CN113224382B - Solid polymer electrolyte containing ketone group and battery - Google Patents
Solid polymer electrolyte containing ketone group and battery Download PDFInfo
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- CN113224382B CN113224382B CN202110196190.9A CN202110196190A CN113224382B CN 113224382 B CN113224382 B CN 113224382B CN 202110196190 A CN202110196190 A CN 202110196190A CN 113224382 B CN113224382 B CN 113224382B
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- 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
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- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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- 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
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- 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
Abstract
The present invention relates to a solid polymer electrolyte containing a ketone group, which includes a polymer matrix, an initiator, a lithium salt and an additive, and is cured to a film under heat or ultraviolet radiation, and a lithium metal battery including the same. The electrolyte prepared by the present invention shows high room temperature ionic conductivity (1.1X 10) compared to PEO-based polymer electrolytes ‑4 S cm ‑1 ) And a wide electrochemical window (5.5V); in addition, the polymer electrolyte has excellent film forming property and electrochemical property, and has good application prospect in batteries with high energy density.
Description
Technical Field
The present invention relates to a solid polymer electrolyte containing a ketone group and a lithium battery comprising the same.
Background
As one of the most potential energy storage devices, lithium ion batteries have advantages of high energy density, small self-discharge, fast response time, no memory effect, etc. compared with other secondary batteries. Because the theoretical specific capacity of the graphite cathode is 370mAh g -1 Therefore, the energy density of the traditional lithium ion battery is improved to a bottleneck period, and the application requirements in the fields of electronic equipment, new energy automobiles, aerospace energy storage and the like in the future can not be met. The lithium metal electrode has high theoretical specific capacity (3860 mAh g) -1 ) And a low electrode potential, which is considered to be one of the most promising high energy density anode materials to replace graphite anodes. However, lithium metal has extremely high reactivity, and is liable to undergo side reactions with an electrolyte during charge and discharge, resulting in loss of the electrolyte, and irreversible degradation of battery capacity and efficiency. In addition, during the long-term use of the battery, the electrolyte has the risk of leakage and combustion, and the self-ignition of new energy automobiles can be observed in recent reports. In order to solve the above-mentioned potential safety hazard and to improve the energy density of the battery, solid-state lithium metal batteries have been produced, and have received a lot of attention and intensive research in recent years.
The solid polymer electrolyte system consists of two parts of polymer and lithium salt. The lithium ion transmission in the film mainly depends on the complexation-decomplexing action with the polar group on the polymer chain segment, and the short-range motion of the chain segment is used for proceeding in the mediumMigrate directionally. The polymer matrix is mainly classified into several types of polyether, polycarbonate, polyurethane, polysiloxane, etc. according to the difference of polar groups (-O-, = O, -N-, -P-, -S-, C = O, C ≡ N, etc.) in the molecular structure. Among them, the most studied is polyethylene oxide (PEO) -based polymer electrolyte, which has relatively soft molecular segments, a high dielectric constant, and high electrochemical stability to lithium metal, but single PEO has high crystallinity at room temperature, resulting in low ionic conductivity under the corresponding conditions (10) -7 -10 -6 S cm -1 ) (ii) a In addition, the electrochemical window of the battery is also narrow (less than or equal to 4V), so that the high-voltage anode material is difficult to match, and the improvement on the energy density of the solid-state battery is limited.
The carbonyl (C = O) group has a higher polarity and dielectric constant than the ether (-O-) group, and reacts with Li, lithium ion + The acting force is relatively weak during coordination, and coordination bonds are easy to break and dissociate, which is beneficial to Li + Fast migration of (2). Thus, the carbonyl-based polymer material exhibits great research value and application prospects in the application of lithium batteries including organic cathode materials and polymer electrolytes [ j.mater.chem.a,2020,8,11906; MRS Energy&Sustain.,2020,7,E2]. At present, most researches on carbonyl solid polymer electrolytes are aliphatic polycarbonates and polyesters, the electrolytes can adapt to the condition of high lithium salt concentration, and the room-temperature ionic conductivity of the electrolytes can be increased to 10 -4 S cm -1 (ii) a In addition, compared with polyether, the ester electrolyte has low HOMO energy level, so that the oxidation resistance is strong, and the electrochemical window is wide. And so on [ adv. Energy mater, 2015,5,1501082]A polypropylene carbonate polymer electrolyte was prepared, and the membrane had high ionic conductivity and an electrochemical window of 4.6V at room temperature. Yoichi Tominaga topic group [ Macromol. Rapid Commun.,2017,38,1600652]The poly (ethylene carbonate)/ethylene oxide (P (EC/EO)) copolymer electrolyte is designed and synthesized, and the ion conductivity and the lithium ion migration number of the membrane are effectively improved by utilizing the synergistic effect between carbonate and ether. In view of the above, it is important to further explore the development of carbonyl-based polymer electrolytes to realize a solid-state lithium metal battery having high ionic conductivity, wide electrochemical window, and high energy densityMeaning.
