CN111769236B - Nano cellulose based shell-like structure composite lithium battery diaphragm and preparation method and application thereof - Google Patents
Nano cellulose based shell-like structure composite lithium battery diaphragm and preparation method and application thereof Download PDFInfo
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- CN111769236B CN111769236B CN202010522071.3A CN202010522071A CN111769236B CN 111769236 B CN111769236 B CN 111769236B CN 202010522071 A CN202010522071 A CN 202010522071A CN 111769236 B CN111769236 B CN 111769236B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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- 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
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Abstract
The invention relates to the technical field of lithium ion batteries, and particularly discloses a nanocellulose-based shell-like structure composite lithium battery diaphragm and a preparation method thereof. The invention takes nano cellulose fiber as a base material, and the nano cellulose fiber is uniformly dispersed in deionized water through high-pressure homogenization to form stable dispersion colloid; uniformly dispersing magnesium lithium silicate in deionized water to prepare a sol, and modifying the magnesium lithium silicate sol by using polyethylene glycol to obtain a modified magnesium lithium silicate sol; then uniformly mixing the nano cellulose fiber sol and the modified magnesium lithium silicate sol to obtain a composite sol solution, pouring the composite sol solution on a flat plate, and drying to form a film; and finally, soaking the composite membrane in ethanol to remove polyethylene glycol, and performing vacuum drying to form the porous lithium battery diaphragm. According to the invention, the biobased material with the bionic structure is introduced into the lithium battery as the diaphragm for the first time, the preparation process is simple, and the raw materials are environment-friendly and nontoxic; the nanocellulose based shell-like structure diaphragm has the characteristics of porosity, high thermal stability, excellent mechanical stability and good electrolyte wettability.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a nanocellulose-based shell-like structure composite lithium battery diaphragm and a preparation method and application thereof.
Background
With the increasing application demand of lithium ion batteries in the fields of digital products and new energy automobiles, the requirements of rapidly developing markets on the cycle performance and the safety performance of the lithium ion batteries are also continuously improved. The diaphragm mainly plays a role in separating a positive electrode from a negative electrode in the lithium ion battery and providing a channel for ion transportation, and has important significance for the safety performance and the cycle service life of the lithium ion battery. Traditional commercial diaphragm mainly adopts polyolefin group material, and this type of diaphragm easily takes place deformation when battery local high temperature, leads to positive negative pole contact and then triggers conflagration even explosion. The polyolefin diaphragm has poor air permeability and wettability, low ionic conductivity, and can not meet the requirements of rapid charge and discharge, and the cycle service life of the lithium ion battery is influenced.
The nano-cellulose can be prepared from cellulose which is the most abundant in natural resources, and has the advantages of biodegradability, environmental protection, no pollution, high specific strength, repeated utilization and the like compared with polyolefin artificial organic polymers.
Chun et al (j. mater. chem.22,16618-16626(2012)) have investigated the possibility of pure nanocellulose paper with adjustable pore size as a lithium ion battery separator, which can be used as a core component for next generation flexible lithium ion batteries. Chinese patent document CN105355818A (application No. 201510934410.8) discloses a composite nano-fiber lithium battery diaphragm and a preparation method thereof, and the composite lithium battery diaphragm with a three-layer structure is prepared by utilizing an electrostatic spinning and sol-gel combination method and comprises an upper nano-fiber film layer, a middle nano-fiber gel layer and a lower nano-fiber film layer.
However, as the surface of the nano-cellulose is rich in polar groups such as hydroxyl groups, carboxyl groups and the like, in the solvent evaporation film-forming process, the polar groups cause mutual winding among fibers due to the hydrogen bond effect, the formed diaphragm has a compact structure, and the porosity is greatly influenced. Although most researches effectively adjust the porosity, most of the researches have complicated preparation and extraction processes or use a large amount of environmentally-friendly organic solvents, thereby generating huge obstacles to the practical application of the diaphragm.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims at providing a preparation method of a nano cellulose based shell-like structure composite lithium battery diaphragm, and aims at preparing a lithium battery diaphragm with excellent thermal and mechanical stability and high ionic conductivity.
