Solvent annealing device

Abstract

The utility model provides a solvent annealing device and belongs to the technical field of solid-state battery production equipment. The device comprises an annealing chamber, a heater, external gas and at least one solvent storage tank, the solvent storage tank is communicated with the annealing chamber through a pipeline, an electrolyte membrane can be placed in the annealing chamber, and the external gas provides gas for the solvent storage tank to enable a solvent in the solvent storage tank to blister. The heater regulates and controls the vapor pressure of the saturated solvent in the solvent storage tank, and solvent molecules are carried by external gas to enter the annealing chamber to be in contact with the electrolyte membrane and then enter the electrolyte membrane to finish solvent annealing. According to the device, residual solvents in samples can be removed through purging of a large amount of dry gas, and the repeatability of the annealing process is guaranteed. In addition, the content of solvent molecules entering the annealing chamber can be regulated and controlled by means of regulating and controlling gas flow and heating, so that the solvent annealing process has obvious flexibility and reliability.

Description

Technical Field

[0001] This utility model relates to the field of solid-state battery production equipment technology, and in particular to a solvent annealing device. Background Technology

[0002] Currently, solid polymer electrolytes still have significant room for improvement in terms of high room-temperature ionic conductivity, low electrolyte / electrode interfacial resistance, and high energy density. To improve the room-temperature ionic conductivity of solid polymer electrolytes, the polymer matrix is ​​typically doped or modified to suppress polymer crystallization or lower its glass transition temperature; however, these processes are often complex and unreliable. To reduce the interfacial resistance of the electrolyte / electrode materials, researchers often improve interfacial contact by adding liquid electrolyte dropwise between the two surfaces or by applying high pressure across the battery; however, these processes also suffer from poor reliability. Meanwhile, some researchers have attempted to prepare solid polymer electrolytes through in-situ polymerization, which has initially addressed the issues of low room-temperature ionic conductivity and high electrolyte / electrode interfacial impedance. However, this process still faces challenges such as difficulty in controlling the reaction process, the presence of small molecule residues in the reaction products, and the complexity of the polymerization process.

[0003] Therefore, how to provide a simple and easily scalable device to solve the problems of low room temperature ionic conductivity, high electrolyte / electrode interface impedance, and low battery energy density of solid polymer electrolyte thin film samples is an urgent technical problem to be solved. Utility Model Content

[0004] The purpose of this invention is to address the shortcomings of the prior art by providing a solvent annealing device. This device regulates the content of solvent molecules entering the annealing chamber by controlling the gas flow rate and heating, thereby achieving surface softening of the solid polymer electrolyte membrane through solvent annealing. This improves the contact between the membrane and the solid electrode material, reduces the interfacial resistance between the electrolyte and the electrode, and facilitates the transport of metal cations during the charging and discharging process.

[0005] This invention provides a solvent annealing apparatus, comprising an annealing chamber, a heater, an external gas supply, and at least one solvent storage tank. The solvent storage tank is connected to the annealing chamber via a pipeline. A solid electrolyte membrane can be placed inside the annealing chamber. The external gas supply gas to the solvent storage tank causes the solvent inside the tank to foam. The heater is located below the solvent storage tank and regulates the saturated solvent vapor pressure in the solvent storage tank. Solvent molecules are carried by the external gas into the annealing chamber and come into contact with the electrolyte membrane, thus completing the solvent annealing process. Multiple solvent storage tanks are connected in series or in parallel via pipelines.

[0006] Furthermore, the solvent storage tank is connected to the external gas via a first pipe, the annealing chamber is connected to the solvent storage tank via a second pipe, the annealing chamber is connected to the first pipe via a connecting component, and the second pipe is connected to the connecting component.

[0007] Furthermore, each solvent storage tank is provided with a sealing cap on top, and each tank is provided with a first pipe and a second pipe communicating with the sealing cap. One end of the first pipe is inserted into the solvent in the solvent storage tank, and the other end of the first pipe is connected to the external gas. One end of the second pipe is located above the solvent in the solvent storage tank, and the other end of the second pipe is connected to the annealing chamber.

