CN114552124A - Cellulose membrane rich in nano-pores, preparation method and application - Google Patents
Cellulose membrane rich in nano-pores, preparation method and application Download PDFInfo
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- CN114552124A CN114552124A CN202210190012.XA CN202210190012A CN114552124A CN 114552124 A CN114552124 A CN 114552124A CN 202210190012 A CN202210190012 A CN 202210190012A CN 114552124 A CN114552124 A CN 114552124A
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Images
Classifications
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/429—Natural polymers
- H01M50/4295—Natural cotton, cellulose or wood
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/52—Separators
-
- 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
- H01M10/05—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
-
- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- 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 invention discloses a cellulose membrane rich in nanopores, a preparation method and application, and belongs to the technical field of cellulose membranes. The cellulose membrane comprises a plurality of structural units stacked layer by layer and a nanoscale pore canal penetrating through the whole cellulose membrane, wherein the structural units are two-dimensional cellulose nanosheets. The cellulose membrane has a unique hierarchical structure, uniformly distributed nano-scale pore canals and ultrathin thickness, shows excellent performances of high mechanical strength, acid and alkali resistance, good hydrophilicity and high ionic conductivity, and the method for preparing the cellulose membrane has the advantages of rich raw materials, low cost, simple preparation process, environmental friendliness, safety and no toxicity.
Description
Technical Field
The invention belongs to the technical field of cellulose membranes, and particularly relates to a cellulose membrane rich in nano-pores, a preparation method and application.
Background
The membrane is a material with selective separation function, and under the action of certain driving force, the separation, purification and concentration of different components can be realized by utilizing the selective separation of the membrane. The membrane technology occupies an irreplaceable position in the fields of battery separators, water treatment, biochemical pharmacy, food manufacturing, petrochemical industry, medical health and the like.
At present, the diaphragm commonly used for the lithium ion battery is a polyolefin diaphragm which has good aperture controllability, high strength and controllable thickness, but the polyolefin diaphragm has poor wettability and high internal resistance, is a derivative from non-renewable petroleum and has high manufacturing cost. In addition, glass fiber separators are also one of the separators commonly used in batteries due to their low internal resistance and high wettability by the electrolyte, but the voids of the glass fiber separators result from the inability to prevent the growth of metal anode dendrites due to the large porosity of the stacked fibers. In addition, the brittleness of the glass material makes the glass fiber diaphragm hard to bear the internal stress caused by the volume change of the electrode in the operation process of the battery, and the glass fiber diaphragm is easy to be penetrated and damaged by the dendrite generated by the electrode, so that the short circuit of the battery is caused, the service life of the battery is shortened, and the manufacturing cost is high.
In addition, the electrolyte of the battery is strongly acidic, the electrolyte of the nickel-metal hydride battery is strongly alkaline, and the side reaction hydrogen evolution reaction in the water-based battery is inevitable, which causes the local pH change of the interface between the electrolyte and the electrode surface. The strong acid and strong base environment can corrode the diaphragm, so an ideal battery diaphragm should have high mechanical strength to resist stress, appropriate pore size to pass ions and block dendrites, good chemical stability in a wide pH window, and excellent hydrophilicity to match the water electrolyte for water-based batteries.
Patent application with publication number CN108448028A discloses a new lithium ion battery diaphragm and a preparation method thereof, which combines a ceramic membrane formed by a nano cellulose membrane and inorganic particles together, improves the strength of the diaphragm, and can hinder the growth of lithium dendrites. However, the hydrophilicity of the separator is not specified, and this determines whether or not the separator is suitable for use in an aqueous battery. In the prior art of the water-based battery separator, the improvement of the hydrophilicity of the water-based battery separator by methods such as coating, molecular chain modification and the like is mostly focused. Patent application No. CN110707268A discloses a novel water-based battery separator made of SiO2Polymers fibrillate and interact to form films, but this is also solving the problem of membrane hydrophilicity. None of these techniques, without exception, have suggested the use of a film structure to increase strength while having the effect of retarding dendrite growth.
