Method for manufacturing gel type electrolyte

Abstract

The present disclosure provides a method for manufacturing a gel-type electrolyte, the method being performed by using an apparatus for manufacturing a gel-type electrolyte, the method comprising: 1) filling an inner cavity of a housing with a first material; (2) supplying a first material through a first feeding pipe and supplying a second material at the temperature of 0-3 DEG C through a second feeding part at the same flow speed, and enabling a discharging pipe to be in an open state; and (3) enabling the first feeding pipe, the second feeding part and the discharging pipe to be in a closed state, and electrifying the inner cavity of the shell through the electrode, so that heteropolyacid-doped polyaniline is formed by the second material within first preset time, and meanwhile, the heteropolyacid-doped polyaniline is oriented in a second direction, the formed first material around the heteropoly acid doped polyaniline forms an acrylate polymer; and (4) heating the shell for a second preset time at the preset temperature through the heating part in the electrified state.

Description

Technical Field

[0001] Aspects of embodiments of the present disclosure are directed to a method for manufacturing a gel-type electrolyte. Background Art

[0002] Although liquid electrolytes have high ionic conductivity and good electrode wettability, they have safety issues such as easy leakage, strong corrosion, flammability and explosion. These problems not only limit the application scenarios of lithium-ion batteries (LIBs), but also pose a potential threat to the environment and personal safety.

[0003] In order to improve these shortcomings, gel-type electrolytes (GPEs) have gradually been valued, which combine the advantages of liquid electrolytes and solid electrolytes. GPEs have better safety and their electrochemical properties are close to those of liquid electrolytes, which makes them the focus of research in recent years.

[0004] The research on GPE is mainly focused on improving its electrochemical performance and safety. For example, by modifying the traditional polymer matrix through cross-linking, copolymerization or blending, a polymer matrix with better electrochemical properties can be prepared to improve safety. In addition, researchers are also exploring the use of renewable and degradable polymer materials to prepare GPE, which will not only help reduce environmental pressure, but also reduce production costs and increase the feasibility of industrial production.

[0005] However, the research and application of GPE still face challenges. For example, although the addition of a large amount of liquid plasticizer can improve ionic conductivity, it may also reduce the chemical stability of the polymer matrix, affecting the safety and service life of GPE. Therefore, effectively improving conductivity has become the primary goal of current gel electrolytes. Summary of the invention

[0006] The object of the present disclosure is to provide a device for manufacturing a gel-type electrolyte, which can make polyaniline have a certain orientation in the gel-type electrolyte.

[0007] Another object of the present disclosure is to provide a method for manufacturing a gel-type electrolyte having high electrical conductivity.

[0008] According to one aspect of the present disclosure, there is provided an apparatus for manufacturing a gel-type electrolyte, the apparatus comprising: a shell having an inner cavity for accommodating a material of the gel-type electrolyte and an opening partially opened in a first direction; a door rotatably mounted at the opening of the shell to place the shell in a closed or open state; a first feed pipe passing through a first side wall of the shell in a second direction perpendicular to the first direction and communicating with the inner cavity to supply a first material of the gel-type electrolyte to the inner cavity; a discharge pipe passing through a second side wall of the shell opposite to the first side wall in a second direction opposite to the first feed pipe and communicating with the inner cavity; a second feed portion comprising a first sub-feed pipe passing through the shell in the first direction, a second sub-feed pipe extending from an end of the first sub-feed pipe located in the inner cavity of the shell toward the discharge pipe in the second direction, and a nozzle disposed on the second sub-feed pipe to spray the second material of the gel-type electrolyte toward the discharge pipe; a heating portion disposed outside the shell to heat the material of the gel-type electrolyte in the inner cavity of the shell; and electrodes disposed on the first side wall and the second side wall of the shell in the inner cavity of the shell, respectively, to energize the material of the gel-type electrolyte.

[0009] According to an embodiment of the present disclosure, the second feed portion may be disposed close to the first feed pipe, and the nozzle may be located on an extension line between the first feed pipe and the discharge pipe in the second direction.

[0010] According to an embodiment of the present disclosure, the nozzle may include: a main board having a through hole sleeved on the outer wall of a second sub-feed pipe; a sub-board arranged along the edge of the main board and extending from the edge of the main board toward the discharge pipe; and a nozzle arranged on the sub-board and having a plurality of holes.

