CN113851697B - Preparation method and application of thin layered solid electrolyte membrane - Google Patents
Preparation method and application of thin layered solid electrolyte membrane Download PDFInfo
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- CN113851697B CN113851697B CN202111135453.1A CN202111135453A CN113851697B CN 113851697 B CN113851697 B CN 113851697B CN 202111135453 A CN202111135453 A CN 202111135453A CN 113851697 B CN113851697 B CN 113851697B
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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
- H01M10/0561—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
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- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to the technical field of all-solid-state lithium batteries, and discloses a preparation method and application of a thin layered solid electrolyte membrane. The thin layered solid electrolyte membrane prepared by the invention has good room temperature ionic conductivity, migration number, high mechanical strength and low specific surface resistance, and can effectively inhibit the growth of lithium dendrites. Excellent electrochemical performance and safety performance can be realized in the application of the all-solid-state lithium battery, the attenuation of the battery capacity is restrained, the rate capability of the battery is improved, and the service life of the battery is prolonged.
Description
Technical Field
The invention relates to the technical field of all-solid-state lithium batteries, in particular to a preparation method and application of a thin layered solid electrolyte membrane.
Background
Safety issues raised by liquid electrolytes have seriously hampered practical use of lithium metal batteries for decades, such as electrolyte leakage, combustion, and even explosion caused by lithium dendrite growth. The use of solid-state electrolytes instead of traditional organic liquid electrolytes is considered as an effective approach to solve the battery safety problem, making all-solid-state lithium batteries with high safety and energy density the next generation of the most promising energy storage devices.
The development of thin solid electrolytes with excellent ion conductivity and stable mechanical properties is critical to obtain high performance all-solid lithium batteries. An inorganic solid electrolyte comprising garnet-type Li 7 La 3 Zr 2 O 12 (LLZO), perovskite type Li 0.34 La 0.56 TiO 3 (LLTO), NASICON type Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 (LAGP) and sulfide Li 10 GeP 2 S 12 (LGPS) having excellent ion conductivity at room temperature>10 -4 S cm -1 ) 3 orders of magnitude higher than solid polymer electrolytes, approaching or even exceeding liquid electrolytes. Meanwhile, the strong compressive strength endows the inorganic solid electrolyte with the capability of effectively inhibiting the growth of lithium dendrites. These advantages, combined with excellent thermal stability and a broad electrochemical stability window, have led to widespread attention of the scholars. However, currently inorganic solid electrolytes are typically pressed from ceramic powders. To maintain structural stability, these electrolytes are typically greater than 1mm thick. An excessive thickness causes an increase in the diffusion distance of lithium ions inside the electrolyte, decreasing the ability of the electrolyte to conduct lithium ions, and simultaneously causing an increase in the internal resistance of the battery and a sharp decrease in the energy density. Based on the above, there is an urgent need for improvement of inorganic solid electrolyte to develop a layered solid electrolyte membrane having high ionic conductivity, high mechanical strength and thinness, thereby obtaining a high-performance all-solid lithium battery.
Disclosure of Invention
The invention aims to overcome the defects and provide a preparation method and application of a thin layered solid electrolyte membrane.
In order to achieve the above purpose, the invention is implemented according to the following technical scheme:
a preparation method of a thin layered solid electrolyte membrane comprises the following steps:
s1, preparing a fast ion conductor two-dimensional nano sheet dispersion liquid;
s2, self-stacking the fast ion conductor two-dimensional nano sheets in the fast ion conductor two-dimensional nano sheet dispersion liquid to obtain a layered framework;
s3, inserting the binder solution or the fast ion conductor nanoparticle dispersion liquid into the layered frame obtained in the step S2 to prepare a layered film;
s4, adopting a hot pressing process to treat the layered membrane prepared in the step S3 to obtain the thin layered solid electrolyte membrane.
