CN117374383A - Eutectic solid electrolyte for lithium metal battery and preparation method and application thereof - Google Patents
Eutectic solid electrolyte for lithium metal battery and preparation method and application thereof Download PDFInfo
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- CN117374383A CN117374383A CN202311326656.8A CN202311326656A CN117374383A CN 117374383 A CN117374383 A CN 117374383A CN 202311326656 A CN202311326656 A CN 202311326656A CN 117374383 A CN117374383 A CN 117374383A
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- lithium
- eutectic
- solid electrolyte
- eutectic solvent
- lithium metal
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- 230000005496 eutectics Effects 0.000 title claims abstract description 150
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 81
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 239000002904 solvent Substances 0.000 claims abstract description 86
- 150000002148 esters Chemical class 0.000 claims abstract description 82
- 239000000178 monomer Substances 0.000 claims abstract description 50
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 49
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 49
- 239000011261 inert gas Substances 0.000 claims abstract description 44
- 239000003999 initiator Substances 0.000 claims abstract description 38
- 239000011259 mixed solution Substances 0.000 claims abstract description 38
- 238000002156 mixing Methods 0.000 claims abstract description 34
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 29
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 11
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 18
- -1 lithium tetrafluoroborate Chemical compound 0.000 claims description 14
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 12
- 229910001416 lithium ion Inorganic materials 0.000 claims description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 11
- 230000000379 polymerizing effect Effects 0.000 claims description 9
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 3
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 2
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 11
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 4
- 239000011245 gel electrolyte Substances 0.000 abstract description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 32
- 229910052786 argon Inorganic materials 0.000 description 16
- 210000004027 cell Anatomy 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- UBESIXFCSFYQNK-UHFFFAOYSA-N ethyl 1,3-oxazole-4-carboxylate Chemical compound CCOC(=O)C1=COC=N1 UBESIXFCSFYQNK-UHFFFAOYSA-N 0.000 description 7
- 239000003365 glass fiber Substances 0.000 description 7
- 239000012528 membrane Substances 0.000 description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000001307 helium Substances 0.000 description 4
- 229910052734 helium Inorganic materials 0.000 description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 4
- 239000011244 liquid electrolyte Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 3
- 230000022131 cell cycle Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000001453 impedance spectrum Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- PAEYAKGINDQUCT-UHFFFAOYSA-N Ethyl 2-pyrrolecarboxylate Chemical compound CCOC(=O)C1=CC=CN1 PAEYAKGINDQUCT-UHFFFAOYSA-N 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229910001251 solid state electrolyte alloy Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UXPXQSWKWHQUCB-UHFFFAOYSA-N 5-(furan-2-yl)-1h-indole Chemical compound C1=COC(C=2C=C3C=CNC3=CC=2)=C1 UXPXQSWKWHQUCB-UHFFFAOYSA-N 0.000 description 1
- NHXSTXWKZVAVOQ-UHFFFAOYSA-N Ethyl furoate Chemical compound CCOC(=O)C1=CC=CO1 NHXSTXWKZVAVOQ-UHFFFAOYSA-N 0.000 description 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- MVMPKHJUPNWMDZ-UHFFFAOYSA-N ethyl 1,3-thiazole-2-carboxylate Chemical compound CCOC(=O)C1=NC=CS1 MVMPKHJUPNWMDZ-UHFFFAOYSA-N 0.000 description 1
- XDOKFEJMEJKVGX-UHFFFAOYSA-N ethyl 1,3-thiazole-4-carboxylate Chemical compound CCOC(=O)C1=CSC=N1 XDOKFEJMEJKVGX-UHFFFAOYSA-N 0.000 description 1
- KACZQOKEFKFNDB-UHFFFAOYSA-N ethyl 1h-pyrazole-4-carboxylate Chemical compound CCOC(=O)C=1C=NNC=1 KACZQOKEFKFNDB-UHFFFAOYSA-N 0.000 description 1
- LSMRKPLDOFLBCT-UHFFFAOYSA-N ethyl 3-methylfuran-2-carboxylate Chemical compound CCOC(=O)C=1OC=CC=1C LSMRKPLDOFLBCT-UHFFFAOYSA-N 0.000 description 1
- WISQBJLUORKXNY-UHFFFAOYSA-N ethyl 4-methyl-1,3-thiazole-5-carboxylate Chemical compound CCOC(=O)C=1SC=NC=1C WISQBJLUORKXNY-UHFFFAOYSA-N 0.000 description 1
- QKZGUSXVOYLZTM-UHFFFAOYSA-N ethyl 5-bromo-1,3-thiazole-4-carboxylate Chemical compound CCOC(=O)C=1N=CSC=1Br QKZGUSXVOYLZTM-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- KUWWRNNYEYGSBQ-UHFFFAOYSA-N methyl 1,3-thiazole-4-carboxylate Chemical compound COC(=O)C1=CSC=N1 KUWWRNNYEYGSBQ-UHFFFAOYSA-N 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000001228 spectrum 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
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/12—Esters of monohydric alcohols or phenols
- C08F120/14—Methyl esters, e.g. methyl (meth)acrylate
-
- 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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
Abstract
