CN113394464B - High-conductivity polymer solid electrolyte and preparation method thereof - Google Patents

High-conductivity polymer solid electrolyte and preparation method thereof Download PDF

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CN113394464B
CN113394464B CN202110549228.6A CN202110549228A CN113394464B CN 113394464 B CN113394464 B CN 113394464B CN 202110549228 A CN202110549228 A CN 202110549228A CN 113394464 B CN113394464 B CN 113394464B
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CN113394464A (en
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张海涛
汪宇辰
徐忠
黄浚峰
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Southwest Jiaotong University
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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—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
    • H01M2300/00—Electrolytes
    • H01M2300/0088—Composites
    • H01M2300/0091—Composites in the form of mixtures
    • 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
    • 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 discloses a high-conductivity polymer solid electrolyte and a preparation method thereof, wherein the preparation method comprises the following steps: adding PEO powder into a solution containing lithium salt, then adding perovskite quantum dots, heating and stirring at 50-70 ℃ for 20-28h to obtain uniform slurry, placing the slurry into a mold to form a film, removing the solvent, and finally drying in vacuum to obtain the high-conductivity polymer solid electrolyte film. According to the invention, the polyethylene oxide polymer solid electrolyte is modified, and the modified polymer solid electrolyte can greatly improve the room-temperature ionic conductivity, lithium ion transference number and compatibility with a lithium metal negative electrode, so that the PEO-based polymer solid electrolyte with high conductivity is obtained finally.

Description

High-conductivity polymer solid electrolyte and preparation method thereof
Technical Field
The invention relates to the technical field of solid electrolytes, in particular to a high-conductivity polymer solid electrolyte and a preparation method thereof.
Background
Batteries are a kind of energy storage device, and have a great importance in the development of the current society. The traditional rechargeable batteries comprise lead-acid batteries, cadmium-nickel batteries and the like, however, the lead-acid batteries and the cadmium-nickel batteries have serious environmental pollution problems, such as heavy metal lead, lead oxide which is difficult to digest, dust, acid mist, waste acid and other pollutants, and heavy metal cadmium, which can cause considerable damage to the environment, and cause unnatural phenomena such as global warming, acid rain and the like. The lithium ion battery as a high-efficiency secondary energy storage device has the advantages of high energy density, large output power, high working voltage, wide working temperature, long cycle life, no memory effect, environmental friendliness and the like, is gradually applied to the fields of mobile phones, computers, electric vehicles, rail transit, large-scale energy storage, aerospace and the like, and becomes a novel chemical power supply with great development potential in the world at present.
At present, a carbonate solution of lithium hexafluorophosphate is generally adopted by a commercial lithium battery as an organic liquid electrolyte, the electrolyte and an electrode material are easy to generate side reactions in the charging and discharging processes, so that the capacity of the battery is irreversibly attenuated, and meanwhile, the organic liquid electrolyte can volatilize, dry, leak and the like in the long-term service process of the battery, so that the service life of the battery is influenced. On the other hand, the conventional lithium battery cannot use the metallic lithium with high energy density as a negative electrode material, and during battery cycle, due to factors such as the surface current density of the metallic lithium and the uneven distribution of lithium ions, the metallic lithium electrode is repeatedly dissolved and deposited to easily form uneven holes and dendrites. The dendrites can pierce through the diaphragm and reach the positive electrode of the battery, so that a series of potential safety hazards such as short circuit, thermal runaway, ignition and explosion of the battery are caused. In addition, the liquid electrolyte lithium ion battery has high packaging requirements, the structural design of the battery is limited, and the thinning, high-voltage integration and the like are difficult to realize.
Therefore, the solid electrolyte is a fundamental way for solving the problems, has the advantages of high safety, high energy density, wide working temperature range, long cycle life, large design elasticity and the like, can well avoid the side effect brought by the liquid electrolyte, and improves the service life and safety of the battery. Solid electrolytes are generally classified into inorganic solid electrolytes and polymer solid electrolytes according to the materials. Solid inorganic electrolytes have poor mechanical strength and high solid-solid interface resistance when contacting electrodes, and have become major obstacles restricting their development. The polymer solid electrolyte has the advantages of no solvent, light weight, good flexibility, easy film formation, wide electrochemical oxidation potential and the like, however, most of the existing polymer solid electrolytes have the problems of low room-temperature ionic conductivity, low lithium ion transport number, poor compatibility with electrode materials and the like, and cannot meet the practical requirement, so that modification research on the polymer solid electrolyte has important significance for applying the polymer solid electrolyte to next-generation all-solid-state lithium metal batteries.