Disclosure of Invention
An object of the present invention is to provide a ketone group-containing solid polymer electrolyte having high room-temperature ionic conductivity, a wide electrochemical stability window, and excellent battery performance.
It is another object of the present invention to provide a use of a solid polymer electrolyte containing a ketone group for an all solid-state lithium metal battery.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a solid polymer electrolyte comprising a ketone group comprising a polymer matrix, an initiator, a lithium salt and an additive, characterized in that: the polymer matrix is obtained by self-crosslinking of polymerized monomers; or the copolymer is obtained by crosslinking and copolymerizing a polymerized monomer and a crosslinking agent, wherein the polymerized monomer has a molecular structure shown in a formula (I):
wherein R is 1 Represents hydrogen, substituted (C) 1 -C 10 ) Alkyl, substituted (C) 1 -C 10 ) Alkoxy, substituted (C) 2 -C 10 ) Alkenyl, substituted (C) 2 -C 10 ) Alkynyl, substituted (C) 3 -C 10 ) Cycloalkyl, substituted aryl, -NR a R b 、-OR a 、-SR a Isocyanate, acrylate, epoxy, substituted benzyl, methacrylate;
wherein X represents O or (C) 1 -C 6 ) Alkylene, halo (C) 1 -C 6 ) Alkylene, - (CH) 2 ) n C(O)O(CH 2 ) m -、-(CH 2 ) n OC(O)(CH 2 ) m -、-(CH 2 ) n NR a (CH 2 ) m -；
Wherein A and B each independently represent-O-, (C) 1 -C 6 ) Alkylene, -NR a -；
Wherein R is 2 Represents hydrogen, substituted (C) 1 -C 10 ) Alkyl, substituted (C) 1 -C 10 ) Alkoxy, substituted (C) 2 -C 10 ) Alkenyl, substituted (C) 2 -C 10 ) Alkynyl, substituted (C) 3 -C 10 ) Cycloalkyl, substituted aryl, -NR a R b 、-OR a 、-SR a Isocyanate, acrylate, epoxy, substituted benzyl, methacrylate;
wherein the above-mentioned substituents represent substituents having 0, 1, 2, 3 structures below: (C) 1 -C 10 ) Alkyl, halogen, -NR a R b 、-OR a 、-SR a Cyano, nitro, or-SO 3 R a An aromatic group;
wherein R is a And R b Each independently represents hydrogen or (C) 1 -C 10 ) An alkyl group;
a. b, n and m are integers; a ranges from 0 to 50, preferably 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10; b ranges from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10; n and m are in the range of 0-100, preferably 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10.
In a preferred embodiment of the present invention, wherein R 1 Is selected from (C) 1 -C 10 ) Alkyl, halo (C) 1 -C 10 ) Alkyl, -NR a R b Aryl, epoxy.
In a preferred embodiment of the present invention, X is selected from the group consisting of-O-, (C) 1 -C 6 ) An alkylene group.
In a preferred embodiment of the present invention, wherein R 2 Is selected from (C) 1 -C 10 ) Alkyl, (C) 1 -C 10 ) Alkoxy group, (C) 2 -C 10 ) An alkenyl group.
In a preferred embodiment of the present invention, a and b each independently represent 0, 1, 2, or 3.
In a preferred embodiment of the present invention, wherein A represents (C) 1 -C 6 ) Alkylene, furtherIs preferably (C) 1 -C 3 ) An alkylene group.
In a preferred embodiment of the present invention, wherein B represents-O-.
In a preferred embodiment of the present invention, the molecular structure of the crosslinking agent is one or more compounds containing vinyl, amino, hydroxyl, epoxy, or mercapto functional groups, including polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, diethylene glycol dimethacrylate, tripropylene glycol diacrylate, tetraethylene glycol diacrylate, triethylene glycol dimethacrylate, 1, 3-butylene glycol dimethacrylate, dipropylene phthalate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, triallyl cyanurate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (mercaptoacetate), dipentaerythritol hexakis (3-mercaptopropionate), polyetheramine D-2000, polyoxyethylene diamine, polyethylene glycol diglycidyl ether, poly (propylene glycol) diglycidyl ether, etc.; the cross-linking agent accounts for 0-50% of the mass fraction of the monomer.
