CN113809392A - Silane modified polyether polyol copolymer solid polymer electrolyte and preparation method thereof - Google Patents

Silane modified polyether polyol copolymer solid polymer electrolyte and preparation method thereof Download PDF

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CN113809392A
CN113809392A CN202010539667.4A CN202010539667A CN113809392A CN 113809392 A CN113809392 A CN 113809392A CN 202010539667 A CN202010539667 A CN 202010539667A CN 113809392 A CN113809392 A CN 113809392A
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lithium
polymer electrolyte
solid polymer
silane
polyether polyol
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曹晓东
郭红霞
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Suzhou Hantuo Material Technology Co ltd
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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
    • 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
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    • 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
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
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Abstract

The invention relates to a silane modified polyether polyol copolymer solid polymer electrolyte and a preparation method thereof. The solid polymer electrolyte comprises: (1) a silane-modified polyether polyol copolymer; (2) a lithium-containing electrolyte compound; (3) optionally a cross-linking agent; and (4) optionally a catalyst. In the invention, the silane modified polyether polyol copolymer solid polymer electrolyte shows good electrochemical stability, the electrochemical window is more than 4.5V, and the room-temperature ionic conductivity is 1 x 10‑5S/cm‑1×10‑3S/cm. In addition, a cross-linked silica network structure is formed in the solid polymer electrolyte, so that a homogeneous membrane with good mechanical property can be obtained, and the mechanical strength of the homogeneous membrane is 0.5MPa-300 MPa.

Description

Silane modified polyether polyol copolymer solid polymer electrolyte and preparation method thereof
Technical Field
The invention relates to a silane modified polyether polyol copolymer solid polymer electrolyte and a preparation method thereof.
Technical Field
The lithium ion battery has the advantages of high energy density and output voltage, no memory effect, environmental friendliness and the like, and is widely applied to the fields of electronics, aerospace, electric vehicles and the like. As one of the key materials, the structure and performance of the lithium ion battery electrolyte play a crucial role in improving the rate capability and the thermal stability of the lithium ion battery, and the power density, the cycle stability, the safety performance, the high and low temperature performance and the service life of the battery are determined to a great extent.
Conventional lithium ion batteries generally employ a liquid electrolyte and polyolefins, such as Polyethylene (PE) and polypropylene (PP) separators, although the liquid polyelectrolyte exhibits high ionic conductivity, can effectively wet electrodes, and form a stable Solid Electrolyte Interface (SEI) film on the surfaces of the electrodes. However, the liquid electrolyte contains a large amount of flammable and volatile organic solvent, and when the battery is used in an irregular manner or short circuit occurs inside the battery, the electrolyte is volatilized due to heat accumulation, so that liquid side leakage is caused, and safety accidents are caused.
The all-solid-state polymer electrolyte (ASPEs) battery adopts polymer electrolyte to replace traditional liquid electrolyte, does not contain organic solvent, has the advantages of good safety performance, high energy density, wide working temperature range, long cycle life and the like, and is one of the research hotspots in the field of lithium ion batteries. Currently, a plurality of ASPEs systems mainly including polyethylene oxide (PEO) -based systems, Polyacrylonitrile (PAN), polymethyl methacrylate (PMMA), polyvinylidene fluoride (PVDF), polyvinyl chloride (PVC), Polycarbonate (PC), Polysiloxane (PS), and the like are being studied.
Among them, PEO-based ASPEs are the first and most studied kind of ASPEs material, however, the electrolyte has problems of low room temperature ionic conductivity, narrow electrochemical window, and the like. Electrolytes composed of PAN, PMMA, PVDF, PVC and lithium salts are typically plasticized with organic electrolytes to form gel polyelectrolytes, not complete all-solid polyelectrolytes. Polycarbonate (PC) -based all-solid-state polyelectrolyte contains strong polar carbonate groups and is in an amorphous state at room temperature, so that lithium salt is more easily dissociated, the interaction of anions and cations in the lithium salt can be reduced, ion aggregation can be inhibited, the concentration of free lithium ions is improved, and further the ionic conductivity and ionic migration number of the electrolyte are improved. The Si-O-Si bond in the polysiloxane has smaller bond rotation potential (0.8kJ/mol), the molecular chain segment has stronger moving capability, an indefinite structure is easy to form, and meanwhile, the electrolyte has the advantages of high electrochemical window, excellent thermal stability, environmental friendliness and the like.