Disclosure of Invention
In order to solve the above-mentioned defects of the prior art, the present invention aims to provide a highly conductive polymer solid electrolyte and a preparation method thereof, so as to solve the problems of low conductivity, low lithium ion transport number and poor compatibility with electrode materials of the existing polymer solid electrolyte.
The technical scheme for solving the technical problems is as follows: the preparation method of the high-conductivity polymer solid electrolyte comprises the following steps:
adding PEO (polyethylene oxide) powder into a solution containing lithium salt, then adding perovskite quantum dots, heating and stirring at 50-70 ℃ for 20-28h to obtain uniform slurry, placing the slurry into a mold to form a film, removing the solvent, and finally drying in vacuum to obtain the high-conductivity polymer solid electrolyte film.
On the basis of the technical scheme, the invention can be further improved as follows:
furthermore, the perovskite quantum dot is CsPbX 3 Wherein X is Cl, br, I.
Further, the size of the perovskite quantum dots is nanometer.
Further, the lithium salt is bis (trifluoromethanesulfonyl) imide lithium or bis (fluorosulfonyl) imide lithium or lithium perchlorate.
Further, the mass ratio of the lithium salt to the PEO powder is 0.4 to 0.5.
Further, csPbI added 3 Mass of perovskite quantum dots CsPbI 3 0.5-1.0% of the total mass of the perovskite quantum dot, the lithium bis (trifluoromethanesulfonimide) and the PEO powder.
Further, the reaction temperature in the reaction process is 60 ℃, and the reaction time is 24h.
Further, the perovskite quantum dot is prepared by the following method:
(1) Preparation of cesium oleate precursor
Mixing cesium source, oleic acid and 1-octadecene, stirring for 50-70min at 110-130 ℃ under the flow of argon, and then heating to 150-170 ℃ to obtain a clear solution, namely a cesium oleate precursor;
(2)CsPbX 3 preparation of perovskite quantum dots
Mixing lead halide and 1-octadecene, stirring for 25-35min under argon atmosphere at room temperature, heating to 110-130 deg.C, and stirring for 25-35min; and then, injecting oleic acid and oleylamine into the reaction system, stirring until the reaction system becomes a clear solution, raising the temperature to 170-190 ℃, then quickly injecting a cesium oleate precursor, reacting for 4-6s, cooling in an ice water bath, and purifying to obtain the cesium oleate.
Further, in the step (1), the cesium source is cesium carbonate, and the dosage ratio of the cesium carbonate, the oleic acid and the 1-octadecene is 0.3-0.5g:1-2mL:18-20mL.
Further, stirring for 60min at 120 ℃ under argon flowing in the step (1), and then heating to 160 ℃ to obtain a clear solution which is a cesium oleate precursor.
Further, lead halide PbX in the step (2) 3 Wherein X is Cl, br, I, pbX 3 The dosage ratio of the 1-octadecene, the oleic acid, the oleylamine and the cesium oleate precursor is 0.3-0.5mmol:20-28mL:0.8-1.2mL:2-5mL:1-4mL.
Further, the purification process in the step (2) is specifically as follows: adding toluene into the cooled solution, centrifuging, removing the supernatant, adding n-hexane into the precipitate to disperse the precipitate in n-hexane, and repeating the purification process for 2-3 times.
A lithium battery comprises the above highly conductive polymer solid electrolyte.
The invention has the following beneficial effects:
in the aspect of inhibiting the crystallinity of a PEO matrix, perovskite quantum dots are uniformly dispersed in the PEO matrix, so that the order of PEO molecular chain segments can be effectively destroyed, the crystallization of PEO is inhibited, and an amorphous region, namely an amorphous region, is increased, thereby promoting the transmission of lithium ions and improving the conductivity. The perovskite quantum dots are preferably of nanometer size, which does not suffer from the problem of reduced ion transport properties due to agglomeration within the polymer matrix caused by the oversized particles of the doped filler.
For improving the ion transmission performance, the perovskite quantum dots (CsPbX) are adopted 3 ) There is instability and phase transition to the orthogonal phase occurs upon addition to the PEO-LiTFSI solution. This transition is due to the electrostatic adsorption of lithium ions by halogen anions, which have strong lewis base properties. In addition, the halogen atom, acting as a lewis base, further competes with oxygen atoms in the PEO chain for absorbing lithium ions, which means perovskite quantum dots (CsPbX) 3 ) Additional static force and steric hindrance can be generated, the dissociation of lithium salt anions is promoted, more free lithium ions are released, and the ion transmission performance is improved.
