CN110010964B - Porous membrane reinforced polymer-plastic crystal solid electrolyte membrane, and preparation method and application thereof - Google Patents
Porous membrane reinforced polymer-plastic crystal solid electrolyte membrane, and preparation method and application thereof Download PDFInfo
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- 150000001450 anions Chemical class 0.000 claims description 8
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- 229910001290 LiPF6 Inorganic materials 0.000 claims description 4
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- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 4
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- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
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- 239000011261 inert gas Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
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- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 56
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 description 42
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 39
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 39
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 230000001351 cycling effect Effects 0.000 description 6
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- 229910032387 LiCoO2 Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
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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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
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- Condensed Matter Physics & Semiconductors (AREA)
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Abstract
The invention discloses a porous membrane reinforced polymer-plastic crystal solid electrolyte membrane, and a preparation method and application thereof. The polymer-plastocrystalline solid electrolyte membrane comprises: the solid electrolyte membrane comprises a supporting layer containing a porous membrane and a polymer-plastic crystal solid electrolyte layer at least covering one side of the surface of the porous membrane; the porous membrane plays a role of a supporting framework, has a continuous three-dimensional network structure, can improve the mechanical property of the solid electrolyte membrane, and is beneficial to preparing a thinner solid electrolyte membrane; the polymer-plastic crystal solid electrolyte layer contains a polymer, a lithium salt and a plastic crystal compound, and a flexible polymer-plastic crystal solid electrolyte membrane with enhanced porous membrane, high voltage resistance and high low-temperature conductivity can be obtained by optimizing the proportion of the polymer, the lithium salt and the plastic crystal. The polymer plastic crystal solid electrolyte membrane can be applied to all-solid-state lithium ion batteries, has simple preparation process and is suitable for industrial production.
Description
Technical Field
The invention relates to a solid electrolyte membrane, in particular to a flexible polymer-plastic crystal solid electrolyte membrane which is reinforced by a porous membrane, resistant to high voltage and high in low-temperature conductivity, and a preparation method and application thereof, belonging to the technical field of new energy and new materials.
Background
The lithium ion battery widely uses liquid electrolyte containing organic solvent, the liquid organic solvent is easy to burn, volatilize and oxidize, and particularly, a large amount of heat is generated under extreme working conditions of overcharge, overdischarge, high-power charge and discharge and the like to accelerate the generation of gas, so that serious potential safety hazard exists. The polymer solid electrolyte is generally composed of a polymer matrix and an inorganic lithium salt, and is represented byThe solid state can support the migration of lithium ions like liquid, and the safety problems of liquid electrolyte, such as leakage, combustion, explosion and the like, can be effectively solved. However, the conductivity of the polymer solid electrolyte at room temperature is generally low, and is only 10-7～10-8Scm-1Limiting its commercial application. In Electrochemistry Communications 2006,8, 1753-; in Advanced Functional Materials 2007,17,2800 and 2807, Journal of Power Sources 2009,189,775-77 and patent CN101045806A, the plastic crystal compound is introduced into the polymer solid electrolyte to obtain the polymer-plastic crystal solid electrolyte, and the electrolyte combines the advantages of flexibility, good mechanical property, high ionic conductivity and the like of the polymer electrolyte, and is a promising solid electrolyte which can be used for room temperature lithium ion batteries. However, the polymer-plastocrystalline solid electrolyte membrane reported so far has several significant drawbacks that inhibit its wide application in solid lithium batteries: 1. the thickness of the polymer-plastic crystal solid electrolyte membrane is difficult to be less than 100 mu m on the premise of self-supporting, the mechanical property of the thin polymer-plastic crystal solid electrolyte membrane is poor, and the volume energy density of the battery is greatly increased by the thick solid electrolyte membrane. 2. The melting point of the plastic crystal compound is greatly influenced by the concentration of the added lithium salt, and the concentration of the lithium salt has a large influence on the conductivity of the plastic crystal electrolyte, particularly the conductivity at low temperature. However, the proportions of the lithium salt, the plastic crystal compound and the polymer reported in the literature are often fixed values, and the study on the influence of different proportions on the conductivity and the electrochemical performance of the polymer-plastic crystal solid electrolyte membrane is not reported.
Disclosure of Invention
The invention mainly aims to provide a polymer-plastic crystal solid electrolyte membrane reinforced by a porous membrane, a preparation method and application thereof, so as to overcome the defects in the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a polymer-plastic crystal solid electrolyte membrane reinforced by a porous membrane, which comprises the following components: the solid electrolyte membrane comprises a supporting layer and a polymer-plastic crystal solid electrolyte layer, wherein the supporting layer comprises a porous membrane, and the polymer-plastic crystal solid electrolyte layer is covered on the surface of the porous membrane; wherein the porous membrane has a continuous three-dimensional network structure; the polymer-plastic crystal solid electrolyte layer comprises a polymer, a lithium salt and a plastic crystal compound.
In some embodiments, the porous membrane has a thickness of 1 to 100 μm, a porosity of 40 to 90%, a pore size of 0.01 to 3 μm, a linear diameter in a network structure of 0.01 to 5 μm, a thickness of 2 to 100 μm, a porosity of less than 10%, a pore size of 0.01 to 0.5 μm, and a conductivity of up to 10 at 25 ℃-3Scm-1At-20 ℃ the conductivity is at most 10-4S/cm。
In some embodiments, one or both of the opposite surfaces of the porous membrane is coated with the polymer-plastocrystalline solid electrolyte layer.
Further, the porous membrane has a thickness of 1 to 50 μm, a porosity of 40 to 90%, a pore diameter of 0.01 to 3 μm, and a linear diameter of 0.01 to 5 μm in a network structure.
