CN115954609A - Spinning diaphragm, manufacturing method thereof and lithium battery - Google Patents
Spinning diaphragm, manufacturing method thereof and lithium battery Download PDFInfo
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- CN115954609A CN115954609A CN202310066195.9A CN202310066195A CN115954609A CN 115954609 A CN115954609 A CN 115954609A CN 202310066195 A CN202310066195 A CN 202310066195A CN 115954609 A CN115954609 A CN 115954609A
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 44
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 86
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 54
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Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The application discloses a spinning diaphragm, a manufacturing method thereof and a lithium battery, and relates to the technical field of batteries. The spinning diaphragm manufacturing method provided by the application combines unstable ring-opening polymerization materials and protein materials into a macromolecular chain through a cross-linking reaction. The protein material has excellent physical and chemical properties, so that the spinning solution with excellent performance can be prepared. The spinning coating is formed on the diaphragm substrate through a spinning means, and the uniformity of the surface thickness of the coating can be ensured. The spinning diaphragm that this application preparation was obtained can promote the more even deposit of lithium ion in order to reach the purpose that restraines the growth of lithium dendrite to the cycling performance of extension battery and assurance battery have the security of preferred. The lithium battery provided by the application has the spinning diaphragm, so that the lithium battery has better cycle performance and safety.
Description
Technical Field
The application relates to the technical field of batteries, in particular to a spinning diaphragm, a manufacturing method of the spinning diaphragm and a lithium battery.
Background
The diaphragm used in the lithium battery has the main functions of physically isolating the positive electrode and the negative electrode, preventing electrons in the battery from passing through the battery and allowing ions to pass through the battery, so that the lithium ions in the electrochemical charge-discharge process are quickly transmitted by being embedded in and out of the positive electrode and the negative electrode. In the charging and discharging process, because of the characteristics of the electrode material, dendritic crystals of metal lithium are easily generated on the surface of the electrode, and the growth of the dendritic crystals pierces a diaphragm, so that the dangers of short circuit failure of the battery, even explosion of fuel and the like are caused. Therefore, the battery separator is a battery safety key, has excellent performance, and can directly influence the cycle performance, internal resistance, safety and other characteristics of the battery.
In view of this, the present application is specifically made.
Disclosure of Invention
The application aims to provide a spinning diaphragm, a manufacturing method thereof and a lithium battery. The spinning diaphragm prepared by the spinning diaphragm manufacturing method has better performance, can inhibit the growth of lithium dendrites, and has better stability, so that the cycle performance of a battery is prolonged, and the lithium battery has better safety.
The application is realized as follows:
in a first aspect, the present application provides a method for making a spinning membrane, comprising:
mixing 1, 3-dioxolane and a lewis acid to obtain a ring-opening polymerization solution;
carrying out a cross-linking reaction on the ring-opening polymerization solution and a protein material to obtain a spinning solution;
and forming a spinning coating on the diaphragm base material by using the spinning solution to obtain the spinning diaphragm.
In an alternative embodiment, the step of mixing the 1, 3-dioxolane, the lewis acid, and the crosslinking solvent to obtain the ring-opening polymerization solution without an ether group in the lewis acid comprises:
mixing Lewis acid and 1, 3-dioxolane according to the volume ratio of (1-2): 100, and standing for 60-180 s to obtain a ring-opening polymerization material;
adding a crosslinking solvent into the ring-opening polymerization material to obtain a ring-opening polymerization solution;
a step of mixing 1, 3-dioxolane, a lewis acid, in the case where the lewis acid contains an ether group, to obtain a ring-opening polymerization solution, comprising:
mixing Lewis acid and 1, 3-dioxolane according to the volume ratio of (1-2): 100, and standing for 60 to 180 seconds to obtain the ring-opening polymerization solution.
In an alternative embodiment, the crosslinking solvent is an ether crosslinker or one or more of glutaraldehyde, maleic anhydride, potassium persulfate, N-hydroxysuccinimide, 1-ethyl- (3-dimethylaminopropyl) carbodiimides.