Preferably, the step S1 includes: the sucrose is used as a structure guiding agent to be mixed with the fast ion conductor precursor liquid, and the fast ion conductor two-dimensional nano-sheet dispersion liquid containing the fast ion conductor two-dimensional nano-sheets is obtained by a two-step sintering and liquid phase stripping method;
the fast ion conductor two-dimensional nano sheet is Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 (abbreviated as LATP) two-dimensional nanoplatelets, li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 (abbreviated as LAGP) two-dimensional nanosheets, li 7 La 3 Zr 2 O 12 (abbreviated as LAZO) two-dimensional nanoplatelets and Li 0.34 La 0.56 TiO 3 (abbreviated as LLTO) two-dimensional nanoplatelets.
Further, the fast ion conductor two-dimensional nano-sheet is an LLZO two-dimensional nano-sheet.
Preferably, in step S1, when sucrose and the precursor liquid of the fast ion conductor are blended, deionized water is adopted as a solvent, and magnetic stirring is carried out for 6-24 hours at room temperature, so as to obtain a mixed solution of sucrose and the precursor liquid of the fast ion conductor; the usage amount of the deionized water is 10-200ml.
In the present invention, the preparation of the mixed solution of sucrose and the fast ion conductor precursor liquid can be carried out in a conventional manner in the prior art. Further, the preparation method of the mixed solution of sucrose and LLZO precursor liquid comprises the following steps: and magnetically stirring and mixing sucrose, lithium nitrate, lanthanum nitrate hexahydrate and zirconyl nitrate in deionized water for 6-24 hours to prepare a mixed solution of sucrose and LLZO precursor liquid. Wherein, the mol ratio of sucrose, lithium nitrate, lanthanum nitrate hexahydrate and zirconyl nitrate is 1.45:7.7:3:2, and the dosage of deionized water is 10-200mL.
Preferably, in step S1, the two-step sintering process is as follows, in which the mixed solution of sucrose and the precursor liquid of the fast ion conductor is sintered at 150-300 ℃ for 2-5 hours, and then sintered at 800-1000 ℃ for 1-4 hours, so as to obtain the sheet-shaped frame of the fast ion conductor.
Further, the two-step sintering process is that the mixed solution of sucrose and LLZO precursor liquid is sintered for 2-5 hours at 150-300 ℃ and sintered for 1-4 hours at 800-1000 ℃ to obtain the LLZO sheet-shaped frame.
Preferably, in step S1, the liquid phase stripping process is as follows, and the fast ion conductor sheet frame is magnetically stirred in acetonitrile solvent for 10-20h at room temperature to obtain a fast ion conductor sheet frame dispersion liquid.
Preferably, in the step S1, the dispersion liquid of the fast ion conductor sheet frame is subjected to ultrasonic treatment at 20-60kHz for 3-10min, and then is subjected to centrifugal treatment at a rotating speed of 800-2000r/min for 5-15min, so that the fast ion conductor two-dimensional nano sheet dispersion liquid is obtained.
Further, the liquid phase stripping process is that the LLZO sheet frame is magnetically stirred for 10-20 hours at room temperature in acetonitrile solvent to obtain LLZO sheet frame dispersion liquid, ultrasonic treatment is carried out for 3-10 minutes at 20-60kHZ, and centrifugal treatment is carried out for 5-15 minutes at 800-2000r/min to obtain LLZO two-dimensional nano sheet dispersion liquid.
Preferably, step S2 includes: the dispersion liquid of the fast ion conductor two-dimensional nano-sheets is subjected to self-stacking on a base film by a method of suction filtration, spin coating, deposition or electrostatic atomization, so that a layered frame is prepared;
the layered framework obtained was dried in an argon-filled glove box for 6-24 hours, and the thickness of the layered framework obtained was 10-200 μm.
Preferably, the base film is a nylon film.
Preferably, in the step S2, the concentration of the fast ion conductor two-dimensional nano sheet dispersion liquid is 0.01-0.1g/L;
the rapid ion conductor two-dimensional nano sheet dispersion liquid enables rapid ion conductor two-dimensional nano sheets to be self-stacked on a base film through a suction filtration method, and a layered frame is prepared; the pressure of the suction filtration is 0.2-6MPa;
the fast ion conductor two-dimensional nano sheet is Li 7 La 3 Zr 2 O 12 The two-dimensional nano-sheet has a transverse dimension of 1-10 mu m and a thickness of 3-6nm.