In 1986, Brocq et al introduced polysiloxane side chain into oligoethylene oxide (PEO) for the first time, and the resulting composite electrolyte showed higher room temperature ionic conductivity (σ ≈ 10) than the PEO-based electrolyte-5S/cm), but the polymer-existing sideThe chain is easy to hydrolyze and has poor stability. CN103208651A discloses a lithium-conducting siloxane polyelectrolyte with a room temperature lithium ion conductivity of 2 x 10-5-1×10-4S/cm. CN106785032B mixing the polyether prepolymer terminated by end silane with conductive lithium salt electrolyte, using organic solvent as plasticizer, preparing gel solid polyelectrolyte on non-woven fabric support with ionic conductivity of 10 at 25 deg.C-4Scm-1. Further, CN108899579A compounds inorganic nanoparticles or organic polymer materials with acidity and alkalinity with terminated silane polyether, and forms self-crosslinking composite solid electrolyte with conductive lithium salt, the shrinkage deformation of the electrolyte is small, and the ionic conductivity is 10 at 25 DEG C-4Scm-1And the electrochemical window is more than 5V, so that the electrochemical stability is stronger. CN108242563A reports that the mechanical strength of alkyl silyl polymer electrolyte prepared by scraping a solution of alkyl silyl polymer, lithium salt and additives onto a porous support material and drying at 60-80 ℃ is 0.5MPa-300 MPa; the electrochemical window is more than 4.3V, the lithium ion battery has good compatibility with a high-voltage anode material, and the room-temperature ionic conductivity is 1 multiplied by 10-5S/cm-10-3S/cm, the assembled battery has excellent long cycle performance. JPH08026162B2 compares the performances of different heteroatom side chain substituted polysiloxanes, and the ionic conductivity is 10 at 20 DEG C-6-10-4S/cm. KR101998119B1 discloses polymers obtained by reacting diols, 3- (triethoxysilyl) propyl isocyanate and compares their room temperature conductivity at different LiTFSI salt concentrations. KR101995836B1 also discloses polymers obtained by reacting diols with 3- (triethoxysilyl) propyl isocyanate and compares their room temperature conductivity at different LiTFSI salt concentrations. KR102026682B1 further discloses a high molecular polymer electrolyte obtained by reacting 2- (2-methoxyethoxy) ethanol, 3- (triethoxysilyl) propyl isocyanate and a diol or carbonate diol.
In the prior art, the all-solid-state polymer electrolyte has excellent advantages and huge application prospects, but most of the currently reported siloxane all-solid-state polymer electrolytes have poor film-forming property, and homogeneous films of the siloxane all-solid-state polymer electrolytes have low mechanical strength and are all-solid-state polymer electrolytes obtained by compounding on a porous support; in addition, most of catalysts adopted in the preparation of siloxane all-solid-state polymer electrolytes in the prior art are organic tin catalysts which are harmful to human health and environment, and are gradually limited to be used along with the improvement of environmental protection requirements of European Union. Therefore, there is still a need for a novel polymer electrolyte having good electrochemical stability, film-forming properties and mechanical strength of the film.
Disclosure of Invention
It is an object of exemplary embodiments of the present invention to solve the above and other disadvantages of the prior art and to provide a high-performance silane-modified polyether polyol copolymer solid polymer electrolyte and a method for preparing the same.
In one aspect, the present invention provides a solid polymer electrolyte comprising:
(1) a silane-modified polyether polyol copolymer;
(2) a lithium-containing electrolyte compound;
(3) optionally a cross-linking agent; and
(4) optionally a catalyst.
In some embodiments of the present invention, the silane-modified polyether polyol copolymer is 10 to 65 weight percent, based on the weight of the solid polymer electrolyte; the lithium-containing electrolyte compound is 5-90 wt%; the cross-linking agent is 0-10 wt%; and the catalyst is 0 to 15 wt%.
In some embodiments of the invention, the silane-modified polyether polyol copolymer has a weight average molecular weight of 1000-45000.
In some embodiments of the invention, the silane-modified polyether polyol copolymer is a polyether polyol copolymer modified with a urethane group-containing silane.
In some embodiments of the present invention, the silane-modified polyether polyol copolymer has the general formula (I):
Figure BDA0002536843830000031
in the formula, R1Is C1-C5 alkyl, C1-C5 alkenyl or C1-C5 alkoxy; r2Is C1-C10 alkyl;
Figure BDA0002536843830000041
or a combination of any two or three thereof; wherein n is an integer selected from 1 to 50, and m, k and x are each an integer selected from 1 to 1000.
In some embodiments of the invention, the lithium-containing electrolyte compound comprises lithium hexafluorophosphate (LiPF)6) Lithium perchlorate (LiClO)4) Lithium difluorophosphate, lithium tetrafluoroborate, lithium bis (oxalato) borate (LiBOB), lithium difluoro (oxalato) borate (LiDFOB), lithium trifluoromethanesulfonate (CF)3SO3Li), lithium bistrifluoromethylsulfonyl imide (LiTFSI), lithium bistrifluorosulfonimide (LiFSI), or any combination thereof.
In some embodiments of the invention, the crosslinking agent is selected from the group consisting of silane coupling agents, silicate-based compounds, and combinations thereof; preferably, it is selected from the group consisting of N-N-butyl-3-aminopropyltrimethoxysilane, aminoethylaminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropyldimethoxysilane, diethylaminomethyltriethoxysilane, gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, methyl orthosilicate, ethyl orthosilicate, butyl orthosilicate, and combinations thereof.
In some embodiments of the invention, the catalyst is an organo-bismuth based catalyst; preferably, the catalyst is selected from the group consisting of bismuth (tris (2-ethylhexanoate), bismuth trioctoate, bismuth neodecanoate, bismuth isooctanoate, bismuth laurate, bismuth naphthenate, bismuth carboxylate, and combinations thereof.
