CN116082640A - Polymer for electrolyte and preparation method and application thereof - Google Patents

Polymer for electrolyte and preparation method and application thereof Download PDF

Info

Publication number
CN116082640A
CN116082640A CN202211664807.6A CN202211664807A CN116082640A CN 116082640 A CN116082640 A CN 116082640A CN 202211664807 A CN202211664807 A CN 202211664807A CN 116082640 A CN116082640 A CN 116082640A
Authority
CN
China
Prior art keywords
polymer
electrolyte
formula
oxide
acid
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.)
Pending
Application number
CN202211664807.6A
Other languages
Chinese (zh)
Inventor
孙国宸
李泓
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Institute of Physics of CAS
Original Assignee
Institute of Physics of CAS
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Institute of Physics of CAS filed Critical Institute of Physics of CAS
Priority to CN202211664807.6A priority Critical patent/CN116082640A/en
Publication of CN116082640A publication Critical patent/CN116082640A/en
Pending legal-status Critical Current

Links

Images

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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • H01M10/05—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
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/04—Polysiloxanes
    • C08J2383/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/10—Block- or graft-copolymers containing polysiloxane sequences
    • C08J2383/12—Block- or graft-copolymers containing polysiloxane sequences containing polyether sequences
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0088—Composites
    • 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 invention provides a polymer for electrolyte, a preparation method and application thereof, wherein the polymer is composed of a repeating unit shown in a formula (1)Polymers and/or alternating polymers and/or block polymers and/or graft polymers and/or random polymers. The electrolyte containing the polymer has higher chain segment movement capability than the common polyether electrolyte, so that the ion conductivity of the polymer electrolyte can be obviously improved. Meanwhile, the ionic conductivity of the polymer electrolyte can be further improved by matching with lithium salt which is easier to dissociate.
Figure DDA0004014365060000011