Perovskite quantum dots (CsPbX) for inhibiting the growth of lithium dendrites during battery cycling 3 ) Has synergistic effect. In one aspect, perovskite quantum dots (CsPbX) 3 ) The cesium ions with the same charge as the lithium ions can play a role in electrostatic shielding to delay the deposition of the residual lithium ions and play a role in self-repairing the surface of the smooth lithium metal anode. On the other hand, due to the strong lewis base character of the halide anion, which has the potential to react with lithium metal negative electrodes, a LiX interfacial layer is formed, which reduces Li + The activation barrier transported at the electrolyte-electrode interface allows it to transport lithium ions in-plane, while at the same time being able to suppress the growth of lithium dendrites due to its higher young's modulus, thus being able to ensure stable cycling of the battery over a long period of time.
According to the invention, polyethylene oxide (PEO) based polymer solid electrolyte is modified, and the modified polymer solid electrolyte can greatly improve the room temperature ionic conductivity and lithium ion transference number and the compatibility with a lithium metal negative electrode, so that the PEO based polymer solid electrolyte with high conductivity is obtained finally.
Drawings
FIG. 1 is a transmission electron micrograph of perovskite quantum dots.
Fig. 2 is an ion conductivity of the composite electrolyte membrane.
Fig. 3 is a lithium ion transport number of the composite electrolyte membrane.
Fig. 4 is an electrochemical stability window of the composite electrolyte membrane.
Fig. 5 shows the lithium stability performance of the composite electrolyte membrane assembled into a lithium symmetric cell.
Fig. 6 is a graph showing rate performance of the composite electrolyte membrane after being assembled into a lithium metal full cell.
Detailed Description
The following examples are given for the purpose of illustration only and are not intended to limit the scope of the invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1:
a preparation method of a high-conductivity polymer solid electrolyte comprises the following steps:
(1) Preparation of cesium oleate precursor
0.391g of cesium carbonate (Cs) 2 CO 3 ) 1.27mL of Oleic Acid (OA), and 18.73mL of 1-Octadecene (ODE) were charged into a 50mL three-necked flask. Stirring for 60 minutes at 120 ℃ under argon flowing, and heating to 160 ℃ to obtain a clear solution to obtain the cesium oleate precursor. Since cesium oleate is easily precipitated from ODE at room temperature, it must be preheated to 80 ℃ or higher before injection, i.e., the cesium oleate precursor is kept warm at 80 ℃ or higher for use.
(2)CsPbI 3 Preparation of perovskite quantum dots
A100 mL three-necked flask was charged with 0.1844g of lead iodide PbI 2 Then 24mL of 1-Octadecene (ODE) was added. After stirring for 30 minutes at room temperature under argon, the mixture was heated to 120 ℃ and stirred for another 30 minutes. Injecting 1ml OA and 3ml oleylamine (OAm) into the reaction flask by a syringe respectively, stirring for several seconds, and then lead iodide PbI 2 Complete dissolution to give a clear solution. The temperature was then raised to 180 ℃ and 2mL of cesium oleate precursor was injected rapidly. After a reaction time of 5s, the reaction mixture was cooled in an ice-water bath for further purification. The resulting solution was added to about 30mL of toluene and centrifuged at 9000rpm for 10 minutes. After centrifugation, the supernatant was decanted and the precipitate at the bottom of the centrifuge tube was redispersed in n-hexane. This purification process was repeated twice. Purified perovskite quantum dot CsPbX 3 Dispersing in n-hexane or chloroform for storage.
The morphology of the prepared perovskite quantum dot is characterized, and a transmission electron microscope picture is shown in figure 1. As can be seen from fig. 1, the perovskite quantum dots have very uniform distribution and uniform size (average size of about 10 nm), exhibit high monodispersity, and do not exhibit significant agglomeration.
(3) Preparation of composite electrolyte (high-conductivity polymer solid electrolyte)
0.408g of lithium bistrifluoromethanesulfonylimide (LiTFSI) was weighed out and dissolved in acetonitrileThe agent (20 mL) was dissolved in a reagent bottle, stirred at 60 ℃ using a thermostatic magnetic stirrer, and the dried PEO powder (1 g) was added in portions to the reagent bottle, after which the dried CsPbI was added 3 Adding the perovskite quantum dots into the solution, and continuously heating and stirring for 24 hours to fully dissolve the solution to obtain uniform slurry. And finally, forming a film from the slurry in a polytetrafluoroethylene mold, transferring the electrolyte film into a vacuum oven after the solvent is volatilized, and drying for 12 hours in vacuum to obtain the uniformly dried composite electrolyte film. Wherein the added CsPbI 3 Mass of perovskite quantum dots CsPbI 3 The total mass of the perovskite quantum dot, the lithium bis (trifluoromethanesulfonyl) imide and the PEO powder is 0.7 percent.
