Preparation and application of solid electrolytes and their MXene-derived titanium dioxide additives

Abstract

This invention relates to the field of zinc-ion battery technology, providing the preparation and application of a solid electrolyte and its MXene-derived titanium dioxide additive. The preparation method of the solid electrolyte includes: mixing zinc trifluoromethanesulfonate and acetamide at a mass ratio of 1:1.137, heating and stirring in an 85°C water bath until a liquid state is achieved; adding 1 wt%, 2 wt%, 3 wt%, 4 wt%, and 5 wt% TiO2@Ti3C2 powder to the solution, and stirring until homogeneous; injecting the electrolyte into a glass fiber membrane at high temperature, and then cooling and solidifying at room temperature to obtain a solid electrolyte for application in batteries. In this invention, the TiO2@Ti3C2 filler improves the ionic conductivity of the solid electrolyte, promotes the dissociation of zinc salts, forms ion transfer channels on the filler surface, and acts as a plasticizer to reduce polymer crystallinity and enhance chain migration, effectively improving the electrochemical performance of solid zinc-ion batteries.

Description

Technical Field

[0001] This invention belongs to the field of zinc-ion battery technology, and particularly relates to the preparation and application of solid electrolytes and their MXene-derived titanium dioxide additives. Background Technology

[0002] With global population growth and economic development, the demand for energy is constantly increasing. Global warming and climate change are also impacting energy supply. Developing renewable energy, nuclear energy, and clean energy can increase the stability of energy supply. However, new energy sources suffer from intermittent supply issues. Electrochemical energy storage refers to the process of converting electrical energy into chemical energy using chemical reactions, and then converting chemical energy back into electrical energy when needed. It can store energy when energy supply is abundant, and release it during peak demand periods or when energy supply is unstable. Solid-state batteries use solid electrolytes instead of traditional liquid electrolytes. Compared to liquid electrolytes, solid-state batteries are more stable, have higher fire and explosion safety performance; can store more energy in the same volume and weight; have longer cycle life and better cycle stability; and can achieve higher charging speeds and faster energy release in a short time. They are expected to be widely used in electric vehicles, wearable devices, mobile power supplies, and energy storage systems, driving the development of energy storage and electrification technologies.

[0003] Zinc-ion solid-state batteries are a special type of solid-state battery whose electrolyte uses solid zinc ions as conductors. Compared to other types of solid-state batteries, zinc-ion solid-state batteries have some unique characteristics and advantages: zinc ions have high ionic conductivity in solid electrolytes, meaning that zinc-ion solid-state batteries can achieve faster charge and discharge speeds and higher power densities. Compared to other rare or expensive materials, zinc-ion solid-state batteries have lower manufacturing costs and broader sustainability potential. Despite these advantages, some challenges and limitations still exist. For example, the preparation process and stability of solid electrolytes still require further research and improvement, and there is room for improvement in battery cycle life and energy density. Currently, the poor ionic conductivity of solid electrolytes cannot ensure rapid charge movement between the positive and negative electrodes, limiting the battery performance and power density of solid-state zinc-ion batteries. Summary of the Invention

[0004] The purpose of this invention is to provide the preparation and application of solid electrolytes and their MXene-derived titanium dioxide additives, aiming to solve the problems mentioned in the background art.

[0005] To achieve the above objectives, the present invention provides the following technical solution:

[0006] A method for preparing solid electrolyte MXene-derived titanium dioxide additives includes the following steps:

[0007] 400 mL of 6 M HCl was poured into a polytetrafluoroethylene beaker, 20 g of LiF was added, and the reaction was carried out for 30 min. Then, 80 mL of 40% HF was added, and the reaction was carried out for 10 min. Subsequently, 20 g of Ti3AlC2 was slowly added, and the reaction temperature was 30 °C for 24 h. The product was centrifuged, and the supernatant was poured into an acidic waste liquid container. The steps were repeated until pH > 5. An appropriate amount of ethanol was added, and the mixture was sonicated. After centrifugation and sonication, the supernatant ethanol was poured off, and an appropriate amount of deionized water was added to the precipitate. The mixture was sonicated to remove Mxene, and the supernatant was collected by centrifugation to obtain Mxene. The obtained dispersion was placed in a beaker and heated and stirred to 60 °C for 5 h. After the reaction was completed, TiO2@Ti3C2 powder was collected and vacuum dried.

[0008] Furthermore, the centrifuged product was centrifuged at 3500 rpm for 4 min; the solution after centrifugation and sonication was centrifuged at 3500 rpm for 5 min; and the supernatant was collected by centrifugation at 3500 rpm for 30 min.

[0009] Furthermore, each ultrasound session lasts at least 1 hour.

[0010] A method for preparing solid electrolyte MXene-derived titanium dioxide additives.

[0011] Solid electrolytes, including solid electrolyte MXene-derived titanium dioxide additives.

