阅读说明：本技术 纤维素气凝胶-明胶固态电解质薄膜材料、超组装方法、瞬态Zn-MnO2二次电池系统 (Cellulose aerogel-gelatin solid electrolyte film material, super-assembly method and transient Zn-MnO2Secondary battery system ) 是由 孔彪 周俊杰 李勇 谢磊 于 2021-08-10 设计创作，主要内容包括：本发明属于瞬态能源器件技术领域,提供了一种纤维素气凝胶-明胶固态电解质薄膜材料、超组装方法、瞬态Zn-MnO2二次电池系统。该方法通过简便的冷冻干燥方法制造纤维素气凝胶；然后将基于明胶的固体电解质接枝到CA三维多孔骨架中以形成纤维素气凝胶-明胶电解质复合薄膜。该薄膜可生物降解,降解过程中产生的物质无毒无害,用于支撑高性能的可完全生物降解的二次Zn-MnO-(2)二次电池系统。该二次电池系统拥有高达1.6V的稳定输出电压和相对宽松的电压范围。该瞬态固态电解质薄膜的设计有望成为瞬态能源器件的基础组成器件,并将在未来的医学研究和临床治疗中发挥重要作用。本发明具有生产工艺和过程简单易操作等优点,可以大规模工业化生产。(The invention belongs to the technical field of transient energy devices, and provides a cellulose aerogel-gelatin solid electrolyte film material, a super-assembly method and a transient Zn-MnO2 secondary battery system. The method prepares cellulose aerogel by simple freeze drying method; then charging the gelatin-based solidThe electrolyte is grafted into the three-dimensional porous framework of CA to form the cellulose aerogel-gelatin electrolyte composite membrane. The film is biodegradable, the substances generated in the degradation process are non-toxic and harmless, and the film is used for supporting high-performance fully biodegradable secondary Zn-MnO 2 A secondary battery system. The secondary battery system has a stable output voltage of up to 1.6V and a relatively wide voltage range. The design of the transient solid electrolyte film is expected to become a basic component device of a transient energy device and plays an important role in future medical research and clinical treatment. The invention has the advantages of simple production process and process, easy operation and the like, and can be used for large-scale industrial production.)

1. A super-assembly method of a cellulose aerogel-gelatin solid electrolyte film material is characterized by comprising the following steps:

step S1, adding 0.016g to 0.032g of 2,2,6, 6-tetramethylpiperidine and 0.1g of NaBr into 100ml of an aqueous solution containing 1g of alpha-cellulose, and then stirring until the 2,2,6, 6-tetramethylpiperidine and the NaBr are dissolved to obtain a first mixed solution;

step S2, adding 12mmol of NaClO into the first mixed solution, stirring at 0 ℃ for a period of time, adjusting the pH value of the first mixed solution to 10, and dropwise adding ethanol to terminate the reaction to obtain a reaction termination solution;

step S3, adding 0.3g of PVA into the reaction termination solution, heating and dissolving, then adding 1.2g of citric acid and 1.2ml of phosphoric acid, quickly freezing, and freeze-drying for a period of time to obtain a CA three-dimensional porous framework;

step S4, add 2g of gelatin to 2mL of L^-1ZnSO₄And 0.1mol L^-1MnSO₄Then heating and stirring the mixture until the gelatin is dissolved to obtain gelatin-based electrolyte;

step S5, injecting the gelatin-based electrolyte into the CA three-dimensional porous framework to obtain a composite membrane, cooling, and immersing the composite membrane into 2mol L of electrolyte^-1ZnSO₄And 0.1mol L^-1MnSO₄And after the second mixed solution is in an equilibrium state for a period of time, the biodegradable cellulose aerogel-gelatin solid electrolyte film material is obtained.

2. The method for super-assembling a cellulose aerogel-gelatin solid electrolyte membrane material as claimed in claim 1, wherein:

in step S1, the 2,2,6, 6-tetramethylpiperidine and NaBr are dissolved by vigorous stirring at 25 ℃ to obtain the first mixed solution.