The patent application with the publication number of CN108822315B discloses a high-strength transparent hydrophobic cellulose nano-film and a preparation method thereof, and particularly discloses a method for preparing the high-strength transparent hydrophobic cellulose nano-film, wherein natural cellulose is used as a raw material, the cellulose raw material is hydrolyzed by formic acid, and separated cellulose solids are subjected to solvent replacement, mechanical treatment and drying forming in sequence. The cellulose membrane prepared by the method has excellent property, compact structure, high strength and high transparency, but the cellulose surface generates molecular rearrangement and recrystallization, so the cellulose membrane is difficult to be applied to a battery diaphragm, and an improvement space exists.
In view of the above, it is desirable to develop a battery separator having high mechanical strength and suitable pore size.
Disclosure of Invention
Aiming at the defects or improvement requirements of the prior art, the invention provides a cellulose membrane rich in nanopores, a preparation method and application, wherein the cellulose membrane is formed by self-assembling two-dimensional cellulose nanosheets to form a multilayer laminated structure, has a nanoscale pore canal penetrating through the whole body, can be used as a battery diaphragm and is particularly suitable for a water-system battery, the preparation method of the membrane is simple, the problems of poor corrosion resistance, low strength and large pores of the battery diaphragm in the prior art can be solved, the service life of the battery can be finally prolonged, and the membrane is more environment-friendly.
In order to achieve the above object, according to one aspect of the present invention, there is provided a nanopore-rich cellulose membrane, comprising a plurality of stacked structural units and nanopores penetrating through the entire cellulose membrane, wherein the structural units are two-dimensional cellulose nanosheets.
Furthermore, the thickness of the structural unit is not more than 20nm, and the adjacent layers are stacked layer by layer through intermolecular force.
Furthermore, the pore diameter of the nanometer pore canal penetrating through the whole cellulose membrane is 5 nm-100 nm.
Furthermore, the number of the structural units of the cellulose membrane is more than 50 layers, and the total thickness of the whole cellulose membrane is 1-100 μm.
Further, the two-dimensional cellulose nano-sheet is of a two-dimensional planar structure and is formed by self-assembling pure natural cellulose nano-fibers through hydrogen bonds, wherein the pure natural cellulose nano-fibers comprise one or more of moso bamboo, arrowroot bamboo, spruce, fir, red pine, poplar, sorghum stalks, corn stalks, mulberry bark, wild goose skin, straw, wheat straw, reed, cotton linter, kenaf, jute, flax, banana leaf, agave hemp, agrimony, saltwater and bagasse.
According to a second aspect of the present invention, there is also provided a method of preparing a nanopore-rich cellulose membrane, comprising the steps of:
(1) dispersing a two-dimensional cellulose nanosheet in a solvent to obtain a dispersion liquid;
(2) driving two-dimensional cellulose nanosheets in the dispersion liquid to perform self-assembly by a film forming method to obtain a wet film;
(3) and drying the wet film to remove the solvent, so that the two-dimensional cellulose nano-fibers self-shrink to spontaneously form nano-scale structural pores in the cellulose film, and the nano-scale structural pores penetrate through the whole cellulose film.
Further, in the step (2), the film forming method includes at least one of a vacuum filtration method, a hot pressing method, a cold pressing method, a phase inversion method and a freeze drying method.
Further, the solvent includes at least one of water, methanol, ethanol, propanol, isopropanol, tert-butanol, acetone, and butanone.
According to a third aspect of the present invention there is also provided the use of a nanopore-rich cellulose membrane as described above as a filtration membrane, a nanofiltration membrane, a septum or a permeation membrane.
Further, it is used for a separator in an electronic device including a lithium ion battery, a sodium ion battery, a zinc ion battery, a potassium ion battery, an aluminum ion battery, and a magnesium ion battery, and further including a carbon capacitor, a mixed ion battery, and a mixed supercapacitor.