The invention also aims to provide the nano cellulose based shell-like structure composite lithium battery diaphragm prepared by the method;
the invention further aims to provide application of the nano cellulose based shell-like structure composite lithium battery diaphragm in a lithium ion battery.
In order to solve the technical problems, the invention provides a technical solution:
a preparation method of a nanocellulose-based shell-like structure composite lithium battery diaphragm comprises the following specific steps:
(1) mixing and stirring nano cellulose fibers and deionized water, and homogenizing under high pressure to obtain nano cellulose fiber sol;
(2) dispersing magnesium lithium silicate in deionized water, uniformly stirring to obtain magnesium lithium silicate sol, blending polyethylene glycol and the magnesium lithium silicate sol, and performing modification reaction to obtain polyethylene glycol modified magnesium lithium silicate sol;
(3) mixing the nano cellulose fiber sol with polyethylene glycol modified magnesium lithium silicate sol to obtain uniformly dispersed mixed sol, and drying the mixed sol to obtain a semi-finished lithium battery diaphragm;
(4) and soaking the semi-finished lithium battery diaphragm in an organic solvent, and drying to obtain the finished lithium battery diaphragm.
The mass fraction of the nano cellulose fiber sol in the step (1) is 0.1-0.8%; preferably 0.3%.
The high-pressure homogenizing condition in the step (1) is that the mixture is homogenized for 10 to 20 times under the pressure of 800-1000bar by a high-pressure homogenizer and is subjected to ultrasonic treatment for 10 to 30 minutes to obtain the uniformly dispersed nano cellulose fiber sol.
Preferably, the nano-cellulose is any one of wood pulp fiber, cotton fiber and bacterial cellulose, and is prepared by a TEMPO oxidation method.
The mass fraction of the magnesium silicate sol in the step (2) is 0.5-3%, preferably 1%;
the mass ratio of the polyethylene glycol to the lithium magnesium silicate sol in the step (2) is 1: 3-1: 20;
the molecular weight of the polyethylene glycol in the step (2) is 600-2000, preferably 600, 800, 1000 or 2000.
The temperature of the modification reaction in the step (2) is 60-90 ℃, and the reaction time is 2-4 hours. Preferably, the temperature is 80 ℃.
The mass ratio of the magnesium lithium silicate in the polyethylene glycol modified magnesium lithium silicate sol to the nano cellulose fiber in the nano cellulose fiber sol in the step (3) is 0.05: 1-1: 1.
Soaking in an organic solvent for 24-72 hours in the step (4); the drying mode is any one of vacuum drying at 40-60 ℃, critical carbon dioxide drying or freeze vacuum drying.
A nanocellulose-based shell-like structure composite lithium battery diaphragm is prepared by the method.
The application of the nano cellulose based shell-like structure composite lithium battery diaphragm in a lithium ion battery is provided.
The shell-like structure nano composite diaphragm is prepared from lithium magnesium silicate and nano cellulose by a simple sol-gel method. The shell-like structure nano composite membrane has a structure similar to brick cement, flexible nano cellulose is used as the cement, magnesium lithium silicate is used as the brick, and a composite membrane material with higher strength and better heat resistance than a pure nano cellulose membrane can be obtained after self-assembly, so that the shell-like structure nano composite membrane has an important significance for improving the safety performance of a lithium battery. In addition, the magnesium lithium silicate has a nanoscale effect, is environment-friendly, non-toxic, good in biocompatibility, high in heat resistance and strong in hydrophilicity, and silicon-oxygen bonds on the surface layer of the magnesium lithium silicate can promote the transportation of lithium ions and improve the ionic conductivity of the diaphragm. More importantly, the preparation method provided by the invention has the advantages that through simple polyethylene glycol modification and ethanol bath treatment, the uniform dispersion of the magnesium lithium silicate is promoted, the porosity of the composite membrane is more effectively adjusted, and the practical application of the bionic lithium battery diaphragm is well promoted by the environment-friendly and simple preparation technology.
