CN114927751A - Preparation method and application of solid electrolyte composite membrane - Google Patents

Preparation method and application of solid electrolyte composite membrane Download PDF

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CN114927751A
CN114927751A CN202210431095.7A CN202210431095A CN114927751A CN 114927751 A CN114927751 A CN 114927751A CN 202210431095 A CN202210431095 A CN 202210431095A CN 114927751 A CN114927751 A CN 114927751A
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solid electrolyte
lithium
composite membrane
battery
electrolyte composite
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曹正鑫
李星
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Ningbo University
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Ningbo 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
    • H01M10/052—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
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
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  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a preparation method of a solid electrolyte composite membrane, which adopts LITP as a main raw material, adds a proper amount of polymer polyacrylonitrile as an adhesive into DMF (dimethyl formamide), and adds LITP ceramic powder with different contents after fully dissolving; and stirred at 80 ℃. After stirring uniformly, the suspension was poured onto a polypropylene film (pp film), dried in a vacuum oven at 40 ℃ for 24 hours to remove the residual solvent, and cut into a circular piece with a diameter of 19mm to obtain a composite solid electrolyte separator. Electrochemical experiments prove that the solid electrolyte composite membrane prepared by the method can effectively inhibit the growth of lithium dendrites in the charging and discharging processes of the battery when being used as an electrode protective layer of the lithium metal battery, so that the cycle performance of the lithium battery is improved, and the solid electrolyte composite membrane has wide application prospect. In the whole preparation process, the operation is simple, the raw material cost is low, the equipment investment is low, and the method is suitable for batch production.