Description

Polymer for electrolyte and preparation method and application thereof
Technical Field
The invention belongs to the technical field of electrolyte materials, and particularly relates to a polymer for electrolyte, a polymer electrolyte and a preparation method thereof, a composite solid electrolyte, a composite electrolyte solution and a secondary battery.
Background
The increasingly developed new energy industries such as consumer electronics, electric automobiles, power station energy storage and the like put higher requirements on the safety and energy density of secondary batteries. At present, the liquid electrolyte in the secondary battery has the phenomena of inflammability, explosiveness, easy eruption and the like under the condition of failure or abuse, so that the secondary battery has certain safety problem when in use. Therefore, how to improve the safety performance of the liquid electrolyte is a problem to be solved. The solid electrolyte has the characteristics of higher thermal decomposition temperature, difficult eruption and the like, so that the solid electrolyte is one of research directions for remarkably improving the safety problem of the lithium battery at present.
Common solid electrolytes are classified into oxides, sulfides and polymer electrolytes. Among them, the polymer electrolyte has more excellent properties than oxide and sulfide electrolytes, and is mainly represented by the following aspects: 1. the interface contact performance of the polymer electrolyte is obviously superior to that of oxide and sulfide electrolytes, so that the interface impedance is smaller; 2. the polymer does not react in the air, and the performance is stable; and unlike sulfide solid electrolyte and garnet type oxide solid electrolyte, the polymer electrolyte is not easy to decompose when meeting water, so that the safety performance is higher; 3. the polymer electrolyte has good mechanical property, is easy to process, and is beneficial to large-scale production and application; 4. the polymer electrolyte has higher stability to low potential negative electrodes (such as metallic lithium negative electrodes).
However, currently commonly used polymer electrolyte materials such as polyethylene oxide and polyether polymers are not only poor in oxidation resistance, but also unsuitable for high-voltage battery systems (including positive electrode systems of lithium cobaltate positive electrode materials, ternary positive electrode materials, nickel manganese positive electrode materials, lithium-rich positive electrode materials, etc.), so that secondary batteries including the polymer electrolyte have low energy density and are not suitable for commercial use.
The conventional polyalkyleneether polymer has improved compatibility with lithium cobaltate positive electrode materials at high voltage, but is not suitable for charging to high voltage, and therefore, the positive electrode capacity cannot be fully exerted. As for the polymer electrolyte materials of polyacrylonitrile, polyethylene carbonate and polyethylene carbonate type, although oxidation resistance is improved as compared with conventional polyethylene oxide and polyether polymers, there are problems of low ion conductivity, low solubility of lithium salt and/or sodium salt, and/or less kinds of matched lithium salt. Thus, the above-mentioned disadvantages limit the application of the polymer solid electrolyte.
Disclosure of Invention
Aiming at the defects of the prior polymer electrolyte, the invention aims to overcome the defects of poor oxidation resistance, inapplicability to a high-voltage battery system, low ion conductivity, low solubility of lithium salt and/or sodium salt, less matched lithium salt types and the like of the polymer electrolyte in the prior art, and provides a polymer for the electrolyte, the polymer electrolyte, a preparation method thereof, a composite solid electrolyte, a composite electrolyte and a secondary battery with better performance.
1. Polymer for electrolyte
In a first aspect, the present invention provides a polymer for an electrolyte, which is a homopolymer and/or an alternating polymer and/or a block polymer and/or a graft polymer and/or a random polymer composed of a repeating unit represented by formula (1):
Figure BDA0004014365040000021
wherein:
R 1 、R 2 、R 3 、R 4 、R 5 and R is 6 Each independently selected from C1-C20 alkylene, C1-C20 alkylene substituted fully or partially with halogen, fully or partially carbonC1-C20 alkylene having atoms replaced by silicon atoms, wherein R 1 、R 2 、R 3 、R 4 、R 5 And R is 6 Comprises a halogen atom;
k. l, m, n, o and p are each independently integers of 0 to 100, q is an integer of 1 to 300000, and (k+l+m+n+o+p) ×q >3.
Preferably, (k+l+m+n+o+p) x q is between 3000 and 3000000; more preferably, (k+l+m+n+o+p) ×q is between 10000 ～ 2000000; particularly preferably, (k+l+m+n+o+p) ×q is between 30000 ～ 1500000.
In the repeating unit represented by formula (1), the terminal group is represented. In the polymer provided by the invention, the end group can be one or more groups of ether, alcohol, ester, carbonate, carboxylic acid, aldehyde, ketone, C1-C20 alkyl, C1-C20 alkenyl and C1-C20 halogenated hydrocarbon groups.
In a preferred embodiment of the invention, q is an integer from 3000 to 300000.
In some embodiments of the invention, R 1 、R 2 、R 3 、R 4 、R 5 And R is 6 Each independently selected from the structures of formulas (1 a) to (1 j):
Figure BDA0004014365040000031
wherein each R x Each independently is silicon or carbon, and each X is independently hydrogen, halogen, or a repeating unit represented by formula (1).
In a preferred embodiment of the invention, R 1 、R 2 、R 3 、R 4 、R 5 And R is 6 Wherein X is a halogen in a total mole percent of between 1% and 50%, i.e., 1% to 50% of the total X substituents are halogen.
In the structures of the formulae (1 a) to (1 j), the broken line represents a dangling bond connected to the polymer main chain.
In some embodiments of the invention, the polymer has one of the structures shown as formula (2 a) to formula (2 h):
Figure BDA0004014365040000032
Figure BDA0004014365040000041
wherein X is selected from hydrogen or halogen, and
in the formula (2 a), kxq is more than 3; in the formulae (2 b) and (2 d) to (2 h), (k+l) ×q is more than 3; in the formula (2 c), (k+l+m) ×q is more than 3.
In a preferred embodiment of the invention, in formula (2 a), kxq is between 3000 and 3000000; in the formulas (2 b) and (2 d) to (2 h), (k+l) ×q is between 3000 and 3000000; in the formula (2 c), (k+l+m) ×q is between 3000 and 3000000.
In a more preferred embodiment of the invention, in formula (2 a), kxq is between 10000 ～ 2000000; in the formulae (2 b) and (2 d) to (2 h), (k+l) ×q is between 10000 ～ 2000000; in the formula (2 c), (k+l+m) ×q is between 10000 ～ 2000000.
In a particularly preferred embodiment of the invention, in formula (2 a), kxq is between 30000 ～ 1500000; in the formulae (2 b) and (2 d) to (2 h), (k+l) ×q is between 30000 ～ 1500000; in the formula (2 c), (k+l+m) ×q is between 30000 ～ 1500000.
In other embodiments of the present invention, the polymer has one of the structures shown in formulas (3 a) to (3 f):
Figure BDA0004014365040000042
Figure BDA0004014365040000051
wherein k, l, m are not simultaneously 0, and
in the formula (3 a), k multiplied by q is more than 3; (k+l) ×q in the formulae (3 b) and (3 d) to (3 h) is more than 3; in the formula (3 c), (k+l+m) ×q is more than 3.
In a preferred embodiment of the invention, in formula (3 a), kxq is between 3000 and 3000000; in the formulas (3 b) and (3 d) to (3 h), (k+l) ×q is between 3000 and 3000000; in the formula (3 c), (k+l+m) ×q is between 3000 and 3000000.
In a more preferred embodiment of the invention, in formula (3 a), kxq is between 10000 ～ 2000000; in the formulae (3 b) and (3 d) to (3 h), (k+l) ×q is between 10000 ～ 2000000; in the formula (3 c), (k+l+m) ×q is between 10000 ～ 2000000.
In a particularly preferred embodiment of the invention, in formula (3 a), kxq is between 30000 ～ 1500000; in the formulae (3 b) and (3 d) to (3 h), (k+l) ×q is between 30000 ～ 1500000; in the formula (3 c), (k+l+m) ×q is between 30000 ～ 1500000.
2. Method for preparing polymer for electrolyte
The second aspect of the present invention provides a method for producing the above polymer for an electrolyte, the method comprising preparing or preparing a precursor, and obtaining the polymer by a vapor phase synthesis method.
In some embodiments of the invention, the method of preparation comprises the steps of:
(1) Mixing the precursors, optionally activated by preheating;
(2) And (3) heating the precursor obtained in the step (1) to perform gas phase synthesis, and drying to obtain the polymer for the electrolyte.
Preferably, the preheating temperature in the step (1) is 40 to 400 ℃, for example, 40 ℃, 60 ℃, 80 ℃, 100 ℃, 120 ℃, 140 ℃, 160 ℃, 180 ℃, 200 ℃, 220 ℃, 240 ℃, 260 ℃, 280 ℃, 300 ℃, 320 ℃, 340 ℃, 360 ℃, 380 ℃, 400 ℃; the preheating time is 1-30 min, for example, 1min, 2min, 4min, 6min, 8min, 10min, 12min, 14min, 16min, 18min, 20min, 22min, 24min, 26min, 28min, 30min.
In various embodiments of the present invention, the precursor may include, but is not limited to: any one or a combination of a plurality of amide compounds, naphthene compounds, alkylene oxide compounds, cyclic ketone compounds, cyclic vinyl ester compounds, fluorine-containing compounds, chlorine-containing compounds, silicic acid-containing compounds, ether compounds, cyclic ester compounds, silicate compounds and acid compounds.
In some embodiments of the invention, the precursor may include, but is not limited to: 1, 3-dioxolane, 1, 3-cyclopentanedione, 1, 4-dioxane-2, 5-hexanedione, 1, 4-cyclohexanedione, 2-fluoroethylene oxide, 2-difluoroethylene oxide, 2, 3-difluoroethylene oxide, fluoropropane, ethylene carbonate, diethylaminosulfur trifluoride, trifluoropropyltrichlorosilane, tetrafluoroboric acid, hexafluorophosphoric acid, hexafluorotitanic acid, fluoroethylene carbonate, ethylene oxide, thionyl chloride, phosphoric acid, sulfuric acid, boric acid, polytetrafluoroethylene micropowder, fluorosilicic acid, hydrofluoric acid, trifluoromethyl carbonate, stannous octoate, ethylene glycol dimethyl ether, glycolaldehyde dimer, glycolide, N-fluorobenzenesulfonamide, 1-chloromethyl-4-fluoro-1, 4-diazotized bicyclo 2.2.2 octane bis (tetrafluoroboric acid) salt, silica, sulfur tetrafluoride.
According to the preparation method provided by the invention, the heating temperature in the step (2) may be 40-400 ℃, for example 40 ℃, 60 ℃, 80 ℃, 100 ℃, 120 ℃, 140 ℃, 160 ℃, 180 ℃, 200 ℃, 220 ℃, 240 ℃, 260 ℃, 280 ℃, 300 ℃, 320 ℃, 340 ℃, 360 ℃, 380 ℃, 400 ℃.
Preferably, the vapor phase synthesis in step (2) comprises vacuum evaporation or vapor deposition. In some embodiments of the invention, the gas is introduced during vacuum evaporation or vapor deposition. Wherein the gas includes, but is not limited to, an ethylene oxide-containing gas, a halogen-containing gas, or ozone.
Preferably, the halogen-containing gas includes, but is not limited to, one or more combinations of 1, 1-dichloro-2, 2-difluoroethylene, 2-chloro-1, 2-dibromo-1, 2-trifluoroethane, chlorotrifluoroethylene, nitrogen trifluoride, trifluoromethyl trifluoroethylene ether, carbon tetrafluoride, sulfur hexafluoride, hexafluoropropylene oxide, octafluorocyclobutane, trans-1, 3-tetrafluoropropene, fluorine gas, sulfuryl fluoride, hydrogen chloride gas, chlorine gas, hydrofluoric acid gas, and isoflurane.
Preferably, a solid catalyst is used during vacuum evaporation or vapor deposition. The solid catalyst may include one or more of an oxide, a silicic acid compound, a boric acid compound, and a metal catalyst.