Preferably, step S3 includes: the binder solution is a mixed solution of a binder, lithium salt and acetonitrile;
the fast ion conductor nanoparticle dispersion liquid is a dispersion liquid obtained by mixing fast ion conductor nanoparticles with acetonitrile;
inserting the binder solution or the fast ion conductor nanoparticle dispersion liquid into a layered framework in a suction filtration mode, and then standing and drying in a glove box filled with argon to obtain a layered membrane;
the binder is at least one of polyethylene oxide (PEO for short), polyvinylidene fluoride (PVDF for short) and polytetrafluoroethylene (PTFE for short); the lithium salt is lithium perchlorate (LiClO) 4 ) Lithium bis (trifluoromethanesulfonyl) imide (LiTFSI) and lithium tetrafluoroborate (LiBF) 4 ) At least one of (a) and (b);
the fast ion conductor nano-particles are Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 Nanoparticles, li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 Nanoparticles, li 7 La 3 Zr 2 O 12 Nanoparticles and Li 0.34 La 0.56 TiO 3 At least one of the nanoparticles.
Preferably, in the step S3, the molar ratio of the binder to the lithium salt in the binder solution is 8:1-15:1, and the concentration of the binder is 0.01-1g/L;
the suction filtration pressure is 3-8MPa, and the drying time is 6-24h;
further, the binder is polyvinylidene fluoride, and the lithium salt is lithium bistrifluoro methanesulfonimide.
Preferably, the suction filtration in the step S2 and the step S3 is vacuum filtration.
Preferably, the hot pressing temperature of the hot pressing process in the step S4 is 60-100 ℃, the hot pressing pressure is 2-10MPa, and the hot pressing time is 5-15min.
Preferably, the thin layered solid electrolyte membrane obtained in the step S4 has a thickness of 12-140 μm.
The thin layered solid electrolyte membrane obtained by the preparation method is applied to all-solid lithium batteries. Specifically, the thin layered solid electrolyte membrane can be cut and applied to an all-solid lithium battery; the specific cutting size is required according to the requirement, and is generally cut into a round shape with the diameter of 15-25 mm.
The action principle of the invention is as follows:
1) The quick ion conductor two-dimensional nano-sheet is preferably LLZO two-dimensional nano-sheet with stronger chemical stability with a lithium anode; LLZO two-dimensional nanoplatelets with high aspect ratio features exhibit less grain boundary resistance than pressed LLZO nanoparticles, favoring Li + Low drag transfer on two-dimensional nanoplatelets.
2) The layered framework imparts a thin thickness to the electrolyte, shortening Li + The diffusion distance of the LLZO phase is more continuous by the hot-pressing process; the short and continuous LLZO transmission channels greatly improve the conductivity of the thin layered solid electrolyte membrane.
3) The LLZO two-dimensional nano-sheet with high compressive strength and the interlayer PVDF binder improve the mechanical strength of the thin layered solid electrolyte membrane, and effectively inhibit the growth of lithium dendrites.
4) The thin thickness and high ionic conductivity give the thin layered solid electrolyte membrane super strong Li + The conductivity while PVDF at the LLZO surface reduces the interfacial resistance between the electrolyte and the electrode, so that an all-solid lithium battery using lithium iron phosphate as a positive electrode achieves excellent cycle and rate performance and high energy density.