[0008] Furthermore, multiple solvent storage tanks are connected in series, and the connecting component includes a third pipe. Each of the first pipe and the second pipe is connected in series through the third pipe. One end of the third pipe is connected to the external gas, and the other end of the third pipe is connected to the annealing chamber.

[0009] Furthermore, the external gas is connected to each of the first pipes via a fourth pipe, and the fourth pipe is arranged in parallel with the third pipe.

[0010] Furthermore, multiple solvent storage tanks are arranged in parallel, and the connecting component includes a fifth pipe and multiple branch pipes. Each branch pipe corresponds to one of the solvent storage tanks, and each solvent storage tank is connected in parallel to the fifth pipe through its corresponding branch pipe. The fifth pipe is connected to the annealing chamber through a sixth pipe.

[0011] Furthermore, one end of the branch pipe is connected to the fifth pipe, and the other end of the branch pipe is connected to the external gas. Each branch pipe is connected to the corresponding first pipe and second pipe.

[0012] Furthermore, both the first and second pipes are equipped with flow control valves.

[0013] Furthermore, the connecting component also includes valves, and the third pipe, the branch pipe, and the fifth pipe are all equipped with multiple valves.

[0014] Furthermore, the solvent in the solvent storage tank includes any one or more of cyclic carbonates, linear carbonates and their derivatives, cyclic carboxylic acid esters, linear carboxylic acid esters and their derivatives, cyclic ethers, chain ethers, crown ethers and their derivatives.

[0015] Compared with the prior art, the solvent annealing apparatus provided by this utility model has the following beneficial effects:

[0016] (1) This utility model discloses a solvent annealing apparatus, comprising an annealing chamber, a heater, an external gas supply, and at least one solvent storage tank. The solvent storage tank is connected to the annealing chamber via a pipeline. An electrolyte membrane can be placed inside the annealing chamber. The external gas supply gas to the solvent storage tank causes the solvent inside the tank to foam. The heater regulates the saturated solvent vapor pressure in the solvent storage tank. Solvent molecules are carried by the external gas into the annealing chamber and, after contacting the electrolyte membrane, enter the electrolyte membrane to complete solvent annealing. This apparatus can remove most of the residual solvent by purging with a large amount of dry gas, ensuring the repeatability of the annealing process. Furthermore, the content of solvent molecules entering the annealing chamber can be controlled by adjusting the gas flow rate and heating, making the solvent annealing process significantly more flexible and reliable.

[0017] (2) The solvent annealing apparatus provided by this invention can soften the surface of the solid polymer electrolyte membrane through solvent annealing, improve its contact with the solid electrode material, reduce the interfacial resistance between the electrolyte and the electrode, and facilitate the transport of metal cations during charging and discharging. The complexation between solvent molecules and polymer and electrolyte salt is beneficial to the dissociation of electrolyte salt, thereby obtaining more metal cations that can diffuse freely during charging and discharging. In addition, a small amount of complexed solvent molecules can improve the mobility of polymer molecular chains, which is reflected in inhibiting polymer crystallization or reducing the glass transition temperature of polymer chains. The improved mobility of polymer molecular chains is beneficial to the diffusion of dissociated metal cations, thereby obtaining a polymer electrolyte membrane material with high room temperature ionic conductivity;

[0018] (3) The solvent annealing apparatus provided by the present invention can effectively reduce the influence of residual solvent molecules in the unannealed solid polymer electrolyte membrane and improve the reliability of the annealing process.

[0019] (4) The solvent annealing apparatus provided by the present invention can be widely applied to a variety of solvent molecules with different physical properties based on temperature control and gas flow control technology, and the content of solvent molecules in the gas entering the annealing chamber can be flexibly adjusted as needed.

[0020] (5) The solvent annealing apparatus provided by the present invention can stably control the solvent molecule content in the gas entering the annealing chamber, and the process is reliable.