The invention has the beneficial effects that:
the preparation process of the nano-cellulose-based shell-like structure composite lithium battery diaphragm is simple, green and environment-friendly, no toxic substance is added, and the prepared nano-cellulose-based shell-like structure composite lithium battery diaphragm product is biodegradable. Compared with the traditional commercial diaphragm, the shell-like structure composite diaphragm prepared by combining the magnesium lithium silicate nano particles and the nano cellulose fiber has excellent high-temperature resistance, can still maintain certain mechanical strength at high temperature, and greatly improves the safety performance of the battery diaphragm. In addition, the composite diaphragm has good wettability, and the magnesium lithium silicate component in the composite diaphragm can promote the transportation of lithium ions, improve the ionic conductivity and contribute to prolonging the cycle service life of the lithium battery.
Drawings
FIG. 1 is a scanning electron microscope image of the nano-cellulose based shell-imitated composite lithium battery diaphragm obtained in example 4.
FIG. 2 is an FT-IR spectrum of cellulose-based shell-like composite lithium battery diaphragm obtained in example 4, wherein the cellulose-based shell-like composite lithium battery diaphragm is prepared from nano cellulose and lithium magnesium silicate.
FIG. 3 shows the comparative results of the electrolyte contact angle analysis of the shell-like nanocellulose composite membrane, the commercial PP membrane and the nanocellulose membrane obtained in example 4.
FIG. 4 shows the results of tensile strength tests of the shell-like nanocellulose composite membrane, the commercial PP membrane and the nanocellulose membrane obtained in example 4 at different temperatures; wherein (a) is the tensile strength of different lithium battery separators at 100 ℃; (b) the tensile strength of different lithium battery separators at the temperature of 200 ℃.
Detailed Description
The present invention will be described in detail below with reference to specific examples and drawings, but the present invention is not limited to the following examples.
Measuring the thickness of the film by using a micrometer (the precision is 0.01 mm), measuring the thicknesses of 5 different positions on the film, and averaging to only serve as the thickness of a final sample; observing the surface appearance of the sample by a field emission scanning electron microscope; the infrared spectrum characterizes the microscopic composition and intermolecular force of the lithium magnesium silicate and the nano-cellulose in the composite film; differential scanning calorimetry is used for representing the thermal stability of the composite film; the tensile strength test at different temperatures represents the mechanical stability of the composite membrane;
the magnesium lithium silicate product of the present invention is any one of a gel grade, a temporary sol grade, a long-term sol grade, or a personal care grade.
Example 1
(1) 0.36g of nano-cellulose powder is uniformly dispersed in 119.64g of deionized water to prepare a suspension with the mass concentration of 0.3%, and after the suspension is homogenized for 10 times under the pressure of 1000bar by a high-pressure homogenizer, the nano-cellulose sol is treated by ultrasonic for 30 minutes to obtain the uniformly dispersed nano-cellulose sol.
(2) 0.72g of polyethylene glycol 800 is added into 10.8g of 1 mass percent magnesium lithium silicate sol, and the mixture is stirred for 2 hours at the temperature of 80 ℃ to obtain the modified magnesium lithium silicate sol.
(3) Mixing the nano-cellulose sol and the modified magnesium lithium silicate sol, fully mixing the nano-cellulose and the modified magnesium lithium silicate by magnetic stirring, and carrying out ultrasonic treatment for 30 minutes after bubbles disappear.
(4) And pouring the mixed sol into a polystyrene disposable culture dish to enable the nano-cellulose and the lithium magnesium silicate to be self-assembled, and drying for 24 hours at normal temperature to obtain a precursor of the composite membrane.