In a preferred embodiment of the present invention, the initiator comprises one or more of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyvalerate, 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, 2,4, 6-trimethylbenzoylphenylphosphonic acid ethyl ester, 2-dimethylamino-2-benzyl-1- [4- (4-morpholinyl) phenyl ] -1-butanone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone, and the like; the initiator accounts for 0.1 to 10 percent of the total mass fraction of the polymerization monomer and the cross-linking agent.
In a preferred technical scheme of the present invention, the lithium salt includes one or more of lithium bistrifluoromethylsulfonyl imide, lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium perchlorate, lithium tetrafluoroborate, lithium dioxalate borate, lithium difluorooxalate borate, lithium dimalonate borate, lithium hexafluoroantimonate or lithium trifluoromethanesulfonate, etc.; the molar concentration of the lithium salt is 0.1mol L -1 -15mol L -1 。
In a preferred technical scheme of the present invention, the additive includes graphene oxide, carbon nanotubes, fullerene, silicon dioxide, aluminum oxide, magnesium oxide, zirconium dioxide, cerium oxide, cobalt oxide, halloysite nanotubes, montmorillonite, molecular sieve, carbon triazo, quantum dots, MOF, COF, ZIF, boron nitride, ionic liquid, liquid crystal, li, and the like 6.24 La 3 Zr 2 Al 0.24 O 11.98 、Li 6.91 La 3 Zr 1.98 Al 0.13 O 12 、Li 6.19 Al 0.27 La 3 Zr 2 O 12 、Li 6.17 Al 0.28 La 3 Zr 2 O 12 、Li 6.5 La 3 Zr 1.5 Ta 0.5 O 12 、Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 、Li 0.33 La 0.57 TiO 3 、Li 11-x M 2-x P 1+x S 12 (M＝Ge,Sn,Si)、Li 6 PS 5 X (X = Cl, br, I), one or more of propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate, succinonitrile, tetraethylene glycol dimethyl ether and the like; the additive accounts for 0-80% of the total mass fraction of the polymeric monomer and the cross-linking agent. In addition, the invention also provides a battery, which is formed by sequentially packaging the positive electrode material, the polymer electrolyte and the negative electrode material. The batteries include lithium metal batteries, lithium ion batteries, lithium sulfur batteries, lithium air batteries, and other secondary high performance batteries.
In a preferred technical scheme of the invention, the active material of the positive electrode material is one or more of lithium iron phosphate, lithium cobaltate, lithium manganate, nickel cobalt manganese ternary material, nickel cobalt aluminum ternary material, sulfur, sulfide and the like.
In a preferred technical scheme of the invention, the negative electrode material comprises one or more of lithium metal and an alloy thereof, a magnesium-based alloy, a nitride, a carbon material, a silicon-based material, a boron-based material and the like.
Further, the present invention provides a method for producing the ketone group-containing solid polymer electrolyte according to the present invention, characterized in that:
(1) Sequentially adding a certain amount of cross-linking agent, lithium salt and initiator into the polymerization monomer solution, stirring and carrying out ultrasonic treatment to obtain a uniform mixed solution; among the preferred polymeric monomers are allyl acetoacetate, ethylene glycol acetoacetate methacrylate, 2-methallylbutyrate; preferred cross-linking agents include polyethylene glycol diacrylate, polyethylene glycol dimethacrylate; preferred lithium salts include lithium bis (trifluoromethyl) sulfonyl imide, lithium hexafluorophosphate, lithium perchlorate; preferred initiators include azobisisobutyronitrile, 1-hydroxycyclohexyl phenyl ketone.
(2) And pouring the mixed membrane solution into a polytetrafluoroethylene membrane, initiating polymerization of the monomer and the cross-linking agent by ultraviolet irradiation or heating, and then placing the membrane in a vacuum drying oven to further perform polymerization reaction to finally obtain the polymer electrolyte membrane.
Preferably, heat or uv curing is used in the process of the invention.
