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CN115472900B - Polyurethane type composite solid electrolyte and preparation method and application thereof - Google Patents

Polyurethane type composite solid electrolyte and preparation method and application thereof

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Publication number
CN115472900B
CN115472900B CN202210977194.5A CN202210977194A CN115472900B CN 115472900 B CN115472900 B CN 115472900B CN 202210977194 A CN202210977194 A CN 202210977194A CN 115472900 B CN115472900 B CN 115472900B
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solid electrolyte
polyurethane
inorganic solid
ionic liquid
modified inorganic
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CN115472900A (en
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田军
吴凯强
王守泽
方明旺
罗倩
李志�
宋忆宁
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Zhejiang Lingxiao Energy Technology Co Ltd
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Zhejiang Lingxiao Energy 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
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • 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
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • 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

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  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Conductive Materials (AREA)
  • Secondary Cells (AREA)

Abstract

The invention relates to a polyurethane type composite solid electrolyte, a preparation method and application thereof. The electrolyte comprises polyurethane modified inorganic solid electrolyte and lithium salt dispersed in the polyurethane modified inorganic solid electrolyte, wherein the expression of the polyurethane modified inorganic solid electrolyte is shown as a formula (1),In the formula (1), R 3 isWherein R 1 is selected from alkyl, R 2 is selected from aliphatic hydrocarbon, alicyclic hydrocarbon or aromatic hydrocarbon, M and n are integers, m=5-30, n=5-50, R 4、R5、R6、R7 is selected from alkyl, R 8 is selected from perfluoroalkyl, M is modified inorganic solid electrolyte, and comprises inorganic solid electrolyte and polydopamine layer coating inorganic solid electrolyte, X is selected fromOrY and z are integers, y=5-50, and z=5-50. The electrolyte is used for the solid-state lithium battery, and can improve interface contact with an electrode, reduce interface impedance and improve battery electrical performance.

Description

Polyurethane type composite solid electrolyte and preparation method and application thereof
Technical Field
The invention relates to the technical field of solid electrolytes, in particular to a polyurethane type composite solid electrolyte, and a preparation method and application thereof.
Background
The lithium ion battery is widely applied to the fields of unmanned aerial vehicles, energy storage and new energy automobiles due to the characteristics of high energy density, power density, long service life and the like. However, the commercialized lithium ion battery at present generally adopts liquid electrolyte as electrolyte, so that the safety problems of easy combustion, explosion and the like exist in the use process, and the development of the lithium ion battery in the special fields of high energy density, high power and the like is severely limited.
The solid-state lithium battery can effectively avoid the problems of electrolyte leakage, fire, explosion and the like because the electrolyte does not exist, thereby improving the safety of the battery and improving the energy density of the battery. The solid electrolyte used in the solid lithium battery includes an inorganic solid electrolyte and a polymer solid electrolyte, wherein the polymer solid electrolyte mainly includes a polyurethane solid electrolyte. However, the conventional polyurethane solid electrolyte has the problems of high interfacial resistance and the like caused by poor solid-solid interface contact with the electrode plates, and meanwhile, the ionic conductivity and mechanical strength of the electrolyte membrane are difficult to meet the requirements of the solid lithium battery.
Disclosure of Invention
Based on the above, it is necessary to provide a polyurethane type composite solid electrolyte having excellent ionic conductivity and mechanical strength for a solid lithium battery capable of effectively improving a solid-solid interface contact effect with an electrode sheet, reducing interface resistance, and improving electrical properties of the solid lithium battery, and a method for preparing the same and an application thereof.
A polyurethane type composite solid electrolyte comprises a polyurethane modified inorganic solid electrolyte and lithium salt dispersed in the polyurethane modified inorganic solid electrolyte, wherein the expression of the polyurethane modified inorganic solid electrolyte is shown in the following formula (1),
In the formula (1), R 3 isWherein, R 1 is selected from alkyl, R 2 is selected from aliphatic hydrocarbon, alicyclic hydrocarbon or aromatic hydrocarbon, m and n are integers, m=5-30, n=5-50;
r 4、R5、R6、R7 is independently selected from alkyl;
r 8 is selected from perfluoroalkyl;
M represents a modified inorganic solid electrolyte comprising an inorganic solid electrolyte and a polydopamine layer coating the inorganic solid electrolyte;
X - is selected from
Y and z are integers, y=5-50, and z=5-50.
In one embodiment, R 1 is selected from alkyl groups having 2 to 4 carbon atoms;
and/or, the R 2 is selected from At least one of (a) and (b);
And/or R 4 is selected from alkyl with 2-5 carbon atoms;
And/or R 5 is selected from alkyl with 2-5 carbon atoms;
And/or, R 6 is selected from alkyl with 2 or 3 carbon atoms;
And/or R 7 is selected from alkyl with 1-3 carbon atoms;
and/or R 8 is at least one selected from trifluoromethyl, pentafluoroethyl and heptafluoropropyl.
In one embodiment, the inorganic solid state electrolyte is selected from at least one of Li6.4La3Zr1.4Ta0.6O12、Li3.3La0.56TiO3、Li7La3Zr2O12、Li1.3Al0.3Ti1.7(PO4)3、Li14ZnGe4O16.
In one embodiment, the lithium salt is at least one selected from lithium bis (trifluoromethanesulfonamide) imide, lithium bis (fluorosulfonamide) imide, lithium dioxaborate, lithium oxalyldifluoroborate, lithium tetrafluoroborate, and lithium hexafluorophosphate.
In one embodiment, the mass fraction of the lithium salt in the polyurethane type composite solid electrolyte is 10% -30%.
