CN116598580A - Composite solid electrolyte and preparation method and application thereof - Google Patents

Composite solid electrolyte and preparation method and application thereof Download PDF

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Publication number
CN116598580A
CN116598580A CN202310273625.4A CN202310273625A CN116598580A CN 116598580 A CN116598580 A CN 116598580A CN 202310273625 A CN202310273625 A CN 202310273625A CN 116598580 A CN116598580 A CN 116598580A
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polymer
electrolyte
composite solid
solid electrolyte
zeolite
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陈忠伟
张永光
贾术峰
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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
    • H01M2300/0082—Organic polymers
    • 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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  • Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Dispersion Chemistry (AREA)
  • General Physics & Mathematics (AREA)
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Abstract

The application discloses a composite solid electrolyte, a preparation method and application thereof. The composite solid electrolyte comprises PAN nanofibers, lithiated zeolite and polymer electrolyte; the PAN nanofiber is of a 3D porous skeleton structure; the lithiated zeolite is distributed on the PAN nanofibers, and the polymer electrolyte is polymerized in situ in the 3D porous skeletal structure. The preparation method comprises the steps of carrying out electrostatic spinning on a polyacrylonitrile solution containing lithiated zeolite, and drying to obtain a nanofiber membrane; and then injecting electrolyte precursor solution containing polymer, initiator and lithium salt into the nanofiber membrane prepared in the step S1, and carrying out polymerization reaction to obtain the composite solid electrolyte. Because the active filler is added into the 3D network structure and the in-situ polymer electrolyte, the ionic conductivity is improved, the interface contact is good, and the advantages of higher safety, high energy density and the like are achieved.