3. The method for super-assembling a cellulose aerogel-gelatin solid electrolyte membrane material as claimed in claim 1, wherein:

wherein the PVA has an Mw of 88000.

4. The method for super-assembling a cellulose aerogel-gelatin solid electrolyte membrane material as claimed in claim 1, wherein:

wherein, in step S3, the PVA is added to the reaction termination solution and dissolved for 2h at 95 ℃.

5. The method for super-assembling a cellulose aerogel-gelatin solid electrolyte membrane material as claimed in claim 1, wherein:

wherein, in step S3, the CA three-dimensional porous skeleton is obtained after freeze-drying for 48 hours.

6. The method for super-assembling a cellulose aerogel-gelatin solid electrolyte membrane material as claimed in claim 1, wherein:

in step S4, the gelatin is heated to 80 ℃ and sufficiently stirred until the gelatin is dissolved, thereby obtaining the gelatin-based electrolyte.

7. A cellulose aerogel-gelatin solid electrolyte membrane material, which is prepared by the super-assembly method of the cellulose aerogel-gelatin solid electrolyte membrane material according to any one of claims 1 to 6.

8. Transient Zn-MnO₂A secondary battery system, characterized by being prepared by:

cutting the cellulose aerogel-gelatin solid electrolyte film material of claim 7 into rectangular parallelepiped, and packaging the rectangular parallelepiped with MnO₂Sequentially assembling the positive plate, the cellulose aerogel-gelatin solid electrolyte composite film material, the Zn negative plate and the packaging film, and sealing by using a sealing machine to obtain the transient Zn-MnO based on the cellulose aerogel-gelatin solid electrolyte film material₂Two timesA battery system.

Technical Field

The invention belongs to the technical field of transient energy devices, and particularly relates to a cellulose aerogel-gelatin solid electrolyte film material, a super-assembly method and a transient Zn-MnO2 secondary battery system.

Background

With the development of technology and the increase of environmental awareness, the conventional electronic devices have been unable to meet the current demands. Therefore, emerging products such as transient electronic devices have entered human lives and play increasingly important roles in medical, communication, and national defense. After the transient electronic device performs the designated function, the assembly may degrade at a controlled rate, partially or fully in accordance with the user's needs. Transient electronic devices combine advanced transient materials with conventional electronic processing techniques to achieve the same performance as conventional electronic devices without generating additional electronic waste. In addition, those implantable transient medical electronics devices have wide application in clinical diagnosis and therapy. However, the conventional medical electronic devices still need to be removed by surgery after completing their tasks, and such a cumbersome operation causes secondary trauma to the patient, increases the pain of the patient, and presents a risk of wound infection and various chronic inflammations. Emerging transient medical devices are implantable, biodegradable, and thus can be easily removed from a patient without the need for re-surgery. More importantly, the biocompatibility of the transient electronics is also superior to that of traditional implantable medical electronics because the degradation products of the transient electronics are non-toxic and can degrade in the patient after diagnosis and treatment is completed.

Although biodegradable materials (silk proteins, soluble metals, polymers, etc.) have been extensively studied and have been used in various biosensors, semiconductor functional devices and degradable medical devices, significant challenges remain in developing transient energy devices. There are two main reasons for this, one being the choice of material for the implanted energy device. This greatly limits the choice of materials due to the requirement for a good degradation of the energy device and a high energy storage capacity. Another aspect is the biocompatibility and toxicity of the implantable energy device before and after degradation. There are also currently significant challenges in developing solid-state electrolytes for transient batteries, mainly for two reasons. One is the selection of the material of the implantable electrolyte composite film, and the implantable transient battery electrolyte composite film needs to take controllable degradability and high ion permeability into consideration, so that the selection of the material is greatly limited. Another aspect is the assessment of biocompatibility and toxicity of the implantable energy device before and after degradation of the implantable composite film. Heavy metal ions, polymers, organic electrolytes and other toxic substances generated after the degradation of the traditional solid electrolyte material can greatly endanger the life and health of patients.