Preferably, the solid state catalyst includes, but is not limited to, one or more of silica, manganese dioxide, aluminum oxide, boron trioxide, lithium tetraborate, sodium tetraborate, silicic acid, silicate, boric acid, borate, cobalt oxide, copper oxide, zinc oxide, iron oxide, nickel oxide, manganese oxide, calcium oxide, silver, platinum, gold, iron, cobalt, nickel, molybdenum, niobium, magnesium, aluminum, titanium, zinc, calcium.
3. Electrolyte polymer
A third aspect of the present invention provides a polymer electrolyte comprising the polymer provided by the present invention or the polymer obtained by the preparation method according to the present invention, and a lithium salt and/or a sodium salt, wherein the mass percentage of the polymer in the polymer electrolyte is 5% to 99%, and the mass percentage of the lithium salt and/or the sodium salt in the polymer electrolyte is 1% to 95%.
In various embodiments of the invention, the mass percent of the polymer in the polymer electrolyte may vary from 5% to 99%, for example, may be 5%, 7%, 10%, 12%, 15%, 17%, 20%, 22%, 25%, 27%, 30%, 32%, 35%, 37%, 40%, 42%, 45%, 47%, 50%, 52%, 55%, 57%, 60%, 62%, 65%, 67%, 70%, 72%, 75%, 77%, 80%, 82%, 85%, 87%, 90%, 92%, 95%, 97%, 99%; the mass percentage of the lithium salt in the polymer electrolyte may vary from 1% to 95%, for example, may be 1%, 3%, 5%, 7%, 10%, 12%, 15%, 17%, 20%, 22%, 25%, 27%, 30%, 32%, 35%, 37%, 40%, 42%, 45%, 47%, 50%, 52%, 55%, 57%, 60%, 62%, 65%, 67%, 70%, 72%, 75%, 77%, 80%, 82%, 85%, 87%, 90%, 92%, 95%.
The polymer electrolyte provided by the invention, wherein the lithium salt can be one or a combination of more of organic lithium salt and inorganic lithium salt; the sodium salt may be a combination of one or more of an organic sodium salt and an inorganic sodium salt.
Preferably, the organic lithium salt may be selected from one or more of 1,2,3,4, 5-penta-trifluoromethyl cyclopentadiene lithium, difluoro-lithium oxalate borate, N-trifluoromethyl-lithium trifluoroacetamide, bis-oxalato-lithium borate, bis-trifluoromethylsulfonyl-lithium, bis-fluorosulfonyl-lithium, trifluoromethylsulfonate, trinitromethyl-lithium, tetrakis ((trifluoromethyl) sulfonyl) lithium borate, tetrakis (trifluoromethyl) lithium borate, tetramethyl lithium borate, tetrakis (perfluoro-t-butoxy) lithium aluminate, tetraethyl lithium borate, tetranitrile lithium borate, hexa (trifluoromethyl) lithium aluminate, hexa (trifluoromethyl) lithium phosphate, dodecafluoro-dodecalithium borate; the inorganic lithium salt can be selected from one or more of lithium tetrafluoroborate, lithium hexafluorophosphate and lithium perchlorate.
The polymer electrolyte provided by the invention, wherein the sodium salt can be one or more of organic sodium salt and inorganic sodium salt.
Preferably, the organic sodium salt may be selected from one or more of sodium bis (trifluoromethylsulfonyl) imide, sodium difluorosulfimide, sodium bisoxalato borate, sodium difluorooxalato borate; the inorganic sodium salt can be selected from one or more of sodium hexafluorophosphate, sodium tetrafluoroborate, sodium perchlorate and sodium iodide.
4. Method for preparing electrolyte polymer
A fourth aspect of the present invention provides a method for producing a polymer electrolyte, comprising:
mixing a polymer with lithium salt and/or sodium salt, dissolving in a solvent to obtain solid electrolyte slurry, and drying to obtain the polymer electrolyte; or alternatively
The polymer and lithium salt and/or sodium salt are prepared into polymer electrolyte by using an electrostatic spinning method,
wherein the polymer is the polymer provided by the invention or the polymer obtained by the preparation method of the invention.
In a preferred embodiment of the present invention, the polymer electrolyte is in the form of a film.
Preferably, the drying is vacuum drying at a temperature of 40 to 400 ℃, for example, 40 ℃, 60 ℃, 80 ℃, 100 ℃, 120 ℃, 140 ℃, 160 ℃, 180 ℃, 200 ℃, 220 ℃, 240 ℃, 260 ℃, 280 ℃, 300 ℃, 320 ℃, 340 ℃, 360 ℃, 380 ℃, 400 ℃, or the like.
According to the preparation method of the polymer electrolyte provided by the invention, the solvent can be an organic solvent and/or an inorganic solvent. Preferably, the organic solvent includes, but is not limited to, one or more of N, N-dimethylformamide, dichloromethane, dimethyl sulfoxide, carbon tetrachloride, methyl isobutyl ketone, ethanol, acetonitrile, ethyl acetate, butyl acetate, acetone, pentane, cyclohexane, petroleum ether, isopropanol, N-heptane. The inorganic solvent may be deionized water.
According to the preparation method of the polymer electrolyte provided by the invention, the electrostatic spinning method can comprise the following steps:
stirring and mixing the polymer and the solution to form a spinning solution, and transferring the spinning solution into a syringe;
applying voltage to the needle of the injector and the substrate, slowly extruding the spinning solution to form a film on the substrate,
wherein the solution comprises a lithium salt and/or a sodium salt, as well as a solvent and optionally a thickener.
5. Composite solid electrolyte
A fifth aspect of the present invention provides a composite solid state electrolyte comprising a polymer as provided in the first aspect of the present invention, a polymer as provided in the second aspect of the present invention, a polymer electrolyte as provided in the third aspect of the present invention or a polymer electrolyte as provided in the fourth aspect of the present invention, and at least one further inorganic solid state electrolyte and/or organic solid state electrolyte.
The polymer or polymer electrolyte of the present invention may be 0.5 to 99% by mass in the composite solid electrolyte, and the inorganic solid electrolyte and/or the organic solid electrolyte may be 0.5 to 99% by mass in the composite solid electrolyte. Preferably, the mass percentage of the polymer electrolyte in the composite solid electrolyte is 1% -98%, and the mass percentage of the inorganic solid electrolyte and/or the organic solid electrolyte in the composite solid electrolyte is 1% -98%.
Preferably, when the polymer electrolyte provided in the third aspect of the present invention or the polymer electrolyte obtained by the preparation method provided in the fourth aspect of the present invention is included in the composite solid electrolyte, the mass percentage of the lithium salt and/or sodium salt in the polymer electrolyte in the composite solid electrolyte may be 0.5% to 99%.
In accordance with the present invention, the composite solid state electrolyte may be an inorganic nano-oxide, such as one or more of silica, manganese dioxide, ceria, titania, lanthanum oxide, and aluminum oxide, in some embodiments.
In other embodiments, the inorganic solid state electrolyte may be one or more of a NASICON-type solid state electrolyte, a perovskite-type solid state electrolyte, or a garnet-type solid state electrolyte. Preferably, the NASICON type solid state electrolyte includes, but is not limited to, li 1.3 A1 0.3 Ti 1.7 (PO 4 ) 3 、Li 1.4 A1 0.4 Ti 1.6 (PO 4 ) 3 And Li (lithium) 1.5 A1 0.5 Ge 1.5 (PO 4 ) 3 The method comprises the steps of carrying out a first treatment on the surface of the The perovskite type solid electrolyte includes but is not limited to Li 0.33 La 0.56 TiO 3 And/or Li 0.25 La 0.583 TiO 3 The method comprises the steps of carrying out a first treatment on the surface of the The garnet-type solid state electrolyte includes, but is not limited to, li 7 La 3 Zr 2 O 12 、Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 Or Li (lithium) 6.25 Al 0.25 La 3 Zr 2 O 12 One or more of the following.
The composite solid electrolyte provided according to the present invention, wherein the organic solid electrolyte comprises one or more of an ether-based polymer electrolyte, an ester-based polymer electrolyte, a carbonate-based polymer electrolyte, a nitrile-based polymer electrolyte, an alkyl-based polymer electrolyte.
Wherein the ether-based polymer electrolyte includes, but is not limited to, polyethylene oxide; the ester-based polymer electrolytes include, but are not limited to, polymethacrylates; the carbonate-based polymer electrolytes include, but are not limited to, aliphatic polycarbonates; the nitrile-based polymer electrolyte includes, but is not limited to, polyacrylonitrile; the alkyl-based polymer electrolyte includes, but is not limited to, polyvinylidene fluoride, polytetrafluoroethylene, poly (vinylidene fluoride-co-hexafluoropropylene), polyvinylchloride.
The composite solid electrolyte provided according to the present invention, wherein the mass percentage of the polymer of the present invention in the composite solid electrolyte may vary from 0.5% to 95%, for example, may be 0.5%, 1%, 3%, 5%, 7%, 10%, 12%, 15%, 17%, 20%, 22%, 25%, 27%, 30%, 32%, 35%, 37%, 40%, 42%, 45%, 47%, 50%, 52%, 55%, 57%, 60%, 62%, 65%, 67%, 70%, 72%, 75%, 77%, 80%, 82%, 85%, 87%, 90%, 92%, 95%.
Further, the mass percentage of the inorganic solid electrolyte or the organic solid electrolyte other than the polymer in the composite solid electrolyte may vary in a range of 0.5% to 95%, and may be, for example, 0.5%, 1%, 3%, 5%, 7%, 10%, 12%, 15%, 17%, 20%, 22%, 25%, 27%, 30%, 32%, 35%, 37%, 40%, 42%, 45%, 47%, 50%, 52%, 55%, 57%, 60%, 62%, 65%, 67%, 70%, 72%, 75%, 77%, 80%, 82%, 85%, 87%, 90%, 92%, 95%.
The mass percentage of the lithium salt and/or sodium salt in the composite solid electrolyte may vary from 0.5% to 95%, for example, may be 0.5%, 1%, 3%, 5%, 7%, 10%, 12%, 15%, 17%, 20%, 22%, 25%, 27%, 30%, 32%, 35%, 37%, 40%, 42%, 45%, 47%, 50%, 52%, 55%, 57%, 60%, 62%, 65%, 67%, 70%, 72%, 75%, 77%, 80%, 82%, 85%, 87%, 90%, 92%, 95%.
Preferably, the mass percentage of the lithium salt and/or sodium salt in the composite solid electrolyte is 10-90%.
In a preferred embodiment of the present invention, the composite solid electrolyte is in the form of a film. Preferably, the film-like composite solid electrolyte is prepared using a method including, but not limited to, a dissolution film-forming method, a casting method, an electrospinning method, or a 3D printing casting method.
In one embodiment of the invention, the preparation of the composite solid electrolyte membrane by using a dissolution film-forming method comprises the steps of preparing a mixed solution, stirring, ultrasonic dispersing, volatilizing and drying.
Preferably, the preparation of the mixture comprises mixing the polymer of the invention with a lithium or sodium salt, and one or more additional inorganic solid electrolytes and/or organic solid electrolytes in a solvent. Preferably, the solvent may be selected from one or more of N, N-dimethylformamide, dichloromethane, dimethyl sulfoxide, carbon tetrachloride, methyl isobutyl ketone, ethanol, acetonitrile, ethyl acetate, butyl acetate, acetone, pentane, cyclohexane, petroleum ether, isopropanol, N-heptane, deionized water.
Preferably, the stirring and the ultrasonic dispersion include simultaneously performing ultrasonic and stirring on the mixed solution using an ultrasonic cell grinder.
Preferably, the volatilizing and drying comprises pouring the mixed solution into a flat die, volatilizing and drying. Preferably, the drying comprises vacuum drying.
6. Composite electrolyte
A sixth aspect of the present invention provides a composite electrolyte comprising the polymer electrolyte provided in the third aspect of the present invention or the polymer electrolyte obtained by the production method provided in the fourth aspect of the present invention, and a plasticizer.
Wherein the mass percentage of the plasticizer in the composite electrolyte is 0.1-50%.