In general, sucrose is used as a structure directing agent to be mixed with LLZO precursor liquid, LLZO two-dimensional nano-sheet dispersion liquid is obtained through a two-step sintering and liquid phase stripping method, and a loading technology is adopted to form a LLZO layered frame by self-stacking on a base film. Subsequently, PVDF/LiTFSI/acetonitrile solution (viscousThe binder solution) is introduced between the layered frames of the LLZO, and a thin layered solid electrolyte membrane is obtained through drying and hot pressing steps. LLZO two-dimensional nano-sheets with high aspect ratio features show smaller grain boundary resistance than pressed LLZO particles, and the layered frame imparts a thin thickness to the electrolyte, shortening Li + The hot pressing process makes the transfer path of the LLZO phase more continuous. Short and continuous LLZO transmission channels and low grain boundary resistance enable the layered solid electrolyte membrane to obtain super strong Li + Conductivity capability. Meanwhile, the LLZO two-dimensional nano sheet with high compressive strength and the interlayer PVDF binder are added to improve the mechanical properties of the thin layered solid electrolyte membrane, so that the growth of lithium dendrites is effectively inhibited, and further the high-performance all-solid-state lithium battery is obtained.
Compared with the prior art, the invention has the following beneficial effects:
compared with the traditional composite solid electrolyte and inorganic solid electrolyte, the thin layered solid electrolyte membrane prepared by the invention has good room temperature ion conductivity, migration number, high mechanical strength and low specific surface resistance, and can effectively inhibit the growth of lithium dendrites. Excellent electrochemical performance and safety performance can be realized in the application of the all-solid-state lithium battery, the attenuation of the battery capacity is restrained, the rate capability of the battery is improved, and the service life of the battery is prolonged. In addition, the vacuum suction filtration method used in the preparation process is simple, high in automation degree, high in production efficiency and easy to realize large-scale production.
Drawings
FIG. 1 is a scanning electron microscope image of LLZO two-dimensional nanoplatelets obtained in step 1) of example 1 of the present invention;
FIG. 2 is a sectional scanning electron microscope image and a corresponding physical image of a thin layered solid electrolyte membrane prepared in example 1 of the present invention;
FIG. 3 is a graph of temperature versus conductivity for example 1, comparative example 2;
FIG. 4 is a graph showing the temperature-surface specific resistance of example 1, comparative example 1, and comparative example 2;
FIG. 5 is a nanoindentation curve of the thin layered solid electrolyte membrane obtained in example 1;
fig. 6 is a 0.5C charge-discharge curve of a lithium iron phosphate/lithium battery assembled with a thin layered solid electrolyte membrane obtained in example 1;
fig. 7 is a rate charge-discharge curve of a lithium iron phosphate/lithium battery assembled with a thin layered solid electrolyte membrane obtained in example 1.
Detailed Description
The invention is further described in terms of specific examples, illustrative examples and illustrations of which are provided herein to illustrate the invention, but are not to be construed as limiting the invention.
Example 1
A preparation method of a thin layered solid electrolyte membrane comprises the following steps:
1) 0.531g of lithium nitrate, 1.3g of lanthanum nitrate hexahydrate, 0.462g of zirconyl nitrate and 0.5g of sucrose were magnetically stirred in 70mL of deionized water for 12 hours, and the ph=1.5 of the resulting mixed solution. The obtained mixed solution was sintered at 250℃for 4 hours and at 850℃for 2 hours to obtain an LLZO sheet-like frame. The obtained LLZO sheet frame was magnetically stirred in 50mL of acetonitrile solvent for 12 hours, then sonicated at 40kHZ for 5min, and finally centrifuged at 1000r/min for 10min to obtain a dispersion of LLZO two-dimensional nanoplatelets having a concentration of 0.05g/L.
2) Adding 200mL of LLZO two-dimensional nano-sheet dispersion liquid in 1) into a vacuum suction filtration device, performing suction filtration under the suction filtration pressure of 0.2Mpa, enabling LLZO two-dimensional nano-sheets to be slowly self-stacked on a base film to obtain a LLZO layered frame, and then placing the layered frame into a glove box filled with argon gas for drying for 12h; the base film is a nylon film;
3) Performing vacuum suction filtration on the obtained LLZO layered frame in PVDF/LiTFSI/acetonitrile solution (the molar ratio of PVDF to LiTFSI is 10:1) with the PVDF concentration of 0.02g/L, wherein the suction filtration pressure is 4MPa, obtaining a layered membrane, and then placing the layered membrane into a glove box filled with argon gas for drying for 12 hours;
4) The resulting layered membrane was hot-pressed at 80℃for 10 minutes at a pressure of 5MPa to obtain a thin layered solid electrolyte membrane having a thickness of 12. Mu.m. And (5) cutting the wafer into wafers with the diameter of 19mm, and assembling the wafer into the all-solid-state lithium battery.
