.C(COCCOCCO)O LPEBZWCCILEKJA-UHFFFAOYSA-N 0.000 description 1
- GJEAMHAFPYZYDE-UHFFFAOYSA-N [C].[S] Chemical compound [C].[S] GJEAMHAFPYZYDE-UHFFFAOYSA-N 0.000 description 1
- QYHKLBKLFBZGAI-UHFFFAOYSA-N boron magnesium Chemical class [B].[Mg] QYHKLBKLFBZGAI-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910001914 chlorine tetroxide Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 229940021013 electrolyte solution Drugs 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000615 nonconductor Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
-
- 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
- H01M10/0568—Liquid materials characterised by the solutes
-
- 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)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a kind of monokaryon magnesium cation salt dissolving, preparation method and applications.The chemical formula of the monokaryon magnesium cation salt dissolving is MgRnMX4‑mYm, wherein R is nonaqueous solvents molecule, and M includes Al3+And/or B3+, X, Y include halide ion or class halide ion, any integer of the n in 0~6, any integer of the m in 0~4.Monokaryon magnesium cation salt dissolving structure provided by the invention is simple, electrochemical properties are excellent, and preparation method is inexpensive one-step synthesis technique, raw material is easy to get, preparation process is simple, easy large-scale production, the monokaryon magnesium cation salt dissolving is when being applied to the electrolyte of rechargeable magnesium cell, electrolyte is formed by with high ionic conductivity, reversible deposition-the dissolution efficiency of high magnesium, excellent cycle performance and high anodic oxidation decomposition electric potential, such as when the electrolyte is applied to magnesium cell, its initial discharge capacity can achieve 700mAh/g or more, and 20 circles or more can be recycled.
Description
Technical field
Present invention relates particularly to a kind of monokaryon magnesium cation salt dissolving, preparation method and applications, belong to electrochemical energy neck
Domain.
Background technique
New stage geared to the 21st century to efficiently, cleaning, economy and safety energy system requirement, the green of Development of Novel,
High-performance, extensive energy storage technology simultaneously efficiently utilize new energy, it has also become the whole world common the problem of paying close attention to necessarily becomes with development
Gesture.Lithium ion battery energy storage system is as effective energy storage mode by the concern and again of energy sector, various countries and energy enterprise
Depending on occupying core status in current energy storage industrial circle.But global lithium resource reserves are limited, and uneven (main point of spatial distribution
Cloth is in South America), this not only causes the lithium ion battery cost of raw material high, and there is the wind for being limited by other country's export restrictions in the future
Danger, and in the large-sized batteries such as automobile, energy storage field, application still has serious safety problem, such as tesla to lithium ion battery
The a lot of firing accidents of electric car, 787 aircraft safety Frequent Accidents of Boeing etc., safety problem have become the following lithium ion battery and produce
The main bottleneck of industry and market development.
Compared with lithium, magnesium has higher capacity, richer reserves and less expensive price and higher safety,
It is widely regarded as the candidate of most potential rear lithium ion battery, future is expected to substitution lithium ion battery as green
Battery applications are in electric car and large-scale energy storage field.But magnesium cell is compared with mature lithium ion battery energy storage technology,
There are still many challenges.
The key factor for wherein restricting rechargeable magnesium cell development is mainly golden in most non-proton electrolyte solutions
Belong to magnesium surface and easily form one layer of fine and close passivating film, which is the non-conductor of magnesium ion, causes magnesium ion that can not wear
It crosses, eventually leads to battery cisco unity malfunction.Up to the present, electrolyte is still the maximum bottle for hindering rechargeable magnesium cell development
Neck.