The preparation method of the polyurethane type composite solid electrolyte comprises the following steps:
Carrying out Michael addition reaction on an ionic liquid and dihydric alcohol amine to obtain a dihydroxyl ionic liquid, wherein the ionic liquid has a structural formula selected from the group consisting of Wherein R 7 is selected from alkyl, R 8 is selected from perfluoroalkyl, R 9 is selected from alkylene, and X - is selected from
Mixing polyglycol and diisocyanate to perform a prepolymerization reaction to obtain polyurethane prepolymer with isocyanate double end groups;
carrying out primary polymerization reaction on the polyurethane prepolymer and the modified inorganic solid electrolyte to obtain a prepolymer, carrying out secondary polymerization reaction on the prepolymer and the dihydroxyl ionic liquid to obtain the polyurethane modified inorganic solid electrolyte, and
And mixing the polyurethane modified inorganic solid electrolyte with lithium salt to obtain the polyurethane type composite solid electrolyte.
In one embodiment, the modified inorganic solid electrolyte is obtained by mixing an organic base, dopamine and an inorganic solid electrolyte and performing in-situ oxidative polymerization.
In one embodiment, the ionic liquid is selected from
At least one of (a) and (b);
And/or the dihydric alcohol amine is at least one selected from diethanolamine, diisopropanolamine, dibutanolamine, 2- (hydroxymethyl amino) ethanol, N-ethanol propanolamine and N- (5-hydroxypentyl) ethanolamine;
and/or the polyglycol is selected from at least one of polyethylene glycol, polypropylene glycol and polytetramethylene glycol;
And/or the diisocyanate is at least one selected from diphenylmethane diisocyanate, toluene-2, 3-diisocyanate, p-phenylene diisocyanate, cyclohexane-1, 4-diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate and 1, 6-hexamethylene diisocyanate.
In one embodiment, the molar ratio of the ionic liquid to the glycol amine is 0.7:1 to 1:1;
and/or the mass ratio of the polyglycol to the diisocyanate is 1:2-2:1;
And/or the molar ratio of isocyanate in the polyurethane prepolymer to the sum of hydroxyl in the modified inorganic solid electrolyte and the dihydroxy ionic liquid is 0.7:1-0.95:1.
In one embodiment, the temperature of the Michael addition reaction is from 25℃to 40℃and the time is from 1h to 5h;
And/or the temperature of the prepolymerization reaction is 60-100 ℃ and the time is 2-8 h;
And/or the temperature of the primary polymerization reaction is 60-100 ℃ and the time is 2-8 h;
And/or the temperature of the secondary polymerization reaction is 60-100 ℃ and the time is 2-8 h.
Use of a polyurethane composite solid electrolyte as described above in a solid state lithium battery.
In one of the embodiments, the polyurethane-type composite solid electrolyte is processed into an electrolyte membrane for a solid lithium battery, the electrolyte membrane having a thickness of 10 μm to 100 μm.
According to the invention, the polydopamine layer and the polyurethane are sequentially polymerized in situ on the inorganic solid electrolyte, and the dihydroxyl ionic liquid is used as a chain extender of the polyurethane to form the polyurethane modified inorganic solid electrolyte with a diversified molecular structure, and then the polyurethane modified inorganic solid electrolyte is compounded with the lithium salt to form the polyurethane type composite solid electrolyte, so that the mechanical strength, the heat resistance, the ion mobility and the electrochemical window of the polyurethane type composite solid electrolyte can be improved, the dissociation degree of the lithium salt can be improved to a certain extent, and the ionic conductivity of the polyurethane type composite solid electrolyte can be improved.
Furthermore, when the polyurethane type composite solid electrolyte is used in a solid lithium battery, not only can the solid-solid interface contact effect between the polyurethane type composite solid electrolyte and an electrode plate be improved, the interface impedance is reduced, the electrical performance of the solid lithium battery is improved, but also the perfluoroalkyl structure in the polyurethane modified inorganic solid electrolyte can be subjected to passivation reaction with the surface of the lithium metal negative electrode when the polyurethane type composite solid electrolyte is contacted with the lithium metal negative electrode, and the formed lithium fluoride can effectively improve the cycle performance of the lithium metal negative electrode solid lithium battery.
Drawings
Fig. 1 is a graph for testing the cycle performance of the polyurethane-type composite solid electrolyte membrane prepared in example 1 and comparative example 1 according to the present invention at 25 ℃, wherein a is a cycle performance curve of the polyurethane-type composite solid electrolyte membrane prepared in example 1 at 25 ℃, and B is a cycle performance curve of the polyurethane-type composite solid electrolyte membrane prepared in comparative example 1 at 25 ℃.
Detailed Description
The present invention will be described in more detail below in order to facilitate understanding of the present invention. It should be understood, however, that the invention may be embodied in many different forms and should not be limited to the implementations or embodiments described herein. Rather, these embodiments or examples are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments or examples only and is not intended to be limiting of the invention.
The invention provides a polyurethane type composite solid electrolyte, which comprises a polyurethane modified inorganic solid electrolyte and lithium salt dispersed in the polyurethane modified inorganic solid electrolyte, wherein the expression of the polyurethane modified inorganic solid electrolyte is shown in the following formula (1),
In the formula (1), R 3 isWherein, R 1 is selected from alkyl, R 2 is selected from aliphatic hydrocarbon, alicyclic hydrocarbon or aromatic hydrocarbon, m and n are integers, m=5-30, n=5-50;
r 4、R5、R6、R7 is independently selected from alkyl;
r 8 is selected from perfluoroalkyl;
M represents a modified inorganic solid electrolyte comprising an inorganic solid electrolyte and a polydopamine layer coating the inorganic solid electrolyte;
X - is selected from
Y and z are integers, y=5-50, and z=5-50.