The invention provides a eutectic solid electrolyte of a lithium metal battery, a preparation method and application thereof, and belongs to the technical field of lithium metal batteries. The invention provides a preparation method of a eutectic solid electrolyte of a lithium metal battery, which comprises the following steps: under the inert gas atmosphere, mixing a eutectic solvent, an ester monomer and an initiator to obtain a mixed solution; the eutectic solvent is a binary eutectic solvent of five-membered ring ester and lithium salt; or the eutectic solvent is a ternary eutectic solvent of five-membered ring ester, lithium salt and succinonitrile; and (3) under the inert gas atmosphere, immersing the diaphragm in the obtained mixed solution, and then carrying out polymerization reaction to obtain the eutectic solid electrolyte of the lithium metal battery. The lithium metal battery of the invention is commonThe crystalline solid electrolyte is a solid electrolyte, not a gel electrolyte, and has an ionic conductivity of 0.265 to 0.467 mS.cm at room temperature ‑1 The method comprises the steps of carrying out a first treatment on the surface of the The assembled full battery has higher capacity and better cycle stability; and the raw materials are widely available, the preparation process is simple, the cost is low, the environment is protected, and the method is suitable for large-scale production.
Description
Technical Field
The invention relates to the technical field of lithium metal batteries, in particular to a eutectic solid electrolyte for a lithium metal battery, and a preparation method and application thereof.
Background
Lithium metal batteries have become the primary energy storage device used in everyday life. However, with the rapid development of electric vehicles, portable devices, and various flexible wearable devices, the demand for batteries having light weight, smaller size, and higher output voltage and energy density is expanding. However, lithium metal batteries have limited commercial applications because of the inevitable occurrence of lithium dendrites using conventional liquid electrolytes.
A eutectic solvent, i.e. a mixture comprising at least two substances, both solid at room temperature, wherein the melting point of the mixture is lower than the melting point of either substance. Since the eutectic solvent is solid at room temperature, the problem of lithium dendrite of the liquid electrolyte can be avoided when the eutectic solvent and the polymer are prepared into a solid electrolyte. Furthermore, eutectic solvents have the characteristics of ionic liquids for the most part, such as thermal stability, a wide electrochemical window, low vapor pressure, excellent conditioning and higher ionic conductivity. Meanwhile, the eutectic solvent has more obvious advantages than the ionic liquid solvent, such as simple preparation, low cost and no toxicity. Thus, solid electrolytes can theoretically replace conventional liquid electrolytes. However, since ion transport is difficult in a solid electrolyte relative to a liquid electrolyte, the ionic conductivity of the solid electrolyte is relatively low, and the ionic conductivity is an important indicator for measuring the electrical performance of the battery, reflecting the migration rate of ions inside the battery, and has an important influence on the performance of the battery. For example, the invention patent publication No. CN112687959A discloses a method for producing a solid electrolyte, a solid electrolyte and a solid battery, but the ion conductivity of the produced solid electrolyte is at most only 3.6X10 -6 S·cm -1 Still at a lower level, resulting in a higher internal resistance of the battery,limiting the use of solid state electrolytes in lithium metal batteries.
Therefore, it is needed to provide a method for preparing a eutectic solid electrolyte of a lithium metal battery, so that the prepared eutectic solid electrolyte of the lithium metal battery can have higher ionic conductivity, and the lithium metal battery can have higher capacity and cycle stability when being used for the lithium metal battery.
Disclosure of Invention
The invention aims to provide a eutectic solid electrolyte of a lithium metal battery, a preparation method and application thereof. The lithium metal battery eutectic solid electrolyte prepared by the preparation method provided by the invention has higher ionic conductivity, and the assembled lithium ion secondary battery has higher capacity and cycle stability.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a eutectic solid electrolyte of a lithium metal battery, which comprises the following steps:
(1) Under the inert gas atmosphere, mixing a eutectic solvent, an ester monomer and an initiator to obtain a mixed solution; the eutectic solvent is a binary eutectic solvent of five-membered ring ester and lithium salt; or the eutectic solvent is a ternary eutectic solvent of five-membered ring ester, lithium salt and succinonitrile;
(2) And (3) immersing the diaphragm in the mixed solution obtained in the step (1) in an inert gas atmosphere, and then carrying out polymerization reaction to obtain the eutectic solid electrolyte of the lithium metal battery.
