CN114937811A - Double-layer solid electrolyte and preparation method and application thereof - Google Patents
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Abstract
本发明涉及电解质技术领域，尤其涉及一种双层固态电解质及其制备方法和应用，所述双层固态电解质为硅磷酸锆钠陶瓷层和附着于硅磷酸锆钠陶瓷层表面的聚氧化乙烯基聚合物层；所述聚氧化乙烯基聚合物层为负载钠盐的聚氧化乙烯‑丁二腈膜。本发明以硅磷酸锆钠陶瓷层作为主体，所述硅磷酸锆钠陶瓷层具备较高的离子电导率，可以使钠离子更快速地在电池中传输。同时本发明采用聚氧化乙烯层依附在硅磷酸锆钠陶瓷层上，具备较好的柔韧性，当用于电池中时，可以使双层固态电解质与钠负极的接触更加紧密，从而有效降低界面电阻。而且，本发明采用的聚氧化乙烯聚合物具有较高的还原稳定性，可以有效降低固态电池的放电电压，从而也可以提高电池的容量。The invention relates to the technical field of electrolytes, in particular to a double-layer solid electrolyte and a preparation method and application thereof. The double-layer solid electrolyte is a ceramic layer of sodium zirconium silicophosphate and a polyoxyethylene group attached to the surface of the sodium zirconium silicophosphate ceramic layer. A polymer layer; the polyethylene oxide polymer layer is a sodium salt-loaded polyethylene oxide-succinonitrile film. The present invention uses the sodium zirconium silicophosphate ceramic layer as the main body, and the sodium zirconium silicophosphate ceramic layer has higher ionic conductivity, which can make the sodium ions transmit in the battery more quickly. At the same time, the present invention adopts the polyethylene oxide layer attached to the sodium zirconium silicate phosphate ceramic layer, which has good flexibility. When used in a battery, the contact between the double-layer solid electrolyte and the sodium negative electrode can be made closer, thereby effectively reducing the interface resistance. Moreover, the polyethylene oxide polymer used in the present invention has high reduction stability, which can effectively reduce the discharge voltage of the solid-state battery, thereby increasing the capacity of the battery.
Description
Technical Field
The invention relates to the technical field of electrolytes, in particular to a double-layer solid electrolyte and a preparation method and application thereof.
Background
Over the past two decades, lithium ion batteries have been rapidly developed. However, the price rise hinders the further application of lithium ion batteries, and therefore the search for cheaper batteries to replace lithium ion batteries is urgent. Sodium ion batteries are considered to be the best energy storage device to replace lithium ion batteries due to their abundant sodium resources and low cost. Unlike organic liquid electrolytes, which are prone to leakage, flammable, and ineffective for dendrite suppression, solid sodium electrolytes are widely used in sodium ion batteries to improve safety.
Many types of solid sodium electrolytes, such as ceramic solid electrolytes, polymer solid electrolytes, and ceramic-polymer composite solid electrolytes, have been studied so far. The poor interfacial contact of ceramic solid electrolytes and the low strength of polymer solid electrolytes limit their practical applications. However, ceramic-polymer composite solid electrolytes such as polyoxyethylene-sodium silico-zirconium phosphate composite solid electrolytes are an attractive material because they can ensure high ionic conductivity and improve interfacial contact with electrodes.
At present, the preparation method of the polyoxyethylene-sodium silico-zirconium phosphate composite solid electrolyte generally mixes sodium silico-zirconium phosphate ceramic particles with polyoxyethylene directly, and the sodium silico-zirconium phosphate ceramic particles and the polyoxyethylene are doped with each other to obtain the composite solid electrolyte. However, since the sodium zirconium silicophosphate ceramic particles are easy to agglomerate during the mixing process, the agglomerated sodium zirconium silicophosphate ceramic particles can hinder the transmission of sodium ions in the electrolyte, thereby reducing the ionic conductivity.
Disclosure of Invention
In view of the above, the present invention provides a two-layer solid electrolyte, and a preparation method and applications thereof. The double-layer solid electrolyte provided by the invention has higher ionic conductivity.