In this embodiment, the positive electrode material of the all-solid-state lithium battery is lithium iron phosphate, specifically, lithium iron phosphate: conductive carbon black: binder = 8:1:1 mass ratio of the slurry was coated on an aluminum foil current collector 12mm in diameter and dried in vacuo at 60 ℃ for 12h. The anode material of the all-solid-state lithium battery is a lithium sheet with the commercial diameter of 16 mm.
Performance tests were performed on thin layered solid electrolyte membranes and assembled cells thereof, with the following results: the ionic conductivity of the thin layered solid electrolyte membrane at room temperature was 1.3X10 -4 S cm -1 The method comprises the steps of carrying out a first treatment on the surface of the At 30 ℃, the specific surface resistance is 9.3 Ω cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The compressive strength is 2.9GPa, and the ion migration number is 0.91; initial discharge capacity at 60℃and 0.5℃was 164.1mAh g -1 The discharge capacity after 200 cycles is 142.4mAh g -1 。
As shown in fig. 1, a scanning electron microscope image of the LLZO two-dimensional nanosheets obtained in step 1) of embodiment 1 of the present invention is shown; typical platelet morphology, 3-5 μm in size, can be visually observed from FIG. 1.
As shown in fig. 2, a cross-sectional scanning electron microscope image and a corresponding physical image of a thin layered solid electrolyte membrane are prepared and obtained in embodiment 1 of the present invention; it can be intuitively illustrated from fig. 2 that the layered solid electrolyte membrane prepared in this example has a thin thickness (its thickness is/12 μm).
Example 2
A preparation method of a thin layered solid electrolyte membrane comprises the following steps:
1) Preparation of LLZO two-dimensional nanoplatelet dispersion the same as in example 1;
2) Adding 230mL of the LLZO two-dimensional nano-sheet dispersion liquid in the 1) into a vacuum suction filtration device, performing suction filtration under the suction filtration pressure of 0.2MPa, enabling the LLZO two-dimensional nano-sheets to be slowly self-stacked on a base film to obtain a LLZO layered frame, and then placing the LLZO layered frame into a glove box filled with argon gas for drying for 12 hours; the base film is a nylon film;
3) Vacuum filtering the obtained LLZO layered frame in PVDF/LiTFSI/acetonitrile solution (the molar ratio of PVDF to LiTFSI is 10:1) with the PVDF concentration of 0.03g/L, wherein the suction filtering pressure is 4MPa, obtaining a layered membrane, and then placing the layered membrane into a glove box filled with argon gas for drying for 12 hours;
4) The resulting layered membrane was hot-pressed at 80℃for 10 minutes at a pressure of 5MPa to obtain a thin layered solid electrolyte membrane having a thickness of 20. Mu.m.
Example 3
A preparation method of a thin layered solid electrolyte membrane comprises the following steps:
1) Preparation of LLZO two-dimensional nanoplatelet dispersion the same as in example 1;
2) Adding the LLZO two-dimensional nano-sheet dispersion liquid in 1200mL 1) into a vacuum suction filtration device, performing suction filtration under the suction filtration pressure of 0.4MPa, enabling the LLZO two-dimensional nano-sheets to be slowly self-stacked on a base film to obtain a LLZO layered frame, and then placing the layered frame into a glove box filled with argon gas for drying for 12h; the base film is a nylon film;
3) Performing suction filtration on the obtained LLZO layered frame in a PVDF/LiTFSI/acetonitrile solution (the molar ratio of PVDF to LiTFSI is 10:1) with the PVDF concentration of 0.05g/L, wherein the suction filtration pressure is 6MPa, obtaining a layered membrane, and then placing the layered membrane into a glove box filled with argon gas for drying for 12 hours;
4) The resulting layered membrane was hot-pressed at 80℃for 10 minutes under a pressure of 5MPa to obtain a thin layered solid electrolyte membrane having a thickness of 60. Mu.m.