Definition of terms:
in the technical scheme of the invention, the definition of the substituent is as follows:
the term "alkyl" or "alkylene" as used herein is intended to include both branched and straight chain saturated aliphatic hydrocarbon groups having the indicated number of carbon atoms. For example, "C 1 -C 10 Alkyl "means an alkyl group having 1 to 10 carbon atoms. Examples of alkyl groups include, but are not limited to, methyl (Me), ethyl (Et), propyl (e.g., n-propyl and isopropyl), butyl (e.g., n-butyl, isobutyl, tert-butyl), and pentyl (e.g., n-pentyl, isopentyl, neopentyl).
The term "alkenyl" denotes straight or branched chain hydrocarbon radicals containing one or more double bonds and typically from 2 to 20 carbon atoms in length. For example, "C 2 -C 6 Alkenyl "contains two to six carbon atoms. Alkenyl groups include, but are not limited to, for example, ethenyl, propenyl, butenyl, 1-methyl-2-buten-1-yl, and the like.
The term "alkynyl" denotes a straight or branched chain hydrocarbon group containing one or more triple bonds and typically from 2 to 20 carbon atoms in length. For example, "C 2 -C 6 Alkynyl "contains two to six carbon atoms. Representative alkynyl groups include, but are not limited to, for example, ethynyl, 1-propynyl, 1-butynyl, and the like.
The term "alkoxy" or "alkyloxy" refers to an-O-alkyl group. "C 1 -C 6 Alkoxy "(or alkyloxy) is intended to include C 1 、C 2 、C 3 、C 4 、C 5 、C 6 An alkoxy group. Examples of alkoxy groups include, but are not limited to, methoxy, ethoxy, propoxy (e.g., n-propoxy and isopropoxy), and t-butoxy. Similarly, "alkylthio" or "thioalkoxy" represents an alkyl group as defined above with the specified number of carbon atoms attached via a sulfur bridge; such as methyl-S-and ethyl-S-.
The term "carbonyl" refers to an organic functional group (C = O) formed by double bonding of two atoms, carbon and oxygen.
The term "aryl", alone or as part of a larger moiety such as "aralkyl", "aralkoxy", or "aryloxyalkyl", refers to a monocyclic, bicyclic, or tricyclic ring system having a total of 5 to 12 ring members, wherein at least one ring in the system is aromatic and wherein each ring in the system contains 3 to 7 ring members. In certain embodiments of the present invention, "aryl" refers to an aromatic ring system including, but not limited to, phenyl, biphenyl, indanyl, 1-naphthyl, 2-naphthyl, and tetrahydronaphthyl. The term "aralkyl" or "arylalkyl" refers to an alkyl residue attached to an aryl ring. Non-limiting examples include benzyl, phenethyl, and the like. The fused aryl group may be attached to another group at a suitable position on the cycloalkyl or aromatic ring. For example, a dashed line drawn from the ring system indicates that the bond may be attached to any suitable ring atom.
The term "cycloalkyl" refers to a monocyclic or bicyclic cyclic alkyl group. Monocyclic cyclic alkyl means C 3 -C 8 Including but not limited to cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and norbornyl. Branched cycloalkyl groups such as 1-methylcyclopropyl and 2-methylcyclopropyl are included in the definition of "cycloalkyl". Bicyclic cyclic alkyl groups include bridged, spiro or fused cyclic cycloalkyl groups.
The term "epoxy group" means a monocyclic or bicyclic oxygen atom-containing cyclic alkyl group, such as epoxyethyl, epoxypropyl, epoxybutyl, epoxypentyl, epoxyhexyl.
"halo" or "halogen" includes fluorine, chlorine, bromine and iodine. "haloalkyl" is intended to include both branched and straight-chain saturated aliphatic hydrocarbon groups having the indicated number of carbon atoms and substituted with 1 or more halogens. Examples of haloalkyl groups include, but are not limited to, fluoromethyl, difluoromethyl, trifluoromethyl, trichloromethyl, pentafluoroethyl, pentachloroethyl, 2-trifluoroethyl, heptafluoropropyl, and heptachloropropyl. Examples of haloalkyl also include "fluoroalkyl" groups intended to include branched and straight-chain saturated aliphatic hydrocarbon groups having the specified number of carbon atoms substituted with 1 or more fluorine atoms.