In another aspect, the present invention also provides a method of preparing a solid polymer electrolyte, the method comprising:
(1) dissolving a lithium-containing electrolyte compound in an organic solvent to form a lithium salt solution;
(2) adding the silane modified polyether polyol copolymer into the lithium salt solution, and stirring for 1-24 hours under a sealing condition;
(3) optionally adding a cross-linking agent and/or a catalyst and continuing to stir under sealed conditions; and
(4) forming a film at a relative humidity of 5.0-95.0% and drying at a temperature of 10-80 ℃ to obtain a solid polymer electrolyte comprising the silane-modified polyether polyol copolymer.
In some embodiments of the invention, the organic solvent is selected from the group consisting of a combination of one or more of C1-C5 alcohols, C1-C5 nitriles, C1-C3 chloroalkanes, aliphatic N-alkyl substituted amides, C2-C6 carbonates; preferably, the organic solvent is selected from one or more of methanol, ethanol, ethylene glycol, acetonitrile, trichloromethane, N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, dimethyl carbonate, ethylene carbonate and propylene carbonate.
In the invention, the silane modified polyether polyol copolymer can be crosslinked to form a silica network structure, a porous support body is not needed, a film can be directly formed, the obtained homogeneous film has good mechanical property, and the mechanical strength can reach 0.5MPa-300 MPa. Preferably, the invention adopts silane modified polyether polyol copolymer containing urethane groups (-NHCOO-) to prepare the solid polyelectrolyte membrane, wherein the-NHCOO-has high dielectric constant and polarization density, and can form more hydrogen bonds in the polymer solid electrolyte membrane, so that the prepared silane modified polyether polyol copolymer solid polymer electrolyte shows good electrochemical stability, the electrochemical window is more than 4.5V, and the room-temperature ionic conductivity is 1 multiplied by 10-5S/cm-1×10- 3S/cm, even greater than 4X 10-5S/cm up to 1X 10-3S/cm, which is much higher than the ionic conductivity of the conventional solid polymer electrolyte in the prior art. In addition, the organic bismuth catalyst adopted by the invention is efficient and environment-friendly, can replace an organic tin catalyst used in the prior electrolyte technology, and has the advantages of low cost, good hydrolysis resistance stability, low toxicity, low radioactivity and the like.
The above features as well as additional features, aspects, and advantages of the present invention will become apparent in the following detailed description. The present invention includes combinations of two, three, four or more of the above-described embodiments, as well as combinations of any two, three, four or more of the features or elements set forth herein, whether or not such features or elements are expressly combined in a particular embodiment described herein. This document is intended to be read in its entirety, and any divisible feature or element of the disclosed invention in any of its various aspects and embodiments should be considered to be an combinable feature or element unless the context clearly dictates otherwise. Other aspects and advantages of the invention will become apparent from the following.
Detailed Description
The present invention will be described more fully hereinafter with reference to exemplary embodiments thereof. These exemplary embodiments are described so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. Indeed, this invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein; rather, these embodiments are provided so that this disclosure will satisfy applicable legal requirements.
As used herein, the terms "C1-C5 alkyl group" and "C1-C10 alkyl group" refer to alkyl groups having 1-5 carbon atoms (C1-C5) and alkyl groups having 1-10 carbon atoms (C1-C10), respectively. For example, the "C1-C5 alkyl" includes methyl, ethyl, n-propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, and the like. The "C1-C10 alkyl group" includes methyl, ethyl, n-propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl, heptyl, octyl, nonyl, decyl and the like.
As used herein, the term "C2-C5 alkenyl" refers to an alkenyl group having 2-5 carbon atoms (C2-C5). For example, the "C2-C5 alkenyl group" may include ethenyl, propenyl, butenyl, pentenyl, and the like.
As used herein, the term "C1-C5 alkoxy" refers to alkoxy groups having 1-5 carbon atoms (C1-C5). For example, the "C1-C5 alkoxy" includes methoxy, ethoxy, propoxy, butoxy, pentoxy, and the like.
As used herein, the term "polyether polyol" refers to oligomers having a backbone containing ether linkages (-R-O-R-, wherein R is an alkyl or aromatic hydrocarbon group) and terminal or pendant groups containing greater than 2 hydroxyl groups (-OH).
In the present context, the term "weight average molecular weight" means the sum of the products of the weight fractions of the respective molecules of different molecular weights and the molecular weights corresponding thereto, and in the present invention, the calculation formula of the weight average molecular weight is as follows:
Figure BDA0002536843830000061
in the formula, MwIs the weight average molecular weight, miIs the molecular mass, MiIs the relative molecular mass, niIs provided with MiNumber of molecules of mass, wiIs a mass fraction.
Generally, the method for determining the weight average molecular weight comprises: light scattering method, ultracentrifuge sedimentation velocity method, gel chromatography, and the like.
Silane-modified polyether polyol copolymers
In the present invention, the silane-modified polyether polyol copolymer may be a copolymer that is commercially available or prepared by modifying polyether polyol with functional silane. For example, the silane-modified polyether polyol copolymers of the present invention are available from the Funpoly (Funpoly) series of john shoji technologies, su.
In the present invention, the weight average molecular weight of the silane-modified polyether polyol copolymer can be 1000-, 15000-. In the present invention, if the weight average molecular weight of the silane-modified polyether polyol copolymer is less than 1000, the film-forming property of the resulting solid polyelectrolyte is poor; if the weight average molecular weight of the silane-modified polyether polyol copolymer is higher than 45000, the silane-modified polyether polyol copolymer is not easily dissolved, increasing process complexity and operation difficulty.
