CN114744367A - Preparation and application of modified ultrathin cellulose diaphragm - Google Patents
Preparation and application of modified ultrathin cellulose diaphragm Download PDFInfo
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- CN114744367A CN114744367A CN202210457721.XA CN202210457721A CN114744367A CN 114744367 A CN114744367 A CN 114744367A CN 202210457721 A CN202210457721 A CN 202210457721A CN 114744367 A CN114744367 A CN 114744367A
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- 239000001913 cellulose Substances 0.000 title claims abstract description 298
- 229920002678 cellulose Polymers 0.000 title claims abstract description 298
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 113
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 113
- 239000011701 zinc Substances 0.000 claims abstract description 113
- 239000012528 membrane Substances 0.000 claims abstract description 86
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000000758 substrate Substances 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 35
- 238000004146 energy storage Methods 0.000 claims abstract description 25
- 238000001035 drying Methods 0.000 claims abstract description 17
- 239000002121 nanofiber Substances 0.000 claims description 84
- 238000011068 loading method Methods 0.000 claims description 44
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 41
- 239000006185 dispersion Substances 0.000 claims description 41
- 229910052799 carbon Inorganic materials 0.000 claims description 40
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 39
- 229910052802 copper Inorganic materials 0.000 claims description 36
- 239000010949 copper Substances 0.000 claims description 36
- 239000000463 material Substances 0.000 claims description 28
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 27
- 239000000725 suspension Substances 0.000 claims description 23
- 239000002131 composite material Substances 0.000 claims description 20
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 19
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims description 15
- 229910052621 halloysite Inorganic materials 0.000 claims description 15
- 239000002033 PVDF binder Substances 0.000 claims description 14
- 229910002113 barium titanate Inorganic materials 0.000 claims description 14
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 14
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 claims description 14
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- 239000002071 nanotube Substances 0.000 claims description 13
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 11
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052454 barium strontium titanate Inorganic materials 0.000 claims description 8
- 229910002115 bismuth titanate Inorganic materials 0.000 claims description 8
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- 125000000524 functional group Chemical group 0.000 claims description 5
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
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- 239000011230 binding agent Substances 0.000 claims description 4
- FSAJRXGMUISOIW-UHFFFAOYSA-N bismuth sodium Chemical compound [Na].[Bi] FSAJRXGMUISOIW-UHFFFAOYSA-N 0.000 claims description 4
- 229910052793 cadmium Inorganic materials 0.000 claims description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 4
- QOKYJGZIKILTCY-UHFFFAOYSA-J hydrogen phosphate;zirconium(4+) Chemical compound [Zr+4].OP([O-])([O-])=O.OP([O-])([O-])=O QOKYJGZIKILTCY-UHFFFAOYSA-J 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000002135 nanosheet Substances 0.000 claims description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 4
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 4
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims description 4
- 239000007900 aqueous suspension Substances 0.000 claims description 2
- 239000003791 organic solvent mixture Substances 0.000 claims description 2
- 210000001787 dendrite Anatomy 0.000 abstract description 29
- 230000000694 effects Effects 0.000 abstract description 22
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 abstract description 19
- 238000000151 deposition Methods 0.000 abstract description 15
- 230000008021 deposition Effects 0.000 abstract description 14
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- 238000000265 homogenisation Methods 0.000 abstract description 2
- 238000005457 optimization Methods 0.000 abstract 1
- QNDQILQPPKQROV-UHFFFAOYSA-N dizinc Chemical compound [Zn]=[Zn] QNDQILQPPKQROV-UHFFFAOYSA-N 0.000 description 69
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- 238000012360 testing method Methods 0.000 description 40
- 239000003792 electrolyte Substances 0.000 description 39
- 238000011056 performance test Methods 0.000 description 34
- 239000007864 aqueous solution Substances 0.000 description 19
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 18
- 229960001763 zinc sulfate Drugs 0.000 description 18
- 229910000368 zinc sulfate Inorganic materials 0.000 description 18
- 230000006399 behavior Effects 0.000 description 17
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- 239000008367 deionised water Substances 0.000 description 16
- 229910021641 deionized water Inorganic materials 0.000 description 16
- 238000007599 discharging Methods 0.000 description 16
- 230000005764 inhibitory process Effects 0.000 description 14
- 239000002070 nanowire Substances 0.000 description 14
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- NKZSPGSOXYXWQA-UHFFFAOYSA-N dioxido(oxo)titanium;lead(2+) Chemical compound [Pb+2].[O-][Ti]([O-])=O NKZSPGSOXYXWQA-UHFFFAOYSA-N 0.000 description 11
- 238000002604 ultrasonography Methods 0.000 description 11
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- 239000004745 nonwoven fabric Substances 0.000 description 6
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- 229910052739 hydrogen Inorganic materials 0.000 description 5
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- 150000001450 anions Chemical class 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
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- 238000005036 potential barrier Methods 0.000 description 3
- 238000004080 punching Methods 0.000 description 3
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
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- 150000003839 salts Chemical class 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
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- 238000005411 Van der Waals force Methods 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
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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
- H01M50/44—Fibrous material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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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
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
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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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- 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
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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
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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
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
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- H—ELECTRICITY
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- 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
- H01M50/431—Inorganic material
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- 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
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- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
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- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
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- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/497—Ionic conductivity
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Abstract
The invention belongs to the technical field of electrochemical energy storage, and discloses preparation and application of a modified ultrathin cellulose diaphragm. The invention adopts a vacuum filtration method to directly pump and filter cellulose or cellulose modified by functional materials onto a filter membrane substrate, and the filter membrane substrate is peeled off after drying to construct a modified ultrathin cellulose diaphragm. The modified ultrathin cellulose diaphragm has the effects of high puncture strength, promotion of homogenization of an electric field and an ion field on the surface of a zinc cathode during zinc ion deposition, optimization of zinc deposition crystal face orientation, reduction of nucleation barrier and the like, so that the effect of inhibiting the growth of zinc dendrite is achieved. Therefore, the water system zinc-based energy storage system with high stability and long cycle life is realized, and the method has important significance for promoting the practical application of the water system zinc-based energy storage system.