Currently, the john a rogers (johna. rogers) team uses biodegradable metal foils and polyanhydride packaging materials to produce Mg-Mo electric batteries, powering conventional light emitting diodes and radio transmitters. The tin-doped vanadium pentoxide nanofibers used by the roof lens team do not contain a conductive agent and a binder as anode materials to prepare a high-energy-density transient lithium ion battery. It can be completely dissolved in an alkaline solution within a few minutes, thereby enabling the high energy density battery to be instantly dissolved. The Wallace team uses biodegradable polymer fibrin choline as electrolyte, combines a magnesium membrane electrode and silk packaging to prepare a corresponding degradable battery, and the whole equipment is completely degraded in a protease buffer solution for 45 days.

Disclosure of Invention

The present invention has been made to solve the above problems, and an object of the present invention is to provide a cellulose aerogel-gelatin solid electrolyte membrane material, a super-assembly method, and a transient Zn-MnO2 secondary battery system.

The invention provides a super-thin film material of cellulose aerogel-gelatin solid electrolyteMethod of assembly, characterized in that it comprises the following steps: step S1, adding 0.016g to 0.032g of 2,2,6, 6-tetramethylpiperidine and 0.1g of NaBr into 100ml of an aqueous solution containing 1g of alpha-cellulose, and then stirring until the 2,2,6, 6-tetramethylpiperidine and the NaBr are dissolved to obtain a first mixed solution; step S2, adding 12mmol of NaClO into the first mixed solution, stirring at 0 ℃ for a period of time, adjusting the pH value of the first mixed solution to 10, and dropwise adding ethanol to terminate the reaction to obtain a reaction termination solution; step S3, adding 0.3g of PVA into the reaction termination solution, heating and dissolving, then adding 1.2g of citric acid and 1.2ml of phosphoric acid, quickly freezing, and freeze-drying for a period of time to obtain a CA three-dimensional porous framework; step S4, add 2g of commercial gelatin to 2mL L^{- 1}ZnSO₄And 0.1mol L^-1MnSO₄Then heating and stirring the mixture until gelatin is dissolved to obtain gelatin-based electrolyte; step S5, injecting gelatin-based electrolyte into the CA three-dimensional porous framework to obtain a composite membrane, cooling, and immersing the composite membrane into 2mol L^-1ZnSO₄And 0.1mol L^-1MnSO₄And (3) in the second mixed solution for a period of time, and obtaining the biodegradable cellulose aerogel-gelatin solid electrolyte film material after reaching an equilibrium state.

The cellulose aerogel-gelatin solid electrolyte membrane material super-assembly method provided by the invention can also have the following characteristics: in step S1, 2,6, 6-tetramethylpiperidine and NaBr are dissolved by vigorous stirring at 25 ℃.

The cellulose aerogel-gelatin solid electrolyte membrane material super-assembly method provided by the invention can also have the following characteristics: herein, Mw of PVA is 88000.

The cellulose aerogel-gelatin solid electrolyte membrane material super-assembly method provided by the invention can also have the following characteristics: in step S3, PVA was added to the reaction-terminated solution and dissolved at 95 ℃ for 2 hours.

The cellulose aerogel-gelatin solid electrolyte membrane material super-assembly method provided by the invention can also have the following characteristics: in step S3, the CA three-dimensional porous skeleton was obtained after freeze-drying for 48 hours.

The cellulose aerogel-gelatin solid electrolyte membrane material super-assembly method provided by the invention can also have the following characteristics: in step S4, the mixture is heated to 80 ℃ and sufficiently stirred until gelatin is dissolved, thereby obtaining a gelatin-based electrolyte.

The invention also provides a cellulose aerogel-gelatin solid electrolyte film material which has the characteristics and is prepared by a super-assembly method of the cellulose aerogel-gelatin solid electrolyte film material.

The invention also provides transient Zn-MnO₂A secondary battery system having such features as prepared by the steps of: cutting cellulose aerogel-gelatin solid electrolyte film material into cuboid, and packaging with MnO₂Sequentially assembling the positive plate, the cellulose aerogel-gelatin solid electrolyte composite film material, the Zn negative plate and the packaging film, and sealing by using a sealing machine to obtain the transient Zn-MnO based on the cellulose aerogel-gelatin solid electrolyte film material₂A secondary battery system.