Preferably, when the eutectic solvent in the step (1) is a binary eutectic solvent, the mass ratio of the five-membered ring ester, the lithium salt, the ester monomer and the initiator is (1-5): (0.1-10): (0.1-10): (0.0001 to 0.5); when the eutectic solvent in the step (1) is a ternary eutectic solvent, the mass ratio of the five-membered ring ester, the lithium salt, the succinonitrile, the ester monomer and the initiator is (0.1-10): (0.1-20): (0.1-10): (0.1-10): (0.0001-0.5).
Preferably, the temperature of the mixing in the step (1) is room temperature, and the mixing time is 5-60 min.
Preferably, the five-membered ring ester in the step (1) is obtained by polymerizing a monomer containing a five-membered ring structure and having a melting point lower than 100 ℃.
Preferably, the lithium salt in step (1) comprises one or more of lithium bis (trifluoromethanesulfonyl) imide, lithium tetrafluoroborate, lithium bis (oxalato) borate, lithium difluorooxalato borate, lithium perchlorate, lithium hexafluorophosphate and lithium hexafluoroarsenate.
Preferably, the ester monomer in the step (1) comprises an acrylate or a carbonate.
Preferably, the initiator in the step (1) is azobisisobutyronitrile.
Preferably, the temperature of the polymerization reaction in the step (2) is 50-100 ℃, and the time of the polymerization reaction is 0.5-12 h.
The invention also provides the eutectic solid electrolyte of the lithium metal battery, which is prepared by the preparation method.
The invention also provides application of the eutectic solid electrolyte of the lithium metal battery in a lithium ion secondary battery.
The invention provides a preparation method of a eutectic solid electrolyte of a lithium metal battery, which comprises the following steps: (1) Under the inert gas atmosphere, mixing a eutectic solvent, an ester monomer and an initiator to obtain a mixed solution; the eutectic solvent is a binary eutectic solvent of five-membered ring ester and lithium salt; or the eutectic solvent is a ternary eutectic solvent of five-membered ring ester, lithium salt and succinonitrile; (2) And (3) immersing the diaphragm in the mixed solution obtained in the step (1) in an inert gas atmosphere, and then carrying out polymerization reaction to obtain the eutectic solid electrolyte of the lithium metal battery. The pentatomic ring ester and the lithium salt in the eutectic solid electrolyte of the lithium metal battery can form a binary eutectic solvent, and meanwhile, the pentatomic ring ester, the lithium salt and the succinonitrile can form a ternary eutectic solvent, so that the positive electrode (such as lithium cobaltate and lithium nickel cobalt manganate ternary material) of the lithium metal battery has better stability under high pressure, and meanwhile, lithium ions in the lithium salt have good diffusion rate in the solid electrolyte, so that the solid electrolyte has higher ion conductivity, and higher capacity and cycle stability in the charge and discharge process of the lithium battery are ensured; the ester monomer and the initiator are added to be capable of in-situ polymerization to form binary or ternary eutectic solid electrolyte; wherein succinonitrile, pentatomic cyclic ester and lithium salt are all solid at room temperature, so that the electrolyte polymerized is solid electrolyte, not gel electrolyte. In addition, the solid electrolyte prepared by the preparation method has the advantages of wide sources of raw materials, simple preparation process, low cost, environmental protection and suitability for large-scale production, and can be applied to lithium metal secondary batteries.
The results of the examples show that the ionic conductivity of the eutectic solid electrolyte of the lithium metal battery prepared by the preparation method provided by the invention is 0.265-0.467 mS.cm at room temperature -1 (an increase in ionic conductivity of two orders of magnitude relative to prior art solid state electrolytes); the eutectic solid electrolyte of the lithium metal battery prepared by the preparation method is used for assembling the button battery, the current density of the assembled button battery is 0.5C, and the theoretical capacity of the corresponding NCM811 is 200 mAh.g -1 The voltage window is 2.5-4.8V and circulates at 0.5C, and the capacity is 164.2 mAh.g at 20 th turn -1 Has higher capacity and better cycle stability.
Drawings
FIG. 1 is a graph showing the impedance spectrum at room temperature of a (binary) eutectic solid electrolyte for a lithium metal battery prepared in example 2 of the present invention;
FIG. 2 is a graph showing the impedance of the (ternary) eutectic solid electrolyte of a lithium metal battery prepared in example 5 of the present invention at room temperature;
FIG. 3 is a LSV spectrum of the button cell prepared in application example 5 of the present invention;
FIG. 4 is a fifth charge/discharge curve of the button cell prepared in application example 5 of the present invention at 0.5C;
fig. 5 is a full cell cycle chart at 0.5C of the coin cell battery prepared in application example 5 of the present invention.