Description
Technical Field
The invention belongs to the technical field of electrochemical energy storage, and particularly relates to preparation and application of a modified ultrathin cellulose diaphragm.
Background
The rapid development of human society is accompanied by the huge consumption of fossil fuels and the problem of environmental pollution caused by combustion thereof, and thus electrochemical energy storage devices having advantages of high energy storage/conversion efficiency, environmental protection, and the like are increasingly studied. The aqueous battery has higher safety performance and lower cost due to the adoption of the aqueous solution of the metal salt as the electrolyte; in addition, since the aqueous solution of a metal salt is used as an electrolyte and the ionic conductivity is much higher than that of an organic electrolyte for a lithium ion battery, for example, an aqueous battery has a wide application prospect in the field of energy storage, and is considered to be a battery system suitable for large-scale low-cost energy storage. Among them, the aqueous zinc-based energy storage system (including aqueous zinc ion battery and zinc ion hybrid capacitor) has become a research hotspot in the field of electrochemical energy storage in recent years due to its advantages of high safety, abundant raw materials, low price, environmental friendliness, and the like. The water system zinc-based energy storage system usually adopts metal zinc as a negative electrode, and the high theoretical specific capacity (820mAh/g) and the lower oxidation-reduction potential (-0.762V vs. standard hydrogen electrode) of the zinc-based energy storage system are beneficial to improving the energy density of the battery. However, in practical applications, one of the major problems faced by aqueous zinc-based energy storage systems is the zinc dendrite problem. During the discharge processThe zinc ions dissolved from the surface of the zinc metal can be redeposited on the zinc metal cathode in the charging process, and due to the tip effect of the uneven surface of the zinc metal, the uneven deposition of the zinc ions in the repeated charging and discharging process can cause the growth of zinc dendrites, so that the short circuit of the device is caused, and the service life and the large-scale application of the water system zinc-based energy storage system taking the metal zinc as the cathode are limited. Therefore, solving zinc dendrites has been the core problem in the research of zinc cathodes. One of the solutions is to develop a separator capable of inhibiting the growth of zinc dendrites. Cellulose contains a large number of hydrogen bonds, and thus can be self-assembled into a film under the action of hydrogen bonds, van der waals forces, electrostatic forces or the like in a dehydrated state. Compared with a commercial glass fiber diaphragm, the cellulose diaphragm has the advantages of low cost, reproducibility, high mechanical property, good hydrophilicity and the like, and can be used as a diaphragm matrix material for inhibiting zinc dendrite. However, cellulose membranes prepared, for example, by solution casting have a limited effect on zinc dendrite suppression at 5mA/cm2、2.5mAh/cm2The cycle life of a symmetrical battery based on its assembly is only 20 hours (Nano Energy,2021,89, 106322). Moreover, in order to ensure the zinc dendrite inhibiting effect, the cellulose diaphragm adopting the prior art cannot be thinned, for example, the Chinese patent publication CN 112332026A, a cellulose-based diaphragm prepared by a coating method, preferably the cellulose diaphragm has a thickness of 100 μm; the thickness of the cellulose membrane prepared by Zhou et al was 140 μm (Energy Storage Materials,2022,44, 57-65). The diaphragm is used as one of key components in the water-system zinc-based energy storage equipment, the specific energy (including volumetric specific energy and mass specific energy) of the water-system zinc-based energy storage system is obviously reduced by using the large-thickness diaphragm, and meanwhile, the ionic transmission distance of electrolyte in the charging and discharging process is prolonged, the rapid charging and discharging and the high power density are not facilitated, and the industrial application of the diaphragm is hindered. For example, currently commercially available lithium ion batteries typically have separator thicknesses of no more than 25 μm.