"haloalkoxy" or "haloalkyloxy" denotes a haloalkyl group as defined above with the indicated number of carbon atoms attached via an oxygen bridge. For example, "halo C 1 -C 6 Alkoxy "is intended to include C 1 、C 2 、C 3 、C 4 、C 5 、C 6 A haloalkoxy group. Examples of haloalkoxy groups include, but are not limited to, trifluoromethoxy, 2-trifluoroethoxy, and pentafluoroethoxy. Similarly, "haloalkylthio" or "thiohaloalkoxy" represents a haloalkyl group as defined above with the indicated number of carbon atoms attached through a sulfur bridge; such as trifluoromethyl-S-and pentafluoroethyl-S-.
In this disclosure, C is used when referring to certain substituents x1 -C x2 This means that the number of carbon atoms in the substituent group may be x1 to x 2. For example, C 0 -C 8 Denotes that the radical contains 0, 1, 2, 3, 4, 5, 6, 7 or 8 carbon atoms, C 1 -C 8 Denotes that the radical contains 1, 2, 3, 4, 5, 6, 7 or 8 carbon atoms, C 2 -C 8 Denotes that the radical contains 2, 3, 4, 5, 6, 7 or 8 carbon atoms, C 3 -C 8 Means that the radical contains 3, 4, 5, 6, 7 or 8 carbon atoms, C 4 -C 8 Denotes that the radical contains 4, 5, 6, 7 or 8 carbon atoms, C 0 -C 6 Means that the radical contains 0, 1, 2, 3, 4, 5 or 6 carbon atoms, C 1 -C 6 Denotes that the radical contains 1, 2, 3, 4, 5 or 6 carbon atoms, C 2 -C 6 Means that the radical contains 2, 3, 4, 5 or 6 carbon atoms, C 3 -C 6 Means that the group contains 3, 4, 5 or 6 carbon atoms.
In this disclosure, the expression "x1-x2 membered ring" is used when referring to cyclic groups (e.g., aryl, heteroaryl, cycloalkyl, and heterocycloalkyl), which means that the number of ring atoms of the group may be x1 to x 2. For example, the 3-12 membered cyclic group may be a 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 membered ring, the number of ring atoms of which may be 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12; the 3-6 membered ring means that the cyclic group may be a 3, 4, 5 or 6 membered ring, the number of ring atoms of which may be 3, 4, 5 or 6; by 3-8 membered ring is meant that the cyclic group may be a 3, 4, 5, 6, 7 or 8 membered ring, the number of ring atoms may be 3, 4, 5, 6, 7 or 8; a 3-9 membered ring means that the cyclic group may be a 3, 4, 5, 6, 7, 8 or 9 membered ring, the number of ring atoms of which may be 3, 4, 5, 6, 7, 8 or 9; 4-7 membered ring means that the cyclic group may be 4, 5, 6 or 7 membered, the number of ring atoms may be 4, 5, 6 or 7; 5-8 membered ring means that the cyclic group may be a 5, 6, 7 or 8 membered ring, the number of ring atoms may be 5, 6, 7 or 8; 5-12 membered ring means that the cyclic group may be 5, 6, 7, 8, 9, 10, 11 or 12 membered and the number of ring atoms may be 5, 6, 7, 8, 9, 10, 11 or 12; by 6-12 membered ring is meant that the cyclic group may be 6, 7, 8, 9, 10, 11 or 12 membered and the number of ring atoms may be 6, 7, 8, 9, 10, 11 or 12. The ring atoms may be carbon atoms or heteroatoms, for example heteroatoms selected from N, O and S. When the ring is a heterocycle, the heterocycle may contain 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or more ring heteroatoms, for example heteroatoms selected from N, O and S.
The invention has the following characteristics:
(1) The selected polymeric monomer can be used as the polymeric monomer on one hand and can also be used as a solvent on the other hand in the preparation process of the electrolyte membrane; therefore, the preparation process of the membrane does not involve the use of other organic solvents, and is environment-friendly.
(2) The polymer electrolyte membrane prepared by the invention has good film-forming property under the plasticizing action of high lithium salt, can provide excellent adhesion, and effectively solves the problem of interface contact between the electrolyte membrane and electrodes.
(3) The polymer electrolyte prepared by the invention contains a large amount of ester groups and ketone groups on the molecular structure, and the interaction force of the functional groups is weak when the functional groups coordinate with lithium ions, so that the polymer electrolyte can rapidly conduct the lithium ions. In addition, the HOMO energy level of the C = O group is low, and the oxidation resistance is strong, so that the electrochemical stability of the electrolyte membrane can be effectively improved. Thus, the electrolyte membrane prepared under the condition of high lithium salt concentration has high room temperature ionic conductivity (1.1X 10) -4 S cm -1 ) And a wide electrochemical window (5.5V) with full ability to match high voltage positive electrode materials.