[0021] (6) The solvent annealing device provided by the present invention and the series or parallel connection of multiple solvent storage tanks can be adjusted to realize the mixed steam annealing of two or more solvents, which is flexible and meets the process requirements of multi-component solvent annealing. Attached Figure Description

[0022] Figure 1 This is a schematic diagram of the structure of a solvent annealing apparatus provided by the present invention;

[0023] Figure 2A schematic diagram of the solvent annealing device with multiple solvent storage tanks connected in series provided by this utility model;

[0024] Figure 3 A schematic diagram of the structure of the solvent annealing device with multiple solvent storage tanks connected in parallel according to this utility model.

[0025] In the diagram: 1. Solvent storage tank; 2. Annealing chamber; 3. Heater; 4. External gas; 5. First pipe; 6. Second pipe; 7. Connecting component; 71. Third pipe; 72. Branch pipe; 73. Fifth pipe; 8. Sealing cap; 9. Valve; 10. Solid electrolyte membrane; 11. Flow control valve; 12. Fourth pipe; 13. Sixth pipe. Detailed Implementation

[0026] The embodiments of this utility model will be described in further detail below with reference to the accompanying drawings and examples. The following examples are for illustrative purposes only and should not be construed as limiting the scope of this utility model.

[0027] Please refer to Figures 1 to 3 An embodiment of this utility model provides a solvent annealing apparatus, including an annealing chamber 2, a heater 3, an external gas 4, and at least one solvent storage tank 1. The solvent storage tank 1 is connected to the annealing chamber 2 through a pipe. A solid electrolyte membrane 10 can be placed in the annealing chamber 2. The external gas 4 supplies gas to the solvent storage tank 1, causing the solvent in the solvent storage tank 1 to foam. The heater 3 is placed below the solvent storage tank 1 and regulates the saturated solvent vapor pressure in the solvent storage tank 1. Solvent molecules are carried by the external gas 4 into the annealing chamber 2, come into contact with the electrolyte membrane, and then enter the electrolyte membrane to complete the solvent annealing. Multiple solvent storage tanks 1 are connected in series or in parallel through pipes.

[0028] In some embodiments, in order to better control the effect of solvent annealing and enable the modified solid polymer electrolyte membrane to obtain higher performance (including but not limited to high room temperature ionic conductivity, low interfacial contact resistance, wide electrochemical stability window, and good mechanical properties), the solvent storage tank 1 is connected to the external gas 4 through the first pipe 5, the annealing chamber 2 is connected to the solvent storage tank 1 through the second pipe 6, the annealing chamber 2 is connected to the first pipe 5 through the connecting component 7, and the second pipe 6 is connected to the connecting component 7.

[0029] In some embodiments, to facilitate the operation of the staff, each solvent storage tank 1 is provided with a sealing cover 8 on the top. The first gas pipe 5 and the second gas pipe 6 are respectively installed inside the solvent storage tank 1 through the sealing cover 8. One end of the first gas pipe 5 is inserted into the solvent, and the other end of the first gas pipe 5 is connected to the external gas 4. A flow control valve 11 is provided on the first gas pipe 5 to regulate the gas flow rate entering the solvent. One end of the second gas pipe 6 is located above the solvent, and the other end of the second gas pipe 6 is connected to the annealing chamber 2.

[0030] refer to Figure 2 In some embodiments, multiple solvents are used sequentially, and multiple solvent storage tanks 1 are connected in series. The connecting component 7 includes a third pipe 71, and each of the first pipes and the second pipes 6 is connected in series through the third pipe 71. One end of the third pipe 71 is connected to an external gas 4, and the other end of the third pipe 71 is connected to the annealing chamber 2.

[0031] In some embodiments, the external gas 4 is not limited and can be a dry inert gas, introduced into the solvent storage tank to cause the solvent to foam and generate solvent vapor; argon is preferred. The external gas 4 can be connected to each of the first pipes 5 via the fourth pipe 12, and the fourth pipe 12 is configured in parallel with the third pipe 71.