Action and Effect of the invention

According to the cellulose aerogel-gelatin solid electrolyte film material and the super-assembly preparation method thereof, firstly, the Cellulose Aerogel (CA) is prepared by a simple freeze drying method through steps S1-S4; then, proceeding to steps S5, S6, the gelatin-based solid electrolyte is grafted into the CA three-dimensional porous skeleton to form a cellulose aerogel-gelatin electrolyte composite thin film (CAG film). The method takes 2,2,6, 6-Tetramethylpiperidine (TEMPO) oxidized nano-cellulose as a framework, and prepares the degradable CAG membrane through in-situ synthesis. The cellulose aerogel-gelatin (CAG) solid electrolyte film material is a biodegradable material, and the CAG film and MnO are mixed₂Assembling the positive plate, the Zn negative plate and the like to obtain transient Zn-MnO₂A secondary battery system.

The Zn-MnO2 secondary battery system based on the cellulose aerogel-gelatin (CAG) solid electrolyte film material has stable output voltage up to 1.6V and relatively loose voltage range (0.85V-1.95V). The battery system provides a promising energy solution for unique self-powered transient electronic devices or conventional self-powered implantable medical devices such as implantable cardioverter defibrillators, implantable diagnostic sensors, and rapidly developing implantable diabetes monitors. The cellulose aerogel-gelatin (CAG) solid electrolyte film material can be completely degraded in vivo and in vitro, and substances generated in the degradation process are nontoxic and harmless. Therefore, the design of the transient solid electrolyte film is expected to become a basic component device of a transient energy device and will play an important role in future medical research and clinical treatment.

The invention provides a new material preparation scheme, equipment structure and assembly strategy, and skillfully designs a biodegradable cellulose aerogel-gelatin (CAG) solid electrolyte film material for supporting high-performance fully biodegradable secondary Zn-MnO₂A secondary battery system. The invention has the following remarkable advantages:

(1) the three-dimensional porous framework is prepared by using alpha-cellulose and 2,2,6, 6-Tetramethylpiperidine (TEMPO) as initial raw materials, is cheap and easy to obtain, and has rigidity, good biocompatibility and controllable degradation performance.

(2) The solid electrolyte based on gelatin is grafted to the CA three-dimensional porous framework to form the cellulose aerogel-gelatin electrolyte composite film, and the design is favorable for meeting the requirement of rapid shuttling of ions in the solid electrolyte and is not easily interfered by the external environment.

(3) The method for grafting the gelatin-based solid electrolyte to the CA three-dimensional porous skeleton to form the cellulose aerogel-gelatin electrolyte composite film has the advantages of simple production process and process, easy operation and the like, and can be used for large-scale industrial production.

(4) The cellulose aerogel-gelatin electrolyte composite film material prepared by the method has high specific capacity and good cycle performance.

Drawings

FIG. 1 is a test chart of flexibility and elasticity of a 3D cellulose porous skeleton synthesized in example 1 of the present invention;

FIG. 2 is a graph showing the results of a test for the liquid storage capacity of the 3D cellulose porous skeleton synthesized in example 1 of the present invention;

fig. 3 is an SEM image of the 3D cellulose porous scaffolding material synthesized in example 1 of the present invention;

FIG. 4 is an SEM image of a synthesized cellulose aerogel-gelatin composite thin film material of example 1 of the present invention;

FIG. 5 is a cross-sectional SEM image and elemental analysis spectrum of the cellulose aerogel-gelatin composite thin film material synthesized in example 1 of the present invention;

FIG. 6 is a graph of the quantitative analysis of the energy spectrum of the cellulose aerogel-gelatin composite thin film material (CAG) synthesized in example 1 of the present invention and the 3D cellulose porous skeleton (CA);

FIG. 7 is an AC impedance spectrum (frequency range of 10kHz to 0.01 Hz) of a general water-based electrolyte and a cellulose aerogel-gelatin composite thin film material (CAG) synthesized in example 1 of the present invention; and

FIG. 8 is Zn-MnO of cellulose aerogel-gelatin (CAG) solid electrolyte membrane material synthesized based on example 1 of the present invention₂Constant current charge/discharge curves for the first four cycles (61.6mA g-1) of the secondary battery system.