Experimental results demonstrate with simple lithium ion salt (LiClO common in commercial li-ion battery4, LiPF6、Li
(CF3SO3)2Deng) unlike, in simple monokaryon magnesium cation salt dissolving (such as MgCl2、Mg(ClO4)2、Mg(CF3SO3)2Deng)
One layer of fine and close passivating film for not leading magnesium ion easy to form in aprotic polar solvent electrolyte, causing magnesium ion cannot achieve can
It is inverse to deposit and dissolve (Journal of Electroanalytical Chemistry, 1999,466 (2): 203-217), therefore
It cannot be used for rechargeable magnesium cell.Although research find magnesium in the ethereal solution of Grignard Reagent can reversible deposition and dissolution, by
In common Grignard Reagent electrochemical window is too narrow and high activity, and it cannot be used directly for rechargeable magnesium cell electrolyte.Then, have
The ethereal solution of machine boron magnesium salts and organo-aluminium magnesium salts is also found to may be implemented reversible magnesium deposition and dissolution so that rechargeable magnesium cell to
Practical huge step, but such electrolytic salt cationic portion is usually double-core magnesium cation, volume is bigger, unfavorable
In ionic conduction；And anion part contains organic group, electrochemical stability is poor；In addition their preparation process is more multiple
Miscellaneous, cost is relatively high.
Therefore development structure is simple, synthetic method is efficient, electrochemical performance magnesium eletrolysis matter salt is for that can fill magnesium electricity
The commercialization in pond has great importance.
Summary of the invention
The main purpose of the present invention is to provide a kind of monokaryon magnesium cation salt dissolving, preparation method and applications, to overcome
Deficiency in the prior art.
For realization aforementioned invention purpose, the technical solution adopted by the present invention includes:
The embodiment provides a kind of monokaryon magnesium cation salt dissolving, chemical formula MgRnMX4-mYm, wherein R be
Nonaqueous solvents molecule, M include Al3+And/or B3+, X, Y include halide ion or class halide ion, and n is any whole in 0~6
Number, any integer of the m in 0~4.
Wherein, the halide ion includes F?、Cl?、Br?Or I?。
Wherein, the class halide ion includes CN-Or SCN?。
Further, R preferably from but be not limited to tetrahydrofuran, toluene, glycol dimethyl ether, diethylene glycol dimethyl ether,
Triethylene glycol dimethyl ether, tetraethyleneglycol dimethyl ether, dioxane, pyridine, dimethyl sulfoxide, dimethylformamide, N-methyl imidazoles,
Acetonitrile or polyethylene glycol dimethyl ether.
The embodiments of the present invention also provide a kind of synthetic methods of monokaryon magnesium cation salt dissolving comprising: Mg will be contained2+'s
Lewis acid with contain Al3+And/or B3+Lewis base reacted in nonaqueous solvents, the monokaryon magnesium cation salt dissolving is made.
More preferred, for the reaction temperature that the synthetic method uses for 30~200 DEG C, the reaction time is 3~48h.
Further, the lewis acid includes inorganic magnesium salt, such as MgX2, wherein X includes halide ion or class halogen
Ion.
Further, the lewis base includes inorganic aluminate and/or boron salt, such as AlY3、BY3, wherein Y includes halogen
Ion or class halide ion.
Further, the halide ion includes F?、Cl?、Br?Or I?。
Further, the class halide ion includes CN-Or SCN?。
Further, the nonaqueous solvents is preferably from ionic liquid and/or organic solvent, for example, can be selected from imidazoles from
Bis- (fluoroform sulphonyl) inferior amine salts of sub- liquid such as 1- ethyl-3-methylimidazole tetrafluoroborate and 1- ethyl-3-methylimidazole,
Bis- (fluoroform sulphonyl) inferior amine salts of pyrrole ionic liquid such as N- butyl-N- crassitude, piperidines ionic liquid such as N-
Bis- (fluoroform sulphonyl) inferior amine salts of butyl-N- methyl piperidine and tetrahydrofuran, toluene, glycol dimethyl ether, diethylene glycol
Dimethyl ether, triethylene glycol dimethyl ether, tetraethyleneglycol dimethyl ether, dioxane, pyridine, dimethyl sulfoxide, dimethylformamide, n-formyl sarcolysine
Any one or more in the organic solvents such as base imidazoles, acetonitrile or polyethylene glycol dimethyl ether, and it is without being limited thereto.