Generally, compared with the prior art, the above technical solution conceived by the present invention has the following beneficial effects:
(1) the cellulose membrane rich in the nano-pores has a unique structure, is a layered structure stacked layer by layer, is formed by self-assembling two-dimensional cellulose nano-sheets, and has a plurality of nano-scale pores penetrating through the whole membrane, and the nano-scale pores are uniformly distributed. The cellulose membrane of the invention is taken from plant fiber, and is rich in hydrogen bonds, so that the cellulose membrane has good hydrophilicity. In addition, the material also shows the performances of high mechanical strength, acid and alkali resistance and high ionic conductivity. And the thickness of the whole cellulose membrane is 1-100 μm, and the thickness is adjustable, and the ultrathin thickness is beneficial to improving the volume specific capacity of the battery. The cellulose membrane rich in nano-scale has the advantages of rich raw materials, low cost, simple preparation process, environmental protection, safety and no toxicity.
(2) The nanopore-rich cellulose membrane disclosed by the invention is wide in application scene, not only can be independently used, but also can be used as a substrate to be compounded with other materials. Can be used as a filter membrane, a nanofiltration membrane, a diaphragm or a permeable membrane. The cellulose membrane of the invention can be used as a diaphragm of various batteries, and can work well in water-based batteries and non-neutral environments, such as strong acid lead-acid batteries and strong alkaline nickel-hydrogen batteries.
Drawings
FIG. 1 is a cross-sectional SEM image of the nanopore-rich cellulose membrane prepared in example 1, which enables a multi-layer structure to be seen.
FIG. 2 is a surface SEM image of the nanopore-rich cellulose membrane prepared in example 1, at a smaller magnification, with the surface observed to be lamellar.
FIG. 3 is an SEM photograph of the cellulose film obtained in example 1, at a larger magnification, through-holes on the surface can be observed.
FIG. 4 is a graph comparing the cycle performance of the cellulose membrane prepared in example 1 with that of the commercial glass fiber separator of comparative example 1 in an acid electrolyte.
FIG. 5 is a graph comparing the cycle performance of the cellulose membrane prepared in example 1 with that of the commercial glass fiber separator of comparative example 1 in an alkaline electrolyte.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Examples
Example 1
(1) Carrying out ultrasonic dispersion on pure cellulose extracted from bamboo, and then carrying out freeze drying to obtain a cellulose nanosheet, wherein the thickness of the single-layer cellulose nanosheet is about 18 nm. Dispersing the obtained cellulose nanosheet in water, and performing ultrasonic dispersion to obtain a cellulose nanosheet dispersion liquid, so as to obtain a clear and semitransparent cellulose nanosheet dispersion liquid, wherein the mass solid content of the cellulose nanosheet dispersion liquid is 0.5%.
(2) Then, a translucent wet cellulose film was obtained by vacuum filtration of the cellulose nanosheet dispersion.
(3) Setting the heating rate at 10 deg.C/min, and vacuum drying at 60 deg.C. And drying to obtain the cellulose membrane with smooth surface, translucency and rich nano pores.
In the drying process, the water adsorbed by the hydrophilic cellulose molecular chains is gradually volatilized, so that the natural and uniformly distributed nano-scale through-channels are formed in each layer of cellulose nanosheet by the cellulose nanofiber due to self-contraction, and the membrane with the network structure is different from other membranes with network structures consisting of fibers with larger major diameters, and has micro-scale disordered through-channels. The cellulose membrane is formed by stacking lamellar cellulose nanosheets, so that the cellulose membrane has a unique hierarchical structure, has hydrogen bonds and van der waals force between layers and shows high mechanical strength. Due to the fact that each layer of cellulose sheet is rich in nano-scale through-channels, the cellulose membrane has the characteristic of low tortuosity and is beneficial to ion transmission. The cellulose membrane has a thickness of 10 μm, an average pore diameter of 20nm, and a mechanical strength of 81 MPa. The cellulose membrane which is rich in nano-scale pore canals, high in strength, low in tortuosity and corrosion-resistant has great advantages as a water system battery diaphragm.
FIG. 1 is a cross-sectional SEM image of the nanopore-rich cellulose membrane prepared in example 1, which enables a multi-layer structure to be seen. FIG. 2 is a surface SEM image of the nanopore-rich cellulose membrane prepared in example 1, at a smaller magnification, with the surface observed to be lamellar. FIG. 3 is an SEM photograph of the cellulose film obtained in example 1, at a larger magnification, through-holes on the surface can be observed. The cellulose membrane prepared by the method is a cellulose membrane which takes two-dimensional cellulose nano-sheets as basic units, has natural nano-pores and a unique hierarchical structure, and is different from a cellulose membrane formed by lapping one-dimensional fibers with larger major diameters.