(5) And (3) placing the composite membrane precursor into absolute ethyl alcohol, soaking for 24 hours, and then carrying out vacuum drying for 24 hours at 40 ℃ to obtain the composite membrane.
Example 2
(1) 0.36g of nano cellulose powder is uniformly dispersed in 119.64g of deionized water to prepare a suspension with the mass concentration of 0.3%, and after the suspension is homogenized for 10 times under the pressure of 1000bar by a high-pressure homogenizer, the nano cellulose sol is subjected to ultrasonic treatment for 30 minutes to obtain the uniformly dispersed nano cellulose sol.
(2) 0.36g of polyethylene glycol 1000 is added into 3.6g of 1 mass percent magnesium lithium silicate sol, and the mixture is stirred for 3 hours at the temperature of 80 ℃ to obtain the modified magnesium lithium silicate sol.
(3) Mixing the nano-cellulose sol and the modified magnesium lithium silicate sol, fully mixing the nano-cellulose and the modified magnesium lithium silicate by magnetic stirring, and carrying out ultrasonic treatment for 30 minutes after bubbles disappear.
(4) And pouring the mixed sol into a polystyrene disposable culture dish to enable the nano-cellulose and the lithium magnesium silicate to be self-assembled, and drying for 24 hours at normal temperature to obtain a precursor of the composite membrane.
(5) And (3) placing the composite membrane precursor into absolute ethyl alcohol, soaking for 48 hours, and then carrying out vacuum freeze drying for 24 hours to obtain the composite membrane.
Example 3
(1) 0.36g of nano cellulose powder is uniformly dispersed in 119.64g of deionized water to prepare a suspension with the mass concentration of 0.3%, and after the suspension is homogenized for 10 times under the pressure of 1000bar by a high-pressure homogenizer, the nano cellulose sol is subjected to ultrasonic treatment for 30 minutes to obtain the uniformly dispersed nano cellulose sol.
(2) 0.18g of polyethylene glycol 2000 was added to 1.8g of 1% by mass of magnesium lithium silicate sol, and the mixture was stirred at 80 ℃ for 3 hours to obtain a modified magnesium lithium silicate sol.
(3) Mixing the nano-cellulose sol and the modified magnesium lithium silicate sol, fully mixing the nano-cellulose and the modified magnesium lithium silicate by magnetic stirring, and carrying out ultrasonic treatment for 30 minutes after bubbles disappear.
(4) And pouring the mixed sol into a polystyrene disposable culture dish to enable the nano-cellulose and the lithium magnesium silicate to be self-assembled, and drying for 24 hours at normal temperature to obtain a precursor of the composite membrane.
(5) Placing the composite membrane precursor in absolute ethyl alcohol, soaking for 72 hours, and then critical CO2And drying for 24 hours to obtain the composite membrane.
The performance index data of the separator prepared in the above example are shown in table 1.
TABLE 1 examples 1-3 separator Performance indices
Example 4
(1) 0.36g of nano cellulose powder is uniformly dispersed in 119.64g of deionized water to prepare a suspension with the mass concentration of 0.3%, and after the suspension is homogenized for 10 times under the pressure of 1000bar by a high-pressure homogenizer, the nano cellulose sol is subjected to ultrasonic treatment for 30 minutes to obtain the uniformly dispersed nano cellulose sol.
(2) 0.72g of polyethylene glycol 800 is added into 3.6g of 1 mass percent magnesium lithium silicate sol, and the mixture is stirred for 4 hours at the temperature of 80 ℃ to obtain the modified magnesium lithium silicate sol.
(3) Mixing the nano-cellulose sol and the modified magnesium lithium silicate sol, fully mixing the nano-cellulose and the modified magnesium lithium silicate by magnetic stirring, and carrying out ultrasonic treatment for 30 minutes after bubbles disappear.