Among one more preferred embodiment, the synthetic method includes: to utilize higher boiling and high chemistry
(such as 1- butyl -1- crassitude is double with the green solvent ionic liquid or high boiling organic solvent of electrochemical stability
Bis- (fluoroform sulphonyl) inferior amine salts of (trifluoro methylsulfonyl) inferior amine salt, N- butyl-N- methyl piperidine, diethylene glycol dimethyl ether, three
Glycol dimethyl ether, tetraethyleneglycol dimethyl ether, polyethylene glycol dimethyl ether etc.) as inorganic magnesium salt and inorganic aluminate and/or inorganic
The reaction dissolvent of boron salt, by the lewis acidity using inorganic aluminate and/or inorganic boron salt under heating conditions completely and
The lewis base part of inorganic magnesium salt is reacted, and monokaryon magnesium cation salt dissolving (the also referred to as pure nothing of monokaryon magnesium cation is made
Machine electrolytic salt).
The embodiments of the present invention also provide a kind of electrolyte, it includes nonaqueous solvents, including organic solvent and/or from
Sub- liquid；And it is dissolved in the monokaryon magnesium cation salt dissolving in the nonaqueous solvents.In the electrolyte, the monokaryon
Magnesium cation salt dissolving system is as electrolyte.
More preferred, the electrolyte concentration in the electrolyte is 0.1~1.5mol/L.
Further, the ionic liquid and/or organic solvent include glyoxaline ion liquid such as 1- ethyl -3- methyl miaow
Azoles tetrafluoroborate and bis- (fluoroform sulphonyl) inferior amine salts of 1- ethyl-3-methylimidazole, pyrrole ionic liquid such as N- butyl-
Bis- (fluoroform sulphonyl) inferior amine salts of N- crassitude, the piperidines ionic liquid such as bis- (fluoroforms of N- butyl-N- methyl piperidine
Alkane sulphonyl) inferior amine salt and tetrahydrofuran, toluene, glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, four
Glycol dimethyl ether, dioxane, pyridine, dimethyl sulfoxide, dimethylformamide, N-methyl imidazoles, acetonitrile or polyethylene glycol two
One of organic solvents such as methyl ether are a variety of, and without being limited thereto.
It is electric in preparing magnesium that the embodiments of the present invention also provide the monokaryon magnesium cation salt dissolvings or the electrolyte
Purposes in pond.Wherein, the magnesium cell includes magnesium one-shot battery or Mg secondary cell etc., such as magnesium sulfur rechargeable battery, but not
It is limited to this.
Compared with prior art, the invention has the advantages that
(1) a kind of method of inexpensive one-step synthesis monokaryon magnesium cation salt dissolving is provided, raw material is easy to get, preparation process
Simply, easy large-scale production, overcome existing rechargeable magnesium cell electrolytic salt synthetic method it is cumbersome, at high cost the deficiencies of.
(2) provide monokaryon magnesium cation salt dissolving structure it is simple, cationic portion be monokaryon magnesium ion, be easy to magnesium from
Son conduction；Anion part is free of organic group, and electrochemical properties are relatively stable, and performance is more excellent, on the one hand overcomes
Simple magnesium eletrolysis matter salt can not achieve the problem of reversible deposition and dissolution, on the other hand can overcome it is existing being capable of reversible realization magnesium
Structure is complicated for deposition and the magnesium eletrolysis matter salt of dissolution, it is difficult to the defects of synthesizing, it is important to pushing the development of rechargeable magnesium cell to play
Effect.
(3) the monokaryon magnesium cation salt dissolving provided is formed by electrolyte when being applied to the electrolyte of rechargeable magnesium cell
Electricity is decomposed with high ionic conductivity, the reversible deposition-dissolution efficiency of high magnesium, excellent cycle performance and high anodic oxidation
Position, such as when the electrolyte is applied to magnesium sulfur rechargeable battery, initial discharge capacity can achieve 700mAh/g or more, and
And 20 circles or more can be recycled.