The embodiment of the invention also provides a preparation method of the polymer-plastic crystal solid electrolyte membrane reinforced by the porous membrane, which comprises the following steps:
uniformly mixing a polymer, an inorganic lithium salt and a plastic crystal compound in a solvent to form a homogeneous solution;
and applying the homogeneous solution to the surface of the porous membrane, removing the solvent, and then performing vacuum drying to obtain the polymer-plastic crystal solid electrolyte membrane reinforced by the porous membrane.
The embodiment of the invention also provides application of the polymer-plastic crystal solid electrolyte membrane reinforced by the porous membrane, such as application in preparing a lithium ion battery.
Compared with the prior art, the invention has the beneficial effects that:
the flexible polymer plastic crystal solid electrolyte membrane reinforced by the porous membrane can improve the polymer plastic crystal solid electrolyte membrane by arranging the porous membrane which plays the role of a supporting framework on the polymer plastic crystal solid electrolyte layerThe mechanical property of the polymer plastic crystal solid electrolyte membrane is reduced, the oxidation resistance of the polymer plastic crystal solid electrolyte membrane can be improved and the low-temperature conductivity (the ionic conductivity at 25 ℃ can reach 10) of the polymer plastic crystal solid electrolyte membrane can be increased by optimizing the content of lithium salt and plastic crystal-3Scm-1The conductivity reaches 10 at-20 DEG C-4Scm-1) The prepared flexible polymer plastic crystal solid electrolyte membrane reinforced by the porous membrane has high voltage resistance and higher conductivity (up to 10) at low temperature-4Scm-1) And good mechanical properties, especially when applied to high-voltage all-solid-state lithium ion batteries, the method can also obviously improve the cycling stability of the batteries, and the preparation process is simple and is suitable for industrial production.
Drawings
FIG. 1 is an SEM photograph of a porous membrane of polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) having a porosity of 70% according to an exemplary embodiment of the present invention.
Fig. 2 is an SEM photograph of a PVDF-HFP/LiTFSI/succinonitrile solid electrolyte membrane supported by a porous membrane of polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) having a porosity of less than 10% in an exemplary embodiment of the invention.
FIG. 3 is a schematic representation of PVDF-HFP/LiTFSI/succinonitrile solid electrolyte reinforced with porous PVDF-HFP membrane in an exemplary embodiment of the invention.
Fig. 4 is a graph of the change of electrochemical stability performance of P (VDF-HFP)/LiTFSI/succinonitrile flexible solid electrolyte with different lithium salt and succinonitrile contents reinforced by PVDF-HFP membranes prepared in examples 1, 2, 3, 4 of the present invention.
Fig. 5 is a graph of ion conductivity of P (VDF-HFP)/LiTFSI/succinonitrile flexible solid electrolyte with different lithium salt and succinonitrile contents reinforced by PVDF-HFP porous membranes prepared in examples 1, 2, 3, 4 of the present invention as a function of temperature.
FIG. 6 is a P (VDF-HFP)/LiTFSI/succinonitrile flexible solid electrolyte membrane at LiCoO with different lithium salt and succinonitrile contents reinforced by PVDF-HFP porous membranes prepared in examples 1, 2, 3, 4 of the present invention2/Li4Ti5O12Test chart of cycling stability at 25 ℃ in all-solid-state battery。
FIG. 7 is a P (VDF-HFP)/LiTFSI/succinonitrile flexible solid electrolyte membrane at LiCoO with different lithium salt and succinonitrile contents reinforced by PVDF-HFP porous membranes prepared in examples 1, 2, 3, 4 of the present invention2/Li4Ti5O12Test pattern of cycling stability at-5 ℃ in all-solid-state batteries.
FIG. 8 is a schematic structural view of a polymer plastocrystallized solid electrolyte membrane reinforced by a porous membrane according to an exemplary embodiment of the present invention.
Detailed Description
In view of the deficiencies in the prior art, the inventors of the present invention have made extensive studies and extensive practices to provide technical solutions of the present invention. The technical solution, its implementation and principles, etc. will be further explained as follows.
Based on the above background research, the inventors of the present invention have prepared a flexible polymer-plastic crystal solid electrolyte membrane with high low-temperature conductivity and high voltage resistance reinforced by a porous membrane as a supporting framework by increasing the content of lithium salt and reducing the content of plastic crystal compound.
An aspect of an embodiment of the present invention provides a porous membrane-reinforced polymer-plastocrystalline solid electrolyte membrane, including: the solid electrolyte membrane comprises a supporting layer and a polymer-plastic crystal solid electrolyte layer, wherein the supporting layer comprises a porous membrane, and the polymer-plastic crystal solid electrolyte layer is covered on the surface of the porous membrane; wherein the porous membrane has a continuous three-dimensional network structure; the polymer-plastic crystal solid electrolyte layer contains three components of a polymer, a lithium salt and a plastic crystal compound; and the high voltage resistance and the low temperature ionic conductivity of the polymer-plastic crystal solid electrolyte membrane can be improved by optimizing the proportion of the lithium salt, the plastic crystal compound and the polymer.
In some preferred embodiments, the porous membrane has a thickness of 1 to 100 μm, a porosity of 40 to 90%, a pore diameter of 0.01 to 3 μm, a linear diameter of 0.01 to 5 μm in a network structure, a thickness of 2 to 100 μm, a porosity of less than 10%, a pore diameter of 0.01 to 0.5 μm, good electrochemical stability, and a conductivity of up to 25 ℃ of at most 0.01 to 0.5 μm10-3Scm-1At-20 ℃ the conductivity is at most 10-4Scm-1The conductivity can reach 10 at-5 deg.C-4Scm-1。
In some preferred embodiments, one or both of the opposite surfaces of the porous membrane is coated with the polymer-plastocrystalline solid electrolyte layer.