In particular embodiments, the polyether polyol copolymer is modified with a functional silane, such as a urethane group (-NHCOO-) containing silane. The urethane group (-NHCOO-) containing silane (or isocyanate group-containing silane) may be reacted with a hydroxyl group-containing polyether polyol, i.e., by reaction of NCO groups with hydroxyl groups, such that the silane groups are grafted to the structure of the polyether polyol. The urethane group has higher dielectric constant and polarization density, and more hydrogen bonds can be formed in the polymer solid electrolyte membrane, so that the prepared silane modified polyether polyol copolymer solid polymer electrolyte has good electrochemical stability, the electrochemical window is more than 4.5V, and the room-temperature ionic conductivity is 1 multiplied by 10-5S/cm-1×10-3S/cm。
In a particular embodiment of the invention, the silane-modified polyether polyol copolymer may have the general formula (I):
Figure BDA0002536843830000071
in the general formula (I), R1Typically it may be a C1-C10 alkanyl radical, a C2-C10 alkenyl radical or a C1-C5 alkoxy radical; or C1-C5 alkyl, C2-C5 alkenyl or C1-C3 alkoxy; or C1-C3 alkyl, C2-C3 alkenyl or C2-C3 alkoxy.
On toolIn one embodiment, R1Can be selected from methyl, ethyl, n-propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl, heptyl, octyl, nonyl, decyl, ethenyl, propenyl, butenyl, pentenyl, methoxy, ethoxy, propoxy, butoxy, pentoxy and the like.
In the general formula (I), R2Can be C1-C10 alkyl; or C1-C5 alkyl; or C1-C3 alkyl.
In a particular embodiment, R2Can be selected from methyl, ethyl, n-propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl, heptyl, octyl, nonyl, decyl, and the like.
In the general formula (I), R3One or more other substituents may optionally be included as polyether polyol units.
In a specific embodiment, R3Can be that
Figure BDA0002536843830000081
Or a combination of any two or three thereof. At R3Wherein m, k and x are each independently selected from integers of 1-1000, 1-800, 1-600, 1-400, 1-200, 1-100, 1-50, 50-1000, 50-800, 50-600, 50-400, 50-200, 50-100, 100-1000, 100-800, 100-600, 100-400, 100-200, 200-800, 200-600, 200-400, 400-1000, 400-800, 400-600, 600-1000, 600-800 or 800-1000.
In the general formula (I), n is an integer selected from 1 to 50, 1 to 40, 1 to 30, 1 to 20, 1 to 10, 1 to 5, 5 to 50, 5 to 40, 5 to 30, 5 to 20, 5 to 10, 10 to 50, 10 to 40, 10 to 30, 10 to 20, 20 to 50, 20 to 40, 20 to 30, 30 to 50, 30 to 40, or 40 to 50.
In the present invention, the amount of the silane-modified polyether polyol copolymer may be 10 to 65 wt%, 10 to 60 wt%, 10 to 55 wt%, 10 to 50 wt%, 10 to 45 wt%, 10 to 40 wt%, 10 to 35 wt%, 10 to 30 wt%, 10 to 25 wt%, 10 to 20 wt%, 10 to 15 wt%, 15 to 65 wt%, 15 to 60 wt%, 15 to 55 wt%, 15 to 50 wt%, 15 to 45 wt%, 15 to 40 wt%, 15 to 35 wt%, 15 to 30 wt%, 15 to 25 wt%, 15 to 20 wt%, 20 to 65 wt%, 20 to 60 wt%, 20 to 55 wt%, based on the weight of the solid polymer electrolyte, 20-50 wt%, 20-45 wt%, 20-40 wt%, 20-35 wt%, 20-30 wt%, 20-25 wt%, 25-65 wt%, 25-60 wt%, 25-55 wt%, 25-50 wt%, 25-45 wt%, 25-40 wt%, 25-35 wt%, 25-30 wt%, 30-65 wt%, 30-60 wt%, 30-55 wt%, 30-50 wt%, 30-45 wt%, 30-40 wt%, 30-35 wt%, 35-65 wt%, 35-60 wt%, 35-55 wt%, 35-50 wt%, 35-45 wt%, 40-65 wt%, 40-60 wt%, 40-55 wt%, 40-50 wt%, 40-45 wt%, 45-65 wt%, 45-60 wt%, 45-55 wt%, 45-50 wt%, 45-45 wt%, 45-40 wt%, 45-35 wt%, 45-30 wt%, 45-25 wt%, 45-20 wt%, 45-15 wt%, 50-65 wt%, 50-60 wt%, 50-55 wt%, 55-65 wt%, 55-60 wt%, 60-65 wt% or any number therebetween.
Lithium-containing electrolyte compound
In the present invention, the lithium-containing electrolyte compound may be any lithium-containing compound as a positive electrode material in a lithium ion battery. The lithium salt anion has a volume greater than
Figure BDA0002536843830000091
The thermal decomposition temperature is higher than 160 ℃, and the organic solvent can be fully dissolved in one or more mixed solvents of C1-C5 alcohol, C1-C5 nitrile, C1-C3 chloralkane, aliphatic N-alkyl substituted amide or C2-C6 carbonate organic matters. Typically, the lithium-containing compounds include, but are not limited to: lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, manganese nickel cobalt composite oxide, lithium vanadium oxide, lithium iron oxide, and the like.