Detailed description of the invention
Fig. 1 is that [Mg (THF) is obtained in the embodiment of the present invention 16][AlCl4]2Crystal structure figure；
Fig. 2 is [Mg (THF) in the embodiment of the present invention 76][AlCl4]2Cyclic voltammogram；
Fig. 3 is [Mg (THF) in the embodiment of the present invention 76][AlCl4]2Linear sweep voltammetry figure；
Fig. 4 is [Mg (DMSO) in the embodiment of the present invention 86][AlCl4]2Cyclic voltammogram；
Fig. 5 is [Mg (DMSO) in the embodiment of the present invention 96][AlF4]2Cyclic voltammogram；
Fig. 6 is the first charge-discharge curve graph of magnesium sulphur battery in the embodiment of the present invention 10；
Fig. 7 is the cycle performance test chart of magnesium sulphur battery in the embodiment of the present invention 10.
Specific embodiment
The exemplary embodiments for embodying feature of present invention and advantage will describe in detail in the following description.It should be understood that this
Invention can have various variations in different embodiments, neither depart from the scope of the present invention, and it is therein explanation and
Diagram inherently is illustrated as being used, rather than to limit the present invention.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention
The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool
The purpose of the embodiment of body, it is not intended that in the limitation present invention.
Embodiment 1:56mg anhydrous magnesium chloride (MgCl2) and 158mg anhydrous aluminum chloride (AlCl3) in 1mL ionic liquid 1- fourth
Bis- (trifluoro methylsulfonyl) inferior amine salt (n-methyl- (n-butyl) the pyrrolidinium bis of base -1- crassitude
(trifluoromethanesulfonyl) imide, PYR14TFSI) in 95 DEG C of reactions obtain lurid solution within 24 hours, it is cold
But to room temperature, another addition 1mL THF, which obtains 0.3M, can fill magnesium eletrolysis liquid, its electrolytic salt of Crystal Structure is [Mg (THF)6]
[AlCl4]2, crystal structure is as shown in Figure 1.Elemental Analysis theory is C 36.28, H 6.09；Measured value is C 36.27%,
N6.10%.Raman spectrum test result 350cm-1For anion AlCl4 -Characteristic peak, have no the drawing of other aluminum chloride anions
Man Feng.
Embodiment 2:56mg anhydrous magnesium chloride (MgCl2) and 158mg anhydrous aluminum chloride (AlCl3) in 1mL triethylene glycol diformazan
30 DEG C of reactions obtain lurid solution in 24 hours in ether (TEGDME), are cooled to room temperature, and magnesium eletrolysis liquid can be filled by obtaining 0.6M, brilliant
Its electrolytic salt of body structural characterization is [Mg (TEGDME)2][AlCl4]2.Elemental Analysis theory is C 22.87, H4.48；Measurement
Being worth is C, 22.89%；N 4.47%.Raman spectrum test result 350cm-1For anion AlCl4 -Characteristic peak, have no other
The Raman peaks of aluminum chloride anion.
Embodiment 3:56mg anhydrous magnesium chloride (MgCl2) and 158mg anhydrous aluminum chloride (AlCl3) 100 DEG C in 1mL toluene
Reaction obtains lurid solution in 24 hours, is cooled to room temperature, and magnesium eletrolysis liquid, its electrolysis of Crystal Structure can be filled by obtaining 0.6M
Matter salt is [Mg (toluene)6][AlCl4]2.Elemental Analysis theory is C 55.15, H 5.29；Measured value is C, 55.10%；
H5.30%.Raman spectrum test result 350cm-1For anion AlCl4 -Characteristic peak, have no the drawing of other aluminum chloride anions
Man Feng.
Embodiment 4:56mg anhydrous magnesium chloride (MgCl2) and 158mg anhydrous aluminum chloride (AlCl3) in 1mL polyethylene glycol diformazan
95 DEG C of reactions obtain lurid solution in 24 hours in ether, are cooled to room temperature, magnesium eletrolysis liquid can be filled by obtaining 0.6M.Raman spectrum is surveyed
Test result 350cm-1For anion AlCl4 -Characteristic peak, have no the Raman peaks of other aluminum chloride anions.