[0011] According to an embodiment of the present disclosure, the plurality of holes may be arranged along a first direction and a third direction perpendicular to the first direction and the second direction.

[0012] According to an embodiment of the present disclosure, the shortest distance between adjacent holes among the plurality of holes may be between 1 mm and 2 mm.

[0013] According to an embodiment of the present disclosure, a hole diameter of each of the plurality of holes may be 0.5 mm to 1 mm.

[0014] According to an embodiment of the present disclosure, an inner diameter of the first feeding pipe and an inner diameter of the second sub-feeding pipe may be substantially equal.

[0015] According to an embodiment of the present disclosure, the second feeding part may further include a pump connected to the first sub-feeding pipe to supply the second material of the gel-type electrolyte to the inner cavity.

[0016] According to an embodiment of the present disclosure, the device may further include a pump connected to the first feeding pipe to supply the first material of the gel-type electrolyte to the inner cavity.

[0017] According to an embodiment of the present disclosure, the device may further include a flow meter disposed in the housing to monitor the flow rate of the material in the housing in real time.

[0018] According to an embodiment of the present disclosure, the device may further include a valve disposed on the discharge pipe to place the discharge pipe in a closed or open state.

[0019] According to another aspect of the present disclosure, a method for manufacturing a gel-type electrolyte is provided, the method being performed by using the above-mentioned device for manufacturing a gel-type electrolyte, the method comprising the following steps: 1) filling the inner cavity of the shell with a first material, the first material comprising an acrylic monomer, an acrylic ester monomer, an ethylene glycol diacrylate crosslinking agent, and a dibenzoyl peroxide initiator; 2) supplying the first material through a first feed pipe at the same flow rate while supplying a second material at a temperature of 0° C. to 3° C. through a second feed part, and opening the discharge pipe, wherein the second material comprises aniline, a ternary heteropoly Acid, ammonium persulfate and water; 3) keeping the first feed pipe, the second feed part and the discharge pipe in a closed state and applying power to the inner cavity of the shell via the electrode, so that the second material forms heteropolyacid-doped polyaniline within a first predetermined time and the heteropolyacid-doped polyaniline is oriented in a second direction, and the first material around the heteropolyacid-doped polyaniline forms an acrylate polymer; and 4) heating the shell at a predetermined temperature to a second predetermined time via the heating part while keeping the power on, so that the remaining part of the first material is polymerized to form an acrylate polymer, thereby forming a gel electrolyte.

[0020] According to an embodiment of the present disclosure, the flow rate satisfies a Re value less than 2000, wherein the Re value is expressed by the following formula:

[0021]

[0022] Wherein, Re is the Reynolds number; d is the diameter or equivalent diameter of the shell, in m; u is the flow rate of the first material, in m / s; ρ is the density of the acrylic monomer, in kg / m 3 ; μ is the viscosity of acrylic monomer, unit N·m -2 ·s.

[0023] According to an embodiment of the present disclosure, energization may be performed at an electric field intensity of 5 V / cm to 25 V / cm.

[0024] According to an embodiment of the present disclosure, the first predetermined time may be 1.5 hours to 3 hours.

[0025] According to an embodiment of the present disclosure, the predetermined temperature may be 50° C. to 60° C., and the second predetermined time may be 14 hours to 16 hours.

[0026] According to an embodiment of the present disclosure, the molar ratio of acrylic monomer, acrylate monomer and ethylene glycol diacrylate crosslinker in the first material is 10:2:0.5, and the added amount of dibenzoyl peroxide initiator is 1wt% of the total weight of the monomers.

[0027] According to an embodiment of the present disclosure, the molar ratio of aniline, tribasic heteropoly acid and ammonium persulfate in the second material can be 1:0.01-0.03:1.4, and the amount of water added is 10 wt % of the total mass of aniline.

[0028] According to an embodiment of the present disclosure, step 2) may be performed for at least 1 minute or less than or equal to 2 minutes.

[0029] According to an embodiment of the present disclosure, the method further includes: after polymerizing the first material, opening the door to take out the gel electrolyte.