Example 2
(1) Carrying out ultrasonic dispersion on pure cellulose extracted from fir, and then carrying out freeze drying to obtain the cellulose nanosheet, wherein the thickness of the single-layer cellulose nanosheet is about 2 nm. Dispersing the obtained cellulose nanosheet in methanol, and performing ultrasonic dispersion to obtain a cellulose nanosheet dispersion liquid, wherein the mass solid content of the cellulose nanosheet dispersion liquid is 0.05%.
(2) Then, a wet cellulose membrane is obtained by carrying out vacuum filtration on the cellulose nanosheet dispersion.
(3) Setting the heating rate to be 10 ℃/min, and drying in vacuum at 60 ℃ to obtain the lamellar cellulose membrane with uniformly distributed nanopores, wherein the thickness of the lamellar cellulose membrane is 1um, the average pore diameter of the pores is 16nm, and the mechanical strength is 30 MPa.
Example 3
(1) And (3) carrying out ultrasonic dispersion on pure cellulose extracted from the reed, and then carrying out freeze drying to obtain the cellulose nanosheet, wherein the thickness of the single-layer cellulose nanosheet is about 8 nm. Dispersing the obtained cellulose nanosheet in propanol, and performing ultrasonic dispersion to obtain a cellulose nanosheet dispersion liquid, wherein the mass solid content of the cellulose nanosheet dispersion liquid is 0.25%.
(2) Then, a wet cellulose membrane is obtained by carrying out vacuum filtration on the cellulose nanosheet dispersion.
(3) Setting the heating rate to be 10 ℃/min, and drying in vacuum at 60 ℃ to obtain the lamellar cellulose membrane with uniformly distributed nanopores, wherein the thickness of the lamellar cellulose membrane is 4 mu m, the average pore diameter of pores is 20nm, and the mechanical strength is 45 MPa.
Example 4
(1) Carrying out ultrasonic dispersion on pure cellulose extracted from moso bamboos, and then carrying out freeze drying to obtain cellulose nanosheets, wherein the thickness of the single-layer cellulose nanosheets is about 14 nm. And dispersing the obtained cellulose nanosheet in ethanol, and performing ultrasonic dispersion to obtain a cellulose nanosheet dispersion liquid, wherein the mass solid content of the cellulose nanosheet dispersion liquid is 0.75%.
(2) Then, a wet cellulose membrane is obtained by carrying out vacuum filtration on the cellulose nanosheet dispersion.
(3) Setting the heating rate to be 12 ℃/min, and drying in vacuum at 60 ℃ to obtain the lamellar cellulose membrane with uniformly distributed nanopores, wherein the thickness of the lamellar cellulose membrane is 10um, the average pore diameter of the pores is 25nm, and the mechanical strength is 78 MPa.
Example 5
(1) And (3) carrying out ultrasonic dispersion on pure cellulose extracted from the Sasa albo-marginata, and carrying out freeze drying to obtain the cellulose nanosheet, wherein the thickness of the single-layer cellulose nanosheet is about 12 nm. Dispersing the obtained cellulose nanosheet in propanol, and performing ultrasonic dispersion to obtain a cellulose nanosheet dispersion liquid, wherein the mass solid content of the cellulose nanosheet dispersion liquid is 1.5%.
(2) Then, a wet cellulose membrane is obtained by carrying out vacuum filtration on the cellulose nanosheet dispersion.
(3) Setting the heating rate to be 12 ℃/min, and drying in vacuum at 75 ℃ to obtain the lamellar cellulose membrane with uniformly distributed nanopores, wherein the thickness of the lamellar cellulose membrane is 16um, the average pore diameter of pores is 29nm, and the mechanical strength is 92 MPa.
Example 6
(1) And (3) carrying out ultrasonic dispersion on pure cellulose extracted from the Korean pine, and then carrying out freeze drying to obtain the cellulose nanosheet, wherein the thickness of the single-layer cellulose nanosheet is about 16 nm. Dispersing the obtained cellulose nanosheet in acetone, and performing ultrasonic dispersion to obtain a cellulose nanosheet dispersion liquid, wherein the mass solid content of the cellulose nanosheet dispersion liquid is 2.3%.