[0032] refer to Figure 3 In some embodiments, multiple solvents are mixed and used simultaneously. Multiple solvent storage tanks 1 are connected in parallel. The connecting component 7 includes a fifth pipe 73 and multiple branch pipes 72. Each branch pipe 72 corresponds to one solvent storage tank 1. Each solvent storage tank 1 is connected in parallel to the fifth pipe 73 via its corresponding branch pipe 72. The fifth pipe 73 is connected to the annealing chamber 2 via a sixth pipe 13. One end of each branch pipe 72 is connected to the fifth pipe 73, and the other end is connected to an external gas 4. Each branch pipe 72 is also connected to its corresponding first pipe 5 and second pipe 6.

[0033] In some embodiments, flow control valves 11 can be installed on the first pipe 5 and the second pipe 6 to control the gas flow rate into the solvent.

[0034] In some embodiments, in order to better control the selection of solvent, the connecting component 7 also includes valves 9, and the third pipe 71, branch pipe 72 and fifth pipe 73 are all provided with multiple valves 9.

[0035] In some embodiments, neither the electrolyte membrane nor the solvent is limited. A suitable solvent can be selected based on the type of polymer and electrolyte salt in the solid polymer electrolyte membrane. The solvent requirements are: 1) it can act as a plasticizer to improve the mobility of polymer chain segments; 2) it can dissociate the electrolyte salt; and 3) it is volatile.

[0036] In some embodiments, the electrolyte membrane 10 can be selected from polyethylene oxide (PEO), polymethyl methacrylate (PMMA), and their block copolymers as polymer matrices, and lithium bis(trifluoromethanesulfonyl)amino (LiTFSI) or zinc trifluoromethanesulfonate (Zn(OTF)2) as the electrolyte membrane matrix. PEO and PMMA contain ether bonds and ester bonds, respectively, and can complex with secondary ionic salts such as lithium, sodium, and zinc to promote salt dissociation, and are therefore widely used. LiTFSI and Zn(OTF)2 are commonly used electrolyte salts for secondary lithium-ion and zinc-ion batteries due to their high ionic conductivity and excellent air stability.

[0037] In some embodiments, the solvent filled in the solvent storage tank may be tetrahydrofuran, acetonitrile, acetone, chloroform, benzene or toluene, and may also include cyclic carbonates, linear carbonates and their derivatives, cyclic carboxylic acid esters, linear carboxylic acid esters and their derivatives, cyclic ethers, chain ethers, crown ethers and their derivatives.

[0038] In some embodiments, the solvent annealing apparatus provided by the present invention can also simultaneously modify the electrode surface.

[0039] The solvent annealing apparatus provided by this invention operates as follows: An external gas 4 is introduced into the solvent storage tank 1, causing partial atomization of the solvent to generate solvent vapor. The dry external gas 4 is then used to send the solvent vapor into the annealing chamber. During the foaming process, a heater 3 can be used to accelerate solvent evaporation, and the airflow speed can be controlled by a flow control valve 11. The annealing chamber 2 can accommodate multiple all-solid polymer electrolyte films and electrodes. The all-solid polymer electrolyte films and electrodes are suspended inside the annealing chamber 2 to ensure sufficient contact between the films and electrodes and the solvent vapor, reducing processing time. As time passes and the solvent evaporates, a large number of gaseous solvent molecules come into contact with the films and electrodes and enter the bulk phase of the films and electrodes, completing the solvent annealing process. After controlling the time, the solvent-annealed polymer electrolyte films and electrodes are removed from the container, and any free solvent molecules that may be present on the surface of the electrolyte film are removed by wiping, high-temperature drying in a vacuum oven, and settling in a glove box, resulting in solvent-annealed surface-modified polymer electrolyte films and electrodes.

[0040] In this document, the directional terms such as front, back, top, and bottom are defined based on the location of the components in the accompanying drawings and their relative positions to each other, solely for the purpose of clarity and convenience in expressing the technical solution. It should be understood that the use of these directional terms should not limit the scope of protection claimed in this application.