In order to achieve the above object, the present invention provides a double-layered solid electrolyte, which is a zirconium sodium silicophosphate ceramic layer and a polyoxyethylene-based polymer layer attached to the surface of the zirconium sodium silicophosphate ceramic layer; the polyoxyethylene-based polymer layer is a sodium salt-loaded polyoxyethylene-succinonitrile film.
Preferably, the sodium salt comprises sodium perchlorate and/or sodium bis (trifluoromethylsulfonyl) imide.
Preferably, the molar ratio of sodium in the sodium salt to ether oxygen of polyoxyethylene in the polyoxyethylene-succinonitrile film is (10-20): 1.
preferably, the mass ratio of polyoxyethylene to succinonitrile in the polyoxyethylene-succinonitrile film is (1-2): 1.
preferably, the thickness ratio of the silicon-zirconium-sodium phosphate ceramic layer to the polyoxyethylene-based polymer layer is 1.2 (0.001-0.1).
The invention also provides a preparation method of the double-layer solid electrolyte, which comprises the following steps:
dissolving polyoxyethylene, sodium salt and succinonitrile to obtain a polyoxyethylene-containing solution;
and pouring the solution containing the polyethylene oxide onto the surface of the silicon-zirconium sodium phosphate ceramic layer, and drying to obtain the double-layer solid electrolyte.
Preferably, the dissolved reagent comprises one or more of acetonitrile, water, methanol and acetone.
Preferably, the drying temperature is 60-80 ℃, and the drying time is 24-36 h.
Preferably, the dissolving is performed by ultrasonic dissolving and stirring dissolving in sequence.
The invention also provides the application of the double-layer solid electrolyte or the double-layer solid electrolyte prepared by the preparation method in a sodium ion battery.
The invention provides a double-layer solid electrolyte, which is a silicon-zirconium sodium phosphate ceramic layer and a polyoxyethylene-based polymer layer attached to the surface of the silicon-zirconium sodium phosphate ceramic layer; the polyoxyethylene-based polymer layer is a sodium salt-loaded polyoxyethylene-succinonitrile film. The succinonitrile in the polyoxyethylene-based polymer layer can effectively reduce the crystallinity of the polyoxyethylene, thereby improving the ionic conductivity of the electrolyte. Meanwhile, when the double-layer solid electrolyte provided by the invention is used in a sodium ion battery, the polyoxyethylene-based polymer layer attached to the silicon zirconium sodium phosphate ceramic layer is used as a transition layer, so that the double-layer solid electrolyte can be in closer contact with a sodium cathode, and the interface resistance between the silicon zirconium sodium phosphate ceramic layer and the sodium cathode is effectively reduced. In addition, the sodium zirconium silicophosphate ceramic layer adopted by the invention has high oxidation stability, and can effectively improve the charging voltage of the solid-state battery, thereby improving the capacity of the battery. Meanwhile, the polyethylene oxide polymer layer has higher reduction stability, can effectively reduce the discharge voltage of the solid-state battery, and improves the capacity of the battery.
The invention provides a preparation method of the double-layer solid electrolyte, which comprises the following steps: dissolving polyoxyethylene, sodium salt and succinonitrile to obtain a polyoxyethylene-containing solution; and pouring the solution containing the polyethylene oxide onto the surface of the silicon-zirconium sodium phosphate ceramic layer, and drying to obtain the double-layer solid electrolyte. According to the invention, the polyoxyethylene solution is poured to the silicon-sodium zirconium phosphate ceramic layer, so that the problem that the ionic conductivity is reduced due to agglomeration caused by blending with the silicon-sodium zirconium phosphate ceramic particles is avoided.
Drawings
FIG. 1 is an SEM photograph of a two-layer solid electrolyte obtained in example 1;
FIG. 2 is an XRD pattern of a two-layer solid electrolyte obtained in example 1;
FIG. 3 is a graph showing the AC impedance of the two-layer solid electrolyte prepared in example 1;
FIG. 4 is an SEM photograph of the polymer solid electrolyte prepared in comparative example 1;
FIG. 5 is an XRD pattern of the polymer solid electrolyte prepared in comparative example 1;
FIG. 6 is a graph of the AC impedance of the polymer solid electrolyte prepared in comparative example 1;
FIG. 7 is a graph showing the cycling performance of a symmetrical cell made with the solid electrolyte described in example 1;
FIG. 8 is a graph showing the cycle performance of half cells prepared from the solid electrolyte described in example 1;
FIG. 9 is a graph showing the cycle performance of a symmetrical cell prepared from the solid electrolyte described in comparative example 1;
fig. 10 is a graph showing the cycle performance of a half cell prepared from the solid electrolyte described in comparative example 1.