In alternative embodiments, the lewis acid is one or more of boron trifluoride etherate, boron trifluoride, aluminum trichloride, sulfur trioxide, dichlorocarbene, ferric chloride, niobium pentachloride, aluminum triflate, lithium difluorooxalato borate.
In alternative embodiments, the protein material is an aqueous or alcoholic solution of the protein.
In an alternative embodiment, the protein concentration in the protein material is from 10 to 30wt.%.
In an alternative embodiment, the step of cross-linking the ring-opening polymerization solution with the proteinaceous material to obtain the spinning solution comprises:
mixing the ring-opening polymerization solution with a protein material according to the volume ratio of (2-4): 1, stirring the mixture at a temperature of between 25 and 50 ℃ for 6 to 8 hours, and standing the mixture at room temperature for 8 to 12 hours to obtain a spinning solution.
In an alternative embodiment, the protein in the protein material is one or more of silk fibroin, zein, hemoglobin, hemocyanin, bovine serum albumin, bovine albumin, sericin, glycoproteins, fibrin, collagen, myoglobin, and soy protein.
In an alternative embodiment, the step of forming a spun coating layer on a separator substrate using a spinning solution to obtain a spun separator comprises:
carrying out electrostatic spinning on the diaphragm base material by using a spinning solution to obtain the diaphragm base material loaded with a spinning material;
and drying the membrane substrate loaded with the spinning material to obtain the spinning membrane with the spinning coating.
In an alternative embodiment, the separator substrate is a PP film or a PE film.
In an alternative embodiment, the spin coating has a thickness of 5 to 35 μm.
In a second aspect, the present application provides a spun separator made by the method of making a spun separator of any of the preceding embodiments.
In a third aspect, the application provides a lithium battery, which comprises the spinning membrane provided by the second aspect.
The application has the following beneficial effects:
the spinning diaphragm manufacturing method provided by the application comprises the steps of mixing 1, 3-dioxolane and Lewis acid to obtain a ring-opening polymerization solution; performing a cross-linking reaction on the ring-opening polymerization solution and a protein material to obtain a spinning solution; and forming a spinning coating on the diaphragm base material by using the spinning solution to obtain the spinning diaphragm. The preparation method provided by the application is based on a ring-opening polymerization material as a coating material, and because the single ring-opening polymerization material does not have excellent mechanical properties, the unstable ring-opening polymerization material and a protein material are combined into a macromolecular chain through a crosslinking reaction. Because the protein material has excellent mechanical property and physicochemical property, and the specific protein has natural high molecular fiber shape, the protein is quite excellent in fiber skeleton structure, and is beneficial to preparing spinning solution with excellent performance. And then a spinning coating is formed on the diaphragm substrate by a spinning means, so that the uniformity of the surface thickness of the coating can be ensured. The spinning diaphragm prepared by the preparation method can promote more uniform deposition of lithium ions so as to achieve the purpose of inhibiting growth of lithium dendrites, thereby prolonging the cycle performance of the battery and ensuring that the battery has better safety.
The spinning diaphragm provided by the application is prepared by the spinning diaphragm manufacturing method. The lithium battery provided by the application comprises the spinning diaphragm.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained from the drawings without inventive effort.
FIG. 1 is a flow chart of a method for making a spinning membrane according to an embodiment of the present disclosure;
FIG. 2 is a scanning electron micrograph of a spin coating in example 1;
fig. 3 is a graph comparing the cycle performance at current density for assembled lithium titanate batteries 2C of comparative example 1 and example 1.
Detailed Description
With the rapid development of electrochemical energy storage devices, lithium ion batteries have received much attention due to the advantages of high energy density, high power density, and the like. The lithium battery diaphragm is generally prepared from polyethylene or polypropylene (PE or PP), and the main function of the battery diaphragm is to physically separate the positive electrode and the negative electrode, prevent electrons in the battery from passing through, and allow ions to pass through, so that the lithium ion insertion and extraction rapid transmission of the electrochemical charge and discharge process at the positive electrode and the negative electrode is completed. In the charging and discharging process, dendritic crystals of metal lithium are easily generated on the surface of the electrode due to the characteristics of the electrode material, and the growth of the dendritic crystals pierces a diaphragm, so that the danger of short circuit failure of the battery, even explosion fuel and the like is caused. Therefore, the battery diaphragm is the key of battery safety, has excellent performance, and can directly influence the cycle performance, internal resistance, safety and other characteristics of the battery.