Detailed Description
The invention provides a preparation method of a eutectic solid electrolyte of a lithium metal battery, which comprises the following steps:
(1) Under the inert gas atmosphere, mixing a eutectic solvent, an ester monomer and an initiator to obtain a mixed solution; the eutectic solvent is a binary eutectic solvent of five-membered ring ester and lithium salt; or the eutectic solvent is a ternary eutectic solvent of five-membered ring ester, lithium salt and succinonitrile;
(2) And (3) immersing the diaphragm in the mixed solution obtained in the step (1) in an inert gas atmosphere, and then carrying out polymerization reaction to obtain the eutectic solid electrolyte of the lithium metal battery.
In the invention, under the inert gas atmosphere, a eutectic solvent, an ester monomer and an initiator are mixed to obtain a mixed solution.
In the present invention, the inert gas atmosphere is preferably argon, helium, or nitrogen. According to the invention, the raw materials are mixed in the inert gas atmosphere, so that air interference can be avoided.
In one technical scheme of the invention, the eutectic solvent is a binary eutectic solvent of five-membered ring ester and lithium salt. In another technical scheme of the invention, the eutectic solvent is a ternary eutectic solvent of five-membered ring ester, lithium salt and succinonitrile.
In the present invention, the five-membered ring ester is preferably obtained by polymerizing a monomer having a five-membered ring structure and a melting point lower than 100 ℃. In the present invention, the monomer having a five-membered ring structure and a melting point lower than 100℃preferably includes ethyl 4-thiazolecarboxylate, ethyl 5-bromo-4-thiazolecarboxylate, methyl 4-thiazolecarboxylate, ethyl 4-pyrazolecarboxylate, ethyl 4-oxazolecarboxylate, ethyl 4-methylthiazole-5-carboxylate, ethyl thiazole-2-carboxylate, ethyl 4, ethyl pyrimidine formate, ethyl pyrrole-2-carboxylate, ethyl 2-furancarboxylate, ethyl furoate or ethyl 3-methyl-2-furancarboxylate. The invention can ensure that the polymerized five-membered ring ester has a stable five-membered ring structure by selecting the monomers, thereby ensuring that the prepared eutectic solid electrolyte has good stability in the battery, and further ensuring that the assembled battery has higher capacitance and cycle stability.
In the present invention, the lithium salt preferably includes one or more of lithium bistrifluoromethane sulfonyl imide, lithium tetrafluoroborate, lithium bisoxalato borate, lithium difluorooxalato borate, lithium perchlorate, lithium hexafluorophosphate and lithium hexafluoroarsenate. According to the invention, by selecting the lithium salt, the lithium ions in the lithium salt can be ensured to have good ion diffusion rate, and the prepared eutectic solid electrolyte is ensured to have higher ion conductivity.
In the present invention, the preparation method of the binary eutectic solvent preferably includes: and mixing the five-membered ring ester and the lithium salt in an inert gas atmosphere to obtain the binary eutectic solvent.
In the present invention, the inert gas atmosphere is preferably argon, helium, or nitrogen.
In the present invention, the mixing is preferably performed by stirring. The stirring operation is not particularly limited, and the raw materials may be uniformly mixed by stirring operation well known to those skilled in the art.
In the present invention, the temperature of the mixing is preferably 30 to 100 ℃, more preferably 50 to 80 ℃; the mixing time is preferably 0.1 to 5 hours, more preferably 1 to 4 hours. The invention can ensure more uniform mixing by controlling the temperature and time of mixing within the above range.
In the present invention, the preparation method of the ternary eutectic solvent preferably includes: and mixing the five-membered ring ester, the lithium salt and the succinonitrile in an inert gas atmosphere to obtain the ternary eutectic solvent.
In the present invention, the inert gas atmosphere is preferably argon, helium, or nitrogen.
In the present invention, the mixing is preferably performed by stirring. The stirring operation is not particularly limited, and the raw materials may be uniformly mixed by stirring operation well known to those skilled in the art.
In the present invention, the temperature of the mixing is preferably 30 to 100 ℃, more preferably 50 to 80 ℃; the mixing time is preferably 0.1 to 5 hours, more preferably 1 to 4 hours. The invention can ensure more uniform mixing by controlling the temperature and time of mixing within the above range.
In the present invention, the ester monomer preferably includes an acrylate or a carbonate. The polyacrylate or polycarbonate prepared by the polymerization of the ester monomer is high in stability, the impedance of the eutectic solid electrolyte can be reduced, the eutectic solid electrolyte is more favorable for having higher ionic conductivity, and the assembled battery is ensured to have higher capacitance and cycle stability.