Drawings
FIG. 1 is a photograph of an actual product of the prepared polyester ketone polymer electrolyte membrane.
Fig. 2 is a graph showing the ion conductivity of the prepared electrolyte membrane as a function of temperature.
Fig. 3 is an electrochemical window of the prepared electrolyte membrane.
Fig. 4 is a dilithium polarization curve of the prepared electrolyte membrane.
FIG. 5 shows Li// LiFePO assembled by electrolyte membrane 4 First charge and discharge curves of the battery.
Detailed Description
The present invention will be described in further detail with reference to the drawings and specific examples, but the present invention is not limited to the following examples, and modifications and equivalents of the technical solution of the present invention are included in the scope of the present invention.
Example 1
1g of allyl acetoacetate was weighed
Adding into a reagent bottle, and then adding 0.3g of cross-linking agent polyethylene glycol diacrylate, 0.7g of lithium salt LiTFSI0.7g and 0.1g of photoinitiator 1-hydroxy cyclohexyl phenyl ketone in sequence. Stirring and ultrasonic processing to obtain uniform mixed solution, then pouring the mixed solution onto a polytetrafluoroethylene substrate, carrying out ultraviolet curing, and finally placing the membrane in a vacuum drying oven at 80 ℃ for 12h. The all-solid-state lithium ion battery is assembled by sequentially superposing a positive electrode material, a polymer electrolyte and a negative electrode material in a CR2025 battery case by taking graphite as a negative electrode material.
Example 2
1g of allyl acetoacetate was weighed
Adding 0.4g of cross-linking agent polyethylene glycol diacrylate, 0.6g of lithium salt LiTFSI0 and 0.1g of initiator azobisisobutyronitrile into a reagent bottle in sequence. Stirring and ultrasonic processing to obtain uniform mixed solution, then pouring the mixed solution onto a polytetrafluoroethylene substrate, and curing for 12h in a vacuum drying oven at 80 ℃. Graphite is used as a negative electrode material, and the positive electrode material, the polymer electrolyte and the negative electrode material are sequentially superposed in a CR2025 battery case to assemble the all-solid-state lithium ion battery.
Example 3
1g of trifluoromethyl allyl acetylbutyrate was weighed
Adding into a reagent bottle, and then sequentially adding 0.2g of cross-linking agent tetraethylene glycol dimethacrylate and lithium salt LiClO 4 0.1g of photoinitiator 1-hydroxycyclohexyl phenyl ketone and 0.1g of photoinitiator.Stirring and ultrasonic treatment to obtain a uniform mixed solution. And directly dripping the film precursor solution on the positive plate, and placing the film and the positive plate in a vacuum drying oven at 80 ℃ for 12h after in-situ ultraviolet curing. Graphite is used as a negative electrode material, and the positive electrode material, the polymer electrolyte and the negative electrode material are sequentially stacked in a CR2025 battery case to assemble the all-solid-state lithium ion battery.
Example 4
1g of benzoylacrylate are weighed out
Then 0.3g of triethylene glycol dimethacrylate serving as a cross-linking agent, 0.1g of lithium salt LiTFSI0 and 0.5g of cumene hydroperoxide serving as an initiator are added into a reagent bottle in sequence. Stirring and ultrasonic treatment to obtain a uniform mixed solution. And (2) taking graphite as a negative electrode material, sequentially superposing the positive electrode material, the cellulose diaphragm, the film precursor solution and the negative electrode material in a CR2025 battery case, packaging, and then placing in a vacuum drying oven at 80 ℃ for 12h to assemble the all-solid-state lithium ion battery.
Example 5
1g of aminopropyl butyrate was weighed
Adding 0.14g of cross-linking agent polyethylene glycol diacrylate, 0.7g of lithium hexafluorophosphate and 0.1g of initiator tert-butyl peroxybenzoate into a reagent bottle in sequence. Stirring and ultrasonic processing to obtain uniform mixed solution, then pouring the mixed solution onto a polytetrafluoroethylene substrate, carrying out ultraviolet curing, and finally placing the membrane in a vacuum drying oven at 80 ℃ for 12h to assemble the all-solid-state lithium ion battery.