Description

Preparation method and application of solid electrolyte composite membrane
Technical Field
The invention belongs to the field of material chemistry, and particularly relates to a preparation method of a solid electrolyte composite membrane and application of the solid electrolyte composite membrane in an electrode protection layer material of a lithium metal battery to improve the cycle performance of the lithium battery.
Background
Metallic lithium is currently known as the lowest density metallic material and has a high theoretical specific capacity (3840 mAh/g). Furthermore, Li compares to a standard hydrogen electrode + The redox couple with Li composition can provide the lowest redox potential(-3.04V), which allows the lithium ion secondary battery to have a higher operating voltage during use (Bruce P G et al, Nature Materials,2012,11(1): 19-29; Jung J W et al, Journal of Materials Chemistry A,2016,4(3):703-&Environmental Science,2014,7(7): 2213-2219). The excellent properties described above have led to the widespread interest of researchers in the field of lithium metal. However, the lithium metal negative electrode still faces many difficulties in practical application, and the main difficulties include the following three aspects: firstly, the interface impedance is continuously increased due to complex reaction on the interface of the metal lithium cathode and the electrolyte, so that the cycle efficiency in the charge-discharge cycle process is reduced; secondly, with the increasing of the number of circulating circles, the repeated embedding and removing reaction of the metal lithium, the lithium cathode can generate a serious volume expansion effect to cause the falling of the cathode active material, thereby reducing the circulating efficiency of the battery; thirdly, a large amount of lithium dendrites are formed on the surface of a negative electrode due to the uneven deposition of metal lithium on the surface of the electrode, and the lithium dendrites fall off from the electrode and enter electrolyte to form 'dead lithium', so that the loss of electrode active substances is caused; if the lithium dendrites continue to grow through the battery separator and contact the positive electrode, the battery can be short-circuited, which can cause the battery to burn or even explode (Xu W et al Energy)&Environmental Science,2014,7(2): 513-; zhamu A et al Energy&Environmental Science,2012,5(2): 5701-; brandt K et al, Solid State Ionics,1994,69(3-4): 173-. To address the challenges faced above, solid electrolytes come into the line of sight of people. The solid electrolyte has a wider electrochemical stability window, can be used together with a high-voltage electrode material, improves the energy density of the battery, and greatly increases the possibility that the metal lithium with high theoretical energy density is used as a negative electrode. Liu et al use PAN-LiClO 4 As the polymer electrolyte matrix, Li was used 0.33 La 0.557 TiO 3 The nano-wires are filled to synthesize the composite solid electrolyte, the lithium ion conductivity is 2.4 multiplied by 10 < -4 > S/cm at room temperature, the lithium ion conductivity is greatly improved, and the electrochemical stability, the mechanical property and the like of the composite solid electrolyte and lithium are not reported. (Liu W, Liu N, Sun J, Hsu PC, Li Y, Lee HW, Cui Y. Nano Lett,2015,15:2740–2745)。
The solid electrolyte has higher mechanical strength due to the structural characteristics of the solid electrolyte, and can effectively inhibit the penetration of lithium dendrites in the cycle process of the lithium battery and enhance the cycle performance. And because the material contains abundant reaction sites, the material has strong affinity with lithium and can effectively capture lithium ions. In 2014, IRIYAMA et al directed to LiCoO 2 The Nb layer with the thickness of 10nm is introduced at the/LLZO interface, so that the growth of an interdiffusion layer can be inhibited, and the interface impedance is obviously reduced. And they propose that the introduced Nb layer may form an ion conductor material Li-Nb-O in situ, improving the cycle and rate performance of the battery (KATO T, HAMANAKA T, YAMAMOTO K, et al 7 La 3 Zr 2 O 12 /LiCoO 2 interface modification for advanced all-solid-state battery[J]Journal of Power Sources,2014,260: 292-. In 2015, Jung et al in polyethylene oxide (PEO)/LiClO 4 Li with NASICON structure 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 And the lithium ion conducting properties of the composite solid electrolyte were investigated. Their composite solid electrolyte is reported to have a lithium ion conductivity of 2.6X 10 at 55 deg.C -4 S/cm, and also better electrochemical stability (Jung YC, Lee SM, Choi JH, Jang SS, Kim DW. J Electrochem Soc,2015,162: A704-A710). The solid electrolyte has advantages in improving the cycle performance of the lithium battery. In order to realize the growth without lithium dendrite, the invention adopts a coating technology and combines with solid electrolyte to prepare the composite membrane which is used for improving the cycle performance of the lithium battery based on the solid electrolyte and is beneficial to improving the cycle performance of the lithium battery.
Disclosure of Invention
The invention aims to solve the technical problem of the prior art and provides a preparation method of a solid electrolyte composite membrane and application of the solid electrolyte composite membrane in a lithium metal battery electrode protective layer material to improve the cycle performance of a lithium battery.
The technical scheme adopted by the invention for solving the technical problems is as follows: a method for preparing a solid electrolyte composite membrane is characterized in that Li is adopted in the preparation method 0.6 In 0.4 Ti 0.3 PO 4 (LITP) is used as main raw material, adding appropriate amount of polymer polyacrylonitrile as adhesive into DMF, dissolving completely, adding LITP powder with different contents, and stirring at 80 deg.C. After stirring well, the suspension was poured onto a polypropylene film (pp film), dried in a vacuum oven at 40 ℃ for 24h to remove residual solvent, and then cut into 19mm diameter disks for use. The solid electrolyte composite membrane is obtained, and specifically comprises the following steps:
1) weighing a certain amount of PAN (polyacrylonitrile) to be dissolved in N, N-Dimethylformamide (DMF) with a certain volume, and stirring for 14-16 h to obtain a gray precursor solution;
2) weighing a certain amount of solid electrolyte Li 0.6 In 0.4 Ti 0.3 PO 4 Dissolving in a precursor solution, and stirring for 12h at 80 ℃ by using a water bath heating device to fully and uniformly mix the solution to obtain a suspension;
3) pouring the obtained suspension on a polypropylene film (pp film), and uniformly coating liquid on the film by using a coater to obtain a white composite film;