In the present invention, the initiator is preferably azobisisobutyronitrile. According to the invention, the ester monomers in the raw materials can be ensured to be polymerized orderly by selecting the initiator of the type.
In the present invention, when the eutectic solvent is a binary eutectic solvent, the mass ratio of the five-membered ring ester, lithium salt, ester monomer and initiator is preferably (1 to 5): (0.1-10): (0.1-10): (0.0001-0.5). In the present invention, when the eutectic solvent is a ternary eutectic solvent, the mass ratio of the five-membered ring ester, the lithium salt, the succinonitrile, the ester monomer and the initiator is preferably (0.1 to 10): (0.1-20): (0.1-10): (0.1-10): (0.0001-0.5). The invention can ensure that the prepared eutectic solid electrolyte has higher ionic conductivity by controlling the mass ratio of the eutectic solvent, the ester monomer and the initiator in the above range, so that the assembled battery has higher capacitance and cycle stability.
In the present invention, the mixing sequence of the five-membered ring ester, lithium salt and/or succinonitrile, ester monomer and initiator is preferably as follows: firstly, mixing five-membered ring ester, lithium salt and/or succinonitrile to obtain a eutectic solvent; and adding the ester monomer and the initiator into the eutectic solvent for mixing to obtain a mixed solution.
In the present invention, the mixing is preferably performed by stirring. The invention has no special requirement on the specific operation of stirring, and can ensure that all raw materials are uniformly mixed.
In the present invention, the temperature of the mixing is preferably room temperature; the mixing time is preferably 5 to 60 minutes, more preferably 10 to 50 minutes. The invention can ensure that the raw materials are mixed more uniformly by controlling the mixing temperature and time within the above range, and is more beneficial to orderly carrying out the polymerization reaction.
After the mixed solution is obtained, under the atmosphere of inert gas, the diaphragm is immersed in the mixed solution and then subjected to polymerization reaction, so that the eutectic solid electrolyte of the lithium metal battery is obtained.
In the present invention, the inert gas atmosphere is preferably argon, helium, or nitrogen. According to the invention, the raw materials are mixed in the inert gas atmosphere, so that air interference can be avoided.
In the present invention, the separator is preferably a glass fiber filter membrane. According to the invention, by selecting the separator of the type, the lithium ions in the solid electrolyte can be ensured to have higher diffusion rate, so that the lithium ions have higher ion conductivity.
In the present invention, the temperature of the polymerization reaction is preferably 50 to 100 ℃, more preferably 60 to 90 ℃; the polymerization time is preferably 0.5 to 12 hours, more preferably 1 to 10 hours. The invention can ensure that the polymerization reaction has proper reaction rate and ensures that the polymerization reaction is orderly carried out by controlling the temperature of the polymerization reaction within the range.
The lithium metal battery eutectic solid electrolyte prepared by the preparation method provided by the invention has higher ionic conductivity, and the assembled lithium ion secondary battery has higher capacity and cycle stability. In addition, the solid electrolyte prepared by the preparation method has the advantages of wide sources of raw materials, simple preparation process, low cost, environmental protection and suitability for large-scale production, and can be applied to lithium metal secondary batteries.
The invention also provides the eutectic solid electrolyte of the lithium metal battery, which is prepared by the preparation method.
In the invention, the eutectic solid electrolyte of the lithium metal battery has higher ionic conductivity, and the assembled lithium ion secondary battery has higher capacity and cycle stability.
The invention also provides application of the eutectic solid electrolyte of the lithium metal battery in a lithium ion secondary battery.
The lithium ion secondary battery assembled by utilizing the eutectic solid electrolyte of the lithium metal battery has higher capacity and cycle stability and good application prospect.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The preparation method of the eutectic solid electrolyte of the lithium metal battery comprises the following steps:
(1) Under the inert gas atmosphere, mixing a eutectic solvent, an ester monomer and an initiator to obtain a mixed solution; wherein the eutectic solvent is a binary eutectic solvent of five-membered ring ester and lithium salt; the mass ratio of the five-membered ring ester, the lithium salt, the ester monomer and the initiator is 1:0.1:0.1:0.0001; specifically: under the atmosphere of inert gas (argon), 1g of five-membered ring ester (obtained by polymerizing 4-oxazolecarboxylic acid ethyl ester monomer) and 0.1g of lithium salt (lithium bistrifluoromethane sulfonyl imide) are added into a sealed bottle, and heated and stirred for 0.1h at 30 ℃ to be dissolved to form a binary eutectic solvent; then, 0.1g of ester monomer (methyl methacrylate) and 0.1mg of initiator (azobisisobutyronitrile) were added to the binary eutectic solvent, and stirred for 5min to dissolve completely.