The R 3 structural unit is obtained by opening a carbon-nitrogen double bond in the polymerization reaction of the polymer of the isocyanate double end group, and the R 6 structural unit is obtained by opening a carbon-carbon double bond in the Michael addition reaction of the olefin group.
The polyurethane type composite solid electrolyte comprises polyurethane modified inorganic solid electrolyte and lithium salt, wherein in the polyurethane modified inorganic solid electrolyte, polyurethane is bonded to the surface of the modified inorganic solid electrolyte through chemical bonds to form a whole.
Specifically, after the surface of the inorganic solid electrolyte is coated with the polydopamine layer, the polyurethane has rich active functional groups such as hydroxyl, amino, catechol and the like, and polyurethane can be polymerized on the surface of the modified inorganic solid electrolyte in situ through the active functional groups to form a whole, so that the mechanical strength and the heat resistance of the polyurethane type composite solid electrolyte can be remarkably improved. In addition, the polydopamine layer has excellent adhesiveness, so that when the polyurethane type composite solid electrolyte is used in a solid lithium battery, the solid-solid interface contact effect between the polyurethane type composite solid electrolyte and an electrode plate can be effectively improved, the interface impedance is reduced, and the electrical performance of the solid lithium battery is improved.
In the modified inorganic solid electrolyte, the polydopamine layer may cover a part of the surface of the inorganic solid electrolyte, or may cover the surface of the inorganic solid electrolyte completely. Further, the thickness of the polydopamine layer is preferably nano-scale.
In some embodiments, the inorganic solid state electrolyte is selected from at least one of Li6.4La3Zr1.4Ta0.6O12、Li3.3La0.56TiO3、Li7La3Zr2O12、Li1.3Al0.3Ti1.7(PO4)3、Li14ZnGe4O16, preferably Li 6.4La3Zr1.4Ta0.6O12.
In addition, the chain extension structure used in the polyurethane can effectively improve the ion mobility and the electrochemical window of the polyurethane type composite solid electrolyte. The lithium fluoride formed by the perfluoroalkyl structure and the lithium metal negative electrode surface can effectively improve the cycle performance of the lithium metal negative electrode solid lithium battery, and the fluorine elements abundant in the perfluoroalkyl structure can realize the flame-retardant effect and can also improve the safety of the battery when the polyurethane type composite solid electrolyte is used in the solid lithium battery.
Specifically, R 8 is at least one selected from trifluoromethyl, pentafluoroethyl and heptafluoropropyl, preferably pentafluoroethyl.
In some embodiments, R 1 in the polyurethane structure is selected from alkyl groups having 2 to 4 carbon atoms, preferably ethyl groups.
In some embodiments, R 2 in the polyurethane structure is selected from At least one, preferably
In some embodiments, R 4 in the polyurethane structure is selected from alkyl groups having 2 to 5 carbon atoms, preferably ethyl.
In some embodiments, R 5 in the polyurethane structure is selected from alkyl groups having 2 to 5 carbon atoms, preferably ethyl.
R 4 and R 5 may be selected from alkyl groups having the same number of carbon atoms, or may be selected from alkyl groups having different numbers of carbon atoms, and the present embodiment is not limited thereto. Further, in order to form a symmetrical structure between R 4 and R 5, R 4 and R 5 are preferably alkyl groups having the same number of carbon atoms.
In some embodiments, R 6 in the polyurethane structure is selected from alkyl groups having 2 or 3 carbon atoms, preferably ethyl.
In some embodiments, R 7 in the polyurethane structure is selected from alkyl groups having 1 to 3 carbon atoms, preferably ethyl groups.
In the polyurethane type composite solid electrolyte, polyurethane is bonded to the surface of a modified inorganic solid electrolyte through chemical bonds to form a whole, and the lithium salt is dispersed in the polyurethane of the polyurethane modified inorganic solid electrolyte.
In some embodiments, the mass fraction of the lithium salt in the polyurethane composite solid state electrolyte is 10% -30%.
In some embodiments, the lithium salt is selected from at least one of lithium bis (trifluoromethanesulfonamide) imide, lithium bis (fluorosulfonamide) imide, lithium dioxaborate, lithium oxalyldifluoroborate, lithium tetrafluoroborate, lithium hexafluorophosphate, preferably lithium bis (trifluoromethanesulfonamide) imide, lithium bis (fluorosulfonamide) imide.
In some embodiments, the polyurethane modified inorganic solid state electrolyte preferably has a structural formula as shown in the following formulas (1-1), (1-2),
Wherein R 3 isM represents a modified inorganic solid electrolyte comprising an inorganic solid electrolyte and a polydopamine layer coating the inorganic solid electrolyte;
wherein R 3 is M represents a modified inorganic solid electrolyte comprising an inorganic solid electrolyte and a polydopamine layer coating the inorganic solid electrolyte.
The invention also provides a preparation method of the polyurethane type composite solid electrolyte, which comprises the following steps:
s1, carrying out Michael addition reaction on ionic liquid and dihydric alcohol amine to obtain dihydroxy ionic liquid, wherein the structural formula of the ionic liquid is selected from Wherein R 7 is selected from alkyl, R 8 is selected from perfluoroalkyl, R 9 is selected from alkylene, and X - is selected from
S2, mixing polyglycol and diisocyanate to perform a prepolymerization reaction to obtain polyurethane prepolymer with isocyanate double end groups;
S3, carrying out primary polymerization reaction on the polyurethane prepolymer and the modified inorganic solid electrolyte to obtain a prepolymer, carrying out secondary polymerization reaction on the prepolymer and the dihydroxyl ionic liquid to obtain the polyurethane modified inorganic solid electrolyte, and
And S4, mixing the polyurethane modified inorganic solid electrolyte with lithium salt to obtain the polyurethane type composite solid electrolyte.