In particular embodiments, the lithium-containing compounds include, but are not limited to: lithium hexafluorophosphate (LiPF)6) Lithium perchlorate (LiClO)4) Lithium difluorophosphate, lithium tetrafluoroborate, lithium bis (oxalato) borate (LiBOB), lithium difluoro (oxalato) borate(LiDFOB), lithium trifluoromethanesulfonate (CF)3SO3Li), lithium bistrifluoromethylsulfonyl imide (LiTFSI), lithium bistrifluorosulfonimide (LiFSI), or any combination thereof.
In the present invention, the lithium-containing electrolyte compound is not particularly limited as long as it is a lithium-containing compound cathode material that is commonly used in lithium ion batteries in the art.
In the present invention, the amount of the lithium electrolyte-containing compound may be 5 to 90 wt%, 5 to 80 wt%, 5 to 70 wt%, 5 to 60 wt%, 5 to 50 wt%, 5 to 40 wt%, 5 to 30 wt%, 5 to 20 wt%, 20 to 90 wt%, 20 to 80 wt%, 20 to 70 wt%, 20 to 60 wt%, 20 to 50 wt%, 20 to 40 wt%, 20 to 30 wt%, 30 to 90 wt%, 30 to 80 wt%, 30 to 70 wt%, 30 to 60 wt%, 30 to 50 wt%, 30 to 40 wt%, 40 to 90 wt%, 40 to 80 wt%, 40 to 70 wt%, 40 to 60 wt%, based on the weight of the solid polymer electrolyte, 40-50 wt%, 50-90 wt%, 50-80 wt%, 50-70 wt%, 50-60 wt%, 60-90 wt%, 60-80 wt%, 60-70 wt%, 70-90 wt%, 70-80 wt%, 8-90 wt%, or any value therebetween.
Crosslinking agent
In the present invention, the solid polymer electrolyte may not contain any crosslinking agent. In an embodiment of the present invention, in order to facilitate the formation of the solid polymer electrolyte, the solid polymer electrolyte may optionally include a crosslinking agent.
In a specific embodiment, the cross-linking agent may be a silane coupling agent or silicate compound, including, but not limited to, one or more of N-butyl-3-aminopropyltrimethoxysilane, aminoethylaminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropyldimethoxysilane, diethylaminomethyltriethoxysilane, gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, methyl orthosilicate, ethyl orthosilicate, and butyl orthosilicate.
In the present invention, the amount of the crosslinking agent may be 0 to 10 wt%, 0 to 6 wt%, 0 to 4 wt%, 0 to 2 wt%, 2 to 10 wt%, 2 to 6 wt%, 2 to 4 wt%, 4 to 10 wt%, 4 to 6 wt%, 6 to 10 wt%, or any value therebetween, based on the weight of the solid polymer electrolyte.
Catalyst and process for preparing same
In the present invention, the solid polymer electrolyte may not contain any catalyst. In an embodiment of the present invention, in order to promote the formation of the solid polymer electrolyte, the solid polymer electrolyte may optionally include a catalyst. In some embodiments, the solid polymer electrolyte does not contain any organotin-based catalyst.
In particular embodiments, the catalyst may be an organo bismuth based catalyst, consisting essentially of bismuth (tris (2-ethylhexanoate), bismuth trioctoate, bismuth neodecanoate, bismuth isooctanoate, bismuth laurate, bismuth naphthenate, bismuth carboxylate, and any combination thereof.
In the present invention, the amount of the crosslinking agent may be 0 to 15 wt%, 0 to 10 wt%, 0 to 5 wt%, 0 to 1 wt%, 1 to 15 wt%, 1 to 10 wt%, 1 to 5 wt%, 5 to 15 wt%, 5 to 10 wt%, 10 to 15 wt%, or any value therebetween, based on the weight of the solid polymer electrolyte.
Solid polymer electrolyte
In the present invention, the solid polymer electrolyte may comprise: a silane-modified polyethylene glycol polyether polyol copolymer, a lithium-containing electrolyte compound, optionally a crosslinker, and optionally a catalyst. In some embodiments, the solid polymer electrolyte may consist essentially of the silane-modified polyethylene glycol polyether polyol copolymer, the lithium-containing electrolyte compound, the optional crosslinker, and the optional catalyst. In some embodiments, the solid polymer electrolyte may be comprised of a silane-modified polyethylene glycol polyether polyol copolymer, a lithium-containing electrolyte compound, an optional crosslinker, and an optional catalyst.
Specifically, the silane-modified polyether polyol copolymer solid polymer electrolyte according to the present invention may be prepared mainly by reacting a mixture of the silane-modified polyether polyol copolymer, a lithium-containing electrolyte compound, a crosslinking agent and a catalyst. The silane-modified polyether polyol copolymer comprises 10-65 wt% or 15-55 wt% of the mixture, based on the weight of the mixture; the cross-linking agent comprises 0-10 wt% or 0.5-5 wt% of the mixture; the catalyst comprises 0-15 wt% or 0.1-6.0 wt% of the mixture; and the lithium-containing electrolyte compound comprises 5 to 90 wt% or 15.0 wt% to 75.0 wt% of the mixture.