Embodiment 5:56mg anhydrous magnesium chloride (MgCl2) and 158mg anhydrous aluminum chloride (AlCl3) in 1mL dimethyl sulfoxide
(DMSO) 120 DEG C of reactions obtain lurid solution in 24 hours in, are cooled to room temperature, magnesium eletrolysis liquid, structure can be filled by obtaining 0.6M
Characterizing its electrolytic salt is [Mg (DMSO)6][AlCl4]2.Elemental Analysis theory is C 17.35, H 4.37；Measured value is C
17.36%, H 4.37%.Raman spectrum test result 350cm-1For anion AlCl4 -Characteristic peak, have no other aluminium chloride
The Raman peaks of anion.
Embodiment 6:56mg anhydrous magnesium chloride (MgCl2) and 100.8mg aluminum fouoride (AlF3) in 1mL ionic liquid 1-
Bis- (trifluoro methylsulfonyl) inferior amine salt (n-methyl- (n-butyl) the pyrrolidinium bis of butyl -1- crassitude
(trifluoromethanesulfonyl) imide, PYR14TFSI) in 150 DEG C of reactions obtain lurid solution within 24 hours,
It is cooled to room temperature, another addition 1mL THF, which obtains 0.3M, can fill magnesium eletrolysis liquid, and it is [Mg (THF) that crystal structure, which tests electrolytic salt,6]
[AlClF3]2.Elemental Analysis theory is C 41.43, H 6.95；Measured value is C 41.40%, H 6.97%.
Embodiment 7:19mg anhydrous magnesium chloride (MgF2) and 100.8mg aluminum fouoride (AlF3) in 1mL dimethyl sulfoxide
(DMSO) 200 DEG C of reactions obtain lurid solution in 24 hours in, are cooled to room temperature, magnesium eletrolysis liquid, structure can be filled by obtaining 0.6M
Characterizing its electrolytic salt is [Mg (DMSO)6][AlF4]2.Elemental Analysis theory is C 20.62, H 5.19；Measured value is
C20.61%, H 5.20%.
Embodiment 8:56mg anhydrous magnesium chloride (MgCl2) and the anhydrous boron chloride (BCl of 69mg3) in 1mL ionic liquid 1- fourth
Bis- (trifluoro methylsulfonyl) inferior amine salt (n-methyl- (n-butyl) the pyrrolidinium bis of base -1- crassitude
(trifluoromethanesulfonyl) imide, PYR14TFSI) in 95 DEG C of reactions obtain colourless solution within 24 hours, be cooled to
Room temperature, another addition 1mL THF, which obtains 0.3M, can fill magnesium eletrolysis liquid, its electrolytic salt of Crystal Structure is [Mg (THF)6]
[BCl4]2.Elemental Analysis theory is C 37.82, H 6.35；Measured value is C 37.82%, H 6.34%.
Embodiment 9: being worked electrode using platinum, the magnesium salts ([Mg (THF) of 0.3M6][AlCl4]2) PYR14TFSI/THF
Solution as electrolyte, make that electrode and reference electrode are assembled into three-electrode system, are followed in argon gas glove box by magnesium metal
The test of ring volt-ampere, scanning speed 25mV/s, cyclic voltammetric and linear sweep voltammetry result are as shown in Figures 2 and 3, can by Fig. 2
Know, the reduction-oxidation process occurred near 0.2V and -0.2V vs.Mg corresponds to the deposition and dissolution of magnesium, anodization potentials
It can achieve 2.5V vs.Mg.
Embodiment 10: being worked electrode using copper, the magnesium salts ([Mg (DMSO) of 0.3M6][AlCl4]2) PYR14TFSI/
THF solution as electrolyte, make to be assembled into three-electrode system to electrode and reference electrode by magnesium metal, in argon gas glove box into
Row cyclic voltammetry, scanning speed 25mV/s, cyclic voltammetric result is as shown in figure 4, as shown in Figure 4, in 0.2V and -0.2V
The reduction-oxidation process that vs.Mg nearby occurs corresponds to the deposition and dissolution of magnesium.