In the step S1, the ionic liquid can be provided with a dihydroxyl active group by utilizing a Michael addition reaction, so that the dihydroxyl ionic liquid is beneficial to chain extension of polyurethane.
In some embodiments, the molar ratio of the ionic liquid to the glycol amine is from 0.7:1 to 1:1, preferably from 0.7:1 to 0.95:1.
In particular, the ionic liquid is selected from
At least one, preferablyThe dihydric alcohol amine is at least one selected from diethanolamine, diisopropanolamine, dibutylamine, 2- (hydroxymethyl amino) ethanol, N-ethanol propanolamine and N- (5-hydroxypentyl) ethanolamine, and preferably diethanolamine.
In some embodiments, the Michael addition reaction is at a temperature of 25℃to 40℃for a period of 1h to 5h.
To further demonstrate the reaction process of step S1, diethanolamine and X - were used asA kind of electronic deviceFor example, the reaction equation of the step S1 is shown in the following formula (2):
The preparation method of the ionic liquid comprises the steps of reacting olefine imidazole with perfluoroiodoalkane in a protective atmosphere to obtain the ionic liquid containing iodine, and then carrying out anion exchange on the ionic liquid containing iodine and bis (fluorosulfonyl) imide (FSI) or bis (trifluoromethanesulfonyl) imide (TFSI) to obtain the ionic liquid.
Specifically, the olefine imidazole is at least one selected from vinyl imidazole and allyl imidazole, and the perfluor iodoalkane is at least one selected from trifluoroiodoethane, trifluoroiodopropane, trifluoroiodobutane, pentafluoroiiodoethane, pentafluoroiodopropane, pentafluoroiodobutane, heptafluoroiodoethane, heptafluoroiodopropane and heptafluoroiodobutane.
In the step S2, polyurethane prepolymer with isocyanate double end groups is prepared, and the polyurethane prepolymer can be used as a bridge, so that isocyanate active groups at one end of the polyurethane prepolymer and the modified inorganic solid electrolyte are chemically bonded, and isocyanate active groups at the other end of the polyurethane prepolymer and the dihydroxyl ionic liquid are chemically bonded, so that the polyurethane modified inorganic solid electrolyte with a diversified molecular structure is constructed.
Specifically, the mass ratio of the polyglycol to the diisocyanate is 1:2-2:1, preferably 4:5-2:1.
Further, the polyglycol is at least one selected from polyethylene glycol, polypropylene glycol and polytetramethylene glycol, preferably polyethylene glycol, wherein the molecular weight of the polyethylene glycol is 1000g/mol-5000g/mol, preferably 1000g/mol-4000g/mol.
The diisocyanate is at least one selected from diphenylmethane diisocyanate, toluene-2, 3-diisocyanate, p-phenylene diisocyanate, cyclohexane-1, 4-diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate and 1, 6-hexamethylene diisocyanate, and preferably diphenylmethane diisocyanate and toluene-2, 3-diisocyanate.
In some embodiments, the step of pre-polymerizing further comprises a catalyst selected from dibutyltin dilaurate.
In some embodiments, the temperature of the prepolymerization is from 60℃to 100℃and the time is from 2h to 8h.
In the step S3, the modified inorganic solid electrolyte is added into the polyurethane prepolymer for one-time polymerization, so that the polyurethane prepolymer is bonded to the surface of the modified inorganic solid electrolyte through chemical bonds, and then the dihydroxy ionic liquid is added for secondary polymerization, so that the dihydroxy ionic liquid is bonded with the polyurethane prepolymer through chemical bonds, and the polyurethane modified inorganic solid electrolyte is obtained.
In some embodiments, the molar ratio of isocyanate in the polyurethane prepolymer to the sum of hydroxyl groups in the modified inorganic solid electrolyte and the dihydroxy ionic liquid is from 0.7:1 to 0.95:1.
In some embodiments, the primary polymerization is at a temperature of 60 ℃ to 100 ℃ for a time of 2 hours to 8 hours, and the secondary polymerization is at a temperature of 60 ℃ to 100 ℃ for a time of 2 hours to 8 hours.
To further demonstrate the reaction process of steps S2 and S3, taking polyethylene glycol, toluene-2, 3-diisocyanate, the dihydroxy ionic liquid obtained by formula (2), and the modified inorganic solid electrolyte as examples, the reaction equations of steps S2 and S3 are shown in the following formula (3):
In the formula (3), R 3 is M represents a modified inorganic solid electrolyte comprising an inorganic solid electrolyte and a polydopamine layer coating the inorganic solid electrolyte.
The preparation method of the modified inorganic solid electrolyte comprises the steps of initiating dopamine on the surface of the inorganic solid electrolyte to perform in-situ oxidative polymerization in organic alkali under a protective atmosphere, so that the surface of the inorganic solid electrolyte is coated to form a polydopamine layer.
The organic base is specifically selected from piperidine organic base, the dopamine is selected from dopamine hydrochloride, the solvent for the mixed reaction of the dopamine and the inorganic solid electrolyte is selected from chlorobenzene solution, and the protective atmosphere is selected from argon.
In step S4, when the lithium salt is dispersed in the polyurethane modified inorganic solid electrolyte, the mass ratio of the polyurethane modified inorganic solid electrolyte to the lithium salt is 7:3 to 9:1.