Preferably, the polymer-plastic crystal solid electrolyte is coated on the two opposite side surfaces of the porous membrane.
Further, the porous membrane has a thickness of 1 to 50 μm, a porosity of 40 to 90%, a pore diameter of 0.01 to 3 μm, and a linear diameter of 0.01 to 5 μm in a network structure.
In some preferred embodiments, the porous membrane comprises an organic porous membrane and/or an inorganic porous membrane.
Preferably, the inorganic porous film includes an aluminum oxide film.
Preferably, the organic porous membrane includes any one or a combination of two or more of a polyolefin porous membrane, a polyvinylidene fluoride porous membrane, a polyester fiber porous membrane, a polyimide porous membrane, a polyacrylonitrile porous membrane, a nylon porous membrane, a cellulose membrane, and a glass fiber membrane, but is not limited thereto.
In some preferred embodiments, the polymer-plastocrystalline solid electrolyte layer consists essentially of a polymer, an inorganic lithium salt, and a plastocrystalline compound.
Preferably, the weight percentages of the polymer, the inorganic lithium salt and the plastic crystal compound in the electrolyte membrane are respectively as follows: 10-30 wt% of polymer, 20-60 wt% of inorganic lithium salt and 20-60 wt% of plastic crystal compound. By increasing the content of lithium salt and reducing the content of plastic crystal compound, the electrochemical stability of the electrolyte membrane is gradually improved, the ionic conductivity at low temperature is gradually increased, and the maximum ionic conductivity of the electrolyte membrane is 10 at 25 DEG C-3Scm-1At-20 ℃ the conductivity is at most 10- 4S/cm。。
Preferably, the polymer includes any one or a combination of two or more of polyethylene oxide, polyvinylidene fluoride, polymethacrylate, polydiacrylate, polyacrylonitrile, copolymer P (VDF-HFP) of vinylidene fluoride and hexafluoropropylene, polyvinyl alcohol, and polycarbonate, but is not limited thereto.
Preferably, the inorganic lithium salt includes LiPF6、LiClO4、LiBF4、LiAsF6、LiCF3SO3、LiN(CF3SO3)2And LiN (C)2F5SO3)2Any one or a combination of two or more of them, but not limited thereto, such as LiTFSI.
Preferably, the plastic crystal compound comprises a non-ionic plastic crystal material and/or an ionic plastic crystal material.
Further, the non-ionic plastic crystal material comprises succinonitrile.
Further, the anion contained in the ionic plastic crystal material comprises PF6 -、ClO4 -、BF4 -、AsF6 -、CF3SO3 -、N(CF3SO3)2 -And N (C)2F5SO3)2 -Any one or a combination of two or more of them, but not limited thereto.
In some preferred embodiments, if the plastic crystal compound is a non-ionic plastic crystal material, the ionic plastic crystal material contains the same anion as the anion contained in the inorganic lithium salt.
Another aspect of an embodiment of the present invention provides a method for preparing a polymer-plastocrystallized solid electrolyte membrane reinforced by a porous membrane, including:
uniformly mixing a polymer, an inorganic lithium salt and a plastic crystal compound in a low-boiling point solvent to form a homogeneous solution;
and applying the homogeneous solution to the surface of the porous membrane, removing the solvent, and then performing vacuum drying to obtain the polymer-plastic crystal solid electrolyte membrane reinforced by the porous membrane.
Further, in some more specific embodiments, the porous separator reinforced polymer-plastic crystal solid electrolyte membrane can be prepared by using a porous membrane as a supporting framework, coating homogeneous solutions of a polymer, an inorganic lithium salt and a plastic crystal compound on two sides of the porous membrane, and drying in vacuum.
In some preferred embodiments, the weight percentages of the polymer, the inorganic lithium salt and the plastic crystal compound in the homogeneous solution are as follows: 10-30 wt% of polymer, 20-60 wt% of inorganic lithium salt and 20-60 wt% of plastic crystal compound.
Further, the solvent is preferably an organic solvent.
Further, the organic solvent includes any one or a combination of two or more of acetone, tetrahydrofuran, N-methylpyrrolidone, dimethyl sulfoxide, N-dimethylformamide, and N, N-dimethylacetamide, without being limited thereto.
In some preferred embodiments, the mass ratio of the polymer to the organic solvent is 1: 5 to 50.
In some more specific embodiments, the preparation method specifically comprises:
(1) uniformly dispersing inorganic lithium salt and a plastic crystal compound in a low-boiling-point organic solvent to form a uniform dispersion system;
(2) dissolving a polymer in the homogeneous dispersion to form the homogeneous solution;
(3) pouring the homogeneous solution onto one or two surfaces of the porous membrane subjected to drying and water removal treatment, and evaporating to remove the organic solvent in the porous membrane in a protective atmosphere;
(4) and (3) carrying out vacuum drying on the porous membrane with the polymer plastic crystal electrolyte coated on the surfaces of the two sides, thereby obtaining the flexible polymer-plastic crystal electrolyte enhanced by the porous membrane.
Preferably, the protective atmosphere is dry air or an inert gas atmosphere.
Preferably, the vacuum drying temperature is 20-80 ℃.
In some more specific embodiments, the preparation method may include:
1) dissolving inorganic lithium salt and plastic crystal compound in low boiling point organic solvent, stirring to disperse homogeneously.