Disclosure of Invention
Aiming at the defects of the existing water system zinc-based energy storage system diaphragm material, the invention aims to provide a preparation method of a modified ultrathin cellulose diaphragm. The method selects the cellulose containing functional groups as a diaphragm base material, improves the transference number of zinc ions by utilizing the inhibiting effect of the functional groups on the anion transfer of the electrolyte, reduces the local space charge accumulation on the surface of zinc metal, and finally achieves the aim of inhibiting the growth of zinc dendrite; furthermore, the cellulose diaphragm substrate is modified by introducing functional materials, on the premise of ensuring the preparation of the ultrathin cellulose diaphragm, zinc ion deposition behaviors are optimized by selecting different functional materials to enhance the puncture strength of the cellulose diaphragm substrate, regulate and control the electric field on the negative electrode surface during zinc ion deposition, the ion field distribution and crystal face orientation during zinc ion deposition, reduce the nucleation barrier and the like, so that the effect of effectively inhibiting zinc dendrites is achieved, the service life of a water system zinc-based energy storage system is prolonged, and the large-scale application of the water system zinc-based energy storage system is promoted.
The invention further aims to provide the modified ultrathin cellulose diaphragm prepared by the method.
The invention also aims to provide application of the modified ultrathin cellulose diaphragm, and the application object is a water system zinc-based energy storage system.
The purpose of the invention is realized by the following scheme:
a preparation method of a modified ultrathin cellulose diaphragm comprises the following steps:
(1) uniformly dispersing cellulose nano-fibers in water to obtain a cellulose water system suspension; dispersing a functional material into a solvent to obtain a suspension 2;
(2) the step is the following step (2.1) or step (2.2):
(2.1) blending the cellulose aqueous suspension and the suspension 2, then carrying out suction filtration on the mixture to obtain a filter membrane substrate, drying the filter membrane substrate at room temperature, and stripping off the filter membrane substrate to obtain a modified ultrathin cellulose diaphragm;
or (2.2) carrying out suction filtration on the cellulose water system suspension to obtain an ultrathin cellulose diaphragm matrix, and immediately carrying out suction filtration on the suspension 2 to obtain the ultrathin cellulose diaphragm matrix to obtain the modified ultrathin cellulose diaphragm.
Taking into account that the separator plays a role of transmitting ions and blocking electrons, and in order to prevent the introduction of the conductive functional layer from causing a short circuit of the battery, the step (2.2) is particularly suitable for the functional material to be a material having conductivity. And when the modified ultrathin cellulose diaphragm of which the functional material is the material with conductivity is prepared in the step (2.2), when the modified ultrathin cellulose diaphragm is used for a zinc-zinc symmetrical battery, two modified ultrathin cellulose diaphragms are required to be superposed for use so as not to cause short circuit of the battery, and the surface functional layer sides of the two modified ultrathin cellulose diaphragms face the two zinc foils respectively.
The cellulose nano-fiber in the step (1) is the cellulose nano-fiber with the surface containing hydroxyl, carboxyl or amino functional groups, the diameter is 5-200nm, and the length is 0.5-20 μm;
the concentration of the cellulose dispersion liquid in the step (1) is 0.5-1mg/mL so as to enable the cellulose nano-fibers to be fully dispersed.
The functional material in the step (1) comprises at least one of zirconium hydrogen phosphate nanosheets, silica nanofibers, nano zinc oxide, nano aluminum oxide, halloysite nanotubes, nano tin, copper nanowires, copper/carbon composite materials, candle ash, cellulose nanofiber derived carbon, barium titanate, strontium titanate, barium strontium titanate, bismuth titanate, lead zirconate, sodium bismuth titanate, barium strontium titanate, cadmium niobate, polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate and polyethylene oxide;
the solvent used for dispersing the functional material in the step (1) is one of water, an organic solvent or a water/organic solvent mixture;
the dosage of the functional material and the solvent in the step (1) meets the following requirements: the concentration of the functional material in the solvent is 0.05-10mg/mL, preferably 0.1-3 mg/mL;
the cellulose water system suspension and the suspension 2 in the step (2.1) and the step (2.2) are used in the following amount: the loading amount of the cellulose nano-fiber is 0.5-10mg/cm2Preferably 1 to 6mg/cm2(ii) a The loading capacity of the functional material is 0.1-9mg/cm2Preferably 0.3 to 5mg/cm2(ii) a The mass fraction of the functional material in the modified ultrathin cellulose diaphragm is 0-90%, preferably 5-50%. The loading is relative to the filter membrane substrate, for example, the loading of the cellulose is 1mg/cm2The membrane of (2) is prepared by mixing 12.56mg of fiberThe element is filtered to a load area of 12.56cm2On the filter membrane.
Preferably, in the step (2.2), in order to ensure the film-forming quality of the surface functional layer for the easily-peeled surface functional layer material, a certain proportion of cellulose nanofibers are often mixed in the suspension 2 in the step (2.2), and the cellulose nanofibers mainly play a role of a binder. Wherein the mixed cellulose nano-fiber accounts for 0 to 20 percent of the functional material by mass percent.
The filter membrane substrate in the step (2.1) and the step (2.2) is a mixed cellulose water system filter membrane (suitable for functional materials and water as a solvent) or a nylon filter membrane (suitable for functional materials and organic solvent or water or a mixture of the organic solvent and the water as a solvent), and the pore diameter is 0.01-2 mu m;
the modified ultrathin cellulose diaphragm prepared by the method has the thickness of 3-80 microns, and preferably 5-40 microns.