The composite electrolyte provided according to the present invention, wherein the plasticizer may be selected from one or more of amide-based plasticizers, ether-based plasticizers, ester-based plasticizers, cyclic ester-based plasticizers, carbonate-based plasticizers, nitrile-based plasticizers, and cycloalkane-based plasticizers.
Preferably, the amide-based plasticizers include, but are not limited to, one or more of acetamides, thioacetamides, sulfonamides, N-dimethylformamide, formamide.
Preferably, the ether-based plasticizer includes, but is not limited to, one or more of dimethyl ether, diethyl ether, dipropyl ether, ethylene glycol dimethyl ether, or methyl ethyl ether.
Preferably, the ester-based plasticizer includes, but is not limited to, one or more of ethylene glycol dimethacrylate, dimethyl oxalate, diethyl oxalate, methyl glycolate, ethylene glycol diacetate, ethylene glycol ethyl ether acetate, or ethylene glycol diacrylate.
Preferably, the cyclic ester-based plasticizers include, but are not limited to, one or more of hydroxymethyl dioxolone, 4-ethyl-1, 3-dioxan-2-one, or butyrolactone.
Preferably, the carbonate-based plasticizer includes, but is not limited to, one or more of dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl propyl carbonate, dibutyl carbonate, vinylene carbonate, fluoroethylene carbonate, ethylene carbonate, propylene carbonate, isopropyl methyl carbonate, methyl acetate, or ethyl acetate.
Preferably, the nitrile-based plasticizers include, but are not limited to, acrylonitrile, succinonitrile.
Preferably, the cycloalkane-based plasticizers include, but are not limited to, one or more of 1, 3-dioxolane, 1, 4-dioxane-2, 5-hexanedione.
The mass percentage of the plasticizer in the composite electrolyte may vary from 0.1% to 50%, and may be, for example, 0.1%, 0.2%, 0.5%, 1%, 2%, 5%, 7%, 10%, 12%, 15%, 17%, 20%, 22%, 25%, 27%, 30%, 32%, 35%, 37%, 40%, 42%, 45%, 47%, 50%.
In some embodiments of the present invention, the method of preparing a composite electrolyte may include: in the process of using the polymer electrolyte provided in the third aspect of the present invention or the polymer electrolyte obtained by the production method provided in the fourth aspect of the present invention for battery assembly, the plasticizer is dropped on the polymer electrolyte.
In other embodiments of the present invention, the method of preparing a composite electrolyte may include: after the polymer electrolyte provided in the third aspect of the present invention or the polymer electrolyte obtained by the preparation method provided in the fourth aspect of the present invention is used for battery assembly, the plasticizer is injected into the battery before the battery is packaged.
7. Composite electrolyte
A seventh aspect of the present invention provides a composite electrolyte comprising the polymer electrolyte provided in the third aspect of the present invention or the polymer electrolyte obtained by the production method provided in the fourth aspect of the present invention as an additive, and an electrolyte main component.
Preferably, the mass percentage of the polymer electrolyte in the composite electrolyte may be 0.1% to 50%, for example, 0.1%, 0.2%, 0.5%, 1%, 2%, 5%, 7%, 10%, 12%, 15%, 17%, 20%, 22%, 25%, 27%, 30%, 32%, 35%, 37%, 40%, 42%, 45%, 47%, 50%.
The composite electrolyte provided by the invention, wherein the electrolyte main component can comprise common electrolyte components such as carbonate-based electrolyte, ether-based electrolyte and the like.
Preferably, the carbonate-based electrolyte may be selected from one of the following electrolytes: 1MLiPF 6 EC：DMC＝1：1、1M LiPF 6 EC：DMC：FEC＝1：1：0.025、1M LiPF 6 EC：DMC：VC＝1：1：0.005、1M LiPF 6 EC：DMC：FEC：VC＝1：1：0.025：0.005、1M LiPF 6 EC：DMC：FEC：VC：PS：PST：LiDFOB＝1：1：0.075：0.025：0.025：0.025、1M LiPF 6 EC：DMC＝3：7、1M LiPF 6 EC：DMC：FEC＝3：7：0.025、1M LiPF 6 EC：DMC：DEC＝1：1：1、1M LiPF 6 EC：DMC：EMC＝1：1：1、1M LiPF 6 EC：DEC：EMC＝1：1：1、1M LiPF 6 EC：EMC＝3：7、1M LiPF 6 EC：DEC＝1：1。
Preferably, the ether-based electrolyte may be selected from one of the following electrolytes: 1MLiTFSI tetraethyleneglycol dimethyl ether, 1M LiTFSI diethylene glycol dimethyl ether, 1M LiLiTFSI diethylene glycol dimethyl ether, 1M LiTFSI DOL: dme=1: 1. 1MLiFSI DOL: dme=1: 1. 0.5M LiCF 3 SO 3 0.5M LiNO 3 DME：DOL＝1：1。
8. Secondary battery
An eighth aspect of the present invention provides a secondary battery comprising a positive electrode, a negative electrode, and an electrolyte, wherein the electrolyte is at least one of the polymer electrolyte provided in the third aspect of the present invention, the polymer electrolyte obtained by the production method provided in the fourth aspect of the present invention, the composite solid-state electrolyte provided in the fifth aspect of the present invention, the composite electrolyte provided in the sixth aspect of the present invention, and the composite electrolyte provided in the seventh aspect of the present invention.
Preferably, the secondary battery is a lithium battery and/or a sodium battery.
Preferably, the positive electrode comprises one or more of a lithium iron phosphate positive electrode, a ternary positive electrode, a lithium cobalt oxide positive electrode, a nickel manganese positive electrode, a lithium-rich positive electrode, a lithium manganate positive electrode, a sodium vanadium phosphate and a sodium vanadium fluorophosphate.
In some embodiments of the present invention, the positive electrode may be a composite positive electrode composed of one or more of the polymer electrolyte provided in the third aspect of the present invention, the polymer electrolyte obtained by the preparation method provided in the fourth aspect of the present invention, the composite solid electrolyte provided in the fifth aspect of the present invention, the composite electrolyte provided in the sixth aspect of the present invention, and one or more of the above positive electrode materials.
Preferably, the negative electrode includes one or more of a carbon negative electrode, a silicon negative electrode, a lithium titanate negative electrode, and an alloy negative electrode.
In some embodiments of the present invention, the negative electrode may be a composite negative electrode composed of one or more of the polymer electrolyte provided in the third aspect of the present invention, the polymer electrolyte obtained by the preparation method provided in the fourth aspect of the present invention, the composite solid electrolyte provided in the fifth aspect of the present invention, the composite electrolyte provided in the sixth aspect of the present invention, and one or more of the above-described negative electrode materials.
Preferably, the carbon negative electrode includes at least one of a graphite negative electrode and a non-graphite negative electrode. Preferably, the non-graphitic negative electrode comprises at least one of a hard carbon negative electrode and a soft carbon negative electrode.
In some embodiments of the present invention, the surface of at least one of the positive electrode and the negative electrode further includes a coating layer formed by one or more of the polymer electrolyte provided in the third aspect of the present invention, the polymer electrolyte obtained by the preparation method provided in the fourth aspect of the present invention, the composite solid electrolyte provided in the fifth aspect of the present invention, the composite electrolyte provided in the sixth aspect of the present invention, and the composite electrolyte provided in the seventh aspect of the present invention.
The technical scheme of the invention has the following advantages:
according to the polymer for the electrolyte provided by the first aspect of the invention, the halogen atoms are adopted to replace the hydrogen atoms on the polyether chain segments, and the strong electronegativity of the halogen atoms can form a remarkable electron withdrawing effect, namely, the structure can reduce the mutual exclusion effect between different electrons adjacent to the oxygen atoms, so that the energy level of molecular orbitals on the oxygen atoms is reduced, and the oxidation resistance of the polymer can be improved; when the halogen atom-substituted silicon structure contained in the polymer main chain can significantly enhance the above electron withdrawing effect, the oxidation resistance of the polymer material can be significantly improved, and therefore the electrolyte containing the polymer material can be suitably used for a high-voltage positive electrode system in a secondary battery. The withstand voltage characteristics of the high voltage system comprising the electrolyte of the polymeric material exhibit a broader electrochemical window over the linear sweep voltammetric characteristic curve. The high-capacity lithium cobalt oxide positive electrode material can be used together with high-voltage high-capacity positive electrode materials such as lithium cobalt oxide positive electrode materials, ternary positive electrode materials, nickel manganese positive electrode materials, lithium-rich positive electrode materials and the like, the high capacity of the high-capacity positive electrode materials under high voltage is developed in the secondary battery, and the energy density of the secondary battery is improved. In addition, the electrolyte containing the polymer can be matched with a high-capacity anode material to further greatly improve the energy density of the secondary battery.
The polymer provided by the invention can weaken Van der Waals attractive force among polyether polymer chain segments through halogen atom substitution, and can promote chain segment movement capacity, so that the ionic conductivity of a polymer electrolyte is greatly improved. In addition, the silicon element is introduced into the main chain of the polymer to form a silicon-oxygen bond or a carbon-silicon bond, and the silicon-oxygen bond or the carbon-silicon bond has good rotatability and can greatly reduce the resistance of chain segment movement. The effect will be more pronounced when both silicon oxygen bonds and carbon silicon bonds are present. Therefore, the electrolyte containing the polymer of the present invention has a higher segment movement capability than a general polyether electrolyte, so that the ion conductivity of the polymer electrolyte can be significantly improved. Meanwhile, the ionic conductivity of the polymer electrolyte can be further improved by matching with lithium salt which is easier to dissociate.
In addition, in the polymer, through proper control of the substitution ratio of halogen atoms in the polymer, namely, the comprehensive design of the halogen atom content and the flexible rotary bond of the chain segment, the capability of the polymer and lithium ions to form a solvation structure, namely, the solvation structure has more negative solvation free energy, so the polymer has the advantage of good solubility to lithium salt. Further, the substitution ratio of halogen atoms is preferably controlled between 0.1% and 50%, and the dissolution performance of lithium salt in the polymer can be further improved on the premise of improving the oxidation resistance of the polymer. This is because a large amount of halogen atoms are substituted for hydrogen atoms on the polyether segment to improve the oxidation resistance of the polyether polymer, but a large amount of halogen atoms are substituted for hydrogen atoms to cause insufficient electronegativity of oxygen atoms on the polyether segment, and coulomb attraction of oxygen atoms to lithium ions and/or sodium ions becomes weak, which prevents the dissociation equilibrium of lithium salts and/or lithium salts to some extent. Therefore, by controlling the ratio of halogen atoms to hydrogen atoms, the solubility of lithium salts and/or sodium salts in the polymer can be effectively improved, and more kinds of lithium salts and/or lithium salts can be matched. Further, the present invention preferably employs a more dissociable lithium salt and the polymer of the present invention to constitute a polymer electrolyte, whereby the solubility of the lithium salt and the ionic conductivity of the electrolyte can be greatly improved.