2) The polymer particles were added to the above solution and stirred to dissolve completely.
3) The porous membrane was dried under vacuum at 80 ℃ to remove water.
4) And (3) putting the dried porous membrane on a stainless steel grinding tool, pouring the mixed solution on the porous membrane, and evaporating the solvent under the protection of inert gas. After the solvent is volatilized, the other side of the porous membrane is covered with a layer of polymer plastic crystal electrolyte in the same operation, and finally vacuum drying is carried out within the range of 20-80 ℃.
Wherein, the thickness of the flexible polymer-plastic crystal solid electrolyte membrane reinforced by the porous membrane obtained in the embodiment is 2-100 μm, the porosity is lower than 10%, the pore diameter is 0.01-0.5 μm, and the conductivity is 10 at the maximum at 25 DEG C-3Scm-1At-20 ℃ the conductivity is at most 10-4S/cm。。
Preferably, the porous membrane has a continuous three-dimensional network structure, the porous membrane has a thickness of 1 to 100 μm, a porosity of 40 to 90%, a pore diameter of 0.01 to 3 μm, and a linear diameter of 0.01 to 5 μm in the network structure.
Further, the porous membrane may be an organic porous membrane or an inorganic porous membrane such as a polyolefin porous membrane, a polyvinylidene fluoride porous membrane, a polyester fiber porous membrane, a polyimide porous membrane, a polyacrylonitrile porous membrane, a nylon porous membrane, a cellulose membrane, a glass fiber membrane, an alumina membrane, or the like, but is not limited thereto.
Further, the polymer may be any one or more of polyethylene oxide, polyvinylidene fluoride, polymethacrylate, polydiacrylate, polyacrylonitrile, copolymer P (VDF-HFP) of vinylidene fluoride and hexafluoropropylene, polyvinyl alcohol, and polycarbonate, but is not limited thereto.
Further, the inorganic lithium salt may be LiPF6、LiClO4、LiBF4、LiAsF6，LiCF3SO3、LiN(CF3SO3)2Or LiN (C)2F5SO3)2Without being limited thereto, such as LiTFSI.
Furthermore, the plastic crystal compound can be non-ionic plastic crystal material succinonitrile or the anion is PF6 -、ClO4 -、BF4 -、AsF6 -、CF3SO3 -、N(CF3SO3)2 -Or N (C)2F5SO3)2 -Any one or more of the ionic plastic crystal materials in (2) are not limited.
In some preferred embodiments, if the plastic crystal compound is an ionic plastic crystal material, the ionic plastic crystal material contains the same anion as the anion contained in the inorganic lithium salt.
In another aspect of the embodiments of the present invention, there is also provided a use of the porous membrane-reinforced polymer-plastic crystal solid electrolyte membrane or the porous membrane-reinforced polymer-plastic crystal solid electrolyte membrane prepared by any one of the aforementioned methods for preparing a lithium ion battery.
Further, the lithium ion battery may include, but is not limited to, an all solid-state lithium ion battery.
The invention adopts the porous membrane as a support framework to support the polymer plastic crystal solid electrolyte membrane, and the prepared high-voltage-resistant plastic crystal solid electrolyte membrane has the conductivity of 10 at the maximum at 25 DEG C-3Scm-1At-20 ℃ the conductivity is at most 10-4Scm-1The polymer solid electrolyte membrane has good mechanical property and practical value. The electrolyte membrane can overcome the defects that the traditional gel polymer electrolyte is easy to leak liquid, the polymer electrolyte has lower room-temperature conductivity, the plastic crystal electrolyte is fragile and cannot resist high voltage, and the like, has the advantages of mechanical property of a porous membrane, high room-temperature ionic conductivity of the plastic crystal electrolyte and the like, can improve the mechanical property of the membrane and inhibit lithium crystal, and can remarkably improve the cycling stability of a battery when being used in an all-solid-state lithium ion battery.
For example, the porous membrane reinforced flexible polymer-plastocrystalline solid electrolyte membrane of the present invention is applied to LiCoO2/Li4Ti5O12All-solid-state batteryWhen the battery was tested for charge and discharge cycle stability, it was found that it had about 120mAhg at 0.1C rate at 25C-1Has a reversible charge-discharge capacity of about 85mAhg at a 0.1C rate at-5 DEG C-1And all exhibit good cycling stability.
The technical scheme of the invention is further explained by combining the attached drawings, the embodiment and the comparative example.
Example 1 this example relates to a process for preparing a PVDF-HFP porous membrane reinforced flexible (PVDF-HFP)/LiTFSI/succinonitrile solid electrolyte membrane having a lithium salt content of 20 wt%, comprising:
weighing 2g of lithium salt LiTFSI and 6g of plastic crystal compound succinonitrile, adding the lithium salt LiTFSI and the plastic crystal compound succinonitrile into N, N-dimethylformamide, adding 2g of polymer (PVDF-HFP) after the lithium salt LiTFSI and the plastic crystal compound succinonitrile are completely dissolved, stirring overnight to completely dissolve and uniformly disperse the polymer, drying a PVDF-HFP porous membrane with the thickness of 10 mu m at 80 ℃, putting the PVDF-HFP porous membrane into a stainless steel grinding tool with the same size, respectively pouring the mixed solution onto the PVDF-HFP porous membrane, evaporating the solvent under the protection of Ar gas, and drying the PVDF-HFP porous membrane in a vacuum drying box at 50 ℃ for 2 days to prepare the PVDF-HFP/LiTFSI/succinonitrile solid electrolyte membrane (named as PPCE-1) of the PVDF-HFP reinforced porous membrane with the thickness of 100 mu m, wherein the mass percentages are respectively 20 wt% PVDF-HFP, 20 wt% LiTFSI.