(2) Under the inert gas atmosphere, immersing the diaphragm in the mixed solution obtained in the step (1) and then carrying out polymerization reaction to obtain the eutectic solid electrolyte of the lithium metal battery; specifically, under the atmosphere of inert gas (argon), a glass fiber filter membrane is immersed into the mixed solution obtained in the step (1), and then the mixed solution is placed on a heating table to be heated to 50 ℃ for polymerization reaction for 0.5h, so that the lithium metal battery (binary) eutectic solid electrolyte is obtained.
Example 2
The preparation method of the eutectic solid electrolyte of the lithium metal battery comprises the following steps:
(1) Under the inert gas atmosphere, mixing a eutectic solvent, an ester monomer and an initiator to obtain a mixed solution; wherein the eutectic solvent is a binary eutectic solvent of five-membered ring ester and lithium salt; the mass ratio of the five-membered ring ester, the lithium salt, the ester monomer and the initiator is 3:5.05:5.05:0.128775; specifically: under the atmosphere of inert gas (argon), 3g of five-membered ring ester (obtained by polymerizing 4-oxazolecarboxylic acid ethyl ester monomer) and 5.05g of lithium salt (lithium bistrifluoromethane sulfonyl imide) are added into a sealed bottle, and heated and stirred for 2.55h at 30 ℃ to be dissolved to form a binary eutectic solvent; then, 5.05g of an ester monomer (methyl methacrylate) and 128.775mg of an initiator (azobisisobutyronitrile) were added to the binary eutectic solvent, and stirred for 32.5 minutes until the mixture was completely dissolved.
(2) Under the inert gas atmosphere, immersing the diaphragm in the mixed solution obtained in the step (1) and then carrying out polymerization reaction to obtain the eutectic solid electrolyte of the lithium metal battery; specifically, under the atmosphere of inert gas (argon), a glass fiber filter membrane is immersed into the mixed solution obtained in the step (1), and then the mixed solution is placed on a heating table to be heated to 75 ℃ for polymerization reaction for 6.25 hours, so that the lithium metal battery (binary) eutectic solid electrolyte is obtained.
Example 3
The preparation method of the eutectic solid electrolyte of the lithium metal battery comprises the following steps:
(1) Under the inert gas atmosphere, mixing a eutectic solvent, an ester monomer and an initiator to obtain a mixed solution; wherein the eutectic solvent is a binary eutectic solvent of five-membered ring ester and lithium salt; the mass ratio of the five-membered ring ester, the lithium salt, the ester monomer and the initiator is 5:10:10:0.5; specifically: under the atmosphere of inert gas (argon), 5g of five-membered ring ester (obtained by polymerizing 4-oxazolecarboxylic acid ethyl ester monomer) and 10g of lithium salt (lithium bistrifluoromethane sulfonyl imide) are added into a sealed bottle, and heated and stirred for 5 hours at 100 ℃ to be dissolved to form a binary eutectic solvent; 10g of ester monomer (methyl methacrylate) and 500mg of initiator (azobisisobutyronitrile) were added to the binary eutectic solvent and stirred for 60min to complete dissolution.
(2) Under the inert gas atmosphere, immersing the diaphragm in the mixed solution obtained in the step (1) and then carrying out polymerization reaction to obtain the eutectic solid electrolyte of the lithium metal battery; specifically, under the atmosphere of inert gas (argon), a glass fiber filter membrane is immersed into the mixed solution obtained in the step (1), and then the mixed solution is placed on a heating table to be heated to 100 ℃ for polymerization reaction for 12 hours, so that the (binary) eutectic solid electrolyte of the lithium metal battery is obtained.
Example 4
The preparation method of the eutectic solid electrolyte of the lithium metal battery comprises the following steps:
(1) Under the inert gas atmosphere, mixing a eutectic solvent, an ester monomer and an initiator to obtain a mixed solution; wherein, the eutectic solvent is a ternary eutectic solvent of five-membered cyclic ester, lithium salt and succinonitrile; the mass ratio of the five-membered ring ester, the lithium salt, the succinonitrile, the ester monomer and the initiator is 1:0.1:0.11:0.1:0.0001; specifically: under the atmosphere of inert gas (argon), 1g of five-membered ring ester (obtained by polymerizing 4-oxazolecarboxylic acid ethyl ester monomer), 0.1g of lithium salt (lithium bistrifluoromethane sulfonyl imide) and 0.11g of succinonitrile are added into a sealed bottle, and heated and stirred for 0.1h at 30 ℃ to be dissolved to form a ternary eutectic solvent; then, 0.1g of ester monomer (methyl methacrylate) and 0.1mg of initiator (azobisisobutyronitrile) were added to the ternary eutectic solvent, and stirred for 5min to dissolve completely.