The invention also provides application of the polyurethane type composite solid electrolyte in a solid lithium battery.
The polyurethane type composite solid electrolyte provided by the invention is used in a solid lithium battery, can improve the solid-solid interface contact effect between the polyurethane type composite solid electrolyte and an electrode plate, and reduce interface impedance, so that the electrical property of the solid lithium battery is improved, meanwhile, the ionic conductivity is improved, the cycle performance and the safety of the solid lithium battery are improved, and the market demand of the high-performance solid lithium battery is further met.
In some embodiments, the polyurethane composite solid electrolyte is processed into an electrolyte membrane for a solid lithium battery, the electrolyte membrane having a thickness of 10 μm to 100 μm, preferably 20 μm to 80 μm.
Hereinafter, the polyurethane type composite solid electrolyte, and the preparation method and application thereof will be further described by way of the following specific examples.
Example 1
Adding 1mol of ionic liquid and 1.1mol of diethanolamine into a reaction vessel, and preparing the dihydroxyl ionic liquid by Michael addition reaction at 25 ℃, wherein the ionic liquid has a structural formula selected fromWherein X - is
80G of polyethylene glycol with the molecular weight of 4000g/mol and 25g of diphenylmethane diisocyanate are placed in a reaction vessel, a trace of dibutyltin dilaurate is added, the temperature is raised to 85 ℃, and the reaction is carried out for 3 hours, so as to obtain the polyurethane prepolymer with the double end groups of isocyanate.
Uniformly dispersing 0.05g of dopamine hydrochloride and 1g of Li 6.4La3Zr1.4Ta0.6O12 in chlorobenzene solution, adding piperidine organic base, continuously oxidatively polymerizing for 3 hours at 25 ℃ under the protection of argon, and filtering, cleaning and drying to obtain the modified Li 6.4La3Zr1.4Ta0.6O12.
15.5G of modified Li 6.4La3Zr1.4Ta0.6O12 is added into polyurethane prepolymer to be polymerized for 2 hours at 85 ℃, 50g of the prepared dihydroxy ionic liquid is added after the reaction is finished, and further polymerized for 3 hours at 85 ℃ to prepare the polyurethane modified inorganic solid electrolyte, the structural formula of which is shown as the formula (1-1),
Wherein R 3 isM is modified Li 6.4La3Zr1.4Ta0.6O12.
And uniformly mixing 90 parts by mass of polyurethane modified inorganic solid electrolyte with 10 parts by mass of lithium bistrifluoromethane sulfonamide imine to obtain the polyurethane type composite solid electrolyte.
Example 2
Adding 1mol of ionic liquid and 1.1mol of diethanolamine into a reaction vessel, and preparing the dihydroxyl ionic liquid by Michael addition reaction at 25 ℃, wherein the ionic liquid has a structural formula selected fromWherein X - is
80G of polyethylene glycol with the molecular weight of 4000g/mol and 25g of toluene-2, 3-diisocyanate are placed in a reaction vessel, a trace of dibutyltin dilaurate is added, the temperature is raised to 85 ℃, and the reaction is carried out for 3 hours, so as to obtain the polyurethane prepolymer with the isocyanate double end groups.
Uniformly dispersing 0.05g of dopamine hydrochloride and 1g of Li 3.3La0.56TiO3 in chlorobenzene solution, adding piperidine organic base, continuously oxidatively polymerizing for 3 hours at 25 ℃ under the protection of argon, and filtering, cleaning and drying to obtain the modified Li 3.3La0.56TiO3.
15.5G of modified Li 3.3La0.56TiO3 is added into polyurethane prepolymer to be polymerized for 2 hours at 85 ℃, 50g of the prepared dihydroxy ionic liquid is added after the reaction is finished, and further polymerized for 2 hours at 90 ℃ to prepare the polyurethane modified inorganic solid electrolyte, the structural formula of which is shown as the formula (1-2),
Wherein R 3 isM is modified Li 3.3La0.56TiO3.
And uniformly mixing 80 parts by mass of polyurethane modified inorganic solid electrolyte with 20 parts by mass of lithium bis (fluorosulfonamide) imide to obtain the polyurethane type composite solid electrolyte.
Example 3
Adding 0.9mol of ionic liquid and 1.1mol of diethanolamine into a reaction vessel, and preparing the dihydroxyl ionic liquid by Michael addition reaction at 25 ℃, wherein the ionic liquid has a structural formula selected fromWherein X - is
80G of polyethylene glycol with the molecular weight of 4000g/mol and 25g of diphenylmethane diisocyanate are placed in a reaction vessel, a trace of dibutyltin dilaurate is added, the temperature is raised to 85 ℃, and the reaction is carried out for 3 hours, so as to obtain the polyurethane prepolymer with the double end groups of isocyanate.
The preparation method of the modified inorganic solid electrolyte was the same as in example 1.
15.5G of modified Li 6.4La3Zr1.4Ta0.6O12 is added into polyurethane prepolymer to be polymerized for 4 hours at 80 ℃ in situ, 50g of the prepared dihydroxy ionic liquid is added after the reaction is finished, and the reaction is further polymerized for 3 hours at 85 ℃ to prepare the polyurethane modified inorganic solid electrolyte.
And uniformly mixing 70 parts by mass of polyurethane modified inorganic solid electrolyte with 30 parts by mass of lithium dioxalate borate to obtain the polyurethane type composite solid electrolyte.