The composite solid electrolyte provided by the fifth aspect of the invention has higher mechanical strength and can also effectively reduce the possibility of breakage and lithium dendrite puncture of the composite solid electrolyte. In addition, the higher mechanical strength is also beneficial to further processing the composite solid electrolyte into a thin film which is not easy to break, thereby reducing the thickness of the composite solid electrolyte and improving the energy density of the battery. On the other hand, the composite solid electrolyte can regulate and control the uniformity of interfacial ion transport, and is beneficial to improving the ion migration capacity and the interfacial performance.
The ion conductivity can be further improved by forming the composite electrolyte according to the sixth aspect of the present invention, and the interfacial properties can be improved by forming the composite electrolyte according to the seventh aspect of the present invention.
In addition, the electrolyte can be mixed into the electrode pole piece or coated on the surface of the pole piece, so that the contact property of the electrolyte and electrode particles is improved, and the interface ionic resistance is reduced.
Drawings
Embodiments of the present invention are described in detail below with reference to the attached drawing figures, wherein:
FIG. 1 is a linear sweep voltammetric oxidation curve of a polymeric material shown in formula (3 a);
FIG. 2 is an infrared transmission absorption spectrum of a polymer material represented by formula (3 a);
FIG. 3 is a scanning electron micrograph of a polymeric material of formula (3 a);
FIG. 4 is a graph showing a comparison of linear sweep voltammetric characteristic curves of the polymer and polyethylene oxide shown in the formula (3 a), the formula (3 b) and the formula (3 c).
Detailed Description
The following detailed description of the invention is provided in connection with the accompanying drawings that are presented to illustrate the invention and not to limit the scope thereof.
The experimental examples do not specify specific experimental procedures or conditions, and can be performed according to the operations or conditions of conventional experimental procedures described in the literature in the field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
In the present invention, the explanation of the related art terms is as follows:
the "solubility" of the salt in the polymer means a case where the polymer and the salt are dissolved in a solvent at the time of preparing the polyelectrolyte membrane, and crystalline salt is precipitated on the membrane surface formed after the solvent is dried or after extrusion-drying by a spinning method. When no crystalline salt is found on the surface of the polymer electrolyte membrane in the visual range, the dissolution performance is good; and when a small amount of crystalline salt exists, the dissolution performance is general; when a large amount of the crystalline salt appears, it indicates poor dissolution performance.
By "composite solid electrolyte" is meant a solid electrolyte in which the polymer and/or polymer electrolyte of the present invention, as well as additional inorganic solid electrolytes and/or organic solid electrolytes, lithium salts and/or sodium salts, are compounded.
The "composite electrolyte" means an electrolyte formed by compositing the polymer electrolyte of the present invention with a lithium salt or sodium salt and a plasticizer. The plasticizer is within the scope of the present invention as long as it can be used together with the polymer electrolyte of the present invention to exert plasticizing effect.
The "composite electrolyte" refers to an electrolyte obtained by compositing the polymer electrolyte of the present invention with various common electrolytes.
The term "oxidation resistance" means resistance to chemical oxidation and electrochemical oxidation at a high potential on the positive electrode side in a battery.
The polyethylene oxide and solvent used in the following comparative examples were purchased from Shanghai Ala Biochemical technologies Co., ltd, liTFSI from Suzhou Duoduo chemical technologies Co., ltd; the plasticizers and solvents used in the examples were purchased from Shanghai Ala Biochemical technologies Co., ltd; liB (CN) 4 Prepared according to the method described in J.am.chem.Soc.2000,122,32, 7735-7741; the model of the ultrasonic cell grinder is Xinzhihe JY92-IIN.
Example 1
This example prepares a polymer of formula (3 a):
Figure BDA0004014365040000161
the preparation method comprises the following steps:
(1) Fluoroethylene carbonate, tetrafluoroboric acid, hexafluorotitanic acid were prepared according to 98:1:1, uniformly mixing in a container to prepare a precursor mixture;
(2) Preheating the precursor mixture at 200 ℃ for 15 minutes;
(3) Heating the precursor mixture to 200 ℃ under vacuum;
(4) After the temperature is raised, slowly introducing hydrogen fluoride and sulfur tetrafluoride gas, and preserving heat for 180 minutes;
(5) Cooling to room temperature, drying, and obtaining the polymer shown in the formula (3 a) on the substrate.
Example 2
This example prepares a polymer of formula (3 b):
Figure BDA0004014365040000162
the preparation method comprises the following steps:
(1) Fluoroethylene carbonate, tetrafluoroboric acid, fluorosilicic acid were prepared according to 98:1:1, uniformly mixing in a container to prepare a precursor mixture;
(2) Preheating the precursor mixture at 160 ℃ for 10 minutes;
(3) Heating the precursor mixture to 160 ℃ under vacuum;
(4) After the temperature is raised, slowly introducing hydrogen fluoride and sulfur tetrafluoride gas, and preserving the temperature for 60 minutes;
(5) Cooling to room temperature, and drying to obtain the polymer shown in formula (3 b) on the substrate.
Example 3
This example prepares a polymer of formula (3 c):
Figure BDA0004014365040000171
The preparation method comprises the following steps:
(1) 1, 3-dioxolane, bis (fluoroethylene carbonate), fluoroethylene carbonate, tetrafluoroboric acid, fluosilicic acid according to the following weight ratio of 10:44:44:1:1, uniformly mixing in a container to prepare a precursor mixture;
(2) Preheating the precursor mixture at 120 ℃ for 15 minutes;
(3) Heating the precursor mixture to 160 ℃ under vacuum;
(4) After the temperature is raised, hydrogen fluoride, sulfur tetrafluoride and ethylene oxide gas are slowly introduced, and the temperature is kept for 60 minutes;
(5) Cooling to room temperature, and drying to obtain the polymer shown in the formula (3 c) on the substrate.
Example 4
A film-like polymer electrolyte was prepared using the polymer prepared in example 1.
(1) 0.5g of lithium bistrifluoromethylsulfonylimide LiTFSI was dissolved together with 2.2g of the polymer obtained in example 1 in 75ml of acetonitrile solution in an argon glove box;
(2) Sealing the prepared solution in a container, heating in an oil bath at 60 ℃, mixing and stirring for 24 hours;
(3) Cooling the container to room temperature, and then placing the sealed container in a stirring deaerator for defoaming for 10 minutes, wherein the rotating speed of the stirring deaerator is 1000rpm;
(4) Transferring the container into an argon glove box, opening a sealed container, pouring the solution into a rectangular die with an inner groove of 11 cm long, 11 cm wide and 2 cm deep, naturally volatilizing acetonitrile at room temperature, and airing for 24 hours to form a film;
(5) The mold was placed in a 55 ℃ vacuum oven for 24 hours to dry, after which the polymer electrolyte membrane was peeled off in an argon glove box after cooling and cut into wafers without visible crystalline salts.
Example 5
A film-like polymer electrolyte was prepared by the same method as in example 4 using the polymer prepared in example 2.
Example 6
A film-like polymer electrolyte was prepared by using the polymer obtained in example 3 in a similar manner to example 4, except that 0.22g of lithium tetra-nitrile borate LiB (CN) was used in the step (1) 4 Instead of 0.5g LiTFSI.
Example 7
A film-like composite solid electrolyte was prepared using the polymer prepared in example 1.
(1) 1.1g of the polymer obtained in example 1, 0.25g of LiTFSI and 0.2. 0.2gLi are combined 1.3 A1 0.3 Ti 1.7 (PO 4 ) 3 And 30ml acetonitrile in a round bottom flask;
(2) Adding a magneton into a round-bottom flask, placing the round-bottom flask and a heating magnetic stirrer into an ultrasonic cell grinder, setting the rotating speed of the heating magnetic stirrer to be 300rpm, heating the round-bottom flask to be 60 ℃, and setting the output power of the ultrasonic cell grinder to be 195W for 15 minutes;
(3) After the reaction is finished, the round bottom flask is moved into an argon glove box, the mixed solution is poured into a rectangular mold with an inner groove of 8 cm long, 5 cm wide and 2 cm deep in the argon glove box, and the mixed solution is volatilized and dried;
(4) The mold was placed in a 55 ℃ vacuum oven for 24 hours to dry and cool, after which the polymer electrolyte membrane was peeled off in an argon glove box and cut into wafers, without visible crystalline salts.
Example 8
This example prepares the composite electrolyte of the present invention.
A film-shaped polymer electrolyte was prepared in the same manner as in example 4, except that after the completion of step (5), dimethylformamide plasticizer was added dropwise to the film surface in an amount of 20% by weight based on the film weight.
Example 9
A solid-state battery was produced using the polymer produced in example 1 and the polymer electrolyte produced in example 4.
(1) Dissolving 80% by mass of lithium cobaltate, 12% by mass of polymer of example 1, 3% by mass of LiTFSI, 3% by mass of carbon nano tube and 2% by mass of PVDF in N-methylpyrrolidone, stirring and defoaming to prepare anode slurry;
(2) Coating the positive electrode slurry on a carbon-coated aluminum foil by using a 100-micrometer scraper, drying in a 55 ℃ oven for 4 hours, and then cutting into wafers;
(3) The button cell was assembled and packaged in the order of lithium sheets, stacked polymer electrolyte prepared in example 4, stacked positive electrode sheets, stacked stainless steel gaskets, stacked stainless steel spring sheets.
Example 10
A liquid battery was prepared using the polymer prepared in example 1.
(1) Dissolving 90% of lithium cobaltate, 5% of carbon nano tube and 5% of PVDF in mass fraction into N-methylpyrrolidone, stirring and defoaming to prepare anode slurry;
(2) Coating the positive electrode slurry on a carbon-coated aluminum foil by using a 100-micrometer scraper, drying in a 55 ℃ oven for 4 hours, cutting into wafers, and drying in a 120 ℃ vacuum oven for 6 hours;
(3) 0.02g of the polymer obtained in example 1 was dissolved in 1m as liquid electrolyte additiveol/L LiPF 6 In electrolyte of 5ml EC and 5ml DMC;
(4) And (3) assembling and packaging the button cell according to the sequence of lithium sheets, adding 100 microliters of electrolyte containing the polymer additive in the step (3), stacking the separator, stacking the positive electrode sheets, stacking the stainless steel gaskets and stacking the stainless steel shrapnel.
Example 11