Example 2 this example relates to a process for preparing a PVDF-HFP porous membrane reinforced flexible (PVDF-HFP)/LiTFSI/succinonitrile solid electrolyte membrane having a lithium salt content of 30wt%, comprising:
weighing 3g of lithium salt LiTFSI and 5g of succinonitrile, adding the lithium salt LiTFSI and the succinonitrile into N, N-dimethylformamide, adding 2g of polymer (PVDF-HFP) after the lithium salt LiTFSI and the succinonitrile are completely dissolved, stirring overnight to completely dissolve and uniformly disperse the polymer, drying a PVDF-HFP porous membrane with the thickness of 10 mu m at 80 ℃, putting the dried PVDF-HFP porous membrane into a stainless steel grinding tool with the same size, pouring the mixed solution on the PVDF-HFP porous membrane respectively, evaporating the solvent under the protection of Ar gas, and drying the PVDF-HFP porous membrane in a vacuum drying oven at 50 ℃ for 2 days to prepare a PVDF-HFP/LiTFSI/succinonitrile solid electrolyte membrane (named as PPCE-2) reinforced by the PVDF-HFP porous membrane with the thickness of 100 mu m, wherein the mass percentages are respectively 20 wt% of PVDF-HFP, 30wt% of LiTFSI and.
Example 3 this example relates to a process for preparing a PVDF-HFP porous membrane reinforced flexible (PVDF-HFP)/LiTFSI/succinonitrile solid electrolyte membrane having a lithium salt content of 40 wt%, comprising:
weighing 4g of lithium salt LiTFSI and 4g of succinonitrile, adding the lithium salt LiTFSI and the succinonitrile into N, N-dimethylformamide, adding 2g of polymer (PVDF-HFP) after the lithium salt LiTFSI and the succinonitrile are completely dissolved, stirring overnight to completely dissolve and uniformly disperse the lithium salt LiTFSI and the succinonitrile, drying a PVDF-HFP porous membrane with the thickness of 10 mu m at 80 ℃, putting the dried PVDF-HFP porous membrane into a stainless steel grinding tool with the same size, pouring the mixed solution on the PVDF-HFP porous membrane respectively, evaporating the solvent under the protection of Ar gas, and drying the PVDF-HFP porous membrane in a vacuum drying box at 50 ℃ for 2 days to prepare a PVDF-HFP porous membrane reinforced (PVDF-HFP)/LiTFSI/succinonitrile solid electrolyte membrane (named as PPCE-3) with the thickness of 100 mu m, wherein the mass percentages are respectively 20 wt% PVDF-HFP, 40 wt% Li.
Example 4 this example relates to a process for preparing a PVDF-HFP porous membrane reinforced flexible (PVDF-HFP)/LiTFSI/succinonitrile solid electrolyte membrane having a lithium salt content of 60wt%, comprising:
weighing 6g of lithium salt LiTFSI and 2g of succinonitrile, adding the lithium salt LiTFSI and the succinonitrile into N, N-dimethylformamide, adding 2g of polymer (PVDF-HFP) after the lithium salt LiTFSI and the succinonitrile are completely dissolved, stirring overnight to completely dissolve and uniformly disperse the lithium salt LiTFSI and the succinonitrile, drying a PVDF-HFP porous membrane with the thickness of 10 mu m at 80 ℃, putting the dried PVDF-HFP porous membrane into a stainless steel grinding tool with the same size, pouring the mixed solution on the PVDF-HFP porous membrane respectively, evaporating the solvent under the protection of Ar gas, and drying the PVDF-HFP porous membrane in a vacuum drying box at 50 ℃ for 2 days to prepare a PVDF-HFP porous membrane reinforced (PVDF-HFP)/LiTFSI/succinonitrile solid electrolyte membrane (named as PPCE-4) with the thickness of 100 mu m, wherein the mass percentages are respectively 20 wt% PVDF-HFP, 60wt% Li.
The linear sweep voltammetry curves of the four solid electrolyte membranes described above were tested by an electrochemical workstation and the results are shown in fig. 4, where the electrochemical stability of the PPCE membrane gradually improved with increasing lithium salt content.
The ionic conductivities of the four solid electrolyte membranes described above at different temperatures were measured using an electrochemical workstation and the results are shown in fig. 5, where the percentages are mass percentages of the different plastic crystals. As can be seen, PPCE-2 showed higher low temperature conductivity.
Application of four electrolyte membranes to LiCoO2(LCO)/Li4Ti5O12(LTO) all solid state battery, the electrochemical performance of the battery was tested at 25 ℃ and-5 ℃ over a potential window of 1.5-3.0V. The test result shows that: all four films had about 120mAhg at 0.1C magnification at 25 deg.C-1The capacity remained at 99% after 50 cycles, and the results are shown in fig. 6. The four films with different conductivities at-5 ℃ show obvious difference, and PPCE-1 and PPCE-2 have higher reversible charge-discharge capacity at 0.1C multiplying power, about 85mAhg-1While the PPCE-3 capacity is only about 60mAhg-1PPCE-4 capacity of only 5mAhg-1The results are shown in FIG. 7.
SEM photographs and physical images of the porous membranes and the solid electrolyte membranes obtained in examples 1 to 3 are similar to those of FIGS. 1 to 3.