Example 4
Adding 1mol of ionic liquid and 1.1mol of dipropylamine into a reaction vessel, and preparing the dihydroxyl ionic liquid by Michael addition reaction under the condition of 25 ℃, wherein the structural formula of the ionic liquid is selected fromWherein X - is
80G of polyethylene glycol with the molecular weight of 4000g/mol and 40g of toluene-2, 3-diisocyanate are placed in a reaction vessel, a trace of dibutyltin dilaurate is added, the temperature is raised to 85 ℃, and the reaction is carried out for 3 hours, so as to obtain the polyurethane prepolymer with the isocyanate double end groups.
The preparation method of the modified inorganic solid electrolyte was the same as in example 1.
15.5G of modified Li 6.4La3Zr1.4Ta0.6O12 is added into polyurethane prepolymer to be polymerized for 2 hours at 85 ℃ in situ, 90g of the prepared dihydroxy ionic liquid is added after the reaction is finished, and the polyurethane modified inorganic solid electrolyte is prepared after the reaction is further polymerized for 3 hours at 85 ℃.
And uniformly mixing 80 parts by mass of polyurethane modified inorganic solid electrolyte with 20 parts by mass of lithium oxalyldifluoroborate to obtain the polyurethane type composite solid electrolyte.
Example 5
Adding 1mol of ionic liquid and 1.1mol of diethanolamine into a reaction vessel, and preparing the dihydroxyl ionic liquid by Michael addition reaction at the temperature of 30 ℃, wherein the ionic liquid has a structural formula selected fromWherein X - is
80G of polyethylene glycol with the molecular weight of 4000g/mol and 40g of toluene-2, 3-diisocyanate are placed in a reaction vessel, a trace of dibutyltin dilaurate is added, the temperature is raised to 85 ℃, and the reaction is carried out for 3 hours, so as to obtain the polyurethane prepolymer with the isocyanate double end groups.
The preparation method of the modified inorganic solid electrolyte was the same as in example 1.
23G of modified Li 6.4La3Zr1.4Ta0.6O12 is added into polyurethane prepolymer to be polymerized for 2 hours at 85 ℃, 90g of the prepared dihydroxy ionic liquid is added after the reaction is finished, and the polyurethane modified inorganic solid electrolyte is prepared after the reaction is further polymerized for 3 hours at 85 ℃.
And uniformly mixing 80 parts by mass of polyurethane modified inorganic solid electrolyte with 20 parts by mass of lithium bis (fluorosulfonamide) imide to obtain the polyurethane type composite solid electrolyte.
Example 6
Adding 1mol of ionic liquid and 1.1mol of diethanolamine into a reaction vessel, and preparing the dihydroxyl ionic liquid by Michael addition reaction at 25 ℃, wherein the ionic liquid has a structural formula selected fromWherein X - is
80G of polyethylene glycol with the molecular weight of 4000g/mol and 25g of diphenylmethane diisocyanate are placed in a reaction vessel, a trace of dibutyltin dilaurate is added, the temperature is raised to 85 ℃, and the reaction is carried out for 3 hours, so as to obtain the polyurethane prepolymer with the double end groups of isocyanate.
The preparation method of the modified inorganic solid electrolyte was the same as in example 1.
7.75G of modified Li 6.4La3Zr1.4Ta0.6O12 is added into polyurethane prepolymer to be polymerized for 2 hours at 85 ℃, 50g of the prepared dihydroxy ionic liquid is added after the reaction is finished, and the polyurethane modified inorganic solid electrolyte is prepared after the reaction is further polymerized for 3 hours at 85 ℃.
And uniformly mixing 80 parts by mass of polyurethane modified inorganic solid electrolyte with 20 parts by mass of lithium dioxalate borate to obtain the polyurethane type composite solid electrolyte.
Example 7
Adding 1mol of ionic liquid and 1.1mol of diethanolamine into a reaction vessel, and preparing the dihydroxyl ionic liquid by Michael addition reaction at 35 ℃, wherein the ionic liquid has a structural formula selected fromWherein X - is
20G of polyethylene glycol with the molecular weight of 1000g/mol and 25g of diphenylmethane diisocyanate are placed in a reaction vessel, a trace of dibutyltin dilaurate is added, the temperature is raised to 85 ℃, and the reaction is carried out for 3 hours, so as to obtain the polyurethane prepolymer with the double end groups of isocyanate.
The preparation method of the modified inorganic solid electrolyte was the same as in example 1.
15.5G of modified Li 6.4La3Zr1.4Ta0.6O12 is added into polyurethane prepolymer to be polymerized for 2 hours at 85 ℃ in situ, 50g of the prepared dihydroxy ionic liquid is added after the reaction is finished, and the polyurethane modified inorganic solid electrolyte is prepared after the reaction is further polymerized for 3 hours at 85 ℃.
And uniformly mixing 80 parts by mass of polyurethane modified inorganic solid electrolyte with 20 parts by mass of lithium bistrifluoromethane sulfonamide imine to obtain the polyurethane type composite solid electrolyte.
Comparative example 1
80G of polyethylene glycol with the molecular weight of 4000g/mol and 25g of diphenylmethane diisocyanate are placed in a reaction vessel, a trace of dibutyltin dilaurate is added, the temperature is raised to 85 ℃, and the reaction is carried out for 3 hours, so as to obtain the polyurethane prepolymer with the double end groups of isocyanate. Then 8g of 1, 4-butanediol was added and further polymerized at 85℃for 3 hours to prepare polyurethane.
15.5G of Li 6.4La3Zr1.4Ta0.6O12 is mixed with polyurethane to obtain a mixture, and 80 parts by mass of the mixture and 20 parts by mass of lithium bistrifluoromethane sulfonamide imine are uniformly mixed to obtain the polyurethane type composite solid electrolyte.