Detailed Description

In order to make the technical means, the creation characteristics, the achievement objects and the effects of the present invention easy to understand, the following embodiments and the accompanying drawings are used to specifically describe a cellulose aerogel-gelatin solid electrolyte membrane material, a super-assembly method, and a transient Zn-MnO2 secondary battery system according to the present invention.

The methods in the examples of the present invention are conventional methods unless otherwise specified, and the starting materials in the examples of the present invention are commercially available from public sources unless otherwise specified.

The invention discloses a super-assembly method of a cellulose aerogel-gelatin solid electrolyte film material, which comprises the following steps:

step S1, 0.016 g-0.032 g of 2,2,6, 6-Tetramethylpiperidine (TEMPO) and 0.1g of NaBr are added into 100ml of an aqueous solution containing 1g of alpha-cellulose, and then the mixture is vigorously stirred at 25 ℃ until the 2,2,6, 6-tetramethylpiperidine and NaBr are dissolved, so as to obtain a first mixed solution.

Step S2, adding 12mmol of NaClO into the first mixed solution, stirring at 0 ℃ for a period of time, adjusting the pH value of the first mixed solution to 10, and adding ethanol dropwise to terminate the reaction to obtain a reaction termination solution.

In step S3, 0.3g of PVA (Mw 88000) was added to the reaction-terminated solution, and the mixture was heated to 95 ℃ to dissolve for 2 hours, followed by addition of 1.2g of citric acid (C)₆H₈O₇) And 1.2ml phosphoric acid (H)₃PO₄) Then, quickly freezing, and freeze-drying for 48h to obtain a CA three-dimensional porous skeleton, namely a 3D cellulose porous skeleton;

step S4, add 2g of gelatin to 2mL of L^-1ZnSO₄And 0.1mol L^-1MnSO₄Then heating to 80 ℃ and fully stirring until gelatin is dissolved to obtain gelatin-based electrolyte;

step S5, injecting gelatin-based electrolyte into a CA three-dimensional porous skeleton with the size of 1cm multiplied by 1cm to obtain a composite membrane, cooling, and immersing the composite membrane into 2mol L^-1ZnSO₄And 0.1mol L^-1MnSO₄And (4) in the second mixed solution for 1h, obtaining the biodegradable cellulose aerogel-gelatin solid electrolyte film material after reaching the equilibrium state.

The gelatin is a camera grade commercial gelatin from alatin corporation; ZnSO₄、MnSO₄Are all of analytical grade purity from Sigma.

Cutting the cellulose aerogel-gelatin (CAG) solid electrolyte composite film material prepared by the method into uniform cuboids (1cm by 0.05cm), and packaging the film and MnO₂Sequentially assembling the positive plate, the cellulose aerogel-gelatin solid electrolyte composite film, the Zn negative plate and the packaging film, and sealing the battery by using a sealing machine to obtain the transient Zn-MnO based on the cellulose aerogel-gelatin solid electrolyte film material₂A secondary battery system.

Transient Zn-MnO based on cellulose aerogel-gelatin solid electrolyte film material₂Secondary battery systemAnd the stable output voltage of 1.6V and a relatively loose voltage range (0.85V-1.95V) are provided. The battery system provides a promising energy solution for unique self-powered transient electronic devices or conventional self-powered implantable medical devices such as implantable cardioverter defibrillators, implantable diagnostic sensors, and rapidly developing implantable diabetes monitors. The cellulose aerogel-gelatin (CAG) solid electrolyte film material can be completely degraded in vivo and in vitro, and substances generated in the degradation process are nontoxic and harmless. Therefore, the design of the transient solid electrolyte film is expected to become a basic component device of a transient energy device and will play an important role in future medical research and clinical treatment.

Example 1:

this example describes the cellulose aerogel-gelatin solid electrolyte membrane material and the super-assembly preparation method thereof in detail.