In recent years, the lithium battery diaphragm coating technology is rapidly developed, and scientific researchers prepare different gel polymer materials by initiating a polymerization reaction to apply the gel polymer materials to diaphragm materials. Some scientific researchers prepare gel polymer materials with high price under complex process conditions such as high temperature, ultraviolet illumination, high-concentration lithium salt initiator and the like. For example, patent document CN114094176A discloses a method for processing a surface-initiated lewis acid separator, in which a pre-solution prepared from a lewis acid initiator is applied to the surface of the separator, then an electrolyte is added dropwise to induce ring-opening polymerization, after DME (ethylene glycol dimethyl ether) is volatilized, a battery is assembled, and after standing for 6 hours, a gel electrolyte separator with lewis acid on the surface can be obtained in the battery. The method has simple preparation process and low cost, and has certain practicability when being applied to the lithium-sulfur battery. Researchers (Nyalaliska w. Utomo, yue Deng, qing Zhao, xiaotun Liu, lyden a. Archer, structure and solution of quadrature-solid-state electrolytes, 2022, adv. Mater.) have reported, however, that such ring-opening polymerization is reversible, meaning that a broad distribution of macromolecules is present in the cell at any given time, and the ring-opening polymerized separator coating material does not have stability in the cell. And the uniformity of the surface thickness of the coating cannot be guaranteed by virtue of the free volatilization of DME.
In this regard, it is necessary to find a relatively simple method for further optimizing the ring-opening polymerized material as a coating material since the ring-opening polymerized material alone does not have excellent mechanical properties. Therefore, the application provides a spinning diaphragm and a manufacturing method thereof, unstable ring-opening polymerization materials and protein materials are combined into a macromolecular chain through a cross-linking reaction, and thus a spinning solution with excellent performance is prepared. And then coating by means of electrostatic spinning, thereby ensuring the stability of the ring-opening polymerization material and the uniformity of the surface thickness of the coating. The method can promote more uniform deposition of lithium ions, achieve the aim of inhibiting the growth of lithium dendrites, prolong the cycle performance and safety of the battery and the like.
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions of the embodiments of the present application will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
FIG. 1 is a flow chart of a method of making a spinning membrane according to an embodiment of the present application. As shown in fig. 1, a method for manufacturing a spinning membrane provided in the embodiment of the present application includes:
step S100, mixing 1, 3-dioxolane and Lewis acid to obtain a ring-opening polymerization solution.
In an alternative embodiment, the lewis acid may be first mixed with 1, 3-Dioxolane (DOL) in a volume ratio (1 to 2): 100, and standing for 60 to 180 seconds to obtain the ring-opening polymerization material. The Lewis acid used may be one or more of boron trifluoride diethyl etherate, boron trifluoride, aluminium trichloride, sulphur trioxide, dichlorocarbene, ferric chloride, niobium pentachloride, aluminium triflate, lithium difluoro-oxalato-borate. In the case where the Lewis acid does not contain an ether group, a crosslinking solvent is added to the ring-opening polymeric material to obtain a ring-opening polymeric solution. Specifically, the crosslinking solvent may be one or more selected from ether crosslinking agents or glutaraldehyde, maleic anhydride, potassium persulfate, N-hydroxysuccinimide, and 1-ethyl- (3-dimethylaminopropyl) carbodiimide. The ether crosslinking agent can be one or more selected from diethyl ether, dimethyl ethylene glycol, glycerol dimethyl ether, triethylene glycol propyl ether, tetrafluoroethyl ether, polyethylene glycol glycidyl ether and diglycidyl ethyl ether. Optionally, the crosslinking solvent accounts for 1-2% of the total volume of the ring-opening polymerization solution.
In the case where the lewis acid contains an ether group, the crosslinking solvent may not be added. In one embodiment, the Lewis acid is boron trifluoride etherate (BTEE), BF of BTEE 3 Is a strong Lewis acid capable of undergoing protonation reaction with trace water in a DOL solvent, BF 3 And (3) inducing water molecules in the DOL to perform a monomer ring-opening polymerization reaction by the cations.