Comparative example 2
Comparative example 2 differs from example 1 in that 1, 4-butanediol was used instead of the dihydroxyionic liquid.
Comparative example 3
Comparative example 3 is different from example 1 in that Li 6.4La3Zr1.4Ta0.6O12 is not modified and the surface has no polydopamine layer.
Application examples
The polyurethane type composite solid electrolyte prepared in examples 1 to 7 was processed into electrolyte membrane samples 1 to 7 of 80 μm, respectively.
Comparative examples of application
The polyurethane type composite solid electrolyte prepared in comparative examples 1 to 3 was processed into electrolyte membrane samples 8 to 10 of 80 μm, respectively.
Samples 1-10 were subjected to 25 ℃ and 60 ℃ ionic conductivity tests and mechanical strength tests, respectively. Ion conductivity test method the electrolyte membrane sample (Φ18mm) was taken in a glove box and assembled with a positive electrode sheet (Φ15mm) and a lithium sheet (Φ15mm) to form a solid-state battery. Electrochemical impedance tests were performed at 25 ℃ and 60 ℃ in the frequency range of 1Hz to 8MHz, respectively, and the ionic conductivity of the electrolyte was calculated according to the measured electrolyte impedance and formula (1),
Sigma = l/RS formula (1);
Wherein sigma is the ion conductivity of the electrolyte, l is the thickness of the electrolyte membrane, R is the bulk impedance of the electrolyte measured by electrochemical impedance method, and S is the contact area of the electrolyte and the lithium sheet.
The test results are shown in Table 1.
TABLE 1
As can be seen from Table 1, the electrolyte membranes prepared in examples 1 to 7 were higher in ionic conductivity at 25℃and 60℃than comparative examples 1 to 4, and were excellent in mechanical strength. In contrast, in the electrolyte membrane prepared in comparative example 1, since the electrolyte membrane does not contain perfluoroalkyl groups, the dissociation degree of lithium salt is weak, so that the ionic conductivity at 25 ℃ and 60 ℃ is far lower than that of the electrolyte membrane prepared in example, and the inorganic solid electrolyte is not modified, and after polyurethane, the inorganic solid electrolyte and the lithium salt are mixed, the obtained polyurethane type composite solid electrolyte is only a physical combination of the components, and no chemical bonding exists, so that the mechanical strength of the electrolyte membrane is also poor. In the electrolyte membrane prepared in comparative example 2, 1, 4-butanediol was used as a chain extender, and the dissociation degree of lithium salt was far less than that of example 1, so that the ionic conductivity was low at 25 ℃ and 60 ℃. In contrast, in the electrolyte membrane prepared in comparative example 3, since the inorganic solid electrolyte was not modified, chemical bonding with other components was weak, so that the mechanical strength of the electrolyte membrane was low and the ionic conductivity was also lower than in example.
Samples 1 and 8 were subjected to cycle performance testing. The cycle performance test method comprises the steps of respectively charging solid-state batteries from 3.0V constant current to 4.2V at a rate of 0.33 ℃ under the condition of 25 ℃, standing for 5 minutes, charging to 0.02C cut-off at a constant voltage of 4.2V, discharging to 3.0V at a rate of 0.33 ℃, and standing for 5 minutes. The cycle was repeated 50-200 times, and the test results are shown in FIG. 1.
As can be seen from fig. 1, the electrolyte membrane prepared in example 1 has excellent cycle stability, and can maintain about 97% of capacitance after about 100 times of cycle test, and about 94% of capacitance after about 150 times of cycle test, and the capacitance starts to decrease slowly after more than 150 times of cycle test. The electrolyte membrane prepared in comparative example 1 has a greatly reduced capacitance in the cycle test, and the capacitance has been reduced to about 80% after about 50 times of the cycle test, resulting in poor cycle stability.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.

Claims (12)

1. A polyurethane-modified composite solid electrolyte comprising a polyurethane-modified inorganic solid electrolyte and a lithium salt dispersed in the polyurethane-modified inorganic solid electrolyte, wherein the polyurethane-modified inorganic solid electrolyte has the expression of formula (1),
;
In the formula (1), R 3 isWherein R 1 is selected from alkyl, R 2 is selected from aliphatic hydrocarbon, alicyclic hydrocarbon or aromatic hydrocarbon, m and n are integers, m=5-30, n=5-50;
r 4、R5、R6、R7 is independently selected from alkyl;
r 8 is selected from perfluoroalkyl;
M represents a modified inorganic solid electrolyte comprising an inorganic solid electrolyte and a polydopamine layer coating the inorganic solid electrolyte;
X - is selected from Or (b);
Y and z are integers, y=5-50, and z=5-50;
the preparation method of the polyurethane type composite solid electrolyte comprises the following steps:
Carrying out Michael addition reaction on an ionic liquid and dihydric alcohol amine to obtain a dihydroxyl ionic liquid, wherein the ionic liquid has a structural formula selected from the group consisting of Wherein R 9 is selected from the group consisting of alkylene;
Mixing polyglycol and diisocyanate to perform a prepolymerization reaction to obtain polyurethane prepolymer with isocyanate double end groups;
carrying out primary polymerization reaction on the polyurethane prepolymer and the modified inorganic solid electrolyte to obtain a prepolymer, and carrying out secondary polymerization reaction on the prepolymer and the dihydroxyl ionic liquid to obtain the polyurethane modified inorganic solid electrolyte;
And mixing the polyurethane modified inorganic solid electrolyte with lithium salt to obtain the polyurethane type composite solid electrolyte.