(2) Then, a wet cellulose membrane is obtained by carrying out vacuum filtration on the cellulose nanosheet dispersion.
(3) Setting the heating rate to be 15 ℃/min, and drying in vacuum at 75 ℃ to obtain the lamellar cellulose membrane with uniformly distributed nanopores, wherein the thickness of the lamellar cellulose membrane is 20um, the average pore diameter of the pores is 34nm, and the mechanical strength is 89 MPa.
Example 7
(1) And (3) carrying out ultrasonic dispersion on pure cellulose extracted from the moso bamboo, and then carrying out freeze drying to obtain the cellulose nanosheet, wherein the thickness of the single-layer cellulose nanosheet is about 20 nm. And dispersing the obtained cellulose nanosheet in water, and performing ultrasonic dispersion to obtain a cellulose nanosheet dispersion liquid, wherein the mass solid content of the cellulose nanosheet dispersion liquid is 3.2%.
(2) Then, a wet cellulose membrane is obtained by carrying out vacuum filtration on the cellulose nanosheet dispersion.
(3) And drying at normal temperature to obtain the lamellar cellulose membrane with uniformly distributed nanopores, wherein the thickness of the lamellar cellulose membrane is 45um, the average pore diameter of pores is 5nm, and the mechanical strength is 112 MPa.
Example 8
(1) And (3) carrying out ultrasonic dispersion on pure cellulose extracted from the reed, and then carrying out freeze drying to obtain the cellulose nanosheet, wherein the thickness of the single-layer cellulose nanosheet is about 14 nm. And dispersing the obtained cellulose nanosheet in water, and performing ultrasonic dispersion to obtain a cellulose nanosheet dispersion liquid, wherein the mass solid content of the cellulose nanosheet dispersion liquid is 4.3%.
(2) Then, a wet cellulose membrane is obtained by carrying out vacuum filtration on the cellulose nanosheet dispersion.
(3) Setting the heating rate to be 10 ℃/min, and drying in vacuum at 55 ℃ to obtain the lamellar cellulose membrane with uniformly distributed nanopores, wherein the thickness of the lamellar cellulose membrane is 69um, the average pore diameter of the pores is 10nm, and the mechanical strength is 152 MPa.
Example 9
(1) And (3) carrying out ultrasonic dispersion on pure cellulose extracted from straws, and carrying out freeze drying to obtain the cellulose nanosheet, wherein the thickness of the single-layer cellulose nanosheet is about 4 nm. And dispersing the obtained cellulose nanosheet in water, and performing ultrasonic dispersion to obtain a cellulose nanosheet dispersion liquid, wherein the mass solid content of the cellulose nanosheet dispersion liquid is 3.6%.
(2) Then, a wet cellulose membrane is obtained by carrying out vacuum filtration on the cellulose nanosheet dispersion.
(3) Setting the heating rate to be 25 ℃/min, and drying in vacuum at 75 ℃ to obtain the lamellar cellulose membrane with uniformly distributed nanopores, wherein the thickness of the lamellar cellulose membrane is 55um, the average pore diameter of the pores is 60nm, and the mechanical strength is 141 MPa.
Example 10
(1) And (3) carrying out ultrasonic dispersion on pure cellulose extracted from cornstalks, and then carrying out freeze drying to obtain the cellulose nanosheets, wherein the thickness of the single-layer cellulose nanosheets is about 18 nm. Dispersing the obtained cellulose nanosheet in propanol, and performing ultrasonic dispersion to obtain a cellulose nanosheet dispersion liquid, wherein the mass solid content of the cellulose nanosheet dispersion liquid is 5%.
(2) Then, a wet cellulose membrane is obtained by carrying out vacuum filtration on the cellulose nanosheet dispersion.
(3) Setting the heating rate to be 5 ℃/min, and drying in vacuum at 50 ℃ to obtain the lamellar cellulose membrane with uniformly distributed nanopores, wherein the thickness of the lamellar cellulose membrane is 100um, the average pore diameter of the pores is 7nm, and the mechanical strength is 213 MPa.