Specifically, a suitable amount of 1, 3-dioxolane may be placed in a beaker using a pipette gun, and then a lewis acid may be added to the beaker.
And step S200, performing a cross-linking reaction on the ring-opening polymerization solution and the protein material to obtain a spinning solution.
Optionally, the protein material is an aqueous or alcoholic solution of the protein. Further, the protein concentration in the protein material is 10-30 wt.%, such as 10wt.%, 15wt.%, 20wt.%, 25wt.%, 30wt.%, or a value between any two of these values. The protein in the protein material is one or more of silk fibroin, zein, hemoglobin, hemocyanin, bovine serum albumin, bovine albumin, sericin, glycoprotein, fibrin, collagen, myoglobin and soybean protein.
In a specific embodiment, the protein in the protein material is silk fibroin. The silk fibroin has acidic and basic functional groups in the molecule, so that the silk fibroin can stably exist in a spinning solution and an alkaline electrolyte environment, has good mechanical properties and physicochemical properties, is a natural polymer fiber form, and is a quite excellent fiber framework structure. Since the mechanical property of the silk fibroin material is related to the concentration of the silk fibroin aqueous solution, a proper amount of silk fibroin can be dissolved in deionized water in advance to obtain a protein material for later use.
Optionally, step S200 may include: mixing the ring-opening polymerization solution with a protein material according to the volume ratio of (2-4): 1, mixing, stirring for 6-8 h at the temperature of 25-50 ℃, and standing for 8-12 h at room temperature to obtain a spinning solution. Specifically, 5-30 mg of protein can be taken out of a beaker, 50-100 mL of deionized water or ethanol is added for dissolution, and the mixture is stirred for 1-3 h at room temperature by using a stirrer until the protein is completely dissolved.
Under the condition that Lewis acid is boron trifluoride ether (BTEE), ether molecules in the BTEE can generate a crosslinking effect with silk fibroin of an aqueous solution, so that a finally spun coating has good flexibility, tensile strength, wettability and slow release property, and the compatibility of the finally formed spun coating and a diaphragm base material can be improved. Because BTEE has high ionic conductivity, a stable macromolecular chain is generated through the ring-opening polymerization reaction with DOL, and the chain has high ionic conductivity, and the crosslinking of serine and glycine in a spinning coating and ether in BTEE can play a role in excellent moisture retention and slow release, so that lithium ions can be promoted to be more uniformly inserted and extracted, and the charge transfer rate of an electrode interface is improved.
It will be appreciated that similar effects may be obtained when using ring-opening polymerisation solutions prepared from other starting materials (e.g. other than BTEE as the Lewis acid used in the above list) or other types of proteinaceous materials.
And step S300, forming a spinning coating on the diaphragm base material by using the spinning solution to obtain a spinning diaphragm.
Optionally, step S300 may include: carrying out electrostatic spinning on the diaphragm base material by using a spinning solution to obtain the diaphragm base material loaded with a spinning material; and drying the membrane substrate loaded with the spinning material to obtain the spinning membrane with the spinning coating.
The spinning machine can be used for electrostatic spinning, the existing spinning machine can be selected as the spinning machine, and the specific implementation mode of electrostatic spinning by using the spinning machine can refer to the prior art. Specifically, the diaphragm base material can be selected from a PP film or a PE film; the thickness of the spin coating can be selected to be 5-35 μm.
In a specific embodiment, step S300 can be accomplished by the following steps: the spinning solution is sucked into the tube by a 10mL liquid injector, a precise steel needle head is used as a spinning nozzle, the inner diameter of the spinning nozzle is 0.8mm, the spacing distance between the spinning nozzle and a rotary drum provided with a diaphragm base material is controlled to be 8-15cm, the flow velocity of the spinning solution is 0.1-1.0mm/min, and the spinning thickness is controlled to be 5-35 mu m. And after the electrostatic spinning operation is finished, transferring the membrane substrate attached with the spinning solution into a vacuum oven, and drying for 12 hours at 35-45 ℃ to obtain the spinning membrane with the spinning coating.