The invention relates to a modified ultrathin cellulose diaphragm, which selects cellulose nano-fiber containing functional groups as a diaphragm substrate, has the characteristics of ultrathin property, puncture resistance, high liquid retention and high porosity, and is modified by introducing functional materials (comprising zirconium hydrogen phosphate nano-sheets, silicon dioxide nano-fibers, nano-zinc oxide, nano-aluminum oxide, halloysite nanotubes, nano-tin, copper nanowires, copper/carbon composite materials, candle ash, cellulose nano-fiber derived carbon, barium titanate, strontium titanate, barium strontium titanate, bismuth titanate, lead zirconate, sodium bismuth titanate, barium strontium titanate, cadmium niobate, polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate and polyethylene oxide). Has important significance for promoting the practical application of the water system zinc-based energy storage system.
An aqueous zinc-based energy storage system comprising the modified ultrathin cellulose membrane.
The mechanism of the invention is as follows:
the functions of the functional materials selected by the invention are respectively as follows: (1) inorganic matter reinforcing phases such as zirconium hydrogen phosphate nanosheets, silicon dioxide nanofibers, nano zinc oxide, nano aluminum oxide and the like are adopted to improve the puncture strength of the diaphragm so as to mechanically inhibit the growth of zinc dendrites; (2) the halloysite nanotube with the ion screening function is used for regulating and controlling the selective deposition path of anions and cations in the electrolyte so as to limit the movement of the anions, improve the transference number of zinc ions and weaken the phenomenon that the local space charge effect on the surface of a zinc cathode induces the formation of zinc dendrites; (3) conductive zinc-philic materials such as nano tin, copper nanowires, copper/carbon composite materials, candle ash, cellulose nanofiber derived carbon and the like are adopted for reducing the zinc ion nucleation potential barrier, accelerating the deposition kinetics of the zinc ion nucleation potential barrier, reducing the local current density of the surface of a zinc cathode, and promoting the uniformity of an electric field so as to uniformly deposit zinc ions; (4) barium titanate, strontium titanate, barium strontium titanate, bismuth titanate, lead zirconate, sodium bismuth titanate, barium strontium titanate, cadmium niobate, polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate and polyethylene oxide materials with high dielectric constants are adopted, and the Maxwell-Wagner polarization effect of the materials under an external electric field is utilized to regulate and control the surface ion transmission path of the zinc cathode, accelerate zinc ion transmission and reject anions to inhibit the generation of byproducts such as basic zinc sulfate, so that the uniform deposition of zinc is promoted, the growth of zinc dendrites is inhibited, and the cycling stability of the zinc cathode is improved.
From the practical application angle, the invention designs and prepares the ultrathin cellulose diaphragm for the water system zinc-based energy storage system, improves the specific energy of the water system zinc-based energy storage system and reduces the production cost; directly mixing a functional material and cellulose into a film by introducing a cellulose diaphragm functional material layer; or an independent functional layer is introduced to regulate and control an electric field/ion field, a nucleation barrier and the like of zinc ions in the charging and discharging processes, and finally the purposes of uniformly depositing the zinc ions on the surface of zinc metal, inhibiting the growth of zinc dendrites and prolonging the cycle service life of the zinc metal are achieved.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) according to the modified ultrathin cellulose diaphragm constructed by the invention, the puncture strength of a cellulose diaphragm substrate is enhanced by selecting different functional materials, the homogenization of a zinc negative electrode surface electric field and an ion field during zinc ion deposition is promoted, the orientation of a zinc deposition crystal face is optimized, the nucleation potential barrier is reduced and other modes are adopted to regulate and control the zinc ion deposition behavior, so that a water system zinc-based energy storage system with high stability and long cycle life is realized;
(2) compared with the reported diaphragm for a water system zinc-based energy storage system and the reported prior art for inhibiting the formation of zinc dendrites, the modified ultrathin cellulose diaphragm disclosed by the invention is simple in preparation method, low in cost, good in effect and suitable for large-scale production and practical application.