Example 2:
example 2 the same as example 1 except that the lead source added was lead chloride in an amount of 0.1112 g.
Example 3:
example 3 the same as example 1 except that the lead source added was lead bromide in an amount of 0.149 g.
The composite electrolyte membrane obtained in example 1 was assembled into a button cell and subjected to the following performance tests:
(1) Ion conductivity test
The composite electrolyte membrane was punched into a 16.2mm diameter disk, the resulting disk was sandwiched between two 16mm diameter stainless steel gaskets, and the thickness difference between the stainless steel gaskets before and after sandwiching the electrolyte membrane was measured by a micrometer screw to obtain the thickness of the polymer membrane. And then the polymerization film and the stainless steel sheets on the two sides are placed in a button cell shell to assemble the button cell. And (4) carrying out alternating current impedance spectroscopy test by adopting an electrochemical workstation. Then the following formula is used for calculation:
Figure BDA0003074740640000061
where σ is the ionic conductivity, L is the thickness of the electrolyte membrane, R is the measured resistance, and S is the area of the electrolyte membrane.
The test results are shown in FIG. 2, in which the upper curve in FIG. 2 is PEO-LiTFSI @ CsPbI 3 The lower curve is PEO-LiTFSI, and it can be seen from FIG. 2 that the ionic conductivity of the electrolyte membrane at 30 ℃ can reach 1X 10 -4 S·cm -1 。
(2) Determination of transference number of lithium ion
Firstly, a polymer electrolyte membrane and two lithium metal sheets are assembled into a lithium metal symmetrical battery. Measuring the bulk resistance R of the polymer electrolyte membrane by alternating current impedance spectroscopy b 0 And a charge transfer resistance R ct 0 . A constant polarization voltage (relative to the open circuit potential of the cell) is applied to the cell by the dc polarization mode of the electrochemical workstation until the current is reduced to a steady value. By recording the current change, the initial current I can be obtained o And steady state current I s . Maintaining the polarization voltage, measuring the bulk resistance R of the polymer film after reaching steady state current again by AC impedance b s And a charge transfer resistance R ct s . Then the following formula is used for calculation:
Figure BDA0003074740640000071
wherein, t Li + Δ E is the polarization voltage (10 mV) for the transport number of lithium ions.
The test result is shown in fig. 3, and it can be seen from fig. 3 that the transference number of lithium ions at room temperature can reach up to 0.66; as shown in fig. 4, the electrochemical stability window can reach 5.1V at 30 ℃. As shown in FIG. 5, the capacity of the lithium metal full cell can be 0.5mA cm -2 Stable cycling of over 400 hours at current densities of (a). As shown in FIG. 6 (in FIG. 6-2, the upper part represents PEO-LiTFSI @ CsPbI at each magnification 3 Hereinafter, PEO-LiTFSI) with a capacity of about 160mAh g at 0.1C rate -1 The capacity can still reach about 100 mAh.g at 5C multiplying power -1 。
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (6)

1. A preparation method of a high-conductivity polymer solid electrolyte is characterized by comprising the following steps:
adding PEO powder into a solution containing lithium salt, then adding perovskite quantum dots, heating and stirring at 50-70 ℃ for 20-28h to obtain uniform slurry, placing the slurry into a mold to form a film, removing the solvent, and finally drying in vacuum to obtain a high-conductivity polymer solid electrolyte film;
the size of the perovskite quantum dot is nano-scale; the lithium salt is bis (trifluoromethanesulfonyl) imide lithium; the mass ratio of the lithium salt to the PEO powder is 0.408.
2. The method for preparing a highly conductive polymer solid electrolyte as claimed in claim 1, wherein the perovskite quantum dot is CsPbX 3 Wherein X is Cl, br, I.
3. The method for preparing a highly conductive polymer solid electrolyte as claimed in claim 1, wherein the reaction temperature is 60 ℃ and the reaction time is 24 hours.
4. A highly conductive polymer solid electrolyte obtained by the method for producing a highly conductive polymer solid electrolyte as claimed in any one of claims 1 to 3.
5. Use of the highly conductive polymer solid electrolyte as claimed in claim 4 for the preparation of a lithium battery.
6. A lithium battery comprising the highly conductive polymer solid electrolyte according to claim 4.
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