Description

Composite solid electrolyte and preparation method and application thereof
Technical Field
The application relates to a composite solid electrolyte, a preparation method and application thereof, and belongs to the technical field of lithium-sulfur battery materials.
Background
Among various battery technologies, lithium-sulfur batteries are the most promising next-generation energy storage devices, whose energy density is more than 3 times that of conventional lithium-ion batteries. However, safety issues with respect to the use of high energy lithium sulfur batteries are increasing due to the use of highly volatile and flammable organic solvent-based liquid electrolytes. Compared with a liquid electrolyte lithium sulfur battery, the all-solid-state lithium sulfur battery is safer and longer in cycle life. As a key material of solid-state lithium-sulfur batteries, solid-state electrolytes, there are currently mainly inorganic solid ceramic electrolytes, organic solid polymer electrolytes, and solid composite electrolytes. However, each electrolyte has its advantages and disadvantages, so few solid electrolytes have a combination of properties to meet commercial application requirements. The composite solid electrolyte can make up the defects of each component, and the solid electrolyte with comprehensive performance is prepared. Currently, the most common method of preparing composite solid electrolytes is mechanical mixing followed by solvent casting/coating or hot embossing. By coating the solid electrolyte slurry on the positive electrode, the slurry permeates into the gaps of the positive electrode layer under the action of gravity, so that the interface contact effect of the solid electrolyte and the positive electrode is improved, and the interface impedance is reduced. However, the organic solvent casting or coating method has the problems of unfriendly environment, high manufacturing cost, low production efficiency, flatness of electrolyte membranes, poor material mixing effect, poor interface contact between electrodes and electrolyte, high interface impedance and the like.
Conventional methods result in random dispersion of particles, which tend to dynamically agglomerate in the composite solid electrolyte due to high surface energy, and thus it is difficult to form a continuous ion transport pathway. In addition, the surface energy difference between the particles and the polymer matrix is large, resulting in poor solid-solid contact in the electrolyte. And currently composite solid electrolytes focus mainly on inert fillers, which do not transport lithium ions.
Disclosure of Invention
Aiming at the problems of 'shuttle effect' of polysulfide in the traditional liquid battery electrolyte and low ionic conductivity and poor contact with an electrode interface of the solid electrolyte prepared by the prior art. The application improves the chain segment movement capability of the polymer and establishes faster Li by adding the inorganic filler with good dispersibility + The transmission channel solves the problems, and the prepared composite solid electrolyte has higher safety and higher energy density.
According to one aspect of the present application, there is provided a composite solid state electrolyte comprising PAN nanofibers, lithiated zeolite, and a polymer electrolyte;
the PAN nanofiber is of a 3D porous skeleton structure;
the lithiated zeolite is distributed on the PAN nanofibers, and the polymer electrolyte is polymerized in situ in the 3D porous skeletal structure.
The lithiated zeolite is prepared by mixing with PAN spinning solution and then carrying out electrostatic spinning, wherein the lithiated zeolite and the PAN nanofiber are distributed on the PAN nanofiber, namely, the lithiated zeolite and the PAN nanofiber are integrated.
Optionally, the lithiated zeolite is an X-type zeolite.
According to still another aspect of the present application, there is provided a method for preparing a composite solid electrolyte, comprising the steps of:
s1, carrying out electrostatic spinning on a polyacrylonitrile solution containing lithiated zeolite, and drying to obtain a nanofiber membrane;
s2, injecting electrolyte precursor solution containing polymer, initiator and lithium salt into the nanofiber membrane prepared in the step S1, and performing polymerization reaction to obtain the composite solid electrolyte.
The lithiated zeolite in the application is used as inorganic filler, has good dispersibility, and can realize the dispersion of nano particles in a polymer matrix by adopting an electrostatic spinning technology so as to reduce the agglomeration of the nano particles. Inorganic filler is doped in the polymer, and the high viscosity of the polymer and the rich functional group of the polymer can prevent the aggregation of the nano particles, so that the utilization rate of the material is improved. The application prepares a 3D network composite structure through electrostatic spinning, and solves the problems of poor mechanical stability, low ionic conductivity and interface contact/compatibility of a solid-state lithium-sulfur metal battery.
Optionally, the mass fraction of the lithiated zeolite in the polyacrylonitrile solution is 1wt% to 10wt%.
Optionally, the mass fraction of the lithiated zeolite in the polyacrylonitrile solution is any value or range of values between 1wt%, 2.5wt%, 5wt%, 7.5wt%, 10wt%.
Optionally, the polyacrylonitrile solution is obtained by mixing polyacrylonitrile powder with a solvent;
the solvent is N, N-dimethylformamide;
the solid-to-liquid ratio of the polyacrylonitrile powder to the solvent is 1g: 5-10 mL.
Optionally, in step S1, the conditions of the electrospinning are: the voltage is 18-22 kv, the height is 15cm, and the spinning time is 0.5-2 h.
Optionally, in step S1, the voltage of the electrospinning is any value or a range of values between two values of 18kv, 19kv, 20kv, 21kv, 22 kv.
Optionally, the time of the electrospinning is any value or a range of values between two values of 0.5h, 1h, 1.5h, 2h.
Optionally, the drying is performed under vacuum for 12-24 hours at a temperature of 70-90 ℃.
Optionally, the polymer comprises polymer a and polymer B;
the polymer A is at least one selected from succinonitrile and dimethyl carbonate;
the polymer B is at least one selected from ethoxy trimethylolpropane triacrylate, ionic liquid IL monomer and trioxymethyl propane methacrylic acid.
Optionally, the solid to liquid ratio of polymer a to polymer B is 1g: 0.05-0.2 mL.
Optionally, the lithium salt is selected from at least one of LiTFSI, liFSI.
Optionally, the mass ratio of the polymer a to the lithium salt is 1:0.5 to 1.5.
Optionally, the initiator is at least one selected from azodiisobutyronitrile and azodiisoheptonitrile.
Optionally, the mass ratio of the polymer B to the initiator is 1:0.1 to 0.5.
Optionally, in step S2, the polymerization conditions are as follows: the temperature is 70-90 ℃ and the time is 1-1.5 h.
In the present application, "PAN" refers to polyacrylonitrile;
"DMF" refers to N, N-dimethylformamide;
"LiTFSI" refers to lithium bis (trifluoromethane) sulfonyl imide;
"LiFSI" refers to lithium bis-fluorosulfonyl imide.
According to a further aspect of the present application there is provided the use of a composite solid electrolyte as described above or obtained according to the preparation method described above in a solid lithium sulphur battery.
The application has the beneficial effects that:
1) The composite solid electrolyte provided by the application has the advantages that the first complexation of the lithiated zeolite and the PAN nanofiber not only improves the mechanical strength of the solid electrolyte, but also can avoid the aggregation of lithiated zeolite particles.