Detailed Description
The invention provides a double-layer solid electrolyte, which is a silicon-zirconium sodium phosphate ceramic layer and a polyoxyethylene-based polymer layer attached to the surface of the silicon-zirconium sodium phosphate ceramic layer; the polyoxyethylene-based polymer layer is a sodium salt-loaded polyoxyethylene-succinonitrile film.
In the present invention, unless otherwise specified, the starting materials used in the present invention are preferably commercially available products.
In the invention, the thickness ratio of the silicon zirconium sodium phosphate ceramic layer to the polyoxyethylene-based polymer layer is preferably 1.2 (0.001-0.1), and more preferably 1.2: 0.02.
In the invention, the silicon-zirconium-sodium phosphate ceramic layer is preferably a silicon-zirconium-sodium phosphate ceramic sheet; the silicon zirconium sodium phosphate ceramic sheet is preferably prepared according to the preparation method of CN 114188601A. In the embodiment of the present invention, the diameter of the silicon-zirconium-sodium phosphate ceramic sheet is specifically and preferably 16mm, and the thickness is specifically and preferably 1.2 mm.
In the present invention, the raw materials for preparing the polyoxyethylene polymer layer preferably include polyoxyethylene, sodium salt and succinonitrile. In the present invention, the polyethylene oxide polymer preferably has a weight average molecular weight of 1X 10 4 ～5×10 6 More preferably 1X 10 6 ～5×10 6 . In the present invention, the sodium salt preferably includes sodium perchlorate and/or sodium bis (trifluoromethylsulfonyl) imide, more preferably sodium perchlorate.
In the present invention, the molar ratio of sodium in the sodium salt to ether oxygen of polyoxyethylene in the polyoxyethylene-succinonitrile membrane is preferably (10 to 20): 1, more preferably (12-18): 1. in the invention, the mass ratio of polyoxyethylene to succinonitrile in the polyoxyethylene-succinonitrile film is preferably (1-2): 1, more preferably (1.1-1.6): 1, most preferably (1.2-1.4): 1.
the invention also provides a preparation method of the double-layer solid electrolyte, which comprises the following steps:
dissolving polyoxyethylene, sodium salt and succinonitrile to obtain a polyoxyethylene-containing solution;
and pouring the solution containing the polyethylene oxide onto the surface of the silicon-zirconium sodium phosphate ceramic layer, and drying to obtain the double-layer solid electrolyte.
The invention dissolves polyoxyethylene, sodium salt and succinonitrile to obtain the solution containing polyoxyethylene.
In the present invention, the dissolved reagent preferably comprises one or more of acetonitrile, water, methanol and acetone, more preferably acetonitrile. In the present invention, the mass ratio of the polyethylene oxide to the dissolved reagent is preferably (1 to 20): 100, more preferably (3-7) 100, and most preferably (4-6): 100.
in the invention, the dissolution can couple sodium ions in the sodium salt and ether oxygen bonds of polyoxyethylene to realize the loading of the sodium salt.
In the present invention, the dissolving preferably includes sequentially performing ultrasonic dissolving and agitation dissolving; the ultrasonic dissolving frequency is preferably 20-40 kHz, and more preferably 30-40 kHz; the time is preferably 10 to 90min, more preferably 20 to 80min, and most preferably 30 to 60 min. In the invention, the rotation speed of the stirring is preferably 200-800 rpm, more preferably 300-600 rpm; the time is preferably 12 to 24 hours, and more preferably 18 to 24 hours.
After obtaining the polyoxyethylene solution, the invention pours the polyoxyethylene-containing solution onto the surface of the silicon-zirconium sodium phosphate ceramic layer, and dries to obtain the double-layer solid electrolyte.
In the present invention, the pouring is preferably performed using a pipette gun having a range of 100. mu.L.