Drawings
FIG. 1 shows the prepared loading amount of 3mg/cm2The thickness cross-sectional view of the ultrathin cellulose membrane of (1);
FIG. 2 shows the prepared loading amount of 3mg/cm2The surface topography of the ultrathin cellulose diaphragm is shown;
FIG. 3 shows the current density at 1mA/cm2The cut-off capacity is 0.5mAh/cm2When using, the loading is 1, 3, 9mg/cm2Constant current charge-discharge curve of zinc-zinc symmetrical battery with ultrathin cellulose diaphragm;
FIG. 4 shows the current density at 5mA/cm2The cut-off capacity is 2.5mAh/cm2When the load is 1, 3 and 9mg/cm2Constant current charge-discharge curve of zinc-zinc symmetrical battery with ultrathin cellulose diaphragm;
FIG. 5 shows the current density at 5mA/cm2The cut-off capacity is 2.5mAh/cm2When the battery is used, the constant current charge-discharge curve of the zinc-zinc symmetrical battery of the ultrathin cellulose diaphragm modified by the nano zinc oxide is used;
FIG. 6 shows the current density at 1mA/cm2The cut-off capacity is 0.5mAh/cm2And the current density is 5mA/cm2The cut-off capacity is 2.5mAh/cm2When the zinc-zinc symmetric battery is used, the halloysite nanotube modified ultrathin cellulose diaphragm is used for charging and discharging the constant current of the zinc-zinc symmetric battery;
FIG. 7 shows the current density at 1mA/cm2The cut-off capacity is 0.5mAh/cm2And the current density is 5mA/cm2The cut-off capacity is 2.5mAh/cm2When the copper nanowire surface functional layer is used for modifying the constant current charge-discharge curve of the zinc-zinc symmetrical battery with the ultrathin cellulose diaphragm;
FIG. 8 shows the current density at 1mA/cm2The cut-off capacity is 0.5mAh/cm2And a current density of 5mAcm2The cut-off capacity is 2.5mAh/cm2When the battery is used, the functional layer on the surface of the copper/carbon composite material is used for modifying the constant current charge-discharge curve of the zinc-zinc symmetrical battery of the ultrathin cellulose diaphragm;
FIG. 9 shows the current density at 5mA/cm2And the cut-off capacity is 2.5mAh/cm2When the battery is used, the cellulose nanofiber derived carbon surface functional layer is used for modifying the constant current charge-discharge curve of the zinc-zinc symmetrical battery of the ultrathin cellulose diaphragm;
FIG. 10 is a graph showing a current density of 1mA/cm2And the cut-off capacity is 0.5mAh/cm2When the battery is used, the constant current charge-discharge curve of the zinc-zinc symmetrical battery using the nano barium titanate modified ultrathin cellulose diaphragm is adopted;
FIG. 11 shows the current density at 1mA/cm2The cut-off capacity is 0.5mAh/cm2When the battery is used, a constant current charge-discharge curve of a zinc-zinc symmetrical battery with a non-woven fabric diaphragm is used;
FIG. 12 shows the current density at 1mA/cm2The cut-off capacity is 0.5mAh/cm2When in use, the constant current charge-discharge curve of the zinc-zinc symmetrical battery of the commercial cellulose paper diaphragm is used;
FIG. 13 shows the current density at 1mA/cm2The cut-off capacity is 0.5mAh/cm2The constant current charge-discharge curve of a zinc-zinc symmetric cell using a commercial glass fiber separator.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto. 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.
Example 1
Preparation of ultrathin cellulose diaphragm
(1) The hydroxyl cellulose nano-fiber (purchased from Jinjiahao Green nano-material GmbH, Zhejiang, model number CNF-H1) with the weighed mass of 12.6, 37.7 and 113.1mg respectively is dispersed in deionized water to prepare the hydroxyl cellulose nano-fiber with the concentration of 0.5mg/mLDispersing the dispersion liquid uniformly by ultrasonic. And (3) carrying out suction filtration on the dispersion liquid to a substrate of a mixed cellulose water system filter membrane (type: a Tianjin Jinteng microporous water system filter membrane, the aperture is 0.8 mu m) by a vacuum suction filtration method. Drying at room temperature for 8 hours, stripping off the filter membrane substrate to obtain the hydroxyl cellulose nanofiber with the loading amounts of 1, 3 and 9mg/cm respectively2The loading amount of the ultrathin cellulose membrane is 3mg/cm2The thickness of the ultrathin cellulose membrane is about 16 μm, and the thickness cross-sectional view is shown in FIG. 1. FIG. 2 shows the loading amount of 3mg/cm2The surface topography of the ultrathin cellulose diaphragm can be seen from the figure, the ultrathin cellulose diaphragm is formed by winding cellulose nano fibers, presents a relatively compact topography and has a few nano holes.
(2) A zinc sheet with the diameter of 10mm and an ultrathin cellulose diaphragm with the diameter of 16mm are assembled into a zinc-zinc symmetrical battery by adopting a CR2032 type button battery case to carry out electrochemical performance test so as to discuss the inhibition effect of the ultrathin cellulose diaphragm on zinc dendrites. The electrolyte is 2mol/L zinc sulfate aqueous solution, the assembled battery is stood for 6 hours at room temperature to enable the electrolyte to fully infiltrate the ultrathin cellulose diaphragm, and then electrochemical performance test is carried out.
(3) At 1mA/cm2Current density of 0.5mAh/cm2The cut-off capacity of (d) was used as a test condition to perform a constant current charge and discharge test, and the charge and discharge curve thereof is shown in fig. 3. The adopted load amounts are respectively 1, 3 and 9mg/cm2The zinc-zinc symmetrical battery with the ultrathin cellulose diaphragm can perform normal charging and discharging behaviors for 190, 1450 and 932 hours, wherein the loading amount is 3mg/cm2The ultrathin cellulose diaphragm of comparative example 1, comparative example 2 and comparative example 3 has no short circuit phenomenon after 1450 hours, while the zinc-zinc symmetrical battery assembled by the common non-woven fabric diaphragm, the commercial cellulose paper diaphragm and the commercial glass fiber diaphragm can only complete the normal charging and discharging behaviors of 6 hours, 2 hours and 40 hours respectively, and then has the short circuit phenomenon. The adopted load amounts are respectively 1, 3 and 9mg/cm2The overpotential of the zinc-zinc symmetrical battery of the ultrathin cellulose diaphragm in the charge and discharge processes is respectively 115 mV, 107 mV and 132mV, and the loading capacity of the nano cellulose fiber is overThe over potential of the dissolution and deposition of zinc is increased in large time, which is not beneficial to realizing a stable zinc cathode.