The spinning coating prepared by the spinning solution obtained in the step S200 has better stability, and the thickness of the spinning coating can be effectively controlled, so that the thickness of the spinning coating is more uniform. By using the spinning solution to prepare the spinning coating, the thermal stability, the electrochemical stability and the mechanical property of the spinning diaphragm can be improved, and the growth of lithium dendrites can be inhibited, so that the lithium battery with long cycle life can be prepared.
According to the embodiment of the application, the spinning solution is prepared in a ring-opening polymerization and crosslinking mode, the finally formed spinning coating forms a second redox place on the spinning diaphragm, the ion transmission capacity is improved, the uniform deposition of lithium ions is promoted, the purpose of inhibiting the growth of lithium dendrites is achieved, and the cycle performance of a lithium battery is improved.
In addition, the present application further provides a lithium battery (not shown in the figures), which includes a casing, a positive plate, a negative plate and the spinning membrane obtained by the above manufacturing method, wherein the positive plate, the negative plate and the spinning membrane are arranged in the casing, and the spinning membrane separates the positive plate from the negative plate. Electrolyte is filled in the shell. The lithium battery provided by the application adopts the spinning diaphragm, so that the growth of lithium dendrites is reduced, and the lithium battery has better cycle performance and safety.
The features and properties of the present application are described in further detail below with reference to examples.
Example 1
Weighing 10mg of silk fibroin into a beaker, adding 50mL of deionized water for dissolution, and stirring at room temperature for 1h by using a stirrer to completely dissolve the silk fibroin to obtain the protein material.
A solution for ring-opening polymerization was obtained by introducing 10mL1, 3-Dioxolane (DOL) into a beaker using a pipette, adding 0.2mL of boron trifluoride diethyl etherate, and standing the beaker for about 120 seconds.
Mixing the protein material and the ring-opening polymerization solution according to the volume ratio of 1:3, stirring for 6 hours at 40 ℃ by using a stirrer to ensure that the protein is fully crosslinked with the ring-opening polymerization solution, and standing for 8 hours at room temperature after stirring to obtain the spinning solution.
And (3) carrying out electrostatic spinning operation by using spinning equipment, attaching the spinning solution to the diaphragm base material, and then drying to obtain the spinning diaphragm. Wherein the spinning flow rate is 0.1mm/min, the spinning time is 5h, the thickness of the spinning coating is 30 mu m, and the diaphragm base material is a PP material.
Example 2
Weighing 10mg of zein in a beaker, adding 65mL of ethanol for dissolving, and stirring at room temperature for 1h by using a stirrer to completely dissolve the zein to obtain a protein material.
A pipette was used to collect 10mL1, 3-Dioxolane (DOL) in a beaker, 0.1mL of aluminum trifluoromethanesulfonate was added, and the beaker was left to stand for about 180 seconds to obtain a ring-opening polymerization material, and then 1mL of polyethylene glycol glycidyl ether was added and mixed uniformly to obtain a ring-opening polymerization solution.
Mixing a protein material and a ring-opening polymerization solution according to a volume ratio of 1:3, stirring for 6 hours at 40 ℃ by using a stirrer to ensure that the protein is fully crosslinked with the ring-opening polymerization solution, and standing for 10 hours at room temperature after stirring to obtain the spinning solution.
And (3) carrying out electrostatic spinning operation by using spinning equipment, attaching the spinning solution to the diaphragm base material, and then drying to obtain the spinning diaphragm. Wherein the spinning flow rate is 0.1mm/min, the spinning time is 3h, the thickness of the spinning coating is 20 microns, and the diaphragm base material is a PP material.
Example 3
Weighing 10mg of sericin in a beaker, adding 80mL of deionized water for dissolution, and stirring at room temperature for 2h by using a stirrer to completely dissolve the sericin to obtain a protein material.
Taking 10mL of 1, 3-Dioxolane (DOL) into a beaker by using a pipette, adding 0.15mL of lithium difluoro-oxalato-borate, standing for about 180s to obtain a ring-opening polymerization material, and then adding 1mL of glutaraldehyde and uniformly mixing to obtain a ring-opening polymerization solution.