[0012] The preparation method of solid electrolyte includes the following steps:

[0013] Zinc trifluoromethanesulfonate and acetamide were mixed at a mass ratio of 1:1.137 and heated and stirred in an 85 °C water bath until they reached a liquid state. 1 wt%, 2 wt%, 3 wt%, 4 wt%, and 5 wt% TiO2@Ti3C2 powder were added to the solution and stirred until homogeneous. The electrolyte was then injected into a glass fiber membrane and cooled and solidified at room temperature to obtain a solid electrolyte.

[0014] Solid-state zinc-ion batteries consist of V2O5 as the positive electrode, zinc sheets as the negative electrode, and a solid electrolyte.

[0015] Compared with the prior art, the beneficial effects of the present invention are:

[0016] The preparation and application of this solid electrolyte and its MXene-derived titanium dioxide additives show that TiO2@Ti3C2 filler can improve the ionic conductivity of the solid electrolyte, promote the dissociation of zinc salt, form ion transfer channels on the filler surface, and act as a plasticizer to reduce the crystallinity of the polymer and enhance chain migration, thus effectively improving the electrochemical performance of solid zinc-ion batteries. Attached Figure Description

[0017] Figure 1 The diagram shows the cycle performance of the 2 wt% TiO2@Ti3C2 filler electrolyte battery in this invention. Implementation

[0018] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention.

[0019] The specific implementation of the present invention will be described in detail below with reference to specific embodiments.

[0020] An embodiment of the present invention provides a method for preparing a solid electrolyte MXene-derived titanium dioxide additive, comprising the following steps:

[0021] 400 mL of 6 M HCl was poured into a polytetrafluoroethylene beaker, 20 g of LiF was added, and the reaction was carried out for 30 min. Then, 80 mL of 40% HF was added, and the reaction was carried out for 10 min. Subsequently, 20 g of Ti3AlC2 was slowly added, and the reaction temperature was 30 °C for 24 h. The product was centrifuged, and the supernatant was poured into an acidic waste liquid container. The steps were repeated until pH > 5. An appropriate amount of ethanol was added, and the mixture was sonicated. After centrifugation and sonication, the supernatant ethanol was poured off, and an appropriate amount of deionized water was added to the precipitate. The mixture was sonicated to remove Mxene, and the supernatant solution was collected by centrifugation (to obtain a few layers of MXene). The obtained dispersion was placed in a beaker and heated and stirred to 60 °C for 5 h. After the reaction was completed, TiO2@Ti3C2 powder was collected and vacuum dried.

[0022] In this embodiment of the invention, MXene has a highly conductive two-dimensional layered structure, which enables rapid ion conduction and effectively improves its electrochemical performance.

[0023] In a preferred embodiment of the present invention, the centrifuged product is centrifuged at 3500 rpm for 4 min; the solution after centrifugation and sonication is centrifuged at 3500 rpm for 5 min; and the supernatant is collected by centrifugation at 3500 rpm for 30 min.

[0024] In a preferred embodiment of the present invention, the duration of each ultrasound procedure is at least 1 hour.

[0025] The solid electrolyte MXene-derived titanium dioxide additive is prepared by a method according to one embodiment of the present invention.

[0026] One embodiment of the present invention provides a solid electrolyte comprising a solid electrolyte MXene-derived titanium dioxide additive.

[0027] An embodiment of the present invention provides a method for preparing a solid electrolyte, comprising the following steps:

[0028] Zinc trifluoromethanesulfonate and acetamide were mixed at a mass ratio of 1:1.137 and heated and stirred in an 85 °C water bath until they reached a liquid state. TiO2@Ti3C2 powder was added to the solution and stirred until homogeneous. The electrolyte was then injected into a glass fiber membrane at high temperature and cooled and solidified at room temperature to obtain a solid electrolyte.

[0029] An embodiment of the present invention provides a solid zinc-ion battery comprising V2O5 as the positive electrode, a zinc sheet as the negative electrode, and a solid electrolyte as described in claim 5.

[0030] Example 1: Zinc trifluoromethanesulfonate and acetamide were mixed at a mass ratio of 1:1.137 and heated and stirred in a water bath at 85 °C until a liquid state was formed. 1 wt% of TiO2@Ti3C2 powder was added to the solution and stirred until homogeneous. The electrolyte was injected into a glass fiber membrane at high temperature and then cooled and solidified at room temperature to obtain a solid electrolyte. A coin cell was assembled using V2O5 as the positive electrode and a zinc sheet as the negative electrode. The assembled battery was heated at 80 °C for 1 h in a constant temperature chamber and then subjected to electrochemical performance testing.

[0031] Example 2: Zinc trifluoromethanesulfonate and acetamide were mixed at a mass ratio of 1:1.137 and heated and stirred in a water bath at 85 °C until a liquid state was formed. 2 wt% of TiO2@Ti3C2 powder was added to the solution and stirred until homogeneous. The electrolyte was injected into a glass fiber membrane at high temperature and then cooled and solidified at room temperature to obtain a solid electrolyte. A coin cell was assembled using V2O5 as the positive electrode and zinc sheet as the negative electrode. The assembled battery was heated at 80 °C for 1 h in a constant temperature chamber and then subjected to electrochemical performance testing.