Example 11
(1) Carrying out ultrasonic dispersion on pure cellulose extracted from sorghum stalks, and carrying out freeze drying to obtain cellulose nanosheets, wherein the thickness of the single-layer cellulose nanosheets is about 10 nm. And dispersing the obtained cellulose nanosheet in water, and performing ultrasonic dispersion to obtain a cellulose nanosheet dispersion liquid, wherein the mass solid content of the cellulose nanosheet dispersion liquid is 5%.
(2) Then, a wet cellulose membrane is obtained by carrying out vacuum filtration on the cellulose nanosheet dispersion.
(3) Setting the heating rate to be 20 ℃/min, and drying in vacuum at 80 ℃ to obtain the lamellar cellulose membrane with uniformly distributed nanopores, wherein the thickness of the lamellar cellulose membrane is 82um, the average pore diameter of the pores is 100nm, and the mechanical strength is 183 MPa.
Example 12
(1) Carrying out ultrasonic dispersion on pure cellulose extracted from bamboo, and then carrying out freeze drying to obtain a cellulose nanosheet, wherein the thickness of the single-layer cellulose nanosheet is about 20 nm. And dispersing the obtained cellulose nanosheet in water, and performing ultrasonic dispersion to obtain a cellulose nanosheet dispersion liquid, wherein the mass solid content of the cellulose nanosheet dispersion liquid is 0.4%.
(2) Then, a wet cellulose membrane is obtained by carrying out vacuum filtration on the cellulose nanosheet dispersion.
(3) Setting the heating rate to be 12 ℃/min, and drying in vacuum at 60 ℃ to obtain the lamellar cellulose membrane with uniformly distributed nanopores, wherein the thickness of the lamellar cellulose membrane is 8um, the average pore diameter of the pores is 25nm, and the mechanical strength is 63 MPa.
Example 13
(1) And (3) carrying out ultrasonic dispersion on pure cellulose extracted from bamboo, and then carrying out freeze drying to obtain the cellulose nanosheet, wherein the thickness of the single-layer cellulose nanosheet is about 18 nm. And dispersing the obtained cellulose nanosheet in water, and performing ultrasonic dispersion to obtain a cellulose nanosheet dispersion liquid, wherein the mass solid content of the cellulose nanosheet dispersion liquid is 0.64%.
(2) Then, a wet cellulose membrane is obtained by carrying out vacuum filtration on the cellulose nanosheet dispersion.
(3) Setting the heating rate to be 30 ℃/min, and drying in vacuum at 60 ℃ to obtain the lamellar cellulose membrane with uniformly distributed nanopores, wherein the thickness of the lamellar cellulose membrane is 12um, the average pore diameter of the pores is 35nm, and the mechanical strength is 79 MPa.
Example 14
(1) And (3) carrying out ultrasonic dispersion on pure cellulose extracted from bamboo, and then carrying out freeze drying to obtain the cellulose nanosheet, wherein the thickness of the single-layer cellulose nanosheet is about 20 nm. And dispersing the obtained cellulose nanosheet in water, and performing ultrasonic dispersion to obtain a cellulose nanosheet dispersion liquid, wherein the mass solid content of the cellulose nanosheet dispersion liquid is 0.78%.
(2) Then, a wet cellulose membrane is obtained by carrying out vacuum filtration on the cellulose nanosheet dispersion.
(3) Setting the heating rate at 15 ℃/min, and drying in vacuum at 75 ℃ to obtain the lamellar cellulose membrane with uniformly distributed nanopores, wherein the thickness of the lamellar cellulose membrane is 15um, the average pore diameter of pores is 40nm, and the mechanical strength is 84 MPa.
Indeed, the pure natural cellulose nanofibers are not only from bamboo, fir, reed, red pine, straw, corn stover, and sorghum stover included in the above embodiments, but may also include one or more of spruce, poplar, sorghum stover, mulberry bark, goose skin, wheat straw, cotton linter, kenaf, jute, flax, banana leaf, agave hemp, chinese alpine rush, brackish water plant, bagasse, and the like. In fact, plants which are purely natural sources of cellulose are in principle possible.