[0030] In the embodiments of the present disclosure, since the second material to be formed into heteropolyacid-doped polyaniline is introduced into the unpolymerized first material through the device of the present disclosure and then electricity is applied, the second material is orderly oriented into a linear layer-like structure in the first material while forming heteropolyacid-doped polyaniline, and thus the conductivity of the gel-type electrolyte formed by the present disclosure is significantly increased. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] The above and other aspects and features of the embodiments of the present disclosure will become more apparent through the following description in conjunction with the accompanying drawings, in which:

[0032] Figure 1 is a perspective view of an apparatus for manufacturing a gel-type electrolyte according to an embodiment of the present disclosure;

[0033] Figure 2 is a schematic diagram of an apparatus for manufacturing a gel-type electrolyte according to an embodiment of the present disclosure; and

[0034] Figure 3 is a schematic diagram of a second feeding part in the apparatus for manufacturing a gel-type electrolyte according to an embodiment of the present disclosure. DETAILED DESCRIPTION

[0035] Reference will now be made in detail to embodiments, examples of which are shown in the accompanying drawings. In this regard, the described embodiments may have different forms and should not be construed as being limited to the descriptions set forth herein. Therefore, the embodiments are described below only by reference to the accompanying drawings to explain aspects and features of the present description.

[0036] For ease of description, spatially relative terms such as "under", "below", "below", "above", "on", etc. may be used herein to describe the relationship of one element or feature to another element or features as shown in the figures. It will be understood that in addition to the orientation shown in the figures, the spatially relative terms are also intended to cover different orientations of the device in use or operation. For example, if the device in the figure is turned over, the elements described as "under" or "below" other elements or features will be oriented as "above" or "on" other elements or features. Therefore, the term "below" can cover both above and below orientations. The device can be oriented otherwise (rotated 90 degrees or in other orientations), and the spatially relative descriptors used herein should be interpreted accordingly.

[0037] Hereinafter, embodiments of the present disclosure will be described with reference to the accompanying drawings.

[0038] Figure 1 is a perspective view of an apparatus for manufacturing a gel-type electrolyte according to an embodiment of the present disclosure; Figure 2 is a schematic diagram of an apparatus for manufacturing a gel-type electrolyte according to an embodiment of the present disclosure; and Figure 3 is a schematic diagram of a second feeding part in the apparatus for manufacturing a gel-type electrolyte according to an embodiment of the present disclosure.

[0039] Reference Figure 1 , Figure 2 and Figure 3 , the apparatus for manufacturing a gel-type electrolyte according to an embodiment of the present disclosure includes: a housing 100 , a door 110 , a second feed part 200 , a first feed pipe 300 , a discharge pipe 400 , a heating part, and electrodes.

[0040] The housing 100 may have a rectangular parallelepiped shape and have an inner cavity for accommodating a material of a gel-type electrolyte, however, the embodiments of the present disclosure are not limited thereto, and the rectangular parallelepiped shape has two surfaces in a first direction Z, two other surfaces in a third direction Y perpendicular to the first direction Z, and two side walls in a second direction X perpendicular to the first direction Z and the third direction Y (e.g., a first side wall and a second side wall opposite to each other).

[0041] In addition, in order to facilitate the easy removal of the formed gel electrolyte from the housing 100 , an opening may be provided on the housing 100 . Specifically, the housing 100 may have a partially opened opening in the first direction Z.

[0042] In addition, since an energized electrode will be fixed inside the shell 100, the shell 100 can be formed of an insulating material (for example, glass, ceramic, etc.); however, the present disclosure is not limited thereto, and the shell 100 can be formed of any suitable material that can put the shell 100 in an insulating state.

[0043] The door 110 may be rotatably mounted at the opening of the housing 100 to close or open the housing 100. Specifically, the door 110 may be connected to the opening of the housing 100 by a hinge so that the door 110 may be rotatably opened or closed relative to the housing 100.

[0044] In addition, the door 110 may be formed of the same insulating material as the housing 100 , however, the present disclosure is not limited thereto, and the door 110 may be formed of any suitable material as long as the door 110 is in an insulating state.

[0045] The first feed pipe 300 may pass through the first sidewall of the housing 100 in the second direction X to communicate with the inner cavity to supply the first material of the gel-type electrolyte to the inner cavity. In addition, the first feed pipe 300 may be connected to a pump (eg, a peristaltic pump) to supply the first material.

[0046] The discharge pipe 400 may pass through the second side wall of the housing opposite to the first side wall and communicate with the inner cavity in the second direction X. In addition, a valve may be provided on the discharge pipe 400 to close or open the discharge pipe.

[0047] The first feeding pipe 300 and the discharging pipe 400 may be formed of the same material.

[0048] Reference Figure 3 The second feed part 200 can supply the second material of the gel electrolyte, and can include a first sub-feed pipe 210, a second sub-feed pipe 220, and a nozzle 230. In addition, in order to extend the contact time between the second material and the first material, preferably, the second feed part 230 can be arranged close to the first feed pipe 300.

[0049] The first sub-feed pipe 210 may pass through the housing 100 in the first direction Z to communicate with the inner cavity. Specifically, the first sub-feed pipe 210 may pass through a portion of the housing 100 in the first direction Z except for the opening.

[0050] The second sub-feed pipe 220 may extend from the end of the first sub-feed pipe 210 located in the inner cavity of the housing 100 along the second direction X toward the discharge pipe 400 .

[0051] In addition, the first and second feeding pipes 210 and 220 may be formed of the same material as the first feeding pipe 300 and the discharging pipe 400. Also, the first and second feeding pipes 210 and 220 may be integrally formed, however, the present disclosure is not limited thereto.

[0052] In addition, the diameter (eg, inner diameter) of the second sub-feed pipe 220 may be substantially the same as the diameter (eg, inner diameter) of the first feed pipe 300 , thereby facilitating control of the ratio between the first material and the second material.

[0053] The nozzle 230 may be disposed on the second sub-feed pipe 220 to spray the second material of the gel-type electrolyte toward the discharge pipe 400. In addition, in order to improve the order or orientation of the second material in the first material, preferably, the nozzle 230 may be located on an extension line between the first feed pipe 300 and the discharge pipe 400 in the second direction X.

[0054] The nozzle 230 may include: a main board having a through hole sleeved on the outer wall of the second sub-feed pipe 220; a sub-board arranged along the edge of the main board and extending from the edge of the main board toward the discharge pipe 400; and a nozzle 240 arranged on the sub-board and having a plurality of holes.

[0055] The main board and the sub-board may be integrally formed, however, embodiments of the present disclosure are not limited thereto.

[0056] In addition, a plurality of holes may be arranged along the first direction Z and the third direction Y.

[0057] Furthermore, in order to improve the orderliness or orientation of the second material in the first material, preferably, the shortest distance between adjacent holes among the plurality of holes may be between 1 mm and 2 mm, and the pore size of each of the plurality of holes may be between 0.5 mm and 1 mm.

[0058] In addition, the second feeding part 200 may further include a pump (eg, a peristaltic pump) connected to the first sub-feeding pipe 210 to supply the second material of the gel-type electrolyte to the inner cavity.

[0059] According to an embodiment of the present disclosure, the apparatus may further include a flow meter (eg, a rectangular flow meter) disposed in the interior of the housing 100 to detect a flow rate of the first material in the inner cavity.

[0060] The heating part may be provided outside the housing 100 to heat the material of the gel-type electrolyte in the inner cavity of the housing 100 .

[0061] Electrodes may be disposed on the first side wall and the second side wall of the housing 100 in the inner cavity of the housing 100 to electrify the material of the gel electrolyte, so that the heteropolyacid-doped polyaniline formed by the second material is oriented in the second direction X into a linear-like structure.

[0062] According to the embodiment of the present disclosure, since the polyaniline formed by the second material is oriented in one direction into a linear structure and fixed by the acrylic polymer formed by the first material, the conductivity of the gel electrolyte formed by the present disclosure is significantly increased.

[0063] The process steps for manufacturing a gel-type electrolyte using the apparatus for manufacturing a gel-type electrolyte will be described below.

[0064] According to an embodiment of the present disclosure, a method for manufacturing a gel-type electrolyte is performed by using the above-mentioned device for manufacturing a gel-type electrolyte, and the method includes: step 1), filling the inner cavity of the shell with a first material; step 2), supplying the first material through a first feed pipe at the same flow rate and supplying a second material at a temperature of 0°C to 3°C through a second feed part, and keeping the discharge pipe in an open state; step 3), closing the first feed pipe, the second feed part, and the discharge pipe and energizing the inner cavity of the shell through an electrode, so that the second material forms heteropolyacid-doped polyaniline within a first predetermined time and the polyaniline is oriented in a second direction and the first material around the heteropolyacid-doped polyaniline forms an acrylate polymer; and step 4), heating the shell at a predetermined temperature to a second predetermined time through a heating part while keeping the power on, so that the remaining part of the first material is polymerized to form an acrylate polymer, thereby forming a gel-type electrolyte.

[0065] In step 1), the inner cavity of the housing 100 is filled with the first material. Specifically, the inner cavity of the housing 100 can be filled with the first material through the first feeding pipe 300 by a peristaltic pump, or the door 110 can be opened to fill the inner cavity of the housing 100 with the first material through the opening of the housing 100. When the inner cavity of the housing 100 is filled with the first material through the first feeding pipe 300, the first material can be slowly injected to remove the gas in the inner cavity of the housing.

[0066] The first material may be a main component of the gel-type electrolyte and may include acrylic monomers, acrylic ester monomers, ethylene glycol diacrylate crosslinking agent, and dibenzoyl peroxide (BPO) initiator.

[0067] In an embodiment of the present disclosure, the molar ratio of acrylic monomer, acrylate monomer and ethylene glycol diacrylate crosslinker in the first material may be 10:2:0.5, and the added amount of dibenzoyl peroxide initiator may be 1 wt % of the total weight of the monomers.

[0068] In an embodiment of the present disclosure, the acrylic monomer may include at least one of acrylic acid, methacrylic acid, ethylacrylic acid, propylacrylic acid, and isobutylacrylic acid. The acrylate monomer may include at least one of methyl methacrylate and ethyl methacrylate.

[0069] In an embodiment of the present disclosure, the ethylene glycol diacrylate cross-linking agent may include at least one of ethylene glycol diacrylate, ethylene glycol dimethacrylate, ethylene glycol diethyl acrylate, and ethylene glycol dipropyl acrylate.

[0070] In the embodiments of the present disclosure, dibenzoyl peroxide can initiate polymerization of the monomers of the first material without adversely affecting polymerization of the second material.

[0071] The acrylic monomer and the acrylate monomer may be polymerized at a predetermined temperature (eg, 55° C. to 60° C.) under the action of an initiator and a cross-linking agent to generate an acrylate polymer.

[0072] After the inner cavity of the housing 100 is filled with the first material (step 1), the first material can be supplied at the same flow rate through the first feed pipe 300, and the second material at a temperature of 0° C. to 3° C. can be supplied through the second feed part 200, for example, by a peristaltic pump, that is, the first material and the second material are supplied together into the inner cavity of the housing 100. At the same time, the discharge pipe 400 is opened, so that the discharge pipe 400 is in an open state.

[0073] The second material can be used as a conductive agent for the gel electrolyte and can include aniline, a ternary heteropoly acid, ammonium persulfate and water. In addition, in the embodiment of the present disclosure, the molar ratio of aniline, ternary heteropoly acid and ammonium persulfate in the second material can be 1:0.01 to 0.03:1.4, and the amount of water added can be 10wt% of the total mass of aniline.

[0074] In the embodiments of the present disclosure, the ternary heteropoly acid can be used as a dopant to dope the polymerized aniline, and can include H7SiW9V3O 40 In addition, ammonium persulfate is used as an initiator to polymerize aniline. Under the combined action of the ternary heteropoly acid and the initiator, heteropoly acid-doped polyaniline can be generated, thereby making the polyaniline conductive.

[0075] In addition, in the art, aniline, tribasic heteropoly acid and ammonium persulfate can usually initiate polymerization at a relatively low temperature. Therefore, in the present disclosure, in order to ensure that aniline, tribasic heteropoly acid and ammonium persulfate are polymerized in the shell or the first material in the shell, the second material can be placed at a temperature of 0°C to 3°C before the second material is supplied through the second feed part 200 to slow down the polymerization of aniline, tribasic heteropoly acid and ammonium persulfate in the second feed part to avoid clogging the nozzle 230. When the second material is supplied to the first material, the temperature is higher than 3°C, thereby increasing the polymerization reaction rate of the second material in the first material.

[0076] In the embodiment of the present disclosure, in order to improve the orientation of the heteropolyacid-doped polyaniline formed by the second material in the first material, the first material can be placed in a flat flow state. Specifically, the flow rate (m / s) of the first material can be controlled to satisfy the Re value less than 2000, wherein the Re value is represented by the following formula:

[0077]

[0078] Wherein, Re is the Reynolds number; d is the diameter or equivalent diameter of the shell, in m; u is the flow rate of the first material, in m / s; ρ is the density of the acrylic monomer, in kg / m 3 ; μ is the viscosity of acrylic monomer, unit N·m -2 ·s.

[0079] In the present disclosure, since the first material is in a horizontal flow state, the second material supplied together with the first material can undergo polymerization and be oriented at the same time, and the polymerization of the second material is an exothermic reaction, which can cause the first material around it to undergo polymerization, thereby fixing the heteropolyacid-doped polyaniline generated by the polymerization, and thereby enabling the heteropolyacid-doped polyaniline generated by the polymerization to be orderly oriented in the acrylic polymer formed by the polymerization of the first material.

[0080] In addition, in the embodiments of the present disclosure, if the flow rate of supplying the second material is lower than the flow rate of supplying the first material, the supply of the second material may be interrupted; if the flow rate of supplying the second material is higher than the flow rate of supplying the first material, a large amount of the second material may accumulate at the nozzle. Therefore, the first material and the second material need to be supplied at the same flow rate at the same time.

[0081] Furthermore, in order to arrange the second material uniformly within the first material, preferably, the shortest distance between adjacent holes among the plurality of holes is set between 1 mm and 2 mm, and the diameter of each hole is between 0.5 mm and 1 mm.

[0082] In addition, in order to achieve a balanced ratio between the first material and the second material in the housing 100, step 2) may be performed for at least 1 minute or less than or equal to 5 minutes.

[0083] In step 3), the first feed pipe, the second feed part and the discharge pipe are closed, so that the first material and the second material can maintain a relatively stable state in the shell. Since the temperature of the second material is higher than 3°C, the second material can start to accelerate polymerization, and the heat released by the polymerization of the second material can reach the polymerization reaction of the first material around it, so that the heteropolyacid-doped polyaniline can be oriented and fixed by the acrylic polymer generated around it.

[0084] In the embodiment of the present application, preferably, the electric field strength can be selected from 5V / cm to 25V / cm (for example, 5V / cm to 20V / cm, 10V / cm to 18V / cm, etc.) to make the polyaniline doped with the conductive heteropolyacid be similar to a linear structure in the second direction. In addition, in order to make the second material react completely, preferably, the first predetermined time can be 1.5h to 3h.

[0085] In step 4), the housing may be heated at 50° C. to 60° C. for 14 to 16 hours via a heating unit while being powered on, so that the first material starts to polymerize and then forms an acrylic polymer.

[0086] Since electrodes are added at both ends of the device, an electric field will be generated between the first side wall and the second side wall in the reaction system. The electric field strength can be adjusted by the potential difference between the two electrodes. Due to the generated electric field, the polymerized heteropolyacid-doped polyaniline will be oriented in the direction of the electric field. With the polymerization reaction of the first material, the second material around it begins to polymerize, so the orientation of the polyaniline will be fixed. With the completion of the polymerization, a linear-like structure of polyaniline with a certain orientation exists in the produced gel electrolyte.

[0087] In addition, in the present disclosure, since different monomers require different curing times, after a period of curing, the gel-type electrolyte is prepared in the shell. At this time, the door on the shell can be opened to take out the cured gel-type electrolyte, thereby completing the preparation of the gel-type electrolyte.

[0088] In the present disclosure, since the heteropolyacid-doped polyaniline formed by the application of electricity can be oriented in the second direction, and the polymerization of the first material can fix the heteropolyacid-doped polyaniline, the conductive agent (heteropolyacid-doped polyaniline) in the formed gel-type electrolyte can be oriented into a linear structure. Therefore, the conductivity of the gel-type electrolyte formed by the present disclosure is significantly improved.

[0089] An example is provided below to further illustrate.