Embodiment 11: being worked electrode using platinum, the magnesium salts ([Mg (DMSO) of 0.3M6][AlF4]2) DMSO solution conduct
Electrolyte, magnesium metal are made to be assembled into three-electrode system to electrode and reference electrode, and cyclic voltammetric survey is carried out in argon gas glove box
Examination, scanning speed 25mV/s, cyclic voltammetric result near 0.2V and -0.2V vs.Mg as shown in figure 5, as shown in Figure 5, go out
Existing reduction-oxidation process corresponds to the deposition and dissolution of magnesium, and anodization potentials can achieve 2.6V vs.Mg.
Embodiment 12: electrolyte, the magnesium salts ([Mg (THF) of 0.3M are used as using sulphur carbon complex (S/C)6][AlCl4]2)
PYR14TFSI/THF solution as electrolyte, magnesium metal makees cathode, assembles magnesium sulphur battery, charging and discharging curve and cycle performance
Test is as shown in Figure 6 and Figure 7, by Fig. 6 and Fig. 7 it is found that the first capacity of putting of magnesium sulphur battery can be followed at 700 MAhs/g or so
It is more than the circle of ring 20.
It should be understood that embodiment described in the invention is not intended to limit the invention merely for exemplary purpose
Protection scope, those skilled in the art can be made within the scope of the invention various other replacements, changes and improvements, thus,
The present invention is not limited to the above embodiments, and is only defined by the claims.
Claims (11)
1. a kind of electrolyte, it is characterised in that include: nonaqueous solvents is selected from organic solvent and/or ionic liquid；And it is molten
In the monokaryon magnesium cation salt dissolving in the nonaqueous solvents；The chemical formula of the monokaryon magnesium cation salt dissolving is [MgRn][MX4- mYm]2, wherein R be selected from tetrahydrofuran, toluene, dioxane, pyridine, dimethyl sulfoxide, dimethylformamide, N-methyl imidazoles,
Acetonitrile, glycol dimethyl ether or polyethylene glycol dimethyl ether, M are selected from Al3+And/or B3+, X, Y be selected from halide ion or class halogen from
Son, the class halide ion are selected from CN-Or SCN?, any integer of the n in 0 ~ 6, any integer of the m in 0 ~ 4.
2. electrolyte according to claim 1, it is characterised in that: the polyethylene glycol dimethyl ether is selected from diethylene glycol diformazan
Ether, triethylene glycol dimethyl ether or tetraethyleneglycol dimethyl ether.
3. electrolyte according to claim 1, which is characterized in that the preparation method of the electrolyte includes:
Mg will be contained2+Lewis acid with contain Al3+And/or B3+Lewis base reacted in nonaqueous solvents the electrolyte be made,
The nonaqueous solvents is selected from organic solvent；
Alternatively, Mg will be contained2+Lewis acid with contain Al3+And/or B3+Lewis base reacted in ionic liquid, be added later
Organic solvent, so that the electrolyte be made.
4. electrolyte according to claim 3, it is characterised in that: the reaction temperature that the preparation method uses for 30~
200 DEG C, the reaction time is 3~48h.
5. electrolyte according to claim 3, it is characterised in that: the lewis acid is selected from inorganic magnesium salt, described inorganic
Magnesium salts is MgX2, X is selected from halide ion or class halide ion, and the class halide ion is selected from CN-Or SCN?。
6. electrolyte according to claim 3, it is characterised in that: the lewis base is selected from inorganic aluminate and/or boron salt,
The inorganic aluminate is AlY3, the boron salt is BY3, Y is selected from halide ion or class halide ion, and the class halide ion is selected from
CN-Or SCN?。
7. electrolyte according to claim 1, it is characterised in that: the electrolyte concentration in the electrolyte is 0.1 ~ 1.5
mol/L。
8. electrolyte according to claim 1 or 3, it is characterised in that: the ionic liquid be selected from glyoxaline ion liquid,
Pyrrole ionic liquid or piperidines ionic liquid.