A liquid battery was produced in a similar manner to example 10, except that in step (4), the button cell was assembled and packaged in this order of lithium sheets, stacked separators, electrolyte containing polymer additive 100. Mu.l, stacked positive electrode sheets, stacked stainless steel gaskets, stacked stainless steel spring sheets
Comparative example 1
A polymer electrolyte was prepared in a similar manner to example 4, except that 1.4g of polyethylene oxide was added in the step (1) instead of the polymer of example 1.
Comparative example 2
A solid-state battery was produced in a similar manner to example 9, except that 11 mass% of polyethylene oxide and 4 mass% of LiTFSI were added in step (1) in place of 12 mass% of the example 1 polymer and 3 mass% of LiTFSI in the same Li, O ratio; the polymer electrolyte made of polyethylene oxide in comparative example 1 was stacked in step (5) instead of the polymer electrolyte made of example 4.
Comparative example 3
A liquid battery was produced in a similar manner to example 10, except that 1mol/L LiPF was used in step (4) 6 Instead of the electrolyte to which the polymer of the invention was added, 5ml of EC and 5ml of DMC electrolyte were used.
Characterization of Performance
Test example 1
For the polymer material synthesized in the present invention, taking the product of example 1, i.e., the polymer represented by formula 3a as an example, measurement of X-ray photoelectron spectroscopy (XPS) and infrared absorption spectrum was performed to examine the structure of the product. And the molecular weight is approximately calculated by Scanning Electron Microscopy (SEM).
The X-ray photoelectron spectrum was measured by Thermo Fisher ESCALAB Xi, 150W alkα monochromatic X-ray, scanning range 0 to 1350eV, and the result is shown in fig. 1, and the polymer of formula 3a synthesized according to the synthesis method of the present invention, whose surface element composition ratio (see table 1) matches the description of the chemical structure of the corresponding polymer, was analyzed by the result.
TABLE 1
Element(s) O F C Si
Content of 17.09 31.32 33.08 18.51
The infrared absorption spectrum is measured by using BRUKER VERTEX 70V Fourier transform infrared spectrometer, and the measuring range is 400-4000 cm -1 . The specific operation is as follows: 1mg of the sample was added to 30mg of potassium bromide powder in a desiccation room, ground, pressed into a mold for 2 minutes under 8MPa, and then infrared transmission absorption spectrum was measured. Since the infrared spectrum of organic chemistry corresponds to various vibration modes of organic functional groups, density is utilizedThe infrared absorption spectrum calculated by functional theory and the measurement result of the infrared spectrometer are compared with each other to verify the structure of the substance, and the calculation method is as follows: firstly, carrying out simulated annealing calculation on a model in a polymer with a formula (3 a) with 4 groups of repeated structures, continuously carrying out structural optimization on a stable structure with the lowest energy in the polymer at the level of a B3LYP functional and a 6-31G (d) base group until the energy is extremely small, then verifying that the optimized extremely small energy structure is stable and has no virtual frequency through vibration frequency calculation, and drawing out the peak position of an infrared absorption spectrogram predicted through calculation according to the vibration frequency calculation result.
By comparing and analyzing the measurement result of the infrared spectrometer with the theoretical calculation result (as shown in fig. 2), it can be seen that experimental test peaks are corresponding to the calculated and predicted peak positions, and the synthetic product can be proved to be consistent with the chemical structure of the polymer in the unavoidable calculation error range.
Scanning electron microscopy was performed using a HATACHI S-4800 cold field emission scanning electron microscope. As shown in FIG. 3, SEM photograph shows that the diameter of the synthesized product spherulites is mainly distributed between 20 and 60nm, and the volume of the single segment structure of the polymer represented by the formula (3 a) is about 0.12nm 3 The total polymerization degree kxq of the synthesized product is calculated to be mainly distributed between 35000 and 950000. Limited by the resolution limit of scanning electron microscopy, lower molecular weight structures may exist and are difficult to observe. From the above measurement results, it was found that the polymer obtained by the method of synthesizing the polymer in example 1 was consistent with the chemical structure of the polymer of formula (3 a).
Further, the molecular weights of the polymers represented by the formulas (3 b) and (3 c) were roughly calculated by a Scanning Electron Microscope (SEM), and they were obtained by: the overall degree of polymerization (k+l) x q of the product of formula (3 b) is mainly distributed between 50000 ～ 1350000; the overall degree of polymerization (k+l+m). Times.q of the product of formula (3 c) is mainly distributed between 30000 ～ 1300000.
Test example 2
The electrochemical window of the polymeric material of the present invention was measured by three-electrode linear sweep voltammetry. The specific operation is as follows: the polymer materials represented by the formulas (3 a) to (3 c) and polyethylene oxide were dissolved in ethyl acetate at a concentration of 2g/l, respectively, using acetonitrile as a solvent for the polymer In nitriles as Ag/AgNO 3 As a reference electrode, 0.1M tetrabutylammonium perchlorate as a supporting electrolyte, a glass carbon plate as a counter electrode, a narrow strip-shaped double-sided thin-coated lithium cobaltate electrode sheet, a ternary NCM 811-coated electrode sheet, or a lithium iron phosphate-coated electrode sheet as a working electrode, and stability of the polymer and polyethylene shown in formula (3 a) -formula (3 c) to a high-voltage positive electrode was measured; the linear sweep voltammetry measurement increases the working electrode voltage to a high potential and measures the oxidation reaction current. And converting the reaction current into the reaction current density according to the area of the electrode extending into the liquid level of the solution and the specific surface area of the active particulate matters of the pole piece. By extending the linear segments before and after the oxidation initiation potential to the intersection, the potential at the intersection is used as the electrochemical oxidation window of the polymer material.
Active materials coated by a working electrode are purchased from Rongsheng Guli New energy science and technology Co., ltd, 90% of positive electrode active materials, 5% of carbon nano tubes and 5% of PVDF by mass are dissolved in N-methylpyrrolidone, stirring and defoaming are carried out to prepare positive electrode slurry, the positive electrode slurry is coated on carbon-coated aluminum foil by using a 50-micrometer scraper, the positive electrode plate is dried for 4 hours in a 55 ℃ oven, the positive electrode slurry is coated on the back of the carbon-coated aluminum foil by using a 50-micrometer scraper, the positive electrode plate is dried for 4 hours in a 55 ℃ oven, and the positive electrode plate is dried for 6 hours in a 120 ℃ vacuum oven, so that the positive electrode plate is cut into long strips with the width of 5 mm. The counter electrode and the reference electrode were purchased from Tianjin Aida Hengshig, tetrabutylammonium perchlorate was purchased from Alfa elsa (China) chemical Co., ltd, acetonitrile was purchased from Shanghai Ala Biochemical technology Co., ltd, and the linear sweep voltammetry (linear sweep voltammetry) was measured using Shanghai Cinnabaris CHI604E electrochemical workstation at a sweep rate of 20mV/s.
As shown in FIG. 4, the electrochemical oxidation window of the polymer of formula (3 a) of the present invention with a lithium cobalt oxide positive electrode was measured to be 4.94V vs. Li + Li. The electrochemical oxidation window of the polymer shown in the formula (3 b) and the lithium cobalt oxide positive electrode is 4.55V vs. Li + Li. The electrochemical oxidation window of the polymer shown in the formula (3 c) matched with the ternary NCM811 electrode is 4.58V vs. Li + Li. And the electrochemical oxidation window of the polyethylene oxide and lithium iron phosphate electrode is 3.91V vs. Li + Li. Therefore, the battery system formed by the polymer can be charged to be higher than 4.5V, which is obviously higher than the battery system formed by the prior polymer, so that the polymer has good oxidation resistance compared with the prior polymer, and therefore, the electrolyte formed by the polymer can fully play the capacity of the positive electrode material with a high-voltage positive electrode and keep good interface stability and battery cycle property.
Test example 3
The electrolyte membranes provided in examples 4 to 8 and comparative example 1 were subjected to ion conductivity test as follows: the electrolyte membranes provided in examples 4 to 8 and comparative example 1 were each sandwiched between two circular stainless steel gaskets of known thickness and equal area, and were packaged in button cells with spring plates. Placing the sample in a constant temperature oven for more than 4 hours, and measuring alternating current impedance through an external electrochemical workstation. After measurement, the battery shell is disassembled to measure the whole thickness of the stainless steel gasket and the electrolyte membrane, and the thickness is used for converting the ionic conductivity measured by the alternating current impedance into the ionic conductivity.
Ionic conductivity was tested by ac impedance method using a Zahner IM6 electrochemical workstation with an amplitude of 10mV in the frequency range 0.1Hz to 1MHz and the results are shown in table 2.
TABLE 2
Temperature (. Degree. C.) Ion conductivity (S/cm)
Example 4 60 7.7x10 -4
Example 5 60 1.2x10 -3
Example 6 60 1.8x10 -3
Example 6 30 5.8x10 -4
Example 7 60 9.3x10 -4
Example 8 30 6.1x10 -4
Comparative example 1 60 2.3x10 -4
Comparative example 1 30 6.6x10 -6
As can be seen from the data of Table 2, the electrolyte membranes provided in examples 4 to 8 of the present invention have an ionic conductivity of not less than 7X10 at 60 ℃ -4 S/cm and up to 1.8x10 -3 S/cm, not lower than 5x10 at 30 DEG C -4 S/cm, whereas the electrolyte membrane of comparative example 1 has an ionic conductivity of only 2.3x10 at 60 ℃ -4 S/cm,30℃of only 6.6x10 -6 S/cm, the ionic conductivity of the polymer electrolyte is greatly improved compared with the prior art.
Test example 4
The button cells provided in examples 9 to 11 and comparative examples 2 to 3 were subjected to a battery cycle capacity life test, a charge-discharge cycle performance test was performed at a rate of 0.2C, and the discharge capacity after 50 weeks of cycle was measured to calculate a capacity retention rate, and the results are shown in table 3.
TABLE 3 Table 3
Temperature (. Degree. C.) Capacity retention after 50 weeks cycle (%)
Example 9 60 92
Example 10 30 75
Example 11 30 87
Comparative example 2 60 0
Comparative example 3 30 52
Where "0" indicates that the battery has failed to function properly at 50 weeks.
It should be noted that the process of the present invention is described by the above experimental examples, but the present invention is not limited to the above process steps, i.e. it does not mean that the present invention must rely on the above process steps to be tested. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of selected raw materials, addition of auxiliary components, selection of specific modes, etc. fall within the scope of the present invention and the scope of disclosure.