In step S1, 0.016g of TEMPO and 0.1g of NaBr are added to 100ml of an aqueous solution containing 1g of alpha-cellulose, followed by vigorous stirring at 25 ℃ until TEMPO and NaBr are dissolved to give a first mixed solution.

At step S2, 12mmol of NaClO was added to the first mixed solution and stirred at 0 ℃. And (4) carrying out magnetic stirring treatment for 15 minutes to adjust the pH value of the solution to 10, and dropwise adding ethanol to terminate the reaction to obtain a reaction termination solution.

Step S3, adding 0.3g of PVA (Mw 88000) to the reaction-terminated solution, and dissolving at 95 ℃ for 2 hours; finally, 1.2g of citric acid (C)₆H₈O₇) And 1.2ml phosphoric acid (H)₃PO₄) Adding the mixture into the reaction terminating solution. And (3) rapidly freezing by adopting a liquid nitrogen freezing method, and freeze-drying for 48 hours to obtain the CA three-dimensional porous framework.

Step S4, add 2g of commercial gelatin (camera grade, Aladdin) to 2mL L^-1ZnSO₄(AR grade, Sigma) and 0.1mol L^-1MnSO₄(AR grade, Sigma) in 20mL of a mixed solution, and then stirred well at 80 ℃ until all the gelatin is dissolved to obtain a gelatin-based electrolyte.

Step S5, the gelatin-based electrolyte is injected into a CA three-dimensional porous skeleton (with a size of1cm × 1 cm). Cooling to room temperature, and soaking the prepared composite membrane into 2mol L^-1ZnSO₄And 0.1mol L^-1MnSO₄The cellulose aerogel-gelatin electrolyte composite film as the target material is obtained after the mixed solution reaches an equilibrium state for 1 hour.

Example 2:

this example describes the cellulose aerogel-gelatin solid electrolyte membrane material and the super-assembly preparation method thereof in detail.

In step S1, 0.016g of TEMPO and 0.1g of NaBr are added to 100ml of an aqueous solution containing 1g of alpha-cellulose, followed by vigorous stirring at 25 ℃ until TEMPO and NaBr are dissolved to give a first mixed solution.

Step S2, 12mmol of NaClO was then added to the above first mixed solution and stirred at 0 ℃. And (4) carrying out magnetic stirring treatment for 15 minutes to adjust the pH value of the solution to 10, and dropwise adding ethanol to terminate the reaction to obtain a reaction termination solution.

In step S3, 0.3g of PVA (Mw 88000) was further added to the reaction-terminated solution, and the mixture was dissolved at 95 ℃ for 2 hours, and finally 1.2g of citric acid (C) was added₆H₈O₇) And 1.2ml phosphoric acid (H)₃PO₄) Adding into the above solution. And (3) rapidly freezing by adopting a liquid nitrogen freezing method, and freeze-drying for 48 hours to obtain the CA three-dimensional porous framework.

Step S4, add 2g of commercial gelatin (camera grade, Aladdin) to 1mL L^-1ZnSO₄(AR grade, Sigma) and 0.1mol L^-1MnSO₄(AR grade, Sigma) in 20mL of a mixed solution, and then stirred well at 80 ℃ until all the gelatin is dissolved to obtain a gelatin-based electrolyte.

In step S5, the above gelatin-based electrolyte was injected into a three-dimensional porous CA skeleton (1 cm. times.1 cm in size). Cooling to room temperature, and soaking the prepared composite membrane into 2mol L^-1ZnSO₄And 0.1mol L^-1MnSO₄The cellulose aerogel-gelatin electrolyte composite film as the target material is obtained after the mixed solution reaches an equilibrium state for 1 hour.

Example 3:

this example describes the cellulose aerogel-gelatin solid electrolyte membrane material and the super-assembly preparation method thereof in detail.

In step S1, 0.032g of TEMPO and 0.1g of NaBr are added to 100ml of an aqueous solution containing 1g of α -cellulose, followed by vigorous stirring at 25 ℃ until TEMPO and NaBr are dissolved to obtain a first mixed solution.