9. electrolyte according to claim 1 or 3, it is characterised in that: the organic solvent be selected from tetrahydrofuran, toluene,
Glycol dimethyl ether, dioxane, pyridine, dimethyl sulfoxide, dimethylformamide, N-methyl imidazoles, acetonitrile or polyethylene glycol two
Methyl ether.
10. electrolyte of any of claims 1-9 is in preparing the purposes in magnesium cell.
11. purposes according to claim 10, it is characterised in that: the magnesium cell is selected from magnesium one-shot battery or the secondary electricity of magnesium
Pond.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510996796.5A CN106916173B (en) | 2015-12-28 | 2015-12-28 | Monokaryon magnesium cation salt dissolving, preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510996796.5A CN106916173B (en) | 2015-12-28 | 2015-12-28 | Monokaryon magnesium cation salt dissolving, preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106916173A CN106916173A (en) | 2017-07-04 |
| CN106916173B true CN106916173B (en) | 2019-03-08 |
Family
ID=59455738
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510996796.5A Active CN106916173B (en) | 2015-12-28 | 2015-12-28 | Monokaryon magnesium cation salt dissolving, preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106916173B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109873156A (en) * | 2019-02-18 | 2019-06-11 | 上海交通大学 | A kind of preparation method and its battery assembly of high capacity Mg secondary cell cobalt sulfide positive electrode |
| CN110336079B (en) * | 2019-06-24 | 2020-11-10 | 清华大学 | Magnesium battery electrolyte, preparation method thereof and magnesium battery |
| CN111370759B (en) * | 2020-03-17 | 2023-03-17 | 清华大学 | Magnesium battery electrolyte, preparation method thereof and magnesium battery |
| CN111769282B (en) * | 2020-06-22 | 2021-10-22 | 上海交通大学 | Application method of water-based binder in magnesium-sulfur battery |
| CN112133964A (en) * | 2020-09-23 | 2020-12-25 | 杭州怡莱珂科技有限公司 | Magnesium ion electrolyte solution and preparation method thereof |
| CN114552018A (en) * | 2022-02-15 | 2022-05-27 | 清华大学 | Magnesium battery electrolyte, preparation method thereof and magnesium battery |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101689680A (en) * | 2007-07-11 | 2010-03-31 | 索尼公司 | Magnesium ion-containing nonaqueous electrolyte, process for producing the nonaqueous electrolyte, and electrochemical device |
| CN103066326A (en) * | 2013-01-18 | 2013-04-24 | 上海交通大学 | Electrolyte for chargeable magnesium battery |
| US20130115521A1 (en) * | 2011-03-08 | 2013-05-09 | Pellion Technologies, Inc. | Rechargeable magnesium ion cell components and assembly |
| CN103794815A (en) * | 2014-02-18 | 2014-05-14 | 上海交通大学 | Electrolytic solution of rechargeable magnesium cell and application method thereof |
-
2015
- 2015-12-28 CN CN201510996796.5A patent/CN106916173B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101689680A (en) * | 2007-07-11 | 2010-03-31 | 索尼公司 | Magnesium ion-containing nonaqueous electrolyte, process for producing the nonaqueous electrolyte, and electrochemical device |
| US20130115521A1 (en) * | 2011-03-08 | 2013-05-09 | Pellion Technologies, Inc. | Rechargeable magnesium ion cell components and assembly |
| CN103066326A (en) * | 2013-01-18 | 2013-04-24 | 上海交通大学 | Electrolyte for chargeable magnesium battery |
| CN103794815A (en) * | 2014-02-18 | 2014-05-14 | 上海交通大学 | Electrolytic solution of rechargeable magnesium cell and application method thereof |
Non-Patent Citations (5)
| Title |
|---|
| Influence of MgCl2 on Grignard reagent composition in tetrahydrofuran.III*;Piotr Sobota等;《Journal of Organometallic Chemistry》;19871231;第332卷;第239-245页 * |