Claims (13)

1. A polymer for an electrolyte, which is a homopolymer and/or an alternating polymer and/or a block polymer and/or a graft polymer and/or a random polymer composed of a repeating unit represented by the formula (1):
Figure FDA0004014365030000011
wherein:
R 1 、R 2 、R 3 、R 4 、R 5 and R is 6 Each independently selected from C1-C20 alkylene, C1-C20 alkylene substituted fully or partially by halogen, C1-C20 alkylene substituted fully or partially by silicon atoms, and R 1 、R 2 、R 3 、R 4 、R 5 And R is 6 Comprises a halogen atom;
k. l, m, n, o and p are each independently integers of 0 to 100, q is an integer of 1 to 300000, and (k+l+m+n+o+p) ×q >3.
2. The polymer of claim 1, wherein the end groups of the polymer are one or more of ethers, alcohols, esters, carbonates, carboxylic acids, aldehydes, ketones, C1-C20 alkyl groups, C1-C20 alkenyl groups, C1-C20 halogenated hydrocarbon groups;
preferably, q is an integer from 3000 to 300000.
3. The polymer of claim 1, wherein R 1 、R 2 、R 3 、R 4 、R 5 And R is 6 Each independently selected from the structures of formulas (1 a) to (1 j):
Figure FDA0004014365030000012
wherein each R x Each independently is silicon or carbon, and each X is independently hydrogen, halogen, or a repeating unit represented by formula (1);
preferably, R 1 、R 2 、R 3 、R 4 、R 5 And R is 6 X in the formula (I) is halogen, and the total mole percentage of the halogen is 1-50%.
4. A polymer according to any one of claims 1 to 3, wherein the polymer has one of structures shown as formulae (2 a) to (2 h):
Figure FDA0004014365030000021
wherein X is selected from hydrogen or halogen, and
in the formula (2 a), kxq is more than 3; in the formulae (2 b) and (2 d) to (2 h), (k+l) ×q is more than 3; in the formula (2 c), the (k+l+m) multiplied by q is more than 3;
preferably, in formula (2 a), kxq is between 3000 and 3000000; in the formulas (2 b) and (2 d) to (2 h), (k+l) ×q is between 3000 and 3000000; in the formula (2 c), the (k+l+m) multiplied by q is between 3000 and 3000000;
Or preferably, the polymer has one of structures shown as formula (3 a) to formula (3 f):
Figure FDA0004014365030000031
wherein k, l, m are not simultaneously 0, and
in the formula (3 a), k multiplied by q is more than 3; (k+l) ×q in the formulae (3 b) and (3 d) to (3 h) is more than 3; in the formula (3 c), the (k+l+m) multiplied by q is more than 3;
preferably, in formula (3 a), kxq is between 3000 and 3000000; in the formulas (3 b) and (3 d) to (3 h), (k+l) ×q is between 3000 and 3000000; in the formula (3 c), (k+l+m) ×q is between 3000 and 3000000.
5. A method for producing a polymer for an electrolyte according to any one of claims 1 to 4, which comprises preparing or preparing a precursor, and obtaining the polymer by a vapor phase synthesis method.
6. The preparation method according to claim 5, comprising the steps of:
(1) Mixing the precursors, optionally activated by preheating;
(2) Heating the precursor obtained in the step (1) to perform gas phase synthesis, drying to obtain the polymer for the electrolyte,
preferably, the preheating temperature in the step (1) is 40-400 ℃; preheating time is 1-30 min;
preferably, the precursor is a combination of two or more of 1, 3-dioxolane, 1, 3-cyclopentanedione, 1, 4-dioxane-2, 5-hexanedione, 1, 4-cyclohexanedione, 2-fluoroethylene oxide, 2-difluoroethylene oxide, 2, 3-difluoroethylene oxide, fluoropropane, difluoroethylene carbonate, diethylaminosulfur trifluoride, trifluoropropyltrichlorosilane, tetrafluoroboric acid, hexafluorophosphoric acid, hexafluorotitanic acid, fluoroethylene carbonate, ethylene oxide, thionyl chloride, phosphoric acid, sulfuric acid, boric acid, polytetrafluoroethylene micropowder, fluorosilicic acid, hydrofluoric acid, trifluoromethyl carbonate, stannous octoate, ethylene glycol dimethyl ether, glycolaldehyde dimer, glycolide, N-fluorobis-benzenesulfonamide, 1-chloromethyl-4-fluoro-1, 4-diazotized bicyclo 2.2.2 octane bis (tetrafluoroboric acid) salt, silica, sulfur tetrafluoride;
Preferably, the heating temperature in the step (2) is 40-400 ℃;
preferably, the gas phase synthesis in step (2) comprises vacuum evaporation or vapor deposition, and optionally introducing a gas during the vacuum evaporation or vapor deposition; wherein the gas is selected from the group consisting of ethylene oxide-containing gas, halogen-containing gas, or ozone;
preferably, the halogen-containing gas is one or more combinations of 1, 1-dichloro-2, 2-difluoroethylene, 2-chloro-1, 2-dibromo-1, 2-trifluoroethane, chlorotrifluoroethylene, nitrogen trifluoride, trifluoromethyl trifluoroethylene ether, carbon tetrafluoride, sulfur hexafluoride, hexafluoropropylene oxide, octafluorocyclobutane, trans-1, 3-tetrafluoropropene, fluorine gas, sulfuryl fluoride, hydrogen chloride gas, chlorine gas, hydrofluoric acid gas, and isoflurane;
preferably, a solid catalyst is used during vacuum evaporation or vapor deposition; the solid catalyst is selected from one or more of oxide, silicic acid compound, boric acid compound and metal catalyst;
preferably, the solid state catalyst is one or more of silica, manganese dioxide, aluminum oxide, diboron trioxide, lithium tetraborate, sodium tetraborate, silicic acid, silicates, boric acid, borates, cobalt oxide, copper oxide, zinc oxide, iron oxide, nickel oxide, manganese oxide, calcium oxide, silver, platinum, gold, iron, cobalt, nickel, molybdenum, niobium, magnesium, aluminum, titanium, zinc, calcium.
7. A polymer electrolyte comprising the polymer according to any one of claims 1 to 4 or the polymer produced by the production method according to claim 5 or 6, and a lithium salt and/or a sodium salt, wherein the mass percentage of the polymer in the polymer electrolyte is 5% to 99%, and the mass percentage of the lithium salt and/or sodium salt in the polymer electrolyte is 1% to 95%.
8. A method of preparing a polymer electrolyte comprising:
mixing a polymer with lithium salt and/or sodium salt, dissolving in a solvent to obtain solid electrolyte slurry, and drying to obtain the polymer electrolyte; or alternatively
The polymer and lithium salt and/or sodium salt are prepared into polymer electrolyte by using an electrostatic spinning method,
wherein the polymer is a polymer according to any one of claims 1 to 4 or a polymer produced according to the production method of claim 5 or 6.
9. A composite solid state electrolyte comprising the polymer of any one of claims 1 to 4; or a polymer produced by the production process according to claim 5 or 6; or the electrolyte polymer of claim 7; or a polymer electrolyte produced according to the production method of claim 8, and at least one additional inorganic solid electrolyte and/or organic solid electrolyte.
10. A composite electrolyte comprising the electrolyte polymer of claim 7 or the polymer electrolyte prepared according to the preparation method of claim 8, and a plasticizer.
11. The composite electrolyte according to claim 10, wherein the mass percentage of the plasticizer in the composite electrolyte is 0.1-50%;
preferably, the plasticizer comprises one or more of an amide-based compound, an ether-based compound, an ester-based compound, a cyclic ester-based compound, a carbonate-based compound, a nitrile-based compound, a cycloalkane-based compound.
12. A composite electrolyte comprising the electrolyte polymer according to claim 7 or the polymer electrolyte prepared according to the preparation method of claim 8 as an additive, and an electrolyte body component.
13. A secondary battery comprising a positive electrode, a negative electrode, and an electrolyte, wherein the electrolyte is at least one of the electrolyte polymer according to claim 7, the polymer electrolyte produced according to the production method according to claim 8, the composite solid electrolyte according to claim 9, the composite electrolyte according to claim 10, and the composite electrolyte according to claim 12.
CN202211664807.6A 2022-12-23 2022-12-23 Polymer for electrolyte and preparation method and application thereof Pending CN116082640A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202211664807.6A CN116082640A (en) 2022-12-23 2022-12-23 Polymer for electrolyte and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202211664807.6A CN116082640A (en) 2022-12-23 2022-12-23 Polymer for electrolyte and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN116082640A true CN116082640A (en) 2023-05-09