Example 4
A preparation method of a thin layered solid electrolyte membrane comprises the following steps:
1) Preparation of LLZO two-dimensional nanoplatelet dispersion the same as in example 1;
2) Adding the LLZO two-dimensional nano-sheet dispersion liquid in 210ml 1) into a vacuum suction filtration device, performing suction filtration under the suction filtration pressure of 0.6MPa, enabling the LLZO two-dimensional nano-sheets to be slowly self-stacked on a base film to obtain a LLZO layered frame, and then placing the layered frame into a glove box filled with argon gas for drying for 12 hours; the base film is a nylon film;
3) Performing vacuum filtration on the obtained LLZO layered frame in a PVDF/LiTFSI/acetonitrile solution (the molar ratio of PVDF to LiTFSI is 10:1) with the PVDF concentration of 0.08g/L, wherein the suction filtration pressure is 8MPa, obtaining a layered membrane, and then placing the layered membrane into a glove box filled with argon gas for drying for 12 hours;
4) The resulting layered membrane was hot-pressed at 80℃for 10 minutes under a pressure of 5MPa to obtain a thin layered solid electrolyte membrane having a thickness of 140. Mu.m.
Comparative example 1
A method for preparing a composite solid electrolyte, comprising the steps of:
1) Preparation of LLZO two-dimensional nanosheet dispersion liquid the same as in example 1, drying the dispersion liquid at 60℃to obtain LLZO two-dimensional nanosheet powder;
2) Weighing 0.1g of LLZO two-dimensional nano-sheet powder, 1g of PVDF and 0.42g of LiTFSI in the step 1), adding 40mL of acetonitrile, magnetically stirring for 4 hours in a glove box, and completely dissolving and uniformly mixing to obtain a mixed solution;
3) Pouring the mixed solution obtained in the step 2) onto a clean polytetrafluoroethylene substrate, casting the mixed solution into a film, and vacuum drying the film at 60 ℃ for 24 hours to obtain the composite solid electrolyte with the thickness of 140 mu m.
The performance of the composite solid electrolyte was tested, with the following results: the ionic conductivity of the composite solid electrolyte at room temperature is 3.16X10 -5 S cm -1 The method comprises the steps of carrying out a first treatment on the surface of the Specific surface resistance at 30℃was 442.8. OMEGA cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The compressive strength was 318MPa, and the ion migration number was 0.27.
Comparative example 2
A method for preparing an inorganic solid electrolyte, comprising the steps of:
1) 0.4g of LLZO two-dimensional nano-sheet powder obtained in the step 1) of the comparative example is taken and put into a cold-pressing grinding tool with the diameter of 19mm, and the cold-pressing grinding tool is pressed for 10min under 400MPa, so that an LLZO ceramic sheet is obtained;
2) And sintering the LLZO ceramic plate for 8 hours at the temperature of 1000 ℃ to obtain the compact inorganic solid electrolyte of the LLZO ceramic plate, wherein the thickness of the inorganic solid electrolyte is 200 mu m.
Performance testing was performed on the inorganic solid electrolyte, resulting in: the ionic conductivity of the inorganic solid electrolyte at room temperature was 1.42×10 -5 S cm -1 The method comprises the steps of carrying out a first treatment on the surface of the Specific surface resistance at 30℃is 1402.9 Ω cm 2 。
As shown in fig. 3, temperature-conductivity graphs of example 1, comparative example 1, and comparative example 2 are shown; as shown in FIG. 4, the temperature-surface specific resistance diagrams of example 1, comparative example 1 and comparative example 2 are shown.