(4) At 5mA/cm2Current density of 2.5mAh/cm2The cut-off capacity of (d) was used as a test condition to perform a constant current charge and discharge test, and the charge and discharge curve thereof is shown in fig. 4. The adopted load amounts are respectively 1, 3 and 9mg/cm2The zinc-zinc symmetrical battery with the ultrathin cellulose diaphragm can perform normal charge and discharge behaviors for 56 hours, 256 hours and 57 hours. The adopted load amounts are respectively 1, 3 and 9mg/cm2The overpotential of the ultrathin cellulose diaphragm in the charge-discharge process of the zinc-zinc symmetrical battery is 157 mV, 173 mV and 264mV respectively, and the overpotential of the dissolution and deposition of zinc is increased when the loading capacity of the same cellulose nanofiber is larger, which is not beneficial to realizing a stable zinc cathode.
Example 2
Preparation of nano zinc oxide modified ultrathin cellulose diaphragm
(1) 18.9mg of hydroxycellulose nanofibers (purchased from Jinjiahao Green nanomaterial Co., Ltd., Zhejiang, model number CNF-H1) and 18.9mg of nano zinc oxide were dispersed in deionized water to prepare a dispersion solution with the concentration of the hydroxycellulose nanofibers being 0.5mg/mL and the concentration of the nano zinc oxide being 0.5mg/mL, and the dispersion solution was uniformly dispersed by ultrasound. And (3) carrying out vacuum filtration on the mixed dispersion liquid to obtain a mixed cellulose water system filter membrane (type: Tianjin Jinteng microporous water system filter membrane, aperture is 0.8 μm). Drying for 8 hours at room temperature, stripping off the filter membrane substrate to obtain the hydroxyl cellulose nanofiber with the load of 1.5mg/cm2The loading capacity of the nano zinc oxide is 1.5mg/cm2The nanometer zinc oxide modified ultrathin cellulose diaphragm.
(2) A zinc sheet with the diameter of 10mm and a nano zinc oxide modified ultrathin cellulose diaphragm with the diameter of 16mm are assembled into a zinc-zinc symmetrical battery by adopting a CR2032 type button battery case to carry out electrochemical performance test so as to discuss the inhibition effect of the nano zinc oxide modified ultrathin cellulose diaphragm on zinc dendrites. The electrolyte is 2mol/L zinc sulfate aqueous solution, the assembled battery is stood for 6 hours at room temperature, so that the electrolyte is fully soaked in the nano zinc oxide modified ultrathin cellulose diaphragm, and then the electrochemical performance test is carried out.
(3) At 5mA/cm2Current density of 2.5mAh/cm2The cut-off capacity of (d) was used as a test condition to perform a constant current charge and discharge test, and the charge and discharge curve thereof is shown in fig. 5. The zinc-zinc symmetrical battery adopting the nano zinc oxide modified ultrathin cellulose diaphragm still has no short circuit phenomenon after 650 hours of charging and discharging, and the overpotential is 99mV in the charging and discharging process, which is superior to the unmodified ultrathin cellulose diaphragm in the embodiment 1, and is more beneficial to realizing a stable zinc cathode.
Example 3
Preparation of halloysite nanotube modified ultrathin cellulose diaphragm
(1) 18.9mg of hydroxycellulose nanofibers (purchased from Kinghao, N.Y., model number CNF-H1) and 18.9mg of commercial natural halloysite nanotubes (tube outer diameter of about 50nm, inner diameter of 15-20nm, length of 100-1500nm) were dispersed in deionized water to prepare a dispersion with a hydroxycellulose nanofiber concentration of 0.5mg/mL and a halloysite concentration of 0.5mg/mL, and the dispersion was uniformly dispersed by ultrasound. And (3) carrying out vacuum filtration on the mixed dispersion liquid to obtain a mixed cellulose water system filter membrane (type: Tianjin Jinteng microporous water system filter membrane, aperture is 0.8 μm). Drying for 8 hours at room temperature, stripping off the filter membrane substrate to obtain the hydroxyl cellulose nanofiber with the load of 1.5mg/cm2The load of the halloysite nanotube is 1.5mg/cm2The halloysite nanotube modified ultrathin cellulose diaphragm.