Family

ID=86201769

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202211664807.6A Pending CN116082640A (en) 2022-12-23 2022-12-23 Polymer for electrolyte and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN116082640A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117059878A (en) * 2023-10-11 2023-11-14 中国石油大学(华东) Preparation method of composite solid electrolyte based on vacuum defoaming

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20080052421A (en) * 2006-12-07 2008-06-11 소니 가부시끼가이샤 Electrolytic solution and battery
CN105789695A (en) * 2016-05-17 2016-07-20 中国科学院化学研究所 Composite polymer electrolyte and application thereof in battery cathode protection
CN106785032A (en) * 2017-03-17 2017-05-31 北京工业大学 A kind of lithium ion battery polymer dielectric and preparation method
CN108736062A (en) * 2018-04-28 2018-11-02 浙江天能能源科技股份有限公司 A kind of lithium ion battery composite solid electrolyte and preparation method thereof
WO2018214972A1 (en) * 2017-05-26 2018-11-29 北京师范大学 Flexible all-solid-state lithium-ion secondary battery and manufacturing method therefor
JP2019157008A (en) * 2018-03-14 2019-09-19 セントラル硝子株式会社 Disubstituted halogenated polyether and polymer electrolyte comprising the same
CN112018436A (en) * 2020-07-23 2020-12-01 东营古润特新能源有限公司 Composite polymer electrolyte and preparation method and application thereof
CN114031777A (en) * 2021-11-11 2022-02-11 河南大学 Silicon-containing polymer electrolyte material and lithium battery prepared from same
CN114094178A (en) * 2021-11-17 2022-02-25 珠海恩捷新材料科技有限公司 Solid electrolyte composite membrane and preparation method thereof
CN114243102A (en) * 2021-12-15 2022-03-25 惠州亿纬锂能股份有限公司 Polysiloxane solid electrolyte, solid battery, preparation method and application thereof
CN115051025A (en) * 2022-06-17 2022-09-13 浙江大学衢州研究院 Preparation method of composite solid electrolyte for lithium ion battery

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20080052421A (en) * 2006-12-07 2008-06-11 소니 가부시끼가이샤 Electrolytic solution and battery
CN105789695A (en) * 2016-05-17 2016-07-20 中国科学院化学研究所 Composite polymer electrolyte and application thereof in battery cathode protection
CN106785032A (en) * 2017-03-17 2017-05-31 北京工业大学 A kind of lithium ion battery polymer dielectric and preparation method
WO2018214972A1 (en) * 2017-05-26 2018-11-29 北京师范大学 Flexible all-solid-state lithium-ion secondary battery and manufacturing method therefor
JP2019157008A (en) * 2018-03-14 2019-09-19 セントラル硝子株式会社 Disubstituted halogenated polyether and polymer electrolyte comprising the same
CN108736062A (en) * 2018-04-28 2018-11-02 浙江天能能源科技股份有限公司 A kind of lithium ion battery composite solid electrolyte and preparation method thereof
CN112018436A (en) * 2020-07-23 2020-12-01 东营古润特新能源有限公司 Composite polymer electrolyte and preparation method and application thereof
CN114031777A (en) * 2021-11-11 2022-02-11 河南大学 Silicon-containing polymer electrolyte material and lithium battery prepared from same
CN114094178A (en) * 2021-11-17 2022-02-25 珠海恩捷新材料科技有限公司 Solid electrolyte composite membrane and preparation method thereof
CN114243102A (en) * 2021-12-15 2022-03-25 惠州亿纬锂能股份有限公司 Polysiloxane solid electrolyte, solid battery, preparation method and application thereof
CN115051025A (en) * 2022-06-17 2022-09-13 浙江大学衢州研究院 Preparation method of composite solid electrolyte for lithium ion battery

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
崔孟忠;李竹云;张洁;冯圣玉;: "含硅氢键聚二硅氧烷/聚醚共混聚合物电解质 Ⅰ.离子电导率研究", 化学学报, no. 22, 28 November 2009 (2009-11-28), pages 2624 - 2628 *
张诚;陈月明;李浩;麻小挺;朱宝库;: "聚醚侧链型聚硅氧烷对含氟聚合物凝胶锂离子电解质膜性能的影响", 功能材料, no. 10, 20 October 2010 (2010-10-20), pages 1784 - 1791 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117059878A (en) * 2023-10-11 2023-11-14 中国石油大学(华东) Preparation method of composite solid electrolyte based on vacuum defoaming

Similar Documents

Publication Publication Date Title
AU2020322166B2 (en) Rechargeable battery cell
Che et al. Electrolyte design strategies and research progress for room-temperature sodium-ion batteries
US9806338B2 (en) Nanoporous titanium niobium oxide and titanium tantalum oxide compositions and their use in anodes of lithium ion batteries
CN107666011B (en) Non-aqueous electrolyte and non-aqueous electrolyte secondary battery
EP3096375B1 (en) Lithium air battery and method of manufacturing the same
KR101546251B1 (en) Electrolyte for electrochemical device and the electrochemical device thereof
Liang et al. A 4 V cathode compatible, superionic conductive solid polymer electrolyte for solid lithium metal batteries with long cycle life
CN107417569B (en) Tertiary nitrile compound for non-aqueous electrolyte, non-aqueous electrolyte containing same and secondary battery
CN107417530B (en) Bicarboxylate compound for nonaqueous electrolyte, nonaqueous electrolyte containing same and secondary battery
JP4812067B2 (en) Organic electrolyte and organic electrolyte battery using the same
US10355268B2 (en) Carbon-metal oxide composite materials and their use in anodes of lithium and sodium ion batteries
Wang et al. Effect of electrolyte additives on high-temperature cycling performance of spinel LiMn 2 O 4 cathode
CN116082640A (en) Polymer for electrolyte and preparation method and application thereof
JP6924264B2 (en) Semi-solid electrolyte, semi-solid electrolyte, semi-solid electrolyte layer and secondary battery
Tesemma et al. Investigation of the dipole moment effects of fluorofunctionalized electrolyte additives in a lithium ion battery
KR20180068117A (en) electrolyte for sodium battery and sodium battery using the same
US10622674B2 (en) Polymer gel electrolyte, lithium ion battery and method for producing same
KR101664537B1 (en) Electrochemical device having high power properties
Yu et al. Interface engineering by gelling sulfolane for durable and safe Li/LiCoO2 batteries in wide temperature range
JP7055524B2 (en) Electrolytes for lithium secondary batteries and lithium secondary batteries containing them
JPWO2014133171A1 (en) Gel electrolyte and polymer secondary battery using the same
CN114335735B (en) Low-temperature electrolyte of lithium ion battery at-70 ℃ and preparation method thereof
CN113346132B (en) Fluorinated polyethylene oxide solid electrolyte material and preparation method and application thereof
Wu Electrochemical Study on Mixture of 1M LiPF6 and Carbonate Solvents as an Electrolyte in Graphite/Lithium and Graphene/Lithium-Ion Batteries
CN114069040B (en) Polymer electrolyte suitable for organic battery, and preparation method and application thereof

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