[0032] Example 3: Zinc trifluoromethanesulfonate and acetamide were mixed at a mass ratio of 1:1.137 and heated and stirred in a water bath at 85 °C until a liquid state was formed. 3 wt% of TiO2@Ti3C2 powder was added to the solution and stirred until homogeneous. The electrolyte was injected into a glass fiber membrane at high temperature and then cooled and solidified at room temperature to obtain a solid electrolyte. A coin cell was assembled using V2O5 as the positive electrode and zinc sheet as the negative electrode. The assembled battery was heated at 80 °C for 1 h in a constant temperature chamber and then subjected to electrochemical performance testing.

[0033] Example 4: Zinc trifluoromethanesulfonate and acetamide were mixed at a mass ratio of 1:1.137 and heated and stirred in a water bath at 85 °C until a liquid state was formed. 4 wt% of TiO2@Ti3C2 powder was added to the solution and stirred until homogeneous. The electrolyte was injected into a glass fiber membrane at high temperature and then cooled and solidified at room temperature to obtain a solid electrolyte. A coin cell was assembled using V2O5 as the positive electrode and zinc sheet as the negative electrode. The assembled battery was heated at 80 °C for 1 h in a constant temperature chamber and then subjected to electrochemical performance testing.

[0034] Example 5: Zinc trifluoromethanesulfonate and acetamide were mixed at a mass ratio of 1:1.137 and heated and stirred in a water bath at 85 °C until a liquid state was formed. 5 wt% TiO2@Ti3C2 powder was added to the solution and stirred until homogeneous. The electrolyte was injected into a glass fiber membrane at high temperature and then cooled and solidified at room temperature to obtain a solid electrolyte. A coin cell was assembled using V2O5 as the positive electrode and zinc sheet as the negative electrode. The assembled battery was heated at 80 °C for 1 h in a constant temperature oven and then subjected to electrochemical performance testing.

[0035] The above are merely preferred embodiments of the present invention. It should be noted that those skilled in the art can make several modifications and improvements without departing from the concept of the present invention, and these should also be considered within the scope of protection of the present invention. These modifications and improvements will not affect the effectiveness of the implementation of the present invention or the practicality of the patent.

Claims

1. A method for preparing solid electrolyte MXene-derived titanium dioxide additives, characterized in that, Includes the following steps: 400 mL of 6 M HCl was poured into a polytetrafluoroethylene beaker, 20 g of LiF was added, and the reaction was carried out for 30 min. Then, 80 mL of 40% HF was added, and the reaction was carried out for 10 min. Subsequently, 20 g of Ti3AlC2 was slowly added, and the reaction temperature was 30 °C for 24 h. The product was centrifuged, and the supernatant was poured into an acidic waste liquid tank. The steps were repeated until pH > 5. An appropriate amount of ethanol was added, and the mixture was sonicated. After centrifugation and sonication, the supernatant ethanol was poured off, and an appropriate amount of deionized water was added to the precipitate. The mixture was sonicated to remove Mxene, and the supernatant was collected by centrifugation to obtain Mxene. The obtained dispersion was placed in a beaker and heated and stirred to 60 °C for 5 h. After the reaction was completed, TiO2@Ti3C2 powder was collected and vacuum dried.

2. The method for preparing the solid electrolyte MXene-derived titanium dioxide additive according to claim 1, characterized in that, The centrifuged product was centrifuged at 3500 rpm for 4 min; the sonicated solution was centrifuged at 3500 rpm for 5 min; and the supernatant was collected by centrifugation at 3500 rpm for 30 min.

3. The method for preparing the solid electrolyte MXene-derived titanium dioxide additive according to claim 1, characterized in that, Each ultrasound session should last at least 1 hour.

4. The solid electrolyte MXene-derived titanium dioxide additive prepared by the preparation method of the solid electrolyte MXene-derived titanium dioxide additive according to any one of claims 1-3.

5. A solid electrolyte, characterized in that, Includes the solid electrolyte MXene-derived titanium dioxide additive as described in claim 4.

6. A method for preparing the solid electrolyte according to claim 5, characterized in that, Includes the following steps: Zinc trifluoromethanesulfonate and acetamide were mixed at a mass ratio of 1:1.137 and heated and stirred in an 85 °C water bath until they reached a liquid state. 1 wt%, 2 wt%, 3 wt%, 4 wt%, and 5 wt% TiO2@Ti3C2 powder were added to the solution and stirred until homogeneous. The electrolyte was then injected into a glass fiber membrane and cooled and solidified at room temperature to obtain a solid electrolyte.

7. A solid-state zinc-ion battery, characterized in that, It includes V2O5 as the positive electrode, zinc sheet as the negative electrode, and the solid electrolyte as described in claim 5.

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