| Reaction of MgCl2 with AlCl3 in ethyl acetate. The crystal structure of [Mg(CH3OCOC2H5)6][AlCl4]2;Jozef Utko等;《Journal of Organometallic Chemistry》;19891231;第359卷;第295-300页 * |
| STN检索报告;Columbus, Ohio;《STN Registry》;19841116;第1-3页 * |
| Structural diversity and spectral and thermal properties of thefirst alkaline earth metal tetracyanidoborates: [Mg(H2O)6][B(CN)4]2,[Mg(H2O)2]-[B(CN)4]2,[Mg(DMF)6][B(CN)4]2,[Ca(H2O)3][B(CN)4]2,and [Ca(H2O)2(CH3CN)][B(CN)4]2;Christian Nitschke等;《Dalton Trans.》;20140225;第43卷;第7128-7138页 * |
| Synthesis,Crystal Structure,and Electrochemical Properties of aSimple Magnesium Electrolyte for Magnesium/Sulfur Batteries;Wanfei Li等;《Angew.Chem.Int. Ed. 》;20160420;第55卷;第6406-6410页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106916173A (en) | 2017-07-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106916173B (en) | Monokaryon magnesium cation salt dissolving, preparation method and application | |
| KR102180394B1 (en) | Mononuclear magnesium cationized salt, preparation method and application thereof | |
| Banerjee et al. | Superior lithium storage properties of α-Fe2O3 nano-assembled spindles | |
| Liu et al. | Ionic liquids based on (fluorosulfonyl)(pentafluoroethanesulfonyl) imide with various oniums | |
| Zhao et al. | A novel polyquinone cathode material for rechargeable lithium batteries | |
| Xia et al. | Ionic liquid electrolytes for aluminium secondary battery: Influence of organic solvents | |
| JP5956573B2 (en) | Magnesium battery electrolyte | |
| JP5956175B2 (en) | Magnesium secondary battery, method of using electrolyte in magnesium secondary battery, and electrolyte for magnesium secondary battery | |
| CN102368561B (en) | Chargeable and dischargeable lithium sulfur cell | |
| Reed et al. | A combined experimental and computational study of an aluminum triflate/diglyme electrolyte | |
| CN106384844A (en) | Non-nucleophilic dual-salt-system electrolyte for magnesium cell, and preparation method and application thereof | |
| CN103490094A (en) | Magnesium battery electrolyte and magnesium battery containing it | |
| CN104681300B (en) | Polyaniline-sulfonated graphene composite electrode material and preparation method thereof | |
| CN105938918A (en) | Liquid electrolyte for fluoride ion battery and fluoride ion battery | |
| CN107275615A (en) | A kind of sulphur copper compound C-base composte material is the aluminium ion battery of positive pole | |
| Zhang et al. | New ionic liquids based on a super-delocalized perfluorinated sulfonimide anion: physical and electrochemical properties | |
| Fang et al. | Guanidinium-based ionic liquids as new electrolytes for lithium battery | |
| CN115051033A (en) | Application of fluoroether solvent and electrolyte in energy storage battery | |
| CN105063665A (en) | Method for electrically depositing nanometer platinum powder from ionic liquid | |
| CN113363578B (en) | Boron-based non-nucleophilic rechargeable magnesium battery electrolyte and preparation method thereof | |
| Lu et al. | Aqueous aluminum-zinc hybrid ion batteries with urea-based hydrated eutectic electrolytes | |
| Yu et al. | Separator pore size induced oriented Zn deposition | |
| CN107417588B (en) | A kind of novel ion liquid and the method using its electrolytic preparation nano aluminum | |
| CN104134551B (en) | A kind of electrolyte solute, electrolyte and high tension super capacitor | |
| Xie et al. | Regulating horizontal lamellar Zn to uniformly deposit under and on the hollow porous carbon nanosphere coating for dendrite-free metal Zn anode |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |