CN111525187B - Sulfonated polyvinyl alcohol solid polymer electrolyte membrane for lithium battery and preparation method thereof - Google Patents
Sulfonated polyvinyl alcohol solid polymer electrolyte membrane for lithium battery and preparation method thereof Download PDFInfo
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- CN111525187B CN111525187B CN202010272862.5A CN202010272862A CN111525187B CN 111525187 B CN111525187 B CN 111525187B CN 202010272862 A CN202010272862 A CN 202010272862A CN 111525187 B CN111525187 B CN 111525187B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
- C08F8/36—Sulfonation; Sulfation
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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
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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
- H01M10/058—Construction or manufacture
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention belongs to the field of polymer electrolytes, and particularly relates to a sulfonated polyvinyl alcohol solid polymer electrolyte membrane for a lithium battery and a preparation method thereof. Firstly, adding polyvinyl alcohol and sultone in proportion into an organic solvent, adding NaH after the polyvinyl alcohol and the sultone are completely dissolved, pouring a product into hydrochloric acid for standing after heating reaction, pouring the product into a lithium hydroxide aqueous solution for standing, washing the product to be neutral by deionized water, and drying. And dissolving the product and lithium bis (trifluoromethanesulfonyl) imide in an organic solvent according to a ratio, pouring the solution into a mold, and drying in vacuum to obtain the solid polymer electrolyte membrane. According to the polymer electrolyte membrane based on sulfonated polyvinyl alcohol, lithium ions are replaced on a polymer matrix by adopting a specific structural design, the electrolyte is a single-ion polymer electrolyte, anions are fixed on a polymer framework, only cations are allowed to migrate, and the ion migration number can be as high as 1.
Description
Technical Field
The invention belongs to the field of polymer electrolytes, relates to a solid electrolyte membrane, and particularly relates to a sulfonated polyvinyl alcohol solid polymer electrolyte membrane for a lithium battery and a preparation method thereof.
Background
Lithium ion batteries are widely used in portable electronic devices and electric vehicles due to their high energy density and long life. However, the leakage and volatilization of the liquid electrolyte easily cause fire, and some potential safety hazards exist. The substitution of solid electrolytes for liquid electrolytes to inhibit the growth of lithium dendrites is a fundamental approach to solving this safety problem.
From the practical point of view, an ideal polymer solid electrolyte should meet the following requirements: higher ionic conductivity; higher transference number of lithium ions; certain mechanical strength; the electrochemical window is wide; good chemical stability and thermal stability, etc.
Ionic conductivity and interfacial compatibility are currently two major challenges for solid state electrolytes in lithium battery applications. Recently, although ion conductivity of various inorganic solid electrolytes is comparable to that of liquid electrolytes, solid-solid interfaces have a larger interfacial resistance than solid-liquid interfaces due to insufficient contact, resulting in slow ion transfer. The interaction between the electrodes and the solid-state electrolyte and greater polarization of the battery. In addition, the volume change of the electrode during charge and discharge accelerates the interfacial contact between the electrode and the electrolyte. The interface problem is a problem that is difficult to solve with current solid electrolytes.
Disclosure of Invention
The object of the present invention is to overcome the disadvantages of the prior art by providing a solid polymer electrolyte membrane based on sulfonated polyvinyl alcohol.
In order to achieve the purpose, the invention adopts the technical scheme that: a polymer electrolyte membrane based on sulfonated polyvinyl alcohol, having the general structural formula:
wherein n =3 or 4.
The invention also aims to provide a preparation method based on the sulfonated polyvinyl alcohol, which comprises the following specific steps:
(1) adding polyvinyl alcohol and sultone into an organic solvent according to a certain proportion, adding a proper amount of NaH after the polyvinyl alcohol and the sultone are completely dissolved, and heating and reacting for 10 hours at 95 ℃. The obtained product is poured into 1mol/L hydrochloric acid and stands for 5 hours, the product is poured into lithium hydroxide aqueous solution and stands for 10 hours, the solution is washed to be neutral by deionized water and dried for 24 hours at 60 ℃.
Wherein the sulfolactone is 1, 3-propane sulfolactone or 1, 4-butane sulfolactone.
The organic solvent is absolute ethyl alcohol.
The molar ratio of hydroxyl groups to sultone in the polyvinyl alcohol is less than 4.
The molar ratio of NaH to sultone is 1: 1.
the concentration of the lithium hydroxide aqueous solution was 0.5 mol/L.
(2) And (2) dissolving the product obtained in the step (1) and lithium bis (trifluoromethanesulfonylimide) in an anhydrous organic solvent according to a certain proportion, pouring the solution into a mold, and carrying out vacuum drying at 60 ℃ for 24 hours to obtain the solid polymer electrolyte membrane.
Wherein the mass ratio of the lithium bistrifluoromethanesulfonimide to the sulfonated polyvinyl alcohol is 0.1: 1-0.4: 1.
the organic solvent is DMSO or DMF, and the experiment is carried out in a glove box.
Has the advantages that: due to the application of the technical scheme, compared with the prior art, the invention has the following advantages: according to the polymer electrolyte membrane based on sulfonated polyvinyl alcohol, lithium ions are replaced on a polymer matrix by adopting a specific structural design, the electrolyte is a single-ion polymer electrolyte, anions are fixed on a polymer framework, only cations are allowed to migrate, and the ion migration number can be as high as 1.
Detailed Description
The present invention is further described below with reference to examples, but is not limited thereto.
Example 1
The invention relates to a polymer electrolyte membrane based on sulfonated polyvinyl alcohol, which has the following structural general formula:
wherein n =3 or 4.
Through specific structural design, lithium ions are fixed on a polymer framework, and the problem of low transference number of the lithium ions in the traditional solid electrolyte is solved.
Example 1
The embodiment provides a polymer electrolyte membrane based on sulfonated polyvinyl alcohol and a preparation method thereof, and the preparation method comprises the following specific steps:
(1) dissolving 10.00g of polyvinyl alcohol and 4.00g of 1, 3-propane sultone in 100ml of absolute ethyl alcohol, adding 5.00g of sodium hydride, heating at 90 ℃ for reaction for 10 hours, pouring turbid liquid into hydrochloric acid aqueous solution with the concentration of 1mol/L, standing for 5 hours, precipitating and washing a polymer, pouring the polymer into 1mol/L excessive lithium hydroxide aqueous solution, stirring for reaction for 10 hours, washing a reaction product with deionized water, precipitating to be neutral, and drying at 60 ℃ for 24 hours to obtain sulfonated polyvinyl alcohol, wherein the structure of the sulfonated polyvinyl alcohol is shown as the following formula:
(2) and (2) dissolving 1.00g of the sulfonated polyvinyl alcohol product obtained in the step (1) and 0.40g of lithium bis (trifluoromethanesulfonylimide) in 20ml of anhydrous DMSO, pouring the solution on a mold, and performing vacuum drying at 60 ℃ for 24 hours to obtain the polymer electrolyte membrane.
The polymer electrolyte membrane, a positive electrode (lithium iron phosphate pole piece) and a negative electrode (metal lithium piece) are directly assembled into a button cell, and performance test is carried out: the electrical conductivity at room temperature was found to be 1.25X 10-5S/cm-1. In order to detect the application of the polymer electrolyte membrane in the all-solid-state lithium battery, the polymer electrolyte membrane is assembled into LiFePO4the/SPE/Li cells were tested for charge-discharge cycling at 60 ℃. The first discharge specific capacity of the battery is measured to be 115 mAh.g under the multiplying power of 0.1C-1。
Example 2
This example provides a sulfonated polyvinyl alcohol-based polymer electrolyte membrane and a method for preparing the same, which are substantially the same as in example 1, except that the mass of lithium bistrifluoromethanesulfonylimide in step (2) is 0.30 g. The polymer electrolyte membrane was measured to have an electrical conductivity of 1.12X 10 at room temperature-5S/cm-1. To examine the application of the polymer electrolyte membrane in all-solid-state batteries, it was assembled into LiFePO4the/SPE/Li cells were tested for charge-discharge cycling at 60 ℃. At 0.1CThe first discharge specific capacity of the battery measured under multiplying power is 105 mAh.g-1。
Example 3
This example provides a sulfonated polyvinyl alcohol-based polymer electrolyte and a method for preparing the same, which are substantially the same as in example 1, except that the mass of lithium bistrifluoromethanesulfonylimide in step (2) is 0.25 g. The polymer electrolyte membrane was measured to have a conductivity of 1.06X 10 at room temperature-5S/cm-1. To examine the application of the polymer electrolyte membrane in all-solid-state batteries, it was assembled into LiFePO4the/SPE/Li cells were tested for charge-discharge cycling at 60 ℃. The first discharge specific capacity of the battery is 102 mAh.g measured under the multiplying power of 0.1C-1。
Example 4
This example provides a sulfonated polyvinyl alcohol-based polymer electrolyte membrane and a method for preparing the same, which are substantially the same as in example 1, except that 1, 3-propane sultone is replaced with 1, 4-butane sultone in step (1). The polymer electrolyte membrane was measured to have an electrical conductivity of 1.28X 10 at room temperature-5S/cm-1. To examine the application of the polymer electrolyte membrane in all-solid-state batteries, it was assembled into LiFePO4the/SPE/Li cells were tested for charge-discharge cycling at 60 ℃. The first discharge specific capacity of the battery is 123 mAh.g measured at 0.1C multiplying power-1。
Example 5
This example provides a sulfonated polyvinyl alcohol-based polymer electrolyte membrane and a method for preparing the same, which are substantially the same as in example 1, except that the mass of lithium bistrifluoromethanesulfonylimide in step (2) is 0.10 g. The polymer electrolyte membrane was measured to have an electrical conductivity of 1.15X 10 at room temperature-5S/cm-1. To examine the application of the polymer electrolyte membrane in all-solid-state batteries, it was assembled into LiFePO4the/SPE/Li cells were tested for charge-discharge cycling at 60 ℃. The first discharge specific capacity of the battery is 65 mAh.g measured under the multiplying power of 0.1C-1。
Example 6
This example provides a sulfonated polyvinyl alcohol-based polymer electrolyte membrane and a method for preparing the same, which can be used in a fuel cellExample 4 is essentially the same except that 1, 4-butane sultone was added in step (1) in a mass of 1.5g and the molar ratio of NaH to sultone was 1: 1. the polymer electrolyte membrane was measured to have an electrical conductivity of 1.02X 10 at room temperature-5S/cm-1. To examine the application of the polymer electrolyte membrane in all-solid-state batteries, it was assembled into LiFePO4the/SPE/Li cells were tested for charge-discharge cycling at 60 ℃. The first discharge specific capacity of the battery is 113 mAh.g measured at the multiplying power of 0.1C-1。
Example 7
This example provides a sulfonated polyvinyl alcohol-based polymer electrolyte membrane and a method for preparing the same, which is substantially the same as example 4, except that the mass of 1, 4-butane sultone added in step (1) is 6.8g, and the molar ratio of NaH to sultone is 1: 1. the polymer electrolyte membrane was measured to have an electrical conductivity of 1.43X 10 at room temperature-5S/cm-1. To examine the application of the polymer electrolyte membrane in all-solid-state batteries, it was assembled into LiFePO4the/SPE/Li cells were tested for charge-discharge cycling at 60 ℃. The first discharge specific capacity of the battery is 60 mAh.g measured under the multiplying power of 0.1C-1. This phenomenon occurs because the degree of sulfonation is so high that the film-forming property becomes poor, and the film is easily broken to cause a micro short circuit of the battery.
Comparative example 1
This example provides a method for preparing a polymer electrolyte membrane, which comprises preparing a polymer electrolyte membrane from 1.0g of polyvinyl alcohol and 0.40g of lithium bistrifluoromethanesulfonimide. The polymer electrolyte membrane was measured to have an electrical conductivity of 1.65X 10 at room temperature-8S/cm-1. It was assembled into LiFePO4the/SPE/Li cells were tested for charge-discharge cycling at 60 ℃. The first discharge specific capacity of the battery is 5 mAh.g measured under the multiplying power of 0.1C-1. The reason for this is that lithium salt cannot be delithiated in unmodified polyvinyl alcohol-based films, so that lithium ions cannot freely migrate inside the battery, resulting in extremely low specific discharge capacity.
Comparative example 2
This example provides a method of preparing a polymer electrolyte membrane,
step (1) 10.00g of polyvinyl alcohol and 4.00g of 1, 3-propane sultone are dissolved in 100ml of absolute ethyl alcohol, 5.00g of sodium hydride is added, the mixture is heated and reacted for 10 hours at 90 ℃, and then the polymer precipitate is washed by deionized water to be neutral and dried for 24 hours at 60 ℃ to obtain a product.
And (2) preparing 1.0g of sulfonated polyvinyl alcohol and 0.40g of lithium bistrifluoromethanesulfonimide into a polymer electrolyte membrane.
The polymer electrolyte membrane was measured to have an electrical conductivity of 1.09X 10 at room temperature-5S/cm-1. It was assembled into LiFePO4the/SPE/Li cells were tested for charge-discharge cycling at 60 ℃. The first discharge specific capacity of the battery is measured to be 64 mAh.g under the multiplying power of 0.1C-1. The reason for this phenomenon is that lithium ions are not substituted on the main chain of the polymer, sodium ions exist, and the amount of freely moving lithium ions is too small, so that the specific discharge capacity of the lithium battery is low.
Comparative example 3
1.0g of sulfonated polyether ether was used in place of sulfonated polyvinyl alcohol in the present application and 0.40g of lithium bistrifluoromethanesulfonylimide was used to prepare a polymer electrolyte membrane having a room-temperature conductivity of 1.16X 10-6S/cm-1. It was assembled into LiFePO4the/SPE/Li cells were tested for charge-discharge cycling at 60 ℃. The first discharge specific capacity of the battery is 23 mAh.g measured under the multiplying power of 0.1C-1. The reason for this phenomenon is that the sulfonated polyetheretherketone does not have a C-O-bond in the main chain, which cannot promote the dissolution of lithium, so that lithium ions cannot freely migrate in the battery, resulting in an extremely low specific discharge capacity.
Comparative example 4
This example provides a method for producing a polymer electrolyte membrane, which is substantially the same as in example 1, except that NaH is not added in step (1). It was assembled into LiFePO4the/SPE/Li cells were tested for charge-discharge cycling at 60 ℃. The specific capacity of the battery for the first discharge is measured to be 13 mAh.g under the multiplying power of 0.1C-1. The reason for this is that without NaH, sultone cannot react with polyvinyl alcohol, the lithium ion transfer rate is extremely low, resulting in an extremely low specific discharge capacity.
The above embodiments are merely illustrative of the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement the invention, and not to limit the scope of the invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered by the scope of the present invention.
Claims (8)
1. A sulfonated polyvinyl alcohol solid polymer electrolyte membrane, characterized by: the structural general formula of the solid polymer electrolyte membrane is as follows:
wherein n is 3 or 4.
2. A preparation method of a sulfonated polyvinyl alcohol solid polymer electrolyte membrane is characterized by comprising the following steps: the preparation method comprises the following steps:
(1) adding polyvinyl alcohol and sultone in proportion into an organic solvent, adding NaH after completely dissolving, heating to react for 10 hours at 95 ℃, pouring the obtained product into hydrochloric acid and standing for 5 hours, pouring the product into a lithium hydroxide aqueous solution and standing for 10 hours, washing to be neutral by deionized water, and drying for 24 hours at 60 ℃;
(2) and (2) dissolving the product obtained in the step (1) and lithium bis (trifluoromethanesulfonylimide) in an anhydrous organic solvent in proportion, pouring the solution into a mold, and performing vacuum drying at 60 ℃ for 24 hours to obtain the solid polymer electrolyte membrane.
3. The method for producing a sulfonated polyvinyl alcohol solid polymer electrolyte membrane according to claim 2, wherein: the sultone sulfonate in the step (1) is 1, 3-propane sultone or 1, 4-butane sultone; the molar ratio of hydroxyl groups to sultone in the polyvinyl alcohol is less than 4.
4. The method for producing a sulfonated polyvinyl alcohol solid polymer electrolyte membrane according to claim 2, wherein: the mol ratio of NaH to sultone in the step (1) is 1: 1.
5. the method for producing a sulfonated polyvinyl alcohol solid polymer electrolyte membrane according to claim 2, wherein: the organic solvent in the step (1) is absolute ethyl alcohol; the concentration of hydrochloric acid is 1 mol/L; the concentration of the lithium hydroxide aqueous solution was 0.5 mol/L.
6. The method for producing a sulfonated polyvinyl alcohol solid polymer electrolyte membrane according to claim 2, wherein: the mass ratio of the lithium bistrifluoromethanesulfonimide in the step (2) to the sulfonated polyvinyl alcohol is 0.1: 1-0.4: 1.
7. the method for producing a sulfonated polyvinyl alcohol solid polymer electrolyte membrane according to claim 2, wherein: the organic solvent in the step (2) is DMSO or DMF, and the experiment is carried out in a glove box.
8. Use of a sulfonated polyvinyl alcohol solid polymer electrolyte membrane according to claim 1, wherein: the solid polymer electrolyte membrane is used for a lithium battery electrolyte membrane.
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| CN102646845A (en) * | 2011-02-16 | 2012-08-22 | 财团法人纺织产业综合研究所 | Preparation method and application of solid electrolyte |
| CN104183869A (en) * | 2014-08-25 | 2014-12-03 | 江苏明魁高分子材料技术有限公司 | Lithium single ionic conductive microporous electrolyte membrane and preparation method thereof |
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| KR102320015B1 (en) * | 2017-09-12 | 2021-11-02 | 주식회사 엘지에너지솔루션 | Polymer electrolyte for secondary battery and lithium secondary battery comprising the same |
| KR102255538B1 (en) * | 2017-11-28 | 2021-05-25 | 주식회사 엘지에너지솔루션 | Polymer electrolyte for secondary battery and secondary battery comprising the same |
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| CN102646845A (en) * | 2011-02-16 | 2012-08-22 | 财团法人纺织产业综合研究所 | Preparation method and application of solid electrolyte |
| CN104183869A (en) * | 2014-08-25 | 2014-12-03 | 江苏明魁高分子材料技术有限公司 | Lithium single ionic conductive microporous electrolyte membrane and preparation method thereof |
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| 《Crosslinked sulfonated poly(vinyl alcohol)/sulfonated multi-walled carbon nanotubes nanocomposite membranes for direct methanol fuel cells》;Sungjin Yun et al.;《Journal of Membrane Science》;20110915;第380卷(第1-2期);208-215 * |
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