[0090] Example 1

[0091] First, the first material is pumped into the shell through a peristaltic pump. At the same time, the discharge port is closed to allow the first material to fill the internal space of the shell. The discharge port is opened, and the first material and the second material at a temperature of 3°C are injected into the shell at a constant flow rate. At the same time, a flow meter is used to measure the flow rate in the shell and continuously adjust the flow rates of the first material and the second material so that the fluid flow rate in the shell is 900mL / min. Then balance for 1min to make the first material and the second material in the shell reach a ratio relationship. At this time, the second feed part, the discharge pipe, and the first feed pipe are closed. When the power is turned on at an electric field strength of 5V / cm, the second material in the shell begins to polymerize because it is higher than 3°C, and the acrylic monomers and acrylate monomers around it also begin to polymerize, so that the heteropolyacid-doped polyaniline formed by the second material is fixed by the acrylic polymer around it. After 2h, when the polymerization of the second material is completed, the temperature is heated to 60°C and maintained for 14h to polymerize the remaining first material, thereby completing the preparation of the gel-type electrolyte. The results are shown in Table 1. The conductivity of the obtained gel-type electrolyte is 5.5×10 -4 S / cm.

[0092] The corresponding parameters of the device are as follows: the diameter or equivalent diameter of the shell is 2 cm, the shortest distance between adjacent holes in the hole is 1 mm, and the pore size of each hole is 0.5 mm, and the density and viscosity of acrylic acid are 1.051 g / cm3 and 1.149 mPa·s, respectively. In addition, the ratio relationship between the components used in the first material and the second material is shown in Table 1, wherein the amount of dibenzoyl peroxide initiator added is 1wt% of the total weight of the monomer, and the amount of water added is 10wt% of the total weight of aniline.

[0093] Examples 2 to 6

[0094] Examples 2 to 6 were prepared in the same manner as in Example 1, except that the corresponding parameters of Table 1 were used.

[0095] Comparative Example 1 and Comparative Example 2

[0096] Comparative Example 1 and Comparative Example 2 were prepared in the same manner as in Example 1, except that the corresponding parameters of Table 1 were used.

[0097] Comparison Example 3

[0098] Aniline: ammonium persulfate: ternary heteropoly acid were mixed in water at a molar ratio of 1:1.4:0.01, stirred evenly by mechanical stirring, reacted at room temperature for 2 hours, and the ternary heteropoly acid doped polyaniline produced by the reaction was separated and added to a mixture of acrylic acid: methyl methacrylate: ethylene glycol diacrylate at a ratio of 10:2:0.5, and then 1wt% of the total weight of acrylic acid and acrylate monomers was added as dibenzoyl peroxide initiator, and the mixed solution was poured into a mold, left to stand for 2 hours, and then heated to 60°C for reaction for 12 hours. The results are shown in Table 1.

[0099] Table 1

[0100]

[0101] In Table 1, the ternary heteropoly acid is H7SiW9V3O 40 , where all ratios are molar ratios, the unit of electric field strength is V / cm, and the unit of conductivity is S / cm.

[0102] As can be seen from Table 1, when comparing Examples 1 to 6 with Comparative Example 1, it is found that an excessively large electric field may cause the conductive ions to move toward the two poles and aggregate, resulting in a decrease in the conductivity of Comparative Example 1, so the conductivity of Comparative Example 1 is significantly lower than that of Examples 1 to 6. When comparing Examples 1 to 6 with Comparative Example 2, it is found that an excessively high flow rate may cause the material in the shell to form a turbulent state, resulting in the orientation of the formed polyaniline being affected, so the conductivity of Comparative Example 2 is significantly lower than that of Examples 1 to 6. In addition, the conductivity of Examples 1 to 6 is significantly higher than that of Comparative Example 3 with mechanical stirring, because the polyaniline doped with a conductive heteropolyacid is oriented into a layered linear structure in the gel electrolyte, so that the conductivity can be significantly improved.

[0103] In summary, since the heteropolyacid-doped polyaniline is formed during the process of electrification, the heteropolyacid-doped polyaniline formed can be oriented in the second direction, and the polymerization of the first material can fix the heteropolyacid-doped polyaniline, so the conductive agent (heteropolyacid-doped polyaniline) in the formed gel-type electrolyte can be oriented into a structure similar to a layered distribution. Therefore, the conductivity of the gel-type electrolyte formed by the present disclosure is significantly improved.