Step S2, then 12mmol of NaClO was added to the solution and stirred at 0 deg.C. And (4) carrying out magnetic stirring treatment for 15 minutes to adjust the pH value of the solution to 10, and dropwise adding ethanol to terminate the reaction to obtain a reaction termination solution.

Step S3, adding 0.3g of PVA (Mw 88000) to the reaction-terminated solution, and dissolving at 95 ℃ for 2 hours; finally, 1.2g of citric acid (C)₆H₈O₇) And 1.2ml phosphoric acid (H)₃PO₄) Adding into the above solution. And (3) rapidly freezing by adopting a liquid nitrogen freezing method, and freeze-drying for 48 hours to obtain the CA three-dimensional porous framework.

Step S4, add 2g of commercial gelatin (camera grade, Aladdin) to 1mL L^-1ZnSO₄(AR grade, Sigma) and 0.1mol L^-1MnSO4(AR grade, Sigma) in 20mL of a mixed solution, followed by stirring well at 80 ℃ until all gelatin is dissolved, to obtain a gelatin-based electrolyte.

In step S5, the above gelatin-based electrolyte was injected into a three-dimensional porous CA skeleton (1 cm. times.1 cm in size). Cooling to room temperature, and soaking the prepared composite membrane into 2mol L^-1ZnSO₄And 0.1mol L^-1MnSO₄The cellulose aerogel-gelatin electrolyte composite film as the target material is obtained after the mixed solution reaches an equilibrium state for 1 hour.

Application example:

the cellulose aerogel-gelatin (CAG) solid electrolyte composite film material prepared in example 1 was cut into uniform rectangular parallelepipeds (1cm x 0.05cm) according to the packaging film, MnO₂Sequentially assembling the positive plate, the cellulose aerogel-gelatin solid electrolyte composite film, the Zn negative plate and the packaging film, and sealing the battery by using a sealing machine to obtain the transient Zn-MnO based on the cellulose aerogel-gelatin solid electrolyte film material₂A secondary battery system.

Test example:

the 3D cellulose porous scaffolds prepared in example 1 were tested for flexibility, elasticity and liquid storage capacity, and the results are shown in fig. 1 and 2.

FIG. 1 is a test chart of flexibility and elasticity of a 3D cellulose porous skeleton synthesized in example 1 of the present invention; fig. 2 is a graph showing the results of a liquid storage capacity test on a 3D cellulose porous skeleton synthesized in example 1 of the present invention.

As can be seen from fig. 1, the flexibility and elasticity of the 3D cellulose porous skeleton perform well.

As can be seen from fig. 2, the 3D cellulose porous scaffold showed good liquid storage capacity after repeated storage and release tests.

The surface morphologies of the 3D cellulose porous scaffold material and the cellulose aerogel-gelatin solid electrolyte composite film material prepared in example 1 were characterized by a thermal field emission scanning electron microscope (suprat 55), and the components of the material were analyzed by EDS technique, and the test results are shown in fig. 3 to 6.

Fig. 3 is an SEM image of the 3D cellulose porous scaffolding material synthesized in example 1 of the present invention.

Fig. 4 is an SEM image of the cellulose aerogel-gelatin composite thin film material synthesized in example 1 of the present invention.

Fig. 5 is a cross-sectional SEM image and an elemental analysis spectrum of the cellulose aerogel-gelatin composite thin film material synthesized in example 1 of the present invention.

Fig. 5 (a) is a cross-sectional SEM image of the cellulose aerogel-gelatin composite thin film material synthesized in example 1; (b) is an analysis spectrum of Zn element in the cellulose aerogel-gelatin composite film material synthesized in example 1; (c) is an analysis spectrum of the C element in the cellulose aerogel-gelatin composite thin film material synthesized in example 1; (d) is an analysis spectrum of O element in the cellulose aerogel-gelatin composite thin film material synthesized in example 1.

Fig. 6 is a graph of the quantitative analysis of the energy spectrum of the cellulose aerogel-gelatin composite thin film material (CAG) synthesized in example 1 of the present invention and the 3D cellulose porous skeleton (CA).

From FIG. 6, the product spectrum in the graph is consistent with the target spectrum.