4) placing the obtained white composite film in a vacuum oven, drying for 24h at 40 ℃ to obtain a solid electrolyte composite film, and cutting the solid electrolyte composite film into circular sheets with the diameter of 19mm for later use;
the prepared solid electrolyte composite membrane is used as a lithium metal battery electrode protective layer material, and the current density is 1.0mA cm -2 Under the condition that the battery is cycled for 350h, the lithium deposition on the surface of the electrode is uniform, and the growth of lithium dendrite is inhibited.
The Li 0.6 In 0.4 Ti 0.3 PO 4 The preparation method of (LITP) comprises the following steps: mixing lithium carbonate and In 2 O 3 Tetrabutyl titanate and ammonium phosphate are mixed and stirred, then sintered at the temperature of 600-900 ℃ in a tube furnace under the nitrogen atmosphere, and cooled to the room temperature to obtain the LITP.
Compared with the prior art, the invention has the following characteristics:
the solid electrolyte composite membrane prepared by the invention is used for an electrode protective layer of a lithium metal battery to improve the cycle performance of the lithium battery, and the composite membrane material has high safety and high conductivity; in particular, the doping of indium enhances the plasticity of the material, has ductility and can be pressed into sheets; indium is non-toxic, has variable valence (monovalent and trivalent) and a specific energy level structure, and is a synthetic raw material of materials such as semiconductors, electric light sources and the like; the material prepared by the invention can effectively inhibit the growth of lithium dendrites in the charging and discharging processes of the battery, improve the safety performance of the battery and provide safety guarantee for the large-scale production of commercial lithium metal batteries.
Drawings
Fig. 1 is an SEM image of a composite film provided in an example of the present invention.
Fig. 2 is an XRD pattern of the composite film provided by the example of the present invention.
Fig. 3 is a graph illustrating cycle performance of the composite film provided by the embodiment of the present invention as a protective layer material for an electrode of a lithium metal battery.
Fig. 4 is a resistance diagram of the composite film provided by the embodiment of the present invention as a protective layer material for an electrode of a lithium metal battery.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1
Weighing 1.5g of PAN (polyacrylonitrile) and dissolving in 20mL of N, N-Dimethylformamide (DMF), and stirring for 15h to obtain a gray precursor solution; adding 1.5g of solid electrolyte Li into the gray precursor solution under vigorous stirring 0.6 In 0.4 Ti 0.3 PO 4 And (3) obtaining a precursor solution, stirring the solution in a water bath environment at the temperature of 80 ℃ for 12 hours under the condition of heating in a water bath to fully and uniformly mix the solution, and naturally cooling to room temperature to obtain a suspension. And pouring the obtained suspension on a polypropylene film (pp film), uniformly coating the suspension by using a coater to obtain a white composite film, placing the obtained white composite film in a vacuum oven, then adjusting the temperature of the vacuum oven to 40 ℃ and drying for 24 hours to obtain a solid electrolyte composite film, and cutting the solid electrolyte composite film into a wafer with the diameter of 19mm for later use. Observing the morphology of the material of the obtained composite film by using a Scanning Electron Microscope (SEM) (figure 1); the material compositional structure was tested by X-ray diffraction XRD (fig. 2); the prepared compoundA cycle performance diagram (figure 3) of the composite membrane as a lithium metal battery electrode protective layer material; the prepared composite film was used as an impedance diagram of a lithium metal battery electrode protection layer material (fig. 4).
Example 2
Weighing 1.0g of PAN (polyacrylonitrile) to dissolve in 20mL of N, N-Dimethylformamide (DMF), and stirring for 15h to obtain a gray precursor solution; adding 1.0g of solid electrolyte Li into the light white precursor solution under vigorous stirring 0.6 In 0.4 Ti 0.3 PO 4 And (3) obtaining a precursor solution, stirring the solution for 12 hours in a water bath environment at the temperature of 80 ℃ under the condition of heating in a water bath, fully and uniformly mixing the solution, and naturally cooling to room temperature to obtain a suspension. Pouring the obtained suspension on a clean polypropylene film (pp film), uniformly coating the suspension by using a coater to obtain a white composite film, placing the obtained white composite film in a vacuum oven, adjusting the temperature of the vacuum oven to 40 ℃ and drying for 24 hours to obtain a solid electrolyte composite film, and cutting the solid electrolyte composite film into a wafer with the diameter of 19mm for later use. Observing the morphology of the material by using a Scanning Electron Microscope (SEM) to obtain the composite film; testing the composition structure of the material by X-ray diffraction; the prepared composite membrane is used as a test cycle performance of a lithium metal battery electrode protection layer material; the prepared composite membrane is used as the test impedance of the electrode protection layer material of the lithium metal battery.
Example 3
Weighing 0.5g of PAN (polyacrylonitrile) and dissolving in 20mL of N, N-Dimethylformamide (DMF), and stirring for 15h to obtain a gray precursor solution; adding 0.5g of solid electrolyte Li into the gray precursor solution under vigorous stirring 0.6 In 0.4 Ti 0.3 PO 4 And (3) obtaining a precursor solution, stirring the solution for 12 hours in a water bath environment at the temperature of 80 ℃ under the condition of heating in a water bath, fully and uniformly mixing the solution, and naturally cooling to room temperature to obtain a suspension. Pouring the obtained suspension on clean polypropylene film (PP film), uniformly coating with coater to obtain white composite film, placing the white composite film in vacuum oven, and adjusting the temperature of the vacuum oven to 40 deg.CAnd drying for 24 hours to obtain a solid electrolyte composite membrane, and cutting the solid electrolyte composite membrane into a wafer with the diameter of 19mm for later use. Observing the morphology of the obtained composite film by using a Scanning Electron Microscope (SEM) to observe the morphology of the material; testing the composition structure of the material by X-ray diffraction; the prepared composite membrane is used as a material for testing the cycle performance of the electrode protection layer of the lithium metal battery; the prepared composite membrane is used as the test impedance of the electrode protection layer material of the lithium metal battery.