2. The polyurethane composite solid electrolyte according to claim 1, wherein R 1 is selected from alkyl groups having 2 to 4 carbon atoms;
and/or, the R 2 is selected from 、、、、、、At least one of (a) and (b);
And/or R 4 is selected from alkyl with 2-5 carbon atoms;
And/or R 5 is selected from alkyl with 2-5 carbon atoms;
And/or, R 6 is selected from alkyl with 2 or 3 carbon atoms;
And/or R 7 is selected from alkyl with 1-3 carbon atoms;
and/or R 8 is at least one selected from trifluoromethyl, pentafluoroethyl and heptafluoropropyl.
3. The polyurethane composite solid electrolyte of claim 1, wherein the inorganic solid electrolyte is selected from at least one of Li6.4La3Zr1.4Ta0.6O12、Li3.3La0.56TiO3、Li7La3Zr2O12、Li1.3Al0.3Ti1.7(PO4)3、Li14ZnGe4O16.
4. The polyurethane composite solid electrolyte of claim 1, wherein the lithium salt is selected from at least one of lithium bis (trifluoromethanesulfonamide) imide, lithium bis (fluorosulfonamide) imide, lithium dioxaborate, lithium oxalyldifluoroborate, lithium tetrafluoroborate, and lithium hexafluorophosphate.
5. The polyurethane composite solid electrolyte according to claim 1, wherein the mass fraction of the lithium salt in the polyurethane composite solid electrolyte is 10% to 30%.
6. A method for producing the polyurethane composite solid electrolyte according to any one of claims 1 to 5, comprising the steps of:
Carrying out Michael addition reaction on an ionic liquid and dihydric alcohol amine to obtain a dihydroxyl ionic liquid, wherein the ionic liquid has a structural formula selected from the group consisting of Wherein R 7 is selected from alkyl, R 8 is selected from perfluoroalkyl, R 9 is selected from alkylene, and X - is selected fromOr (b);
Mixing polyglycol and diisocyanate to perform a prepolymerization reaction to obtain polyurethane prepolymer with isocyanate double end groups;
carrying out primary polymerization reaction on the polyurethane prepolymer and the modified inorganic solid electrolyte to obtain a prepolymer, carrying out secondary polymerization reaction on the prepolymer and the dihydroxyl ionic liquid to obtain the polyurethane modified inorganic solid electrolyte, and
And mixing the polyurethane modified inorganic solid electrolyte with lithium salt to obtain the polyurethane type composite solid electrolyte.
7. The method for preparing a polyurethane composite solid electrolyte according to claim 6, wherein the modified inorganic solid electrolyte is obtained by mixing an organic base, dopamine and an inorganic solid electrolyte and performing in-situ oxidative polymerization.
8. The method for producing a polyurethane composite solid electrolyte according to claim 6, wherein the ionic liquid is selected from the group consisting of、、、、、、、、、、、、、、、、、、、、、、、、、、At least one of (a) and (b);
And/or the dihydric alcohol amine is at least one selected from diethanolamine, diisopropanolamine, dibutanolamine, 2- (hydroxymethyl amino) ethanol, N-ethanol propanolamine and N- (5-hydroxypentyl) ethanolamine;
and/or the polyglycol is selected from at least one of polyethylene glycol, polypropylene glycol and polytetramethylene glycol;
And/or the diisocyanate is at least one selected from diphenylmethane diisocyanate, toluene-2, 3-diisocyanate, p-phenylene diisocyanate, cyclohexane-1, 4-diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate and 1, 6-hexamethylene diisocyanate.
9. The method for preparing a polyurethane composite solid electrolyte according to claim 6, wherein the molar ratio of the ionic liquid to the glycol amine is 0.7:1-1:1;
and/or the mass ratio of the polyglycol to the diisocyanate is 1:2-2:1;
And/or the molar ratio of isocyanate in the polyurethane prepolymer to the sum of hydroxyl in the modified inorganic solid electrolyte and the dihydroxy ionic liquid is 0.7:1-0.95:1.
10. The method for preparing a polyurethane composite solid electrolyte according to claim 6, wherein the temperature of the michael addition reaction is 25 ℃ to 40 ℃ for 1h to 5h;
And/or the temperature of the prepolymerization reaction is 60-100 ℃ and the time is 2-8 h;
And/or the temperature of the primary polymerization reaction is 60-100 ℃ and the time is 2-8 h;
And/or the temperature of the secondary polymerization reaction is 60-100 ℃ and the time is 2-8 h.
11. Use of the polyurethane composite solid electrolyte according to any one of claims 1 to 5 in a solid state lithium battery.
12. The use of the polyurethane-based composite solid electrolyte in a solid state lithium battery according to claim 11, wherein the polyurethane-based composite solid electrolyte is processed into an electrolyte membrane for a solid state lithium battery, the electrolyte membrane having a thickness of 10 μm to 100 μm.
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CN111786016A (en) * 2019-04-03 2020-10-16 深圳格林德能源集团有限公司 Fluorine-containing polyurethane solid composite electrolyte and preparation method thereof
CN113363560A (en) * 2021-03-26 2021-09-07 万向一二三股份公司 Organic in-situ interface modified solid electrolyte and preparation method thereof

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Publication number Priority date Publication date Assignee Title
CN111786016A (en) * 2019-04-03 2020-10-16 深圳格林德能源集团有限公司 Fluorine-containing polyurethane solid composite electrolyte and preparation method thereof
CN113363560A (en) * 2021-03-26 2021-09-07 万向一二三股份公司 Organic in-situ interface modified solid electrolyte and preparation method thereof

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