2) According to the preparation method provided by the application, the active filler lithiated zeolite is added into the polymer through electrostatic spinning, so that a firm polymer chain can be effectively contacted with the filler, and meanwhile, as the cation bond of an X zeolite framework in the lithiated zeolite is weaker, the effective shuttling of metal cations can be realized, thereby providing a solid interconnection way to promote the effective transmission of lithium ions and improving the ion conduction of the material.
3) According to the preparation method provided by the application, as the active filler, the 3D network structure and the in-situ polymer electrolyte are added, the ionic conductivity is improved, the interface contact is good, and the preparation method has the advantages of higher safety, high energy density and the like.
4) The application provided by the application, during battery assembly, the polymer electrolyte can penetrate through the electrode and the interstitial gaps in the interface to create a rapid lithium ion transport pathway and maintain intimate contact of the electrolyte and the electrode interface.
Drawings
FIG. 1 is a schematic diagram of the structure of a three-dimensional PAN+Li-X fiber network prepared in example 1 of the present application at a magnification of 100 nm;
FIG. 2 is a schematic view of the structure of the three-dimensional solid-state fiber network prepared in comparative example 1 of the present application at a magnification of 1. Mu.L;
FIG. 3 is a graph showing that the composite solid electrolyte prepared in example 1 of the present application was used in a lithium symmetric battery of 0.2mA cm -1 Constant current circulation at current densityA circular curve;
FIG. 4 is a graph showing that the composite solid electrolyte prepared in comparative example 1 of the present application was used in a lithium symmetric battery of 0.2mA cm -1 Constant current cycling curve at current density.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
Unless otherwise indicated, all starting materials in the examples of the present application were purchased commercially.
The analysis method in the embodiment of the application is as follows:
obtaining a structural schematic diagram of a three-dimensional PAN+Li-X fiber network by using a DNL2002 field emission scanning electron microscope;
obtaining the lithium symmetrical battery 0.2 mA.cm containing the composite electrolyte by using a New Wei battery tester -1 Constant current cycling curve at current density.
The specific preparation method of the lithiated zeolite comprises the following steps:
1. first, 2g of NaOH and 0.98g of Al (OH) were added 3 Dissolved in deionized water and then heated at 100 ℃ to form a clear solution. After cooling to room temperature, 2.9g of NaOH in 32.6g of water was then added and stirring was continued by controlling the temperature with an ice-water bath. Thereafter, 22.35g of Na was added 2 SiO 3 The solution was kept in an ice water bath for 1 hour. After stirring at room temperature for 24 hours, the solution was transferred to a stainless steel reactor and subjected to hydrothermal reaction at 98 ℃ for 8 hours. Filtering and separating to obtain Na-X zeolite powder, and drying at 80 ℃ for 12 hours.
2. The Li-X zeolite was obtained by immersing 5g of Na-X zeolite in LiCl solution (5M) for 2 hours, followed by washing with water and filtering, and the filtered slurry was dried at 80℃for 12 hours to obtain a powder.
Example 1
1. Preparation of three-dimensional PAN+Li-X fiber network by electrostatic spinning
First, 1.5g of polyacrylonitrile powder was dissolved in 10mL of DMF solution. Then adding 10wt% of Li-X into the PAN solution, and stirring for 12 hours to obtain a uniform spinning solution. Subsequently, the spinning solution was transferred to a syringe equipped with a stainless steel needle. In the electrostatic spinning process, a high pressure of 20kv and a receiving distance of 15cm are adopted for spinning for 1h. Finally, the electrospun fibers were collected on aluminum foil and dried overnight in a vacuum oven at 70 ℃ to give a nanofiber membrane of three-dimensional pan+li-X fiber network, as shown in fig. 1.
As can be seen from fig. 1, the interconnection of the optical fibers forms a 3D network. The Li-X zeolite is uniformly wrapped by PAN fibers. The porous 3D crosslinked nanofiber structure can provide space/volume for polymer electrolyte filling, forming a continuous Li pathway.
2. Preparation of polymer electrolyte precursor
First, 0.874g of lithium bis (trifluoromethane) sulfonyl imide, 1.0g of succinonitrile and 5% ethoxy trimethylolpropane triacrylate were mixed at 50℃for 3 hours to obtain a mixed solution; after the mixed solution was cooled to room temperature, 1wt% of azobisisobutyronitrile was added as an initiator, and stirring was continued for 6 hours to obtain a polymer electrolyte precursor solution for further use.
3. In situ polymerization
50. Mu.L of polymer electrolyte precursor solution was injected into PAN+Li-X nanofibers, and then thermally polymerized at 70℃for 1 hour, to obtain a composite solid electrolyte.
Comparative example 1
1. Preparation of three-dimensional PAN fiber network by electrostatic spinning
First, 1.5g of polyacrylonitrile powder was dissolved in 10mL of DMF solution. Li-X is not added, and the mixture is stirred for 12 hours to obtain a uniform spinning solution. Subsequently, the spinning solution was transferred to a syringe equipped with a stainless steel needle. In the electrospinning process, a high pressure of 20kv and a receiving distance of 15cm were used for spinning for 1h. Finally, the electrospun fibers were collected on aluminum foil and dried overnight in a vacuum oven at 70 ℃ to give a fibrous membrane of a three-dimensional PAN fiber network, as shown in fig. 2.
As can be seen from fig. 2, the interconnection of the three-dimensional PAN fibers forms a 3D network structure.
2. Preparation of polymer electrolyte precursor
First, 0.874g of lithium bis (trifluoromethane) sulfonyl imide, 1.0g of succinonitrile and 5% ethoxy trimethylolpropane triacrylate were mixed at 50℃for 3 hours to obtain a mixed solution; after the mixed solution was cooled to room temperature, 1wt% of azobisisobutyronitrile was added as an initiator, and stirring was continued for 6 hours to obtain a polymer electrolyte precursor solution for further use.
3. In situ polymerization
50. Mu.L of the polymer electrolyte precursor solution was injected into the PAN nanofibers, and then thermally polymerized at 70℃for 1 hour.
Test case
Stability between the lithium metal anode and the prepared solid state electrolyte was further evaluated by studying the lithium plating/stripping behavior in symmetric Li/Li batteries.
The Li/comparative SSE/Li cell was short-circuited after 70h of charge/discharge cycles, as shown in fig. 4. The short circuit may be the result of lithium dendrite penetration.
Whereas example 1 was tested, SSE provided stable cycling performance, as shown in FIG. 3, indicating uniform Li deposition behavior and stable interface. The results indicate that Li-X has a large impact on lithium deposition behavior in a composite SSE system.
While the application has been described in terms of preferred embodiments, it will be understood by those skilled in the art that various changes and modifications can be made without departing from the scope of the application, and it is intended that the application is not limited to the specific embodiments disclosed.