And a composite solid electrolyteThe thin layered solid electrolyte membrane obtained in example 1 was found to be short in Li due to its short length as compared with an inorganic solid electrolyte + The diffusion distance, low grain boundary resistance and continuous LLZO transmission channels obtain higher ion conductivity, and the ultra-thin thickness of the film obviously reduces the surface specific resistance of the solid electrolyte.
The nanoindentation curve of the thin layered solid electrolyte membrane obtained in example 1 is shown in fig. 5. This figure demonstrates that the thin layered solid electrolyte membrane obtained in example 1 of the present invention achieves ultra-high compressive strength.
Fig. 6 shows a 0.5C charge-discharge curve of a lithium iron phosphate/lithium battery assembled with a thin layered solid electrolyte membrane obtained in example 1; fig. 7 shows the rate charge-discharge curves of the lithium iron phosphate/lithium battery assembled with the thin layered solid electrolyte membrane obtained in example 1.
The high room temperature ionic conductivity, mechanical strength and low specific surface resistance of the thin layered solid electrolyte membrane obtained in example 1 of the present invention are demonstrated to exhibit excellent cycle performance and rate performance in all-solid lithium battery applications.
Claims (8)
1. A method for preparing a thin layered solid electrolyte membrane, comprising the steps of:
s1, preparing a fast ion conductor two-dimensional nano sheet dispersion liquid;
s2, self-stacking the fast ion conductor two-dimensional nano sheets in the fast ion conductor two-dimensional nano sheet dispersion liquid to obtain a layered framework;
s3, inserting the binder solution or the fast ion conductor nanoparticle dispersion liquid into the layered frame obtained in the step S2 to prepare a layered film;
s4, adopting a hot-pressing process to treat the layered membrane prepared in the step S3 to obtain a thin layered solid electrolyte membrane;
the step S1 includes: the sucrose is used as a structure guiding agent to be mixed with the fast ion conductor precursor liquid, and the fast ion conductor two-dimensional nano-sheet dispersion liquid containing the fast ion conductor two-dimensional nano-sheets is obtained by a two-step sintering and liquid phase stripping method;
the fast ion conductor two-dimensional nano sheet is Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 Two-dimensional nanoplatelets, li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 Two-dimensional nanoplatelets, li 7 La 3 Zr 2 O 12 Two-dimensional nanoplatelets and Li 0.34 La 0.56 TiO 3 At least one of the two-dimensional nanoplatelets;
in the step S1, the two-step sintering process is as follows, the mixed solution of sucrose and the precursor liquid of the fast ion conductor is sintered for 2-5 hours at 150-300 ℃, and then sintered for 1-4 hours at 800-1000 ℃ to obtain the sheet frame of the fast ion conductor;
in the step S1, the liquid phase stripping process is as follows, and the fast ion conductor sheet frame is magnetically stirred in acetonitrile solvent for 10-20h at room temperature to obtain fast ion conductor sheet frame dispersion liquid;
the step S2 comprises the following steps: the dispersion liquid of the fast ion conductor two-dimensional nano-sheets is subjected to self-stacking on a base film by a method of suction filtration, spin coating, deposition or electrostatic atomization, so that a layered frame is prepared;
drying the prepared lamellar framework for 6-24 hours in a glove box filled with argon, wherein the thickness of the obtained lamellar framework is 10-200 mu m;
the step S3 comprises the following steps: the binder solution is a mixed solution of a binder, lithium salt and acetonitrile;
the fast ion conductor nanoparticle dispersion liquid is a dispersion liquid obtained by mixing fast ion conductor nanoparticles with acetonitrile.
2. The method for producing a thin layered solid electrolyte membrane according to claim 1, characterized in that: in the step S1, when sucrose and the precursor liquid of the fast ion conductor are blended, deionized water is adopted as a solvent, and magnetic stirring is carried out for 6-24 hours at room temperature, so as to obtain a mixed solution of sucrose and the precursor liquid of the fast ion conductor.