(2) A zinc sheet with the diameter of 10mm and a halloysite modified ultrathin cellulose diaphragm with the diameter of 16mm are assembled into a zinc-zinc symmetrical battery by adopting a CR2032 button battery case to carry out electrochemical performance test so as to discuss the inhibition effect of the halloysite nanotube modified ultrathin cellulose diaphragm on zinc dendrites. The electrolyte adopts 2mol/L zinc sulfate aqueous solution, the assembled battery is stood for 6 hours at room temperature, so that the electrolyte fully infiltrates the halloysite nanotube modified ultrathin cellulose diaphragm, and then the electrochemical performance test is carried out.
(3) At 1mA/cm2Current density of 0.5mAh/cm2And 5mA/cm2Current density of 2.5mAh/cm2As a cutoff capacity ofTest conditions constant current charge and discharge tests were performed, and the charge and discharge curves are shown in fig. 6. The zinc-zinc symmetrical battery adopting the halloysite nanotube modified ultrathin cellulose membrane still has no short circuit phenomenon after 1775 hours of charge and discharge behaviors under the conditions of lower current density and cut-off capacity, and the overpotential in the charge and discharge process is 52mV (the overpotential is less than and the cycle life is longer than that of the unmodified ultrathin cellulose membrane in the embodiment 1); and at relatively large current densities and cut-off capacities (5 mA/cm)2Current density of 2.5mAh/cm2Cut-off capacity) of 720 hours, and the overpotential during the charge and discharge process is 62mV (the overpotential is less than, and the cycle life is better than that of the unmodified ultrathin cellulose diaphragm in example 1). Compared with the unmodified ultrathin cellulose membrane in the embodiment 1, the halloysite nanotube modified ultrathin cellulose membrane is more beneficial to realizing a stable zinc cathode.
Example 4
Preparation of copper nanowire surface functional layer modified ultrathin cellulose diaphragm
(1) 12.6mg of hydroxycellulose nanofibers (purchased from jinghanhao green nano materials ltd., zhejiang, model number CNF-H1) were dispersed in deionized water to prepare a dispersion with a hydroxycellulose nanofiber concentration of 0.5mg/mL, 6.3mg of copper nanowires (diameter 40-60nm, length 0.8-6 μm) were dispersed in ethanol to prepare a dispersion with a copper nanowire concentration of 0.5mg/mL, and two suspensions were uniformly dispersed by ultrasound. And sequentially pumping and filtering the two dispersions onto a nylon filter membrane (type: Tianjin Jinteng microporous organic filter membrane, the aperture is 0.2 mu m) substrate by a vacuum pumping filtration method, drying for 8 hours at room temperature, and stripping off the filter membrane substrate to obtain the copper nanowire surface functional layer modified ultrathin cellulose diaphragm. Because a zinc-zinc symmetrical battery is adopted in the test, two copper nanowire surface functional layer modified ultrathin cellulose diaphragms are needed to be overlapped for use, and the surfaces of the copper nanowire surface functional layers of the two diaphragms face the two zinc foils respectively to protect two zinc-zinc electrodes. Therefore, the total loading capacity of the modified ultrathin cellulose diaphragm hydroxyl cellulose nanofibers with the copper nanowire surface functional layer is 2mg/cm2The total load of the copper nano-wire is 1mg/cm2Wherein the total loading refers to the total loading in the two copper nanowire surface functional layer modified ultrathin cellulose diaphragms.
(2) A zinc sheet with the diameter of 10mm and a copper nanowire surface functional layer modified ultrathin cellulose diaphragm with the diameter of 16mm are assembled into a zinc-zinc symmetrical battery (wherein the surface of the functional layer faces a zinc cathode) by adopting a CR2032 type button battery case to carry out electrochemical performance test so as to discuss the inhibition effect of the copper nanowire surface functional layer modified ultrathin cellulose diaphragm on zinc dendrites. The electrolyte is 2mol/L zinc sulfate aqueous solution, the assembled battery is stood for 6 hours at room temperature, so that the electrolyte is fully infiltrated into the copper nanowire surface functional layer modified ultrathin cellulose diaphragm, and then the electrochemical performance test is carried out.
(3) Respectively at 1mA/cm2Current density of 0.5mAh/cm2Cut-off capacity and 5mA/cm2Current density of 2.5mAh/cm2The cut-off capacity of (d) was used as a test condition to perform a constant current charge and discharge test, and the charge and discharge curve thereof is shown in fig. 7. The zinc-zinc symmetrical battery adopting the copper nanowire surface functional layer modified ultrathin cellulose diaphragm still has no short circuit phenomenon after 960 hours of charging and discharging behaviors under the conditions of low current density and cut-off capacity, and the overpotential in the charging and discharging process is 66mV (the overpotential is less than that of the unmodified ultrathin cellulose diaphragm in the embodiment 1); and at relatively large current densities and cut-off capacities (5 mA/cm)2Current density of 2.5mAh/cm2Cut-off capacity) for 776 hours, and the overpotential during charging and discharging was 87mV (the overpotential was less than, and the cycle life was better than that of the unmodified ultrathin cellulose separator in example 1). Compared with the unmodified ultrathin cellulose diaphragm in the embodiment 1, the copper nanowire surface functional layer modified ultrathin cellulose diaphragm is more beneficial to realizing a stable zinc cathode, especially under relatively high current density and cut-off capacity.