(2) Under the inert gas atmosphere, immersing the diaphragm in the mixed solution obtained in the step (1) and then carrying out polymerization reaction to obtain the eutectic solid electrolyte of the lithium metal battery; specifically, under the atmosphere of inert gas (argon), a glass fiber filter membrane is immersed into the mixed solution obtained in the step (1), and then the mixed solution is placed on a heating table to be heated to 50 ℃ for polymerization reaction for 0.5h, so that the (ternary) eutectic solid electrolyte of the lithium metal battery is obtained.
Example 5
The preparation method of the eutectic solid electrolyte of the lithium metal battery comprises the following steps:
(1) Under the inert gas atmosphere, mixing a eutectic solvent, an ester monomer and an initiator to obtain a mixed solution; wherein, the eutectic solvent is a ternary eutectic solvent of five-membered cyclic ester, lithium salt and succinonitrile; the mass ratio of the five-membered ring ester, the lithium salt, the succinonitrile, the ester monomer and the initiator is 1.5:5.05:1.5:5.05:0.128775; specifically: under the atmosphere of inert gas (argon), 1.5g of five-membered ring ester (obtained by polymerizing 4-oxazolecarboxylic acid ethyl ester monomer), 5.05g of lithium salt (lithium bistrifluoromethane sulfonyl imide) and 1.5g of succinonitrile are added into a sealed bottle, heated and stirred at 60 ℃ for 2.55h to be dissolved to form a ternary eutectic solvent; then, 5.05g of an ester monomer (methyl methacrylate) and 128.775mg of an initiator (azobisisobutyronitrile) were added to the ternary eutectic solvent, and stirred for 32.5min until the solution was completely dissolved.
(2) Under the inert gas atmosphere, immersing the diaphragm in the mixed solution obtained in the step (1) and then carrying out polymerization reaction to obtain the eutectic solid electrolyte of the lithium metal battery; specifically, a glass fiber filter membrane is immersed into the mixed solution obtained in the step (1) under the atmosphere of inert gas (argon), and then the mixed solution is placed on a heating table to be heated to 75 ℃ for polymerization reaction for 6.25 hours, so that the (ternary) eutectic solid electrolyte of the lithium metal battery is obtained.
Example 6
The preparation method of the eutectic solid electrolyte of the lithium metal battery comprises the following steps:
(1) Under the inert gas atmosphere, mixing a eutectic solvent, an ester monomer and an initiator to obtain a mixed solution; wherein, the eutectic solvent is a ternary eutectic solvent of five-membered cyclic ester, lithium salt and succinonitrile; the mass ratio of the five-membered ring ester, the lithium salt, the succinonitrile, the ester monomer and the initiator is 0.5:10:4.5:10:0.5; specifically: under the atmosphere of inert gas (argon), 0.5g of five-membered ring ester (obtained by polymerizing 4-oxazolecarboxylic acid ethyl ester monomer), 10g of lithium salt (lithium bistrifluoromethane sulfonyl imide) and 4.5g of succinonitrile are added into a sealed bottle, and heated and stirred for 5 hours at 100 ℃ to be dissolved to form a ternary eutectic solvent; 10g of ester monomer (methyl methacrylate) and 500mg of initiator (azobisisobutyronitrile) were added to the ternary eutectic solvent and stirred for 60min to complete dissolution.
(2) Under the inert gas atmosphere, immersing the diaphragm in the mixed solution obtained in the step (1) and then carrying out polymerization reaction to obtain the eutectic solid electrolyte of the lithium metal battery; specifically, under the atmosphere of inert gas (argon), a glass fiber filter membrane is immersed into the mixed solution obtained in the step (1), and then the mixed solution is placed on a heating table to be heated to 100 ℃ for polymerization reaction for 12 hours, so that the (ternary) eutectic solid electrolyte of the lithium metal battery is obtained.
Application examples 1 to 6
The eutectic solid electrolytes of lithium metal batteries prepared in examples 1 to 6 were used to assemble full batteries, respectively, and the specific operations were as follows:
the assembled full cell was assembled into six CR2032 button cells using a metal lithium sheet as the negative electrode, lithium nickel cobalt manganese oxide (NCM 811) as the positive electrode, and the lithium metal battery eutectic solid electrolytes prepared in examples 1 to 6 as solid electrolytes, respectively.
The assembled button cell is placed in a constant temperature box at 25 ℃, and the electrochemical performance function of the button cell is tested on a charge-discharge tester at constant current. The test current density was 0.5C, and the theoretical capacity of the corresponding NCM811 was 200 mAh.g -1 The voltage window is 2.5-4.8V.