Mixing the protein material and the ring-opening polymerization solution according to the volume ratio of 1:3, stirring for 6 hours at 40 ℃ by using a stirrer to ensure that the protein is fully crosslinked with the ring-opening polymerization solution, and standing for 10 hours at room temperature after stirring to obtain the spinning solution.
And (3) carrying out electrostatic spinning operation by using spinning equipment, attaching the spinning solution to the diaphragm base material, and then drying to obtain the spinning diaphragm. Wherein the spinning flow rate is 0.1mm/min, the spinning time is 2h, the thickness of the spinning coating is 10 mu m, and the diaphragm base material is a PP material.
Example 4
Weighing 10mg of soybean protein into a beaker, adding 100mL of deionized water for dissolving, and stirring for 3 hours at room temperature by using a stirrer to dissolve more soybean protein as much as possible to obtain a protein material.
Then, 10mL of 1, 3-Dioxolane (DOL) was placed in a beaker by means of a pipette, and 0.2mL of niobium pentachloride was added thereto, and the beaker was left to stand for about 180 seconds to obtain a ring-opening polymerization material, and then 5mg of N-hydroxysuccinimide was added thereto and mixed well to obtain a ring-opening polymerization solution.
Mixing the protein material and the ring-opening polymerization solution according to the volume ratio of 1:3, stirring for 8 hours at the temperature of 45 ℃ by using a stirrer to ensure that the protein is fully crosslinked with the ring-opening polymerization solution, and standing for 12 hours at room temperature after stirring to obtain the spinning solution.
And (3) carrying out electrostatic spinning operation by using spinning equipment, attaching the spinning solution to the diaphragm base material, and then drying to obtain the spinning diaphragm. Wherein the spinning flow rate is 0.1mm/min, the spinning time is 6h, the thickness of the spinning coating is 30 mu m, and the diaphragm base material is made of PP material.
The manufacturing method of the lithium battery provided by the embodiment of the application can comprise the following steps:
1. preparing a positive plate:
(1) Lithium titanate, a conductive agent and a binder are mixed according to the mass ratio of 8:1:1, then adding an NMP solvent, uniformly mixing to prepare anode slurry, uniformly coating the anode slurry on the aluminum foil coated with the conductive carbon layer according to a certain proportion, and carrying out vacuum drying at 80-120 ℃ to obtain the aluminum foil coated with a layer of anode material. The binder may be selected from PVDF; the conductive agent can be one or more of SP, CNT and graphite;
(2) And (3) performing a tablet press on the aluminum foil coated with the layer of the positive electrode material in the step (1) to obtain the positive electrode plate.
2. Preparing a negative plate:
the negative plate is a lithium metal plate.
3. Preparing a battery: and assembling the positive plate, the spinning diaphragm and the negative plate together to prepare the battery, wherein the diaphragm can completely wrap the positive plate and the negative plate. The electrolyte was injected into the cell. Finally, the lithium titanate battery is manufactured.
The performance test of the spinning membrane provided by the embodiment of the application is described below.
The spinning separator prepared in the above examples 1 to 4 was applied to a lithium battery, and the method for manufacturing the lithium battery can refer to the above-described method. The existing common PP diaphragm is applied to the lithium battery as a comparative example 1, and the manufacturing method of the lithium battery is the same as that of the lithium battery with the spinning diaphragm. The electrolyte uses bis (trifluoromethyl) sulfimide lithium, the concentration is 1.0mol/L, and the solvent is 1,3 dioxolane and ethylene glycol dimethyl ether.
And the lithium batteries of the respective examples and comparative examples were subjected to cycle life tests, and the results are shown in the following table.