Example 6
1g of epoxy acetoacetic acid allyl ester
Adding 0.5g of cross-linking agent pentaerythritol triacrylate, 0.4g of lithium dioxalate borate and 0.2g of photoinitiator di-tert-butyl peroxide into a reagent bottle in sequence. Stirring and ultrasonic treatment to obtain a homogeneous mixed solutionThen pouring the mixed solution onto a polytetrafluoroethylene substrate, carrying out ultraviolet curing, and finally placing the membrane in a vacuum drying oven at 80 ℃ for 12 hours. Lithium metal is used as a negative electrode material, the positive electrode material, the prepared polymer electrolyte and the negative electrode material are sequentially overlapped and placed in a CR2025 battery shell, and the all-solid-state lithium metal battery is assembled.
Example 7
1.5g of allyl acetoacetate were weighed
Adding 0.1g of polyethylene glycol diglycidyl ether serving as a crosslinking agent, 0.2g of LiTFSI0.2g, 0.3g of boron nitride and 0.05g of tert-butyl peroxybenzoate serving as a photoinitiator into a reagent bottle in sequence. Stirring and ultrasonic processing to obtain uniform mixed solution, directly dripping the film precursor solution on the positive plate, and placing the film and the positive plate in a vacuum drying oven at 80 ℃ for 12h after in-situ ultraviolet curing. The prepared polymer electrolyte and the anode material are sequentially placed in a CR2025 battery case according to the anode material to assemble the all-solid-state lithium metal battery.
Example 8
1g of isocyanate propionyl allyl acetate was weighed
Adding 0.14g of cross-linking agent polyethylene glycol diacrylate, 0.576g of lithium trifluoromethanesulfonate and 0.08g of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide into a reagent bottle in sequence. Stirring and ultrasonic processing to obtain uniform mixed solution, directly dripping the film precursor solution on the positive plate, and placing the film and the positive plate in a vacuum drying oven at 80 ℃ for 12h after in-situ ultraviolet curing. The cathode material, the solid polymer electrolyte prepared in the first step and the anode material are sequentially placed in a CR2025 battery case to assemble the all-solid-state lithium metal battery.
Example 9
1g of acetoacetic acid ethylene glycol methacrylate is weighed
Into a reagent bottle, and then adding the reagent bottle0.14g of polyethylene glycol diacrylate as a crosslinking agent, 0.576g of LiTFSI and 0.4g of Li 6.24 La 3 Zr 2 Al 0.24 O 11.98 0.07g of photoinitiator 1-hydroxycyclohexyl phenyl ketone. Stirring and ultrasonic processing to obtain uniform mixed solution, pouring the mixed solution onto a polytetrafluoroethylene substrate, performing ultraviolet curing, and finally placing the membrane in a vacuum drying oven at 80 ℃ for 12 hours. Graphite is used as a negative electrode material, and the positive electrode material, the polymer electrolyte and the negative electrode material are sequentially stacked in a CR2025 battery case to assemble the all-solid-state lithium ion battery.
Example 10
1g of 2-methylallyl-formylmethylene-butyrate was weighed out
Then 0.9g of lithium tetrafluoroborate, 0.01g of 1, 3-butanediol dimethacrylate and 0.5g of MOF0 are added into a reagent bottle in sequence. Stirring and ultrasonic processing to obtain uniform mixed solution, pouring the mixed solution onto a polytetrafluoroethylene substrate, performing ultraviolet curing, and finally placing the membrane in a vacuum drying oven at 80 ℃ for 12 hours. Graphite is used as a negative electrode material, and the positive electrode material, the polymer electrolyte and the negative electrode material are sequentially superposed in a CR2025 battery case to assemble the all-solid-state lithium ion battery.
Example 11
1g of acetoacetic acid ethylene glycol methacrylate is weighed out to
Then, 0.9g of lithium dimalonate borate, 0.06g of photoinitiator tert-butyl peroxypivalate, 0.2g of additive succinonitrile and 0.3g of halloysite nanotubes are added into the reagent bottle in sequence. Stirring and ultrasonic processing to obtain uniform mixed solution, pouring the mixed solution onto a polytetrafluoroethylene substrate, performing ultraviolet curing, and finally placing the membrane in a vacuum drying oven at 80 ℃ for 12 hours. Graphite is used as a negative electrode material, and the positive electrode material, the polymer electrolyte and the negative electrode material are sequentially stacked in a CR2025 battery case to assemble the all-solid-state lithium ion battery.