Claims (2)

1. A method for preparing a solid electrolyte composite membrane, comprising the steps of:
1) weighing a certain amount of PAN (polyacrylonitrile) to be dissolved in a certain volume of N, N-Dimethylformamide (DMF), and stirring for 14-16 h to obtain a gray precursor solution;
2) weighing a certain amount of solid electrolyte Li 0.6 In 0.4 Ti 0.3 PO 4 Dissolving in precursor solution, and stirring at 80 deg.C for 12 hr by water bath heating device to obtain suspension;
3) pouring the obtained suspension on a polypropylene film, and uniformly coating liquid on the film by using a coater to obtain a white composite film;
4) placing the obtained white composite film in a vacuum oven, drying for 24 hours at 40 ℃ to obtain a solid electrolyte composite film, and cutting the solid electrolyte composite film into circular sheets with the diameter of 19mm for later use;
the Li 0.6 In 0.4 Ti 0.3 PO 4 The preparation method of (LITP) comprises the following steps: mixing lithium carbonate and In 2 O 3 Tetrabutyl titanate and ammonium phosphate are mixed and stirred, then sintered at the temperature of 600-900 ℃ in a tube furnace under the nitrogen atmosphere, and cooled to the room temperature to obtain the LITP.
2. Use of the electrolyte composite membrane obtained by the preparation method as described in claim 1 as a protective layer material for lithium metal batteries, characterized in that the current density is 1.0mA cm -2 Under the condition that the battery is cycled for 350h, the lithium deposition on the surface of the electrode is uniform, and the growth of lithium dendrite is inhibited.
CN202210431095.7A 2022-04-22 2022-04-22 Preparation method and application of solid electrolyte composite membrane Pending CN114927751A (en)

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