| Examples/comparative examples | Class of proteins | Thickness of the spin coat (μm) | Cycle life (circle) |
| Example 1 | Silk fibroin | 30 | 3529 |
| Example 2 | |
20 | 3317 |
| Example 3 | Sericin | 10 | 3083 |
| Example 4 | Soy protein | 30 | 3165 |
| Comparative example 1 | / | / | 1385 |
FIG. 2 is a scanning electron micrograph of the spin coating of example 1; fig. 3 is a graph comparing the cycle performance at current density for assembled lithium titanate batteries 2C of comparative example 1 and example 1. As can be seen from the above table, the cycle life of the batteries of examples 1-4 is more than 3000 cycles, while the cycle life of the battery of comparative example 1 (using the conventional PP separator) is 1385 cycles, which is significantly lower than that of the present example. As can be seen from fig. 2, the thickness of the spun coating in example 1 is relatively uniform and flat overall. As can be seen in fig. 3, the cell of comparative example 1 rapidly decayed in capacity less than 1500 cycles, whereas the cell of example 1 cycled over 3500 cycles. Therefore, the spinning diaphragm manufactured by the spinning diaphragm manufacturing method provided by the embodiment of the application has uniform thickness and good cycle performance.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (12)
1. A spinning diaphragm manufacturing method is characterized by comprising the following steps:
mixing 1, 3-dioxolane and a lewis acid to obtain a ring-opening polymerization solution;
carrying out a cross-linking reaction on the ring-opening polymerization solution and a protein material to obtain a spinning solution;
and forming a spinning coating on the diaphragm substrate by using the spinning solution to obtain the spinning diaphragm.
2. The method of making a spinning separator according to claim 1, wherein the step of mixing 1, 3-dioxolane and a lewis acid to obtain a ring-opening polymerization solution without an ether group in the lewis acid comprises:
mixing the Lewis acid and the 1, 3-dioxolane according to the volume ratio of (1-2): 100, and standing for 60-180 s to obtain a ring-opening polymerization material;
adding a crosslinking solvent to the ring-opening polymerization material to obtain a ring-opening polymerization solution;
a step of mixing 1, 3-dioxolane, a lewis acid, in the case where the lewis acid contains an ether group, to obtain a ring-opening polymerization solution, comprising:
mixing the Lewis acid and the 1, 3-dioxolane according to the volume ratio of (1-2): 100, and standing for 60-180 s to obtain the ring-opening polymerization solution.
3. The method of manufacturing a spinning diaphragm according to claim 2, wherein the crosslinking solvent is one or more of an ether crosslinking agent, glutaraldehyde, maleic anhydride, potassium persulfate, N-hydroxysuccinimide, and 1-ethyl- (3-dimethylaminopropyl) carbodiimide.
4. The method for manufacturing the spinning diaphragm according to claim 1, wherein the Lewis acid is one or more of boron trifluoride diethyl etherate, boron trifluoride, aluminum trichloride, sulfur trioxide, dichlorocarbene, ferric chloride, niobium pentachloride, aluminum trifluoromethanesulfonate and lithium difluorooxalato borate.
5. The method of manufacturing a spinning membrane according to claim 1, wherein the protein material is an aqueous or alcoholic solution of protein.
6. The method for producing a spinning diaphragm according to claim 5, wherein the protein concentration in the protein material is 10 to 30wt.%.
7. The method of making a spinning membrane of claim 5 wherein the step of cross-linking the ring-opening polymerization solution with a protein material to obtain a spinning solution comprises:
mixing the ring-opening polymerization solution and the protein material according to the volume ratio of (2-4): 1, stirring for 6-8 h at the temperature of 25-50 ℃, and standing for 8-12 h at room temperature to obtain the spinning solution.
8. The method of making a spinning membrane of claim 1, wherein the protein in the protein material is one or more of silk fibroin, zein, hemoglobin, hemocyanin, bovine serum albumin, bovine albumin, sericin, glycoproteins, fibrin, collagen, myoglobin, and soy protein.
9. The method for manufacturing a spinning membrane according to claim 1, wherein the step of forming a spinning coating layer on a membrane substrate by using the spinning solution to obtain the spinning membrane comprises the steps of:
performing electrostatic spinning on the diaphragm base material by using the spinning solution to obtain the diaphragm base material loaded with a spinning material;
drying the membrane substrate loaded with the spinning material to obtain the spinning membrane with the spinning coating layer.
10. The method of making a spinning membrane of claim 1 wherein said spin coating has a thickness of 5 to 35 μm.
11. A spun separator produced by the method of producing a spun separator according to any one of claims 1 to 10.
12. A lithium battery comprising the spun separator of claim 11.
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