Claims (10)

1. A composite solid electrolyte comprising PAN nanofibers, lithiated zeolite, and a polymer electrolyte;
the PAN nanofiber is of a 3D porous skeleton structure;
the lithiated zeolite is distributed on the PAN nanofibers, and the polymer electrolyte is polymerized in situ in the 3D porous skeletal structure.
2. The composite solid state electrolyte of claim 1 wherein the lithiated zeolite is an X-type zeolite.
3. A method of preparing the composite solid electrolyte of claim 1 or 2, comprising the steps of:
s1, carrying out electrostatic spinning on a polyacrylonitrile solution containing lithiated zeolite, and drying to obtain a nanofiber membrane;
s2, injecting electrolyte precursor solution containing polymer, initiator and lithium salt into the nanofiber membrane prepared in the step S1, and performing polymerization reaction to obtain the composite solid electrolyte.
4. The method according to claim 3, wherein the mass fraction of the lithiated zeolite in the polyacrylonitrile solution is 1wt% to 10wt%;
preferably, the polyacrylonitrile solution is obtained by mixing polyacrylonitrile powder with a solvent;
the solvent is N, N-dimethylformamide;
the solid-to-liquid ratio of the polyacrylonitrile powder to the solvent is 1g: 5-10 mL.
5. A method according to claim 3, wherein in step S1, the conditions for electrospinning are: the voltage is 18-22 kv, the height is 15cm, and the spinning time is 0.5-2 h;
preferably, the drying is carried out under vacuum for 12-24 hours at a temperature of 70-90 ℃.
6. A method of preparation according to claim 3, wherein the polymer comprises polymer a and polymer B;
the polymer A is at least one selected from succinonitrile and dimethyl carbonate;
the polymer B is at least one selected from ethoxy trimethylolpropane triacrylate, ionic liquid IL monomer and trioxymethyl propane methacrylic acid;
preferably, the solid-to-liquid ratio of polymer a to polymer B is 1g: 0.05-0.2 mL.
7. The method according to claim 6, wherein the lithium salt is at least one selected from LiTFSI and LiFSI;
preferably, the mass ratio of the polymer A to the lithium salt is 1:0.5 to 1.5.
8. The method according to claim 6, wherein the initiator is at least one selected from the group consisting of azobisisobutyronitrile and azobisisoheptonitrile;
preferably, the mass ratio of the polymer B to the initiator is 1:0.1 to 0.5.
9. A method according to claim 3, wherein in step S2, the polymerization conditions are: the temperature is 70-90 ℃ and the time is 1-1.5 h.
10. Use of a composite solid electrolyte according to claim 1 or 2 or obtained by a process according to any one of claims 3 to 9 in a solid lithium sulfur battery.
CN202310273625.4A 2023-03-20 2023-03-20 Composite solid electrolyte and preparation method and application thereof Pending CN116598580A (en)

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