Preparation of solid polymer electrolyte
In the present invention, a solid polymer electrolyte is prepared by the following steps:
(1) dissolving a lithium-containing electrolyte compound in an organic solvent to form a lithium salt solution;
(2) adding the silane modified polyether glycol copolymer into the lithium salt solution, and stirring under a sealing condition or an inert atmosphere;
(3) optionally adding a cross-linking agent and/or a catalyst and continuing to stir under sealed conditions; and
(4) and (3) forming a film and drying to obtain the solid polymer electrolyte containing the silane modified polyether polyol copolymer.
In some embodiments, the silane modified polyether polyol copolymer is added to the lithium salt solution and stirred under sealed conditions for 1 to 24 hours, 1 to 16 hours, 1 to 8 hours, 8 to 24 hours, 8 to 16 hours, 16 to 24 hours, or any value therebetween.
In some embodiments, the film formation is performed at the following relative humidities: 5.0-95.0%, 5.0-80.0%, 5.0-60.0%, 5.0-40.0%, 5.0-20.0%, 20.0-95.0%, 20.0-80.0%, 20.0-60.0%, 20.0-40.0%, 40.0-95.0%, 40.0-80.0%, 40.0-60.0%, 60.0-95.0%, 60.0-80.0%, 80.0-95.0%, or any value therebetween.
In some embodiments, the drying is performed at a temperature of: 10-80 deg.C, 10-60 deg.C, 10-40 deg.C, 10-20 deg.C, 20-80 deg.C, 20-60 deg.C, 20-40 deg.C, 40-80 deg.C, 40-60 deg.C, 60-80 deg.C, or any value therebetween.
Organic solvent
In the present invention, the organic solvent used for dissolving the lithium-containing electrolyte compound and allowing the reaction to proceed is not particularly limited. In some embodiments, the organic solvent is selected from the group consisting of a combination of one or more of C1-C5 alcohols, C1-C5 nitriles, C1-C3 chloroalkanes, aliphatic N-alkyl substituted amides, C2-C6 carbonates; preferably, the organic solvent is selected from one or more of methanol, ethanol, ethylene glycol, acetonitrile, trichloromethane, N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, dimethyl carbonate, ethylene carbonate and propylene carbonate.
In a specific embodiment, the preparation method of the silane modified polyether polyol copolymer solid polymer electrolyte comprises the following steps:
dissolving a lithium-containing electrolyte compound in an organic solvent to prepare a conductive lithium salt solution; weighing the silane modified polyether glycol copolymer with the corresponding weight percentage, adding the silane modified polyether glycol copolymer into the conductive lithium salt solution, and fully stirring for 1-24 hours, preferably 2-12 hours, under sealing; adding the cross-linking agent and the catalyst in corresponding weight percentage, and continuing to seal and stir; forming a film under the humidity of 5.0-95.0%, preferably 10.0-85.0%, and fully drying at the temperature of 10-80 ℃, preferably 20-65 ℃ after forming the film to obtain the silane modified polyether polyol copolymer solid polymer electrolyte.
In a specific embodiment, the weight average molecular weight of the silane-modified polyether polyol copolymer is 1000-45000, preferably 2000-36000, and the structure is shown as formula (1):
Figure BDA0002536843830000121
wherein R is1Is C1-C5 alkyl, C1-C5 alkenyl or C1-C5 alkoxy, R2Is C1-C10 alkyl, R3Is composed of
Figure BDA0002536843830000122
Or
Figure BDA0002536843830000123
Or
Figure BDA0002536843830000124
Or a copolymer or blend of any two or three, wherein n is one of integers from 1 to 50, preferably from 1 to 15, and m, k, x are each one of integers from 1 to 1000, preferably from 3 to 500.
In the invention, the organic solvent is one or a mixture of more of C1-C5 alcohol, C1-C5 nitrile, C1-C3 chloralkane, aliphatic N-alkyl substituted amide, or C2-C6 carbonate organic matters. For example, one or more of methanol, ethanol, ethylene glycol, acetonitrile, chloroform, N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, dimethyl carbonate, ethylene carbonate, and propylene carbonate.
In the present invention, the lithium salt anion is larger in volume than
Figure BDA0002536843830000131
The thermal decomposition temperature is higher than 160 ℃, and the organic solvent can be fully dissolved in one or more of C1-C5 alcohol, C1-C5 nitrile, C1-C3 chloralkane, aliphatic N-alkyl substituted amide or C2-C6 carbonate organic matters, such as lithium hexafluorophosphate (LiPF)6) Lithium perchlorate (LiClO)4) Lithium difluorophosphate, lithium tetrafluoroborate, lithium bis (oxalato) borate (LiBOB), lithium difluoro (oxalato) borate (LiDFOB), lithium trifluoromethanesulfonate (CF)3SO3Li), lithium bis (trifluoromethyl) sulfonyl imide (LiTFSI) and lithium bis (fluoro) sulfonyl imide (LiFSI).
In the present invention, the crosslinking agent is one or more of silane coupling agent or silicate compound, such as N-N-butyl-3-aminopropyltrimethoxysilane, aminoethylaminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropyldimethoxysilane, diethylaminomethyltriethoxysilane, gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, methyl orthosilicate, ethyl orthosilicate and butyl orthosilicate.