[0041] For any points not covered above, existing technologies shall apply.

[0042] Although specific embodiments of the present invention have been described in detail by way of examples, those skilled in the art should understand that the above examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Those skilled in the art can make various modifications or additions to the described specific embodiments or use similar methods to replace them, without departing from the direction of the present invention or exceeding the scope defined by the appended claims. Those skilled in the art should understand that any modifications, equivalent substitutions, improvements, etc., made to the above embodiments based on the technical essence of the present invention should be included within the protection scope of the present invention.

Claims

1. A solvent annealing apparatus, characterized in that, The system includes an annealing chamber (2), a heater (3), an external gas (4), and at least one solvent storage tank (1). The solvent storage tank (1) is connected to the annealing chamber (2) via a pipe. A solid electrolyte membrane (10) can be placed in the annealing chamber (2). The external gas (4) supplies gas to the solvent storage tank (1) to cause the solvent in the solvent storage tank (1) to foam. The heater (3) is located below the solvent storage tank (1) to regulate the saturated solvent vapor pressure in the solvent storage tank (1). Solvent molecules are carried by the external gas (4) into the annealing chamber (2) and come into contact with the electrolyte membrane to complete solvent annealing. Multiple solvent storage tanks (1) are connected in series or in parallel via pipes.

2. The solvent annealing apparatus as described in claim 1, characterized in that, The solvent storage tank (1) is connected to the external gas (4) through the first pipe (5), the annealing chamber (2) is connected to the solvent storage tank (1) through the second pipe (6), the annealing chamber (2) is connected to the first pipe (5) through the connecting component (7), and the second pipe (6) is connected to the connecting component (7).

3. The solvent annealing apparatus as described in claim 2, characterized in that, Each solvent storage tank (1) is provided with a sealing cap (8) on top. Each tank is provided with a first pipe (5) and a second pipe (6) that are connected to the sealing cap (8). One end of the first pipe (5) is inserted into the solvent in the solvent storage tank (1), and the other end of the first pipe (5) is connected to the external gas (4). One end of the second pipe (6) is located above the solvent in the solvent storage tank (1), and the other end of the second pipe (6) is connected to the annealing chamber (2).

4. The solvent annealing apparatus as described in claim 3, characterized in that, Multiple solvent storage tanks (1) are connected in series. The connecting component (7) includes a third pipe (71). Each of the first pipes (5) and the second pipes (6) are connected in series through the third pipe (71). One end of the third pipe (71) is connected to the external gas (4), and the other end of the third pipe (71) is connected to the annealing chamber (2).

5. The solvent annealing apparatus as described in claim 4, characterized in that, The external gas (4) is connected to each of the first pipes (5) through the fourth pipe (12), and the fourth pipe (12) is arranged in parallel with the third pipe (71).

6. The solvent annealing apparatus as described in claim 4, characterized in that, Multiple solvent storage tanks (1) are arranged in parallel. The connecting component (7) includes a fifth pipe (73) and multiple branch pipes (72). Each branch pipe (72) corresponds to a solvent storage tank (1). Each solvent storage tank (1) is connected in parallel to the fifth pipe (73) through its corresponding branch pipe (72). The fifth pipe (73) is connected to the annealing chamber (2) through a sixth pipe (13).

7. The solvent annealing apparatus as described in claim 6, characterized in that, One end of the branch pipe (72) is connected to the fifth pipe (73), and the other end of the branch pipe (72) is connected to the external gas (4). The branch pipe (72) is connected to the corresponding first pipe (5) and second pipe (6).

8. A solvent annealing apparatus as described in any one of claims 2 to 7, characterized in that, Both the first pipe (5) and the second pipe (6) are equipped with flow control valves (11).

9. The solvent annealing apparatus as described in claim 7, characterized in that, The connecting component (7) also includes valves (9), and the third pipe (71), the branch pipe (72) and the fifth pipe (73) are each provided with a plurality of valves (9).

Images