Comparative example 1
Conventional water-based batteries were commercially used with membrane glass fibers (Whatman, GF/A).
Test examples
(1) Acidic electrochemical test
The sheet cellulose film obtained in example 1 and a conventional water-based battery commercial separator glass fiber (Whatman, GF/a) were assembled as separators into a symmetric battery, respectively: zinc metal/lamellar cellulose membrane/zinc metal, zinc metal/glass fiber/zinc metal, 3M Zn (CF3SO3)2(pH 3.62) solution was used as the electrolyte.
At 0.5mA cm-2And the cycle stability of the two groups of batteries was tested simultaneously under the condition of 0.5 h. And the zinc foils after the two groups of batteries are cycled are observed by using a scanning electron microscope. The test results are shown in fig. 4, and fig. 4 is a graph comparing the circulation performance of the cellulose membrane prepared in example 1 and the commercial glass fiber separator in comparative example 1 in an acid electrolyte. As can be seen from fig. 4, the cycle life of the battery obtained with the glass fiber as the separator in comparative example 1 was only 30h, and the subsequent voltage-current curve was very disordered. The cycle life of the battery prepared by using the cellulose membrane obtained in example 1 as a diaphragm exceeds 5000 h.
The zinc foil of the cell obtained by using the cellulose film of example 1 as the separator showed a uniform deposition state under different visual fields without obvious dendrites and byproducts. The zinc foil of the battery obtained using the glass fiber of comparative example 1 as the separator showed uneven deposition on the surface and cross section and a large amount of zinc dendrites on the surface.
(2) Weak acid electrochemical test
The sheet cellulose film obtained in example 1 and a conventional water-based battery commercial separator glass fiber (Whatman, GF/a) were assembled as separators into a symmetric battery, respectively: zinc metal/lamellar cellulose membrane/zinc metal, zinc metal/glass fiber/zinc metal, 2M ZnSO4(pH 4.35) solution was used as the electrolyte.
At 1mAcm-2And under the condition of 1h, simultaneously testing the cycling stability of the two groups of batteries. And then observing the zinc foils of the two groups of batteries after circulation by using a scanning electron microscope.
The cellulose membrane obtained in example 1 is used as a diaphragm, and the cycle life of the battery is more than 1600 h. The cycle life of the battery using the glass fiber of comparative example 1 as the separator was only 30 h. The zinc foil of the cell obtained by using the cellulose film of example 1 as the separator showed a uniform deposition state under different visual fields without obvious dendrites and byproducts. The zinc foil of the battery obtained using the glass fiber of comparative example 1 as the separator showed uneven deposition on the surface and cross section and a large amount of zinc dendrites on the surface.
3. Alkaline electrochemical test
The sheet cellulose film obtained in example 1 and a conventional water-based battery commercial separator glass fiber (Whatman, GF/a) were assembled as separators into a symmetric battery, respectively: zinc metal/lamellar cellulose membrane/zinc metal, zinc metal/glass fiber/zinc metal, 1M KOH (pH 13.61) solution was used as the electrolyte.
At 0.5mAcm-2And the cycle stability of the two groups of batteries was tested simultaneously under the condition of 0.5 h. And chemical stability of the cellulose film and the glass fiber in a 1M KOH electrolyte was observed, and the results are shown in fig. 5.
FIG. 5 is a graph comparing the cycle performance of the cellulose membrane prepared in example 1 with that of the commercial glass fiber separator of comparative example 1 in an alkaline electrolyte. As can be seen from FIG. 5, the cycle life of the battery using the cellulose film obtained in example 1 as the separator was over 5000h, and the cycle life of the battery using the glass fiber obtained in comparative example 1 as the separator was only 4 h. The cellulose film obtained in example 1 was immersed in a 1M KOH electrolyte and remained intact for several months. The glass fibers of comparative example 1 were immersed in a 1M KOH electrolyte and decomposed within several days.
4. Mechanical Strength test
The cellulose film obtained in example 14 and the commercial separator glass fiber (Whatman, GF/a) for a conventional water-based battery were cut into 10 samples of 2 × 4cm each, the tensile strength of each sample in different states was measured by an electronic dynamic and static fatigue tester (INSTRON E1000) (refer to national standard GB/T1040.3-2006), after the experiment was completed, software was automatically processed to output the tensile strength data of each sample in different states, and the average value of the tensile strength of the sample was used as the tensile strength of the separator.