In the present invention, the drying is preferably vacuum drying; the vacuum degree of the drying is preferably-0.04 to-0.08 MPa, and more preferably-0.05 to-0.06 MPa; the drying temperature is preferably 60-80 ℃, more preferably 60-70 ℃, and the time is preferably 24-36 h, more preferably 30-36 h. In the present invention, the drying is preferably performed in a vacuum drying oven.
The invention also provides the application of the double-layer solid electrolyte or the double-layer solid electrolyte prepared by the preparation method in a sodium ion battery.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
1.6g of polyethylene oxide (weight average molecular weight: 100 ten thousand), 0.2968g of sodium perchlorate, 1.28g of succinonitrile and 30.4g of acetonitrile were placed in a beaker, and after ultrasonic dissolution for 60min (ultrasonic frequency: 40kHz), a magnetic stirrer was added and stirred at 500rpm for 24 hours to obtain a polyethylene oxide solution.
Pouring 1.5mL of the polyoxyethylene solution onto a silicon zirconium sodium phosphate ceramic chip with the diameter of 16mm and the thickness of 1.2 mm; drying the electrolyte in a vacuum oven with the vacuum degree of-0.06 MPa for 36h at the temperature of 60 ℃ to obtain the double-layer solid electrolyte (the total thickness is 1.22 mm).
The two-layer solid electrolyte prepared in example 1 was subjected to SEM test, and the results are shown in fig. 1. XRD test was performed on the two-layer solid electrolyte prepared in example 1, and the result is shown in fig. 2. As shown in FIGS. 1-2, the double-layer solid electrolyte is mainly composed of sodium zirconium silicophosphate ceramic, and polyethylene oxide polymer with a thickness of only 20 μm is attached to the main body and is very tightly bonded.
FIG. 3 is a graph showing the AC impedance of the two-layer solid electrolyte prepared in example 1, and it can be seen from FIG. 3 that the semicircular part is the high frequency region and the diagonal part is the low frequency region, and the impedance of the electrolyte can be obtained from the boundary between the high frequency and the low frequency in the graph as 176.5. omega. thus, the ionic conductivity was calculated to be 3.44X 10 -4 S·cm -1 。
Comparative example 1
Placing 1.6g of polyoxyethylene (with a molecular weight of 100 ten thousand), 0.2968g of sodium perchlorate, 1.28g of succinonitrile and 30.4g of acetonitrile in a beaker, ultrasonically dissolving for 60min (with an ultrasonic frequency of 40kHz), and then adding a magnetic stirrer for stirring, wherein the stirring speed is 500rpm and the stirring time is 24 hours, so as to obtain a polyoxyethylene solution;
16.5mL of the polyethylene oxide solution was poured into a polytetrafluoroethylene disk having a diameter of 8.2cm, to which was added a polytetrafluoroethylene disk having a diameter of 8cm and a mass of 10 g.m -1 The nonwoven fabric of (1); drying at 60 ℃ for 36h in a vacuum oven with the vacuum degree of-0.06 MPa to obtain the polymer solid electrolyte (the thickness is 100 mu m).
The polymer solid electrolyte prepared in comparative example 1 was subjected to SEM test, and as a result, as shown in fig. 4, it was understood from fig. 4 that the surface of the polymer electrolyte was flat without spherulites, indicating that succinonitrile reduced the crystallinity of polyethylene oxide.
The polymer solid electrolyte prepared in comparative example 1 was subjected to XRD testing, and the result is shown in fig. 5, from which fig. 5 it can be seen that succinonitrile in the polymer solid electrolyte was completely inserted into a polyoxyethylene chain.
FIG. 6 is a graph showing the AC impedance of the polymer solid electrolyte prepared in comparative example 1, and it can be seen from FIG. 6 that the semicircular part is the high frequency region and the diagonal part is the low frequency region, and the impedance of the electrolyte can be obtained from the boundary between the high frequency and the low frequency in the graph as 298.7. omega. thus, the ionic conductivity was calculated to be 1.67X 10 -5 S·cm -1 。
Comparing example 1 and comparative example 1, the two-layered solid electrolyte prepared in example 1 can significantly improve the ionic conductivity.