In the invention, the catalyst is an organic bismuth catalyst, and mainly comprises one or more of bismuth (tri (2-ethyl hexanoate), bismuth trioctoate, bismuth neodecanoate, bismuth isooctanoate, bismuth laurate, bismuth naphthenate and bismuth carboxylate.
The present invention will be described in further detail with reference to specific examples, so that the advantages of the present invention will be more apparent. It should be understood that the description is intended for purposes of illustration only and is not intended to limit the scope of the present disclosure. The experimental procedures, in which specific conditions are not specified, in the following examples are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers.
Example 1
15.0g of lithium hexafluorophosphate (LiPF) was weighed out6) And 27.86g of silane modified polyethylene glycol copolymer with the weight average molecular weight of 2000, sequentially adding the silane modified polyethylene glycol copolymer into a mixed solvent consisting of 35mL of acetonitrile and 5mL of propylene carbonate, fully stirring for 2 hours under sealing, adding 0.22g of 3-aminopropyl methyl diethoxy silane cross-linking agent and 2.6g of bismuth isooctanoate catalyst, continuing to stir under sealing, forming a film under the condition that the humidity is 10.0%, and fully drying at the temperature of 20 ℃ after forming the film to obtain the solid polymer electrolyte of the silane modified polyethylene glycol copolymer.
Example 2
15.0g of lithium hexafluorophosphate (LiPF) was weighed out6) And 5.0g of silane modified polyethylene glycol copolymer with the weight-average molecular weight of 36000 is sequentially added into 35mL of propylene carbonate solvent, the mixture is fully stirred for 12 hours under sealing, 0.022g of 3-aminopropyl methyl diethoxy silane cross-linking agent and 0.043g of bismuth isooctanoate catalyst are added, the mixture is continuously stirred under sealing, a film is formed under the condition that the humidity is 85.0 percent, and the film is fully dried at the temperature of 65 ℃ after being formed, so that the solid polymer electrolyte of the silane modified polyethylene glycol copolymer is obtained.
Example 3
15.0g of lithium hexafluorophosphate (LiPF) was weighed out6) And 25.0g of a weight average molecular weight of 12000And sequentially adding the silane modified polypropylene glycol copolymer containing the urethane group (-NHCOO-) into 15mL of ethylene carbonate solvent, fully stirring for 10 hours under sealing, forming a film under the condition that the humidity is 95.0%, and fully drying at the temperature of 85 ℃ after forming the film to obtain the silane modified polypropylene glycol copolymer solid polymer electrolyte.
Example 4
Weighing 15.0g of lithium bistrifluoromethylsulfonyl imide (LiTFSI) and 25.0g of silane modified polypropylene oxide copolymer with the weight-average molecular weight of 12000, sequentially adding the mixture into 15mL of ethylene carbonate solvent, fully stirring the mixture for 10 hours under a sealed condition, forming a film under the condition that the humidity is 95.0 percent, and fully drying the film at the temperature of 85 ℃ after film formation to obtain the silane modified polypropylene glycol copolymer solid polymer electrolyte.
Example 5
Weighing 25.0g of lithium bistrifluoromethylsulfonyl imide (LiTFSI) and 25.0g of silane modified polyethylene glycol-polyphenylene ether copolymer with the weight-average molecular weight of 12000, sequentially adding the mixture into 15mL of N-methylpyrrolidone solvent, fully stirring for 8 hours under sealing, adding 1.0g of ethyl orthosilicate cross-linking agent and 1.5g of bismuth laurate catalyst, continuously stirring under sealing, forming a film under the condition that the humidity is 65.0%, and fully drying at the temperature of 55 ℃ after forming the film to obtain the silane modified polyethylene glycol-polyphenylene ether copolymer solid polymer electrolyte.
Example 6
Weighing 25.0g of lithium bis (oxalato) borate (LiBOB) and 15.0g of silane modified polyethylene glycol-polypropylene oxide copolymer with the weight-average molecular weight of 8000, sequentially adding the mixture into a mixed solvent consisting of 10mL of ethanol and 5mL of ethylene carbonate, fully stirring the mixture for 7.5 hours under sealing, adding 1.0g of gamma-glycidyl ether oxypropyl trimethoxy silane cross-linking agent and 1.2g of bismuth neodecanoate catalyst, continuously stirring the mixture under sealing, forming a film under the condition that the humidity is 55.0 percent, and fully drying the film at the temperature of 50 ℃ after forming the film, thus obtaining the silane modified polyethylene glycol-polypropylene oxide copolymer solid polymer electrolyte.
Test example
The performance of the silane-modified polyether polyol copolymer solid polymer electrolytes prepared in examples 1 to 6 was tested. The specific test mode is as follows:
film thickness of
The thickness of the solid polymer electrolyte membrane was measured using a micrometer (accuracy 0.01 mm). The 5 points were arbitrarily measured and averaged.
Ionic conductivity
The ionic conductivity of the solid polymer electrolyte was tested using the alternating current impedance (EIS) method. Specifically, a solid polymer electrolyte membrane was sandwiched between two symmetrical Stainless Steel (SS) electrodes, a 2.32 button cell was assembled, the impedance of the cell was measured, and the equation was followed
Figure BDA0002536843830000151
Calculating the ionic conductivity of the solid polyelectrolyte, wherein L is the thickness (cm) of the sample, and S is the area (cm) of the sample2) And R is the impedance (omega) of the sample.