First, the tensile strengths in the virgin state of the above example 14 and comparative example 1 were respectively tested; then randomly taking 5 samples from the 10 samples of the example 14 and the comparative example 1, soaking the samples in 2M ZnSO4 electrolyte for 24 hours, and testing the tensile strength of the samples according to the method after taking the samples out; finally, the above example 14 and comparative example 1 were subjected to 1000 bending tests, and then the tensile strength was measured according to the above method. The test results are shown in table 1.
Table 1 stress-strain test results
As can be seen from table 1, the cellulose film obtained in example 14 exhibited little change in tensile strength in three states (including the original state, after soaking in an electrolyte and bending 1000 times). In contrast, conventional water-based battery commercial separator glass fibers have a significant decrease in tensile strength after soaking and bending, particularly after 1000 bends. In addition, the tensile strength of the cellulose film obtained in example 14 was as high as 81MPa in the virgin state, whereas the commercial separator glass fiber for a conventional water-based battery was only 0.54 MPa.
The cellulose membrane prepared by the method can keep chemical stability, structure stability and battery circulation stability in acidic and alkaline electrolytes, and can remarkably prolong the service life of a battery when being used as a battery diaphragm compared with conventional commercial diaphragm glass fiber of a water-based battery.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. The cellulose membrane rich in the nano-pores is characterized by comprising a plurality of structural units stacked layer by layer and a nano-pore canal penetrating through the whole cellulose membrane, wherein the structural units are two-dimensional cellulose nano-sheets.
2. The cellulose film according to claim 1, wherein the structural units have a thickness of not more than 20nm, and adjacent layers are stacked one on top of another by intermolecular forces.
3. The cellulose membrane according to claim 2, wherein the pore size of the nanoscale pores extending through the entire cellulose membrane is between 5nm and 100 nm.
4. The cellulose membrane according to claim 3, wherein the number of structural units of the cellulose membrane is more than 50 layers, and the total thickness of the whole cellulose membrane is 1 μm to 100 μm.
5. The cellulose membrane according to any one of claims 1 to 4, wherein the two-dimensional cellulose nanosheets are in a two-dimensional planar structure formed by self-assembly of pure natural cellulose nanofibers by hydrogen bonding, the pure natural cellulose nanofibers comprising one or more of Phyllostachys pubescens, Sagittaria indica, Picea japonica, fir, Korean pine, poplar, sorghum stalks, corn stalks, mulberry bark, goose skin, straw, wheat straw, reed, cotton linters, kenaf, jute, flax, banana leaves, agave hemp, Chinese alpine rush, saltwater weed, and bagasse.
6. A preparation method of a cellulose membrane rich in nanopores is characterized by comprising the following steps:
(1) dispersing a two-dimensional cellulose nanosheet in a solvent to obtain a dispersion liquid;
(2) driving two-dimensional cellulose nanosheets in the dispersion liquid to perform self-assembly by a film forming method to obtain a wet film;
(3) and drying the wet film to remove the solvent, so that the two-dimensional cellulose nano-fibers self-shrink to spontaneously form nano-scale structural pores in the cellulose film, and the nano-scale structural pores penetrate through the whole cellulose film.
7. The production method according to claim 6, wherein in the step (2), the film forming method includes at least one of a vacuum filtration method, a hot press method, a cold press method, a phase inversion method, and a freeze-drying method.
8. The production method according to claim 6, wherein the solvent includes at least one of water, methanol, ethanol, propanol, isopropanol, tert-butanol, acetone, and butanone.
9. Use of a nanopore-rich cellulose membrane according to any of claims 1 to 5 as a filter, nanofiltration, membrane or permeable membrane.
10. The use according to claim 9, characterized in that it is used in separators in electronic devices, including lithium ion batteries, sodium ion batteries, zinc ion batteries, potassium ion batteries, aluminum ion batteries and magnesium ion batteries, and also carbon capacitors, hybrid ion batteries and hybrid ultracapacitors.
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