Claims

1. A method for producing a gel-type electrolyte, characterized in that: The method is performed by using an apparatus for manufacturing a gel-type electrolyte, The device comprises: a shell having an inner cavity for accommodating a material of a gel-type electrolyte and an opening partially opened in a first direction; a door rotatably mounted at the opening of the shell to place the shell in a closed or open state; a first feed pipe passing through a first side wall of the shell in a second direction perpendicular to the first direction and communicating with the inner cavity to supply a first material of the gel-type electrolyte to the inner cavity; a discharge pipe passing through a second side wall of the shell opposite to the first side wall in a second direction opposite to the first feed pipe and communicating with the inner cavity; a second feed portion comprising a first sub-feed pipe passing through the shell in the first direction, a second sub-feed pipe extending from an end of the first sub-feed pipe located in the inner cavity of the shell toward the discharge pipe along the second direction, and a nozzle disposed on the second sub-feed pipe to spray the second material of the gel-type electrolyte toward the discharge pipe; a heating portion disposed outside the shell to heat the material of the gel-type electrolyte in the inner cavity of the shell; and electrodes disposed on the first side wall and the second side wall of the shell in the inner cavity of the shell, respectively, to energize the material of the gel-type electrolyte, The method comprises the following steps: 1) filling the inner cavity of the shell with a first material, wherein the first material comprises an acrylic monomer, an acrylic ester monomer, an ethylene glycol diacrylate crosslinking agent and a dibenzoyl peroxide initiator; 2) supplying the first material through a first feed pipe at the same flow rate and supplying a second material at a temperature of 0°C to 3°C through a second feed portion, and opening the discharge pipe, wherein the second material comprises aniline, a ternary heteropoly acid, ammonium persulfate and water; 3) closing the first feed pipe, the second feed portion and the discharge pipe and applying power to the inner cavity of the shell via an electrode, so that the second material forms heteropoly acid-doped polyaniline within a first predetermined time and the heteropoly acid-doped polyaniline is oriented in a second direction, and the first material around the heteropoly acid-doped polyaniline forms an acrylic ester polymer; and 4) heating the shell at a predetermined temperature to a second predetermined time via a heating portion while maintaining power, so that the remaining part of the first material is polymerized to form an acrylic ester polymer, thereby forming a gel electrolyte.

2. The method according to claim 1, characterized in that: The second feeding portion is arranged close to the first feeding pipe, and the nozzle is located on an extension line between the first feeding pipe and the discharging pipe in the second direction.

3. The method according to claim 1, characterized in that The nozzle includes: a main board having a through hole sleeved on the outer wall of the second sub-feed pipe; a sub-board arranged along the edge of the main board and extending from the edge of the main board toward the discharge pipe; and a nozzle arranged on the sub-board and having a plurality of holes.

4. The method according to claim 1, characterized in that The plurality of holes are arranged along a first direction and a third direction perpendicular to the first direction and the second direction.

5. The method according to claim 1, characterized in that The shortest distance between adjacent holes among the plurality of holes is between 1 mm and 2 mm, Each of the plurality of holes has a hole diameter of 0.5 mm to 1 mm.

6. The method according to claim 1, characterized in that The flow rate satisfies the Re value less than 2000, where the Re value is expressed by the following formula: Wherein, Re is the Reynolds number; d is the diameter or equivalent diameter of the shell, in m; u is the flow rate of the first material, in m / s; ρ is the density of the acrylic monomer, in kg / m 3 ; μ is the viscosity of acrylic monomer, unit N·m -2 ·s.

7. The method according to claim 1, characterized in that The energization is performed at an electric field intensity of 5 V / cm to 25 V / cm.

8. The method according to claim 1, characterized in that The first predetermined time is 1.5 h to 3 h, the predetermined temperature is 50° C. to 60° C., and the second predetermined time is 14 h to 16 h.

9. The method according to claim 1, characterized in that: The molar ratio of acrylic acid monomer, acrylic acid ester monomer and ethylene glycol diacrylate crosslinking agent in the first material is 10:2:0.5, and the amount of dibenzoyl peroxide initiator added is 1wt% of the total weight of the monomers. The molar ratio of aniline, tribasic heteropoly acid and ammonium persulfate in the second material is 1:0.01-0.03:1.4, and the amount of water added is 10wt% of the total mass of aniline.

10. The method according to claim 1, characterized in that Perform step 2) for at least 1 minute or less than or equal to 5 minutes.

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