(4) And pouring the mixed sol into a polystyrene disposable culture dish to enable the nano-cellulose and the lithium magnesium silicate to be self-assembled, and drying for 24 hours at normal temperature to obtain a precursor of the composite membrane.
(5) And (3) placing the composite membrane precursor into absolute ethyl alcohol, soaking for 72 hours, and then carrying out vacuum drying at 40 ℃ for 24 hours to obtain the composite membrane.
The embodiment is the composite lithium battery diaphragm prepared by the optimized scheme of the invention, the thermal stability and the mechanical stability are excellent, the indexes of wettability, liquid absorption rate and porosity are mutually compatible, and the ionic conductivity value is the largest. The comparative data of various performance indexes of the lithium battery composite diaphragm and the PP commercial diaphragm and the nano cellulose membrane are shown in a table 2:
table 2 comparison of performance indexes of example 4, PP commercial separator and nanocellulose membrane
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (8)
1. A preparation method of a nanocellulose-based shell-like structure composite lithium battery diaphragm is characterized by comprising the following specific steps:
(1) mixing and stirring nano cellulose fibers and water, and homogenizing under high pressure to obtain nano cellulose fiber sol;
(2) dispersing magnesium lithium silicate in water, uniformly stirring to obtain magnesium lithium silicate sol, blending polyethylene glycol and the magnesium lithium silicate sol, and performing modification reaction to obtain polyethylene glycol modified magnesium lithium silicate sol;
(3) mixing the nano cellulose fiber sol with polyethylene glycol modified magnesium lithium silicate sol to obtain uniformly dispersed mixed sol, and drying the mixed sol to obtain a semi-finished lithium battery diaphragm;
(4) soaking the semi-finished lithium battery diaphragm in an organic solvent, and drying to obtain a finished lithium battery diaphragm;
the mass ratio of the polyethylene glycol to the lithium magnesium silicate sol in the step (2) is 1: 3-1: 20;
the mass ratio of the magnesium lithium silicate in the polyethylene glycol modified magnesium lithium silicate sol to the nano cellulose fiber in the nano cellulose fiber sol in the step (3) is 0.05: 1-1: 1.
2. The method of claim 1, wherein:
the mass fraction of the nano cellulose fiber sol in the step (1) is 0.1-0.8%;
the high-pressure homogenizing condition in the step (1) is that the mixture is homogenized for 10 to 20 times under the pressure of 800-1000bar by a high-pressure homogenizer and is subjected to ultrasonic treatment for 10 to 30 minutes to obtain the uniformly dispersed nano cellulose fiber sol.
3. The method of claim 1, wherein: the mass fraction of the magnesium silicate sol in the step (2) is 0.5-3%; the molecular weight of the polyethylene glycol in the step (2) is 600-2000.
4. The method of claim 1, wherein: the temperature of the modification reaction in the step (2) is 60-90 ℃, and the reaction time is 2-4 hours.
5. The method of claim 1, wherein: the nano-cellulose is any one of wood pulp fiber, cotton fiber and bacterial cellulose.
6. The method of claim 1, wherein:
soaking in an organic solvent for 24-72 hours in the step (4); the drying mode is any one of vacuum drying at 40-60 ℃, critical carbon dioxide drying or freeze vacuum drying.
7. A nanocellulose based shell-like structure composite lithium battery separator prepared by the method of any one of claims 1-6.
8. The application of the nano cellulose base shell-like structure composite lithium battery separator according to claim 7 in a lithium ion battery.
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| CN113224463B (en) * | 2021-05-10 | 2023-02-21 | 燕山大学 | Cellulose-based diaphragm and preparation method and application thereof |
| CN114696035B (en) * | 2022-02-28 | 2023-05-12 | 东华理工大学 | Cellulose-based composite diaphragm for lithium ion battery and preparation method thereof |
| CN114976481B (en) * | 2022-05-31 | 2024-03-26 | 浙江科技学院 | Lightweight full-cellulose-based lithium battery diaphragm and preparation method thereof |
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