Performance test:
the lithium metal battery (binary) eutectic solid electrolyte prepared in example 1 of the present invention was subjected to an ion conductivity test, and the obtained impedance spectrum is shown in fig. 1. As can be seen from FIG. 1, the ionic conductivity of the (binary) eutectic solid electrolyte of the lithium metal battery prepared in example 1 was 0.265 mS.cm at room temperature -1 。
The lithium metal battery (ternary) eutectic solid electrolyte prepared in example 5 of the present invention was subjected to ion conductivity detection, and the obtained impedance spectrum is shown in fig. 2. As can be seen from FIG. 2, the ionic conductivity of the (ternary) eutectic solid electrolyte for lithium metal batteries prepared in example 5 was 0.467 mS.cm at room temperature -1 。
The charging and discharging performance test is carried out on the button cell prepared in application example 5 of the invention, and the obtained LSV spectrogram is shown in figure 3. As can be seen from fig. 3, the button cell prepared in application example 5 has a stable voltage window of 4.95V, which can be ensured to circulate under the high-voltage cathode material.
Five cycles of charge and discharge tests were performed on the button cell prepared in application example 5 of the present invention, and a fifth cycle of charge and discharge curve obtained by the test is shown in fig. 4. As can be seen from fig. 4, the button cell battery prepared in application example 5 was operated at a voltage of 4.3V.
Full cell cycle test was performed on the button cell prepared in application example 5 of the present invention, and a full cell cycle curve obtained by the test is shown in fig. 5. As can be seen from FIG. 5, the button cell prepared in application example 5 has good cycling stability with nickel-cobalt-manganese ternary material (NCM 811) as the positive electrode material and cycling at 0.5C, and the capacity at 20 th cycle is 164.2 mAh.g -1 。
In conclusion, the eutectic solid electrolyte of the lithium metal battery prepared by the preparation method provided by the invention has higher ionic conductivity, and the assembled lithium ion secondary battery has higher capacity and cycle stability. In addition, the solid electrolyte prepared by the preparation method has the advantages of wide sources of raw materials, simple preparation process, low cost, environmental protection and suitability for large-scale production, and can be applied to lithium metal secondary batteries.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The preparation method of the eutectic solid electrolyte of the lithium metal battery is characterized by comprising the following steps of:
(1) Under the inert gas atmosphere, mixing a eutectic solvent, an ester monomer and an initiator to obtain a mixed solution; the eutectic solvent is a binary eutectic solvent of five-membered ring ester and lithium salt; or the eutectic solvent is a ternary eutectic solvent of five-membered ring ester, lithium salt and succinonitrile;
(2) And (3) immersing the diaphragm in the mixed solution obtained in the step (1) in an inert gas atmosphere, and then carrying out polymerization reaction to obtain the eutectic solid electrolyte of the lithium metal battery.
2. The method of claim 1, wherein when the eutectic solvent in step (1) is a binary eutectic solvent, the mass ratio of the five-membered ring ester, lithium salt, ester monomer and initiator is (1 to 5): (0.1-10): (0.1-10): (0.0001 to 0.5); when the eutectic solvent in the step (1) is a ternary eutectic solvent, the mass ratio of the five-membered ring ester, the lithium salt, the succinonitrile, the ester monomer and the initiator is (0.1-10): (0.1-20): (0.1-10): (0.1-10): (0.0001-0.5).
3. The method according to claim 1, wherein the temperature of the mixing in the step (1) is room temperature and the mixing time is 5 to 60 minutes.
4. The process according to claim 1, wherein the five-membered ring ester in step (1) is obtained by polymerizing a monomer having a five-membered ring structure and a melting point lower than 100 ℃.
5. The method of claim 1, wherein the lithium salt in step (1) comprises one or more of lithium bis (trifluoromethanesulfonyl) imide, lithium tetrafluoroborate, lithium bis (oxalato) borate, lithium difluorooxalato borate, lithium perchlorate, lithium hexafluorophosphate, and lithium hexafluoroarsenate.
6. The method of claim 1, wherein the ester monomer in step (1) comprises an acrylate or a carbonate.
7. The process according to claim 1, wherein the initiator in step (1) is azobisisobutyronitrile.
8. The process according to claim 1, wherein the polymerization reaction in the step (2) is carried out at a temperature of 50 to 100℃for a period of 0.5 to 12 hours.
9. The eutectic solid electrolyte for lithium metal batteries prepared by the preparation method according to any one of claims 1 to 8.
10. Use of the lithium metal battery eutectic solid electrolyte according to claim 9 in a lithium ion secondary battery.
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