The test results of examples 1-6 are shown in Table 1.
Figure BDA0002536843830000152
Figure BDA0002536843830000161
As can be seen from Table 1 above, the solid polymer electrolyte membranes described in examples 1-6 have high room-temperature ionic conductivity, all higher than that of the conventional solid polymer electrolytes in the prior art (e.g., the ionic conductivity of the conventional solid polymer electrolyte is usually only σ ≈ 10)-5S/cm, "2X 10" as referred to in CN103208651A-5-1×10-4S/cm "). In example 3, the room-temperature ionic conductivity of the solid polymer electrolyte membrane was even as high as 1.02 × 10-3S/cm。
In addition, the organic bismuth catalyst is adopted to replace an organic tin catalyst used in the existing electrolyte technology in the embodiments 1 to 6, so that the solid polymer electrolyte in the embodiments 1 to 6 has the advantages of environmental friendliness, low cost, good stability against hydrolysis, low toxicity, low radioactivity and the like.

Claims (10)

1. A solid polymer electrolyte comprising:
(1) one or more silane-modified polyether polyol copolymers;
(2) one or more lithium-containing electrolyte compounds;
(3) optionally a cross-linking agent; and
(4) optionally a catalyst.
2. The solid polymer electrolyte of claim 1 wherein, based on the weight of the solid polymer electrolyte,
10-65 wt% of the silane-modified polyether polyol copolymer;
the lithium-containing electrolyte compound is 5-90 wt%;
the cross-linking agent is 0-10 wt%; and
the catalyst is 0-15 wt%.
3. The solid polymer electrolyte as claimed in claim 1, wherein the silane-modified polyether polyol copolymer has a weight average molecular weight of 1000-45000.
4. The solid polymer electrolyte of claim 1 wherein said silane-modified polyether polyol copolymer is a urethane group-containing silane-modified polyether polyol copolymer.
5. The solid polymer electrolyte of claim 1 wherein the silane-modified polyether polyol copolymer has the general formula (I):
Figure FDA0002536843820000011
in the formula (I), the compound is shown in the specification,R1is C1-C5 alkyl, C1-C5 alkenyl or C1-C5 alkoxy; r2Is C1-C10 alkyl; r3Is composed of
Figure FDA0002536843820000012
Or a combination of any two or three thereof;
wherein n is an integer selected from 1 to 50, and m, k and x are each an integer selected from 1 to 1000.
6. The solid polymer electrolyte of claim 1 wherein the lithium-containing electrolyte compound comprises lithium hexafluorophosphate (LiPF)6) Lithium perchlorate (LiClO)4) Lithium difluorophosphate, lithium tetrafluoroborate, lithium bis (oxalato) borate (LiBOB), lithium difluoro (oxalato) borate (LiDFOB), lithium trifluoromethanesulfonate (CF)3SO3Li), lithium bistrifluoromethylsulfonyl imide (LiTFSI), lithium bistrifluorosulfonimide (LiFSI), or any combination thereof.
7. The solid polymer electrolyte of claim 1 wherein said cross-linking agent is selected from the group consisting of silane coupling agents, silicate-based compounds, and combinations thereof;
preferably, it is selected from the group consisting of N-N-butyl-3-aminopropyltrimethoxysilane, aminoethylaminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropyldimethoxysilane, diethylaminomethyltriethoxysilane, gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, methyl orthosilicate, ethyl orthosilicate, butyl orthosilicate, and combinations thereof.
8. The solid polymer electrolyte of claim 1 wherein the catalyst is an organic bismuth-based catalyst;
preferably, the catalyst is selected from the group consisting of bismuth (tris (2-ethylhexanoate), bismuth trioctoate, bismuth neodecanoate, bismuth isooctanoate, bismuth laurate, bismuth naphthenate, bismuth carboxylate, and combinations thereof.
9. A method of making a solid polymer electrolyte, the method comprising:
(1) dissolving a lithium-containing electrolyte compound in an organic solvent to form a lithium salt solution;
(2) adding the silane modified polyether polyol copolymer into the lithium salt solution, and stirring under a sealing condition;
(3) optionally adding a cross-linking agent and/or a catalyst and continuing to stir under sealed conditions; and
(4) and (3) forming a film and drying to obtain the solid polymer electrolyte containing the silane modified polyether polyol copolymer.
10. The process of claim 9, wherein the organic solvent is selected from the group consisting of C1-C5 alcohols, C1-C5 nitriles, C1-C3 chloroalkanes, aliphatic N-alkyl substituted amides, C2-C6 carbonates in combination with one or more;
preferably, the organic solvent is selected from one or more of methanol, ethanol, ethylene glycol, acetonitrile, trichloromethane, N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, dimethyl carbonate, ethylene carbonate and propylene carbonate.
CN202010539667.4A 2020-06-12 2020-06-12 Silane modified polyether polyol copolymer solid polymer electrolyte and preparation method thereof Pending CN113809392A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116864797A (en) * 2023-07-20 2023-10-10 安徽创速新能源科技有限公司 Ultrathin solid polymer electrolyte membrane and preparation method and application thereof

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