3. The method for producing a thin layered solid electrolyte membrane according to claim 2, characterized in that: in the step S1, the dispersion liquid of the fast ion conductor sheet frame is subjected to ultrasonic treatment for 3-10min at 20-60kHz, and then is subjected to centrifugal treatment for 5-15min at the rotating speed of 800-2000r/min, so that the fast ion conductor two-dimensional nano sheet dispersion liquid is obtained.
4. The method for producing a thin layered solid electrolyte membrane according to claim 1, characterized in that: in the step S2, the concentration of the fast ion conductor two-dimensional nano sheet dispersion liquid is 0.01-0.1g/L;
the rapid ion conductor two-dimensional nano sheet dispersion liquid enables rapid ion conductor two-dimensional nano sheets to be self-stacked on a base film through a suction filtration method, and a layered frame is prepared; the pressure of the suction filtration is 0.2-6MPa;
the fast ion conductor two-dimensional nano sheet is Li 7 La 3 Zr 2 O 12 Two-dimensional nanoplatelets.
5. The method for producing a thin layered solid electrolyte membrane according to claim 1 or 4, characterized in that:
inserting the binder solution or the fast ion conductor nanoparticle dispersion liquid into a layered framework in a suction filtration mode, and then standing and drying in a glove box filled with argon to obtain a layered membrane;
the binder is at least one of polyethylene oxide (PEO), polyvinylidene fluoride (PVDF) and Polytetrafluoroethylene (PTFE); the lithium salt is lithium perchlorate (LiClO) 4 ) Lithium bis (trifluoromethanesulfonyl) imide (LiTFSI) and lithium tetrafluoroborate (LiBF) 4 ) At least one of (a) and (b);
the fast ion conductor nano-particles are Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 Nanoparticles, li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 Nanoparticles, li 7 La 3 Zr 2 O 12 Nanoparticles and Li 0.34 La 0.56 TiO 3 At least one of the nanoparticles.
6. The method for producing a thin layered solid electrolyte membrane according to claim 5, characterized in that: in the step S3, in the binder solution, the molar ratio of the binder to the lithium salt is 8:1-15:1, and the concentration of the binder is 0.01-1g/L;
the suction filtration pressure is 3-8MPa, and the drying time is 6-24h;
the binder is polyvinylidene fluoride, and the lithium salt is lithium bis (trifluoromethanesulfonyl) imide.
7. The method for producing a thin layered solid electrolyte membrane according to claim 1, characterized in that: the hot pressing temperature of the hot pressing process in the step S4 is 60-100 ℃, the hot pressing pressure is 2-10MPa, and the hot pressing time is 5-15min.
8. The thin layered solid electrolyte membrane obtained by the production method according to any one of claims 1 to 7 is used in an all-solid lithium battery.
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| CN105762441A (en) * | 2016-02-29 | 2016-07-13 | 苏州大学张家港工业技术研究院 | Preparation method of lithium air battery based on lithium ion solid electrolyte |
| CN108178625A (en) * | 2018-01-19 | 2018-06-19 | 华南理工大学 | A kind of preparation method of layered solid ceramic electrolyte, total solids ultracapacitor |
| CN110911746A (en) * | 2019-11-29 | 2020-03-24 | 华中科技大学 | Two-dimensional nano-structure electrolyte additive, preparation method and application |
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| CN105762441A (en) * | 2016-02-29 | 2016-07-13 | 苏州大学张家港工业技术研究院 | Preparation method of lithium air battery based on lithium ion solid electrolyte |
| CN108178625A (en) * | 2018-01-19 | 2018-06-19 | 华南理工大学 | A kind of preparation method of layered solid ceramic electrolyte, total solids ultracapacitor |
| CN110911746A (en) * | 2019-11-29 | 2020-03-24 | 华中科技大学 | Two-dimensional nano-structure electrolyte additive, preparation method and application |
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| Title |
|---|
| zhihao zhang 等.Lithiated nanosheets hybridized solid polymer electrolyte to construct Li+ conduction highways for advanced all-solid-state lithium battery.Journal of Power Sources.2021,第484卷229287中的第1-8页. * |
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