Test examples:
(1) Ion conductivity test
FIG. 2 shows a method for testing ionic conductivity of an electrolyte membrane, which comprises the steps of assembling a stainless steel electrode/electrolyte membrane/stainless steel electrode cell by using a stainless steel electrode as a blocking electrode, and testing electrochemical impedance spectra of the assembled cell at different temperatures by using an electrochemical workstation. The ionic conductivity of the membrane was calculated using the following formula.
Where σ denotes the ionic conductivity, l denotes the film thickness, R denotes the electrochemical resistance, and A denotes the area of the stainless steel electrode.
(2) Electrochemical window testing
Figure 3 the electrochemical window of the electrolyte membrane was tested using Linear Sweep Voltammetry (LSV). Assembling a lithium electrode/electrolyte membrane/stainless steel electrode cell using a stainless steel electrode as a working electrode and a lithium electrode as a counter electrode, the test parameter settings including a scan rate of 0.1mV s -1 The voltage sweep range is 0 to 8V.
(3) Dual lithium polarization curve test
The double lithium polarization curve test shown in the attached figure 4 adopts a lithium electrode as a working electrode and a counter electrode, a lithium electrode/electrolyte membrane/lithium electrode battery is assembled, and a constant current charging and discharging method is adopted for testing.
(4) Testing of battery charging and discharging performance
FIG. 5 shows that lithium iron phosphate (LiFePO) is used for testing the charging and discharging performance of the battery 4 ) As positive electrode, lithium electrode (Li) as negative electrode, li/electrolyte membrane/LiFePO were assembled 4 The battery is tested by adopting a constant current charging and discharging method.
Claims (7)
1. A solid polymer electrolyte membrane containing a ketone group, characterized by being produced by the steps of:
at 1g of allyl acetoacetate
Sequentially adding 0.3g of cross-linking agent polyethylene glycol diacrylate, 0.7g of lithium salt LiTFSI and 0.1g of photoinitiator 1-hydroxy cyclohexyl phenyl ketone, stirring and carrying out ultrasonic treatment to obtain uniform mixed liquid serving as a membrane precursor;
and then pouring the film precursor onto a polytetrafluoroethylene substrate, initiating polymerization of a monomer and a cross-linking agent by ultraviolet curing, and finally curing the film in a vacuum drying oven at the temperature of 80 ℃ for 12 hours to obtain the polymer electrolyte film.
2. A ketone group-containing solid polymer electrolyte membrane, characterized by being produced by the steps of:
at 1g of allyl acetoacetate
Sequentially adding 0.4g of cross-linking agent polyethylene glycol diacrylate, 0.6g of lithium salt LiTFSI and 0.1g of initiator azodiisobutyronitrile, stirring and carrying out ultrasonic treatment to obtain uniform mixed liquid serving as a membrane precursor;
and then pouring the film precursor onto a polytetrafluoroethylene substrate, curing the film precursor in a vacuum drying oven at the temperature of 80 ℃ for 12 hours, and heating to initiate polymerization of the monomer and the cross-linking agent to obtain the polymer electrolyte film.
3. A ketone group-containing solid polymer electrolyte membrane, characterized by being produced by the steps of:
at 1.5g of allyl acetoacetate
Sequentially adding 0.1g of cross-linking agent polyethylene glycol diglycidyl ether, 0.2g of LiTFSI, 0.3g of boron nitride and 0.05g of photoinitiator tert-butyl peroxybenzoate, stirring and carrying out ultrasonic treatment to obtain uniform mixed solution serving as a membrane precursor;
and directly dripping the film precursor solution on a positive plate, initiating polymerization of a monomer and a cross-linking agent by in-situ ultraviolet curing, and then placing the film and the positive plate in a vacuum drying oven at 80 ℃ for 12h to obtain the polymer electrolyte film.
4. A battery, characterized by: a solid polymer electrolyte membrane comprising a ketone group-containing according to any one of claims 1 to 3.
5. The battery of claim 4, wherein the battery is a lithium metal battery, a lithium ion battery, a lithium sulfur battery, or a lithium air battery.
6. The battery of claim 4, wherein: the active material of the positive electrode material of the battery is one or more of lithium iron phosphate, lithium cobaltate, lithium manganate, a nickel-cobalt-manganese ternary material, a nickel-cobalt-aluminum ternary material or sulfur and sulfide.
7. The battery of claim 4, wherein: the negative electrode material of the battery comprises one or more of lithium metal and alloy thereof, magnesium-based alloy, nitride, carbon material, silicon-based material and boron-based material.
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