Comparative example 1 this example relates to a process for preparing a non-porous membrane supported (PVDF-HFP)/LiTFSI/succinonitrile solid electrolyte membrane having a lithium salt content of 40 wt%, comprising:
weighing 4g of lithium salt LiTFSI and 4g of succinonitrile, adding the lithium salt LiTFSI and the succinonitrile into N, N-dimethylformamide, adding 2g of polymer (PVDF-HFP) after the lithium salt LiTFSI and the succinonitrile are completely dissolved, stirring overnight to completely dissolve and uniformly disperse the lithium salt LiTFSI and the succinonitrile, pouring the mixed solution into a stainless steel grinding tool, evaporating the solvent under the protection of Ar gas, and drying the mixed solution in a vacuum drying oven at 50 ℃ for 2 days to prepare the PVDF-HFP porous membrane reinforced (PVDF-HFP)/LiTFSI/succinonitrile solid electrolyte membrane (named PPCE-3'), wherein the mass percentages are 20 wt% of PVDF-HFP, 40 wt% of LiTFSI and 40 wt% of SN respectively.
Comparing the PPCE-3 film obtained in example 3 with the PPCE-3 ' film obtained in comparative example 1, it was found that the PPCE-3 ' film prepared without the support film was able to have a film thickness of more than 200 μm when it was self-supporting, while the mechanical properties were poor and brittle when the thickness of PPCE-3 ' was less than 100. mu.m.
EXAMPLE 5 this example relates toAlumina porous membrane reinforced polyethylene oxide (PEO)/LiPF with lithium salt content of 50 wt%6/PF6 -A process for preparing a solid electrolyte membrane, comprising:
5g of lithium salt LiPF are weighed62g of PF-containing6 -Adding the ionic plastic crystal material into N, N-dimethylacetamide, adding 3g of polymer PEO after the ionic plastic crystal material is completely dissolved, stirring overnight to completely dissolve and uniformly disperse the polymer PEO, drying an alumina porous membrane at 80 ℃, putting the alumina porous membrane into a stainless steel grinding tool, pouring the mixed solution on the porous membrane, evaporating the solvent under the protection of Ar gas, and drying the alumina porous membrane in a vacuum drying oven at 20 ℃ for 3 days to prepare the PEO/LiPF reinforced by the alumina porous membrane6/PF6 -The solid electrolyte membrane comprises 30wt% of PEO and 50 wt% of LiPF in percentage by mass6、20wt％PF6 -And (3) a plastic crystal compound.
The foregoing solid electrolyte membrane was tested for ionic conductivity at different temperatures using an electrochemical workstation, and the results can be seen in fig. 5.
In LCO/LTO all-solid-state batteries for solid electrolyte membranes obtained in this example, PEO/LiPF reinforced based on alumina porous membrane was found6/PF6 -The cell of the solid electrolyte membrane showed good cycle stability and high capacity exertion at low temperature, and the results can be referred to fig. 6 and 7.
SEM photographs and physical images of the porous membrane and the solid electrolyte membrane obtained in this example are similar to those of fig. 1 to 3.
Example 6 this example relates to polyvinylidene fluoride (PVDF)/LiClO reinforced with a Glass Fiber (GF) porous membrane having a lithium salt content of 60wt%4/ClO4 -A process for preparing a solid electrolyte membrane, comprising:
6g of lithium salt LiClO were weighed43g of ClO-containing compound4 -Adding the ionic plastic crystal material into acetone, adding 1g of PVDF polymer after the ionic plastic crystal material is completely dissolved, stirring overnight to completely dissolve and uniformly disperse the PVDF polymer, drying the GF porous membrane at 80 ℃, putting the GF porous membrane into a stainless steel grinding tool, pouring the mixed solution on the porous membrane, and protecting the porous membrane with Ar gasEvaporating the solvent, and drying in a vacuum drying oven at 80 deg.C for 2 days to obtain PVDF/LiClO reinforced by GF porous membrane4/ClO4 -A solid electrolyte membrane, wherein the mass percentages are respectively 10 wt% PVDF and 60wt% LiClO4、30wt％ClO4 -。
The foregoing solid electrolyte membrane was tested for ionic conductivity at different temperatures using an electrochemical workstation, and the results can be seen in fig. 5.
The solid electrolyte membrane obtained in this example was used in an LCO/LTO all-solid-state battery, and as a result, PVDF/LiClO reinforced with a porous membrane based on a Glass Fiber (GF) porous membrane was found4/ClO4 -The cell of the solid electrolyte membrane has good cycle stability and high capacity exertion at low temperature, and the results can be referred to fig. 6 and 7.
SEM photographs and physical images of the porous membrane and the solid electrolyte membrane obtained in this example are similar to those of fig. 1 to 3.
Example 7 this example relates to a polyimide porous membrane reinforced Polymethylmethacrylate (PMMA)/LiBF having a lithium salt content of 60wt%4/BF4 -A process for preparing a solid electrolyte membrane, comprising:
6g of lithium salt LiBF are weighed42g of BF containing4 -Adding the ionic plastic crystal material into N-methylpyrrolidone, adding 2g of polymer PMMA after the ionic plastic crystal material is completely dissolved, stirring overnight to completely dissolve and uniformly disperse the polymer PMMA, drying the polyimide porous membrane at 80 ℃, putting the polyimide porous membrane into a stainless steel grinding tool, pouring the mixed solution on the porous membrane, evaporating the solvent under the protection of Ar gas, and drying the polyimide porous membrane in a vacuum drying oven at 50 ℃ for 2 days to prepare the polyimide porous membrane reinforced PMMA/LiBF4/BF4 -A solid electrolyte membrane, wherein the mass percentages are respectively 20 wt% PMMA/60 wt% LiBF4/20wt％BF4 -And (3) a plastic crystal compound.
The foregoing solid electrolyte membrane was tested for ionic conductivity at different temperatures using an electrochemical workstation, and the results can be seen in fig. 5.
LCO/LTO all-solid-state battery for solid electrolyte membrane obtained in this exampleIn the cell, it was found that a polyimide porous membrane-based reinforced PMMA/LiBF was obtained4/BF4 -The cell of the solid electrolyte membrane has good cycle stability and high capacity exertion at low temperature, and the results can be referred to fig. 6 and 7.
SEM photographs and physical images of the porous membrane and the solid electrolyte membrane obtained in this example are similar to those of fig. 1 to 3.
Example 8 this example relates to a nylon porous membrane reinforced Polycarbonate (PC)/LiCF having a lithium salt content of 50 wt%3SO3/CF3SO3 -A process for preparing a solid electrolyte membrane, comprising:
5g of lithium salt LiCF were weighed3SO33g of a catalyst containing CF3SO3 -Adding the ionic plastic crystal material into tetrahydrofuran, adding 2g of polymer PC after the ionic plastic crystal material is completely dissolved, stirring overnight to completely dissolve and uniformly disperse the polymer PC, drying a nylon porous membrane at 80 ℃, putting the nylon porous membrane into a stainless steel grinding tool, pouring the mixed solution onto the porous membrane, evaporating the solvent under the protection of Ar gas, drying the nylon porous membrane in a vacuum drying oven at 70 ℃ for 2 days, and preparing the PC/LiCF reinforced by the nylon porous membrane3SO3/CF3SO3 -A solid electrolyte membrane, wherein the mass percentages are respectively 20 wt% of PC and 50 wt% of LiBF4、30wt％CF3SO3 -And (3) a plastic crystal compound.
The foregoing solid electrolyte membrane was tested for ionic conductivity at different temperatures using an electrochemical workstation, and the results can be seen in fig. 5.
In LCO/LTO all-solid-state batteries for solid electrolyte membranes obtained in the present example, PC/LiCF reinforced with a nylon-based porous membrane was found3SO3/CF3SO3 -The cell of the solid electrolyte membrane has good cycle stability and high capacity exertion at low temperature, and the results can be referred to fig. 6 and 7.
SEM photographs and physical images of the porous membrane and the solid electrolyte membrane obtained in this example are similar to those of fig. 1 to 3.
As can be seen from the experimental results, examples 1 to 8 of the present inventionThe flexible polymer-plastic crystal solid electrolyte membrane for reinforcing the porous membrane can improve the mechanical property of the polymer plastic crystal solid electrolyte membrane by arranging the porous membrane which plays the role of a supporting framework on the polymer plastic crystal solid electrolyte layer; by optimizing the content of the lithium salt and the succinonitrile, the electrochemical stability and the ionic conductivity at low temperature of the solid electrolyte membrane can be improved. The flexible polymer plastic crystal solid electrolyte membrane with enhanced porous membrane obtained under the optimized proportion of the polymer, the lithium salt and the plastic crystal compound has high voltage resistance and higher low-temperature conductivity (the temperature of minus 20 ℃ can reach 10)-4Scm-1) And better mechanical property, which is applied to LCO/LTO all-solid-state batteries, the potential window of 1.5-3.0V is charged and discharged, and the battery can play a role of about 120mAhg at 25 ℃ and 0.1C multiplying power-1The reversible charge-discharge capacity of (2) exhibits about 85mAhg at-5 ℃ and 0.1C rate-1The reversible charge-discharge capacity of the lithium ion battery is simultaneously the best cycle stability, and the capacity retention rate after 50 cycles is 99%.
In addition, the present inventors have also conducted experiments with other raw materials and conditions and the like listed in the present specification by referring to the manner of examples 1 to 8, for example, a polyvinylidene fluoride porous film, a polyacrylonitrile porous film, a cellulose film instead of polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP), an aluminum oxide film, a Glass Fiber (GF), a polyimide porous film, a nylon porous film in examples 1 to 8, polyacrylonitrile, polyacrylate, polyvinyl alcohol instead of polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP), polyethylene oxide, polyvinylidene fluoride, polymethacrylate, and polycarbonate in examples 1 to 8, LiAsF6And LiN (C)2F5SO3)2Instead of LiN (CF) in examples 1 to 73SO3)2、LiPF6、LiClO4、LiBF4And LiCF3SO3With AsF6 -、N(CF3SO3)2 -And N (C)2F5SO3)2 -Instead of succinonitrile and PF in examples 1 to 66 -、ClO4 -、BF4 -And CF3SO3 -Dimethyl sulfoxide is used for replacing N, N-dimethylformamide, N-dimethylacetone, N-methylpyrrolidone and tetrahydrofuran in examples 1-8, and the porous membrane reinforced polymer plastic crystal solid electrolyte membrane which is high in conductivity, excellent in mechanical property and capable of remarkably improving the cycling stability of the battery is prepared.
It should be understood that the above-mentioned embodiments are merely illustrative of the technical concepts and features of the present invention, which are intended to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and therefore, the protection scope of the present invention is not limited thereby. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (18)
1. A porous membrane reinforced polymer-plastocrystalline solid electrolyte membrane, comprising: the solid electrolyte membrane comprises a supporting layer and a polymer-plastic crystal solid electrolyte layer, wherein the supporting layer comprises a porous membrane, and the polymer-plastic crystal solid electrolyte layer is covered on the surface of the porous membrane; the porous membrane has a continuous three-dimensional network structure, the thickness of the porous membrane is 1-100 mu m, the porosity is 40-90%, the pore size is 0.01-3 mu m, and the line diameter in the continuous three-dimensional network structure is 0.01-5 mu m; the polymer-plastic crystal solid electrolyte layer is mainly formed by a polymer, an inorganic lithium salt and a plastic crystal compound, and the mass percentage of the polymer, the inorganic lithium salt and the plastic crystal compound in the polymer-plastic crystal solid electrolyte membrane is (10-30%): (20-60%): (20% -60%), the plastic crystal compound is an ionic plastic crystal material, and anions contained in the ionic plastic crystal material are the same as those contained in the inorganic lithium salt;
and the thickness of the polymer-plastic crystal solid electrolyte membrane reinforced by the porous membrane is 2-100 mu m, the porosity is lower than 10%, the pore size is 0.01-0.5 mu m, and the highest conductivity is 10 at 25 DEG C-3 Scm-1At-20 ℃ the conductivity is at most 10-4 Scm-1。
2. The porous membrane-reinforced polymer-plastic crystal solid electrolyte membrane according to claim 1, characterized in that: the thickness of the porous membrane is 1-50 mu m, the porosity is 40-90%, the pore size is 0.01-3 mu m, and the line diameter in the network structure is 0.01-5 mu m.
3. The porous membrane-reinforced polymer-plastic crystal solid electrolyte membrane according to claim 1, characterized in that: and one side surface or two opposite side surfaces of the porous membrane is/are coated with the polymer plastic-crystal solid electrolyte layer.
4. The porous membrane-reinforced polymer-plastic crystalline solid electrolyte membrane according to any one of claims 1 to 3, characterized in that: the porous membrane is selected from an organic porous membrane and/or an inorganic porous membrane.
5. The porous membrane-reinforced polymer-plastic crystal solid electrolyte membrane according to claim 4, characterized in that: the inorganic porous membrane is an aluminum oxide membrane.
6. The porous membrane-reinforced polymer-plastic crystal solid electrolyte membrane according to claim 4, characterized in that: the organic porous membrane is selected from one or the combination of more than two of polyolefin porous membrane, polyvinylidene fluoride porous membrane, polyester fiber porous membrane, polyimide porous membrane, polyacrylonitrile porous membrane, nylon porous membrane, cellulose membrane and glass fiber membrane.
7. The porous membrane-reinforced polymer-plastic crystal solid electrolyte membrane according to claim 1, characterized in that: the polymer is selected from one or the combination of more than two of polyethylene oxide, polyvinylidene fluoride, polymethacrylate, polydiacrylate, polyacrylonitrile, copolymer of vinylidene fluoride and hexafluoropropylene, polyvinyl alcohol and polycarbonate.
8. The porous membrane-reinforced polymer-plastic crystal solid electrolyte membrane according to claim 1, characterized in that: the inorganic lithium salt is selected from LiPF6、LiClO4、LiBF4、LiAsF6、LiCF3SO3、LiN(CF3SO3)2And LiN (C)2F5SO3)2Any one or a combination of two or more of them.
9. The porous membrane-reinforced polymer-plastic crystal solid electrolyte membrane according to claim 1, characterized in that: the anion contained in the ionic plastic crystal material comprises PF6 -、ClO4 -、BF4 -、AsF6 -、CF3SO3 -、N(CF3SO3)2 -And N (C)2F5SO3)2 -Any one or a combination of two or more of them.
10. The method for producing a porous membrane-reinforced polymer-plastic crystal solid electrolyte membrane according to any one of claims 1 to 9, comprising:
uniformly mixing a polymer, an inorganic lithium salt and an ionic plastic crystal compound in a solvent to form a homogeneous solution;
and applying the homogeneous solution to the surface of the porous membrane, removing the solvent, and then performing vacuum drying to obtain the polymer-plastic crystal solid electrolyte membrane reinforced by the porous membrane.
11. The method of claim 10, wherein the homogeneous solution comprises, in weight percent: 10-30 wt% of polymer, 20-60 wt% of inorganic lithium salt and 20-60 wt% of plastic crystal compound.
12. The method of manufacturing according to claim 10, wherein: the solvent is an organic solvent, and the organic solvent is selected from any one or the combination of more than two of acetone, N-methyl pyrrolidone, tetrahydrofuran, dimethyl sulfoxide, N-dimethylformamide and N, N-dimethylacetamide.
13. The method of manufacturing according to claim 10, wherein: the mass ratio of the polymer to the solvent is 1: 5 to 50.
14. The method according to claim 10, comprising:
(1) uniformly dispersing inorganic lithium salt and ionic plastic crystal compound in an organic solvent with low boiling point to form a uniform dispersion system;
(2) dissolving a polymer in the homogeneous dispersion to form the homogeneous solution;
(3) pouring the homogeneous solution onto one or two surfaces of the porous membrane subjected to drying and water removal treatment, and volatilizing to remove the organic solvent at room temperature in a protective atmosphere;
(4) and (3) drying the porous membrane coated with the polymer-plastic crystal electrolyte on one side or two sides in vacuum to obtain the polymer-plastic crystal solid electrolyte membrane reinforced by the porous membrane.
15. The method of claim 14, wherein: the protective atmosphere is dry air or inert gas atmosphere.
16. The method of claim 14, wherein: the temperature of vacuum drying is 20-80 ℃.
17. Use of the porous membrane reinforced polymer-plastocrystalline solid electrolyte membrane according to any one of claims 1 to 9 in the preparation of a lithium ion battery.
18. Use according to claim 17, characterized in that: the lithium ion battery is an all-solid-state lithium ion battery.
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