FIG. 7 is an AC impedance spectrum (frequency range of 10kHz to 0.01 Hz) of a general water-based electrolyte and a cellulose aerogel-gelatin composite thin film material (CAG) synthesized in example 1 of the present invention.

Cyclic Voltammetry (CV) curves were performed by an electrochemical workstation and were based on using Zn as the counter and reference electrodes (negative electrodes) and MnO₂The cathode of the CV curve measured ZIB was used as the working electrode (positive electrode). In order to evaluate the constant current charge and discharge, rate and long cycle electrochemical performance of CR2016 type coin cells (ion transport device is fiberglass membrane and electrolyte) and sandwich cells (ion transport device is cellulose aerogel-gelatin solid electrolyte composite membrane), a blue color electrical test system (CT2001A5V2MA) was used for testing. TZIB area of 2.25cm^-2Approximately 1.5mm thick, the entire electrochemical test was performed at room temperature and the results are shown in figure 8.

FIG. 8 is Zn-MnO of cellulose aerogel-gelatin (CAG) solid electrolyte membrane material synthesized based on example 1 of the present invention₂Constant current charge/discharge curves for the first four cycles (61.6mAg-1) of the secondary battery system.

Effects and effects of the embodiments

According to the cellulose aerogel-gelatin solid electrolyte film material and the super-assembly preparation method thereof provided by the embodiment of the invention, firstly, the Cellulose Aerogel (CA) is prepared by a simple freeze drying method through steps S1-S4; then, proceeding to steps S5, S6, the gelatin-based solid electrolyte is grafted into the CA three-dimensional porous skeleton to form a cellulose aerogel-gelatin electrolyte composite thin film (CAG film). The method takes 2,2,6, 6-Tetramethylpiperidine (TEMPO) oxidized nano-cellulose as a framework, and prepares the degradable CAG membrane through in-situ synthesis. The cellulose aerogel-gelatin (CAG) solid electrolyte film material is a biodegradable material, and the CAG film and MnO are mixed₂Assembling the positive plate, the Zn negative plate and the like to obtain transient Zn-MnO₂A secondary battery system.

The Zn-MnO2 secondary battery system based on the cellulose aerogel-gelatin (CAG) solid electrolyte film material has stable output voltage up to 1.6V and relatively loose voltage range (0.85V-1.95V). The battery system provides a promising energy solution for unique self-powered transient electronic devices or conventional self-powered implantable medical devices such as implantable cardioverter defibrillators, implantable diagnostic sensors, and rapidly developing implantable diabetes monitors. The cellulose aerogel-gelatin (CAG) solid electrolyte film material can be completely degraded in vivo and in vitro, and substances generated in the degradation process are nontoxic and harmless. Therefore, the design of the transient solid electrolyte film is expected to become a basic component device of a transient energy device and will play an important role in future medical research and clinical treatment.

The embodiment of the invention provides a new material preparation scheme, equipment structure and assembly strategy, skillfully designs a biodegradable cellulose aerogel-gelatin (CAG) solid electrolyte film material for supporting high-performance fully biodegradable secondary Zn-MnO₂A secondary battery system. The invention has the following remarkable advantages:

(1) the three-dimensional porous framework is prepared by using alpha-cellulose and 2,2,6, 6-Tetramethylpiperidine (TEMPO) as initial raw materials, is cheap and easy to obtain, and has rigidity, good biocompatibility and controllable degradation performance.

(2) The solid electrolyte based on gelatin is grafted to the CA three-dimensional porous framework to form the cellulose aerogel-gelatin electrolyte composite film, and the design is favorable for meeting the requirement of rapid shuttling of ions in the solid electrolyte and is not easily interfered by the external environment.

(3) The method for grafting the gelatin-based solid electrolyte to the CA three-dimensional porous skeleton to form the cellulose aerogel-gelatin electrolyte composite film has the advantages of simple production process and process, easy operation and the like, and can be used for large-scale industrial production.

(4) The cellulose aerogel-gelatin electrolyte composite film material prepared by the method has high specific capacity and good cycle performance.

The above embodiments are preferred examples of the present invention, and are not intended to limit the scope of the present invention.