Test example 1
The same polyethylene oxide solution was cast on the other side of the solid electrolyte described in example 1 and dried to form a three-layer solid electrolyte, in this order polyethylene oxide layer-zirconium sodium silicophosphate ceramic layer-polyethylene oxide layer. The three layers of solid electrolyte and two sodium sheets with the diameter of 14mm and the thickness of 0.7mm are placed in a CR2032 battery case, and the three layers of solid electrolyte and the sodium sheets are arranged in sequence. Applying (a) toAdding 9.5MPa pressure to press into symmetrical cell, and testing cell at 0.1 mA-cm –2 And 0.1mAh · cm –2 The cycle performance of (c). The test results are shown in fig. 7. As can be seen from fig. 7: the symmetric cell remained stable after 740h cycling, showing stable intercalation and deintercalation of sodium ions.
Mixing and grinding sodium vanadium phosphate, carbon black and polyvinylidene fluoride according to the proportion of 160mg to 20mg, then adding 980 mgN-methyl pyrrolidone and stirring for 5 hours to obtain slurry; the slurry was cast onto aluminum foil. Drying at 80 ℃ for 12h, cutting into circular positive plates with the diameter of 14mm, wherein the loading capacity of each active material is 1.84 mg. The positive plate, the two-layer solid electrolyte and a sodium plate with a diameter of 14mm and a thickness of 0.7mm were placed in a CR2025 battery case, in the order of the positive plate-two-layer solid electrolyte (sodium zirconium silicophosphate-polyethylene oxide) -sodium plate. Applying pressure of 9.5MPa to press the battery into a half battery, and then testing the cycle performance of the battery under the current density of 0.5C and the voltage range of 2.0-4.0V. The test results are shown in fig. 8: the capacity of the half cell after 100 cycles at 0.5C was 106.6mAhg -1 The capacity retention rate is as high as 99.6%.
Test example 2
The polymer solid electrolyte prepared in comparative example 1 and two sodium sheets having a diameter of 14mm and a thickness of 0.7mm were placed in a CR2025 battery case in the order of sodium sheet-polymer solid electrolyte-sodium sheet. The cell was pressed into a symmetrical cell under a pressure of 9.5MPa, and then the cell was tested at 0.1 mA-cm –2 And 0.1mAh · cm –2 The cycle performance of (c). The test results are shown in fig. 9. As can be seen from fig. 9: the symmetric battery has a short circuit phenomenon only at 382h, which shows that the sodium dendrite inhibition capability of the polymer solid electrolyte is weak, and the long-term charge-discharge cycle of the symmetric battery cannot be supported.
Mixing and grinding sodium vanadium phosphate, carbon black and polyvinylidene fluoride according to the proportion of 160mg to 20mg, then adding 980mg of N-methylpyrrolidone and stirring for 5 hours to obtain slurry; the slurry was cast onto aluminum foil. Drying at 80 ℃ for 12h, cutting into circular positive plates with the diameter of 14mm, wherein the loading capacity of each active material is 1.84 mg. Placing a positive plate, a polymer solid electrolyte and a sodium plate with the diameter of 14mm and the thickness of 0.7mm in a containerIn the CR2025 battery case, the order is positive plate-polymer solid electrolyte-sodium plate. And applying a pressure of 9.5MPa to press the battery into a half battery, and then testing the cycle performance of the battery under the current density of 0.5C and the voltage range of 2.5-3.8V. The test results are shown in fig. 10, and it can be seen from fig. 10 that: the capacity of the half cell after 100 cycles at 0.5C was 74.7mAh g –1 The capacity retention rate is 80.7%, which is lower than that of a half-cell assembled by a double-layer electrolyte.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and amendments can be made without departing from the principle of the present invention, and these modifications and amendments should also be considered as the protection scope of the present invention.
Claims (10)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2025065930A1 (en) * | 2023-09-28 | 2025-04-03 | 深圳欣界能源科技有限公司 | Double-layer solid electrolyte membrane and preparation method therefor |
| CN118183672A (en) * | 2024-03-15 | 2024-06-14 | 泉州师范学院 | Preparation and application of ultrafine cubic sodium zirconium phosphate and its loaded antibacterial agent |
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