Example 5
Preparation of nano-tin surface functional layer modified ultrathin cellulose diaphragm
(1) 12.6mg of hydroxycellulose nanofibers (purchased from Zhejiang jinghao green nanomaterial, inc., type)CNF-H2) in deionized water to prepare a dispersion with the concentration of the hydroxycellulose nano-fiber of 0.5mg/mL, dispersing 6.3mg of nano-tin (with the particle size of less than 100nm) in ethanol to prepare a dispersion with the concentration of the nano-tin of 0.5mg/mL, and uniformly dispersing the two suspensions by ultrasound. And sequentially filtering the two dispersions to a nylon filter membrane (type: Tianjin Jinteng microporous organic filter membrane, aperture of 0.2 mu m) substrate by a vacuum filtration method, drying at room temperature for 8 hours, and stripping off the filter membrane substrate to obtain the nano-tin surface functional layer modified ultrathin cellulose membrane. Because a zinc-zinc symmetrical battery is adopted in the test, two nano-tin surface functional layer modified ultrathin cellulose diaphragms are needed to be overlapped for use, and the nano-tin surface functional layer surfaces of the two diaphragms respectively face the two zinc foils to protect two zinc-zinc electrodes. Therefore, the total loading of the nano tin surface functional layer modified ultrathin cellulose diaphragm hydroxyl cellulose nanofiber is 2mg/cm2The total loading capacity of the nano tin is 1mg/cm2Wherein the total loading refers to the total loading in the two nano tin surface functional layer modified ultrathin cellulose diaphragms.
(2) A zinc sheet with the diameter of 10mm and a nano-tin surface functional layer modified ultrathin cellulose diaphragm with the diameter of 16mm are assembled into a zinc-zinc symmetrical battery (wherein the surface of the functional layer faces a zinc cathode) by adopting a CR2032 type button battery case to carry out electrochemical performance test so as to discuss the inhibition effect of the nano-tin surface functional layer modified ultrathin cellulose diaphragm on zinc dendrites. The electrolyte is 2mol/L zinc sulfate aqueous solution, the assembled battery is stood for 6 hours at room temperature, so that the electrolyte is fully soaked in the nano tin surface functional layer modified ultrathin cellulose diaphragm, and then the electrochemical performance test is carried out.
(3) At 1mA/cm2Current density of 0.5mAh/cm2The cut-off capacity of the nano tin surface functional layer ultrathin cellulose membrane is used as a test condition to carry out constant current charge and discharge tests, and the zinc-zinc symmetrical battery adopting the nano tin surface functional layer ultrathin cellulose membrane still has no short circuit phenomenon after 1520 hours of charge and discharge behaviors, so that the zinc-zinc symmetrical battery is more beneficial to realizing a stable zinc cathode compared with the unmodified ultrathin cellulose membrane in the embodiment 1.
Example 6
Preparation of copper/carbon composite material surface functional layer modified ultrathin cellulose diaphragm
(1) 12.6mg of hydroxycellulose nanofiber (purchased from jinghanhao green nano materials ltd., zhejiang, model number CNF-H2) is dispersed in deionized water to prepare a dispersion liquid with the concentration of the hydroxycellulose nanofiber of 0.5mg/mL, 6.3mg of copper/carbon composite material (the size of carbon particles is below 500nm, the size of copper particles is below 150nm, and the mass fraction of copper in the copper/carbon composite material is 27%) and 0.63mg of cellulose nanofiber binder are dispersed in the deionized water to prepare a dispersion liquid with the concentration of the copper/carbon composite material of 0.5mg/mL, and two parts of suspension liquid are uniformly dispersed by ultrasound. And sequentially filtering the dispersion liquid to a mixed cellulose water system filter membrane (type: Tianjin Jinteng microporous water system filter membrane, the aperture is 0.8 mu m) substrate by a vacuum filtration method, drying for 8 hours at room temperature, and stripping off the filter membrane substrate to obtain the copper/carbon composite material surface functional layer modified ultrathin cellulose membrane. Because a zinc-zinc symmetrical battery is adopted in the test, two copper/carbon composite material surface functional layer modified ultrathin cellulose diaphragms are needed to be overlapped for use, and the surfaces of the copper/carbon composite material surface functional layers of the two diaphragms respectively face the two zinc foils so as to protect two zinc-zinc electrodes. Therefore, the total loading of the modified ultrathin cellulose diaphragm hydroxyl cellulose nano-fiber on the surface functional layer of the copper/carbon composite material is 2mg/cm2The total loading capacity of the copper/carbon composite material is 1mg/cm2Wherein the total loading refers to the total loading in the two copper/carbon composite material surface functional layer modified ultrathin cellulose diaphragms. .
(2) A zinc sheet with the diameter of 10mm and a copper/carbon composite material surface functional layer modified ultrathin cellulose diaphragm with the diameter of 16mm are assembled into a zinc-zinc symmetrical battery (wherein the functional layer surface faces a zinc cathode) by adopting a CR2032 type button battery case to carry out an electrochemical performance test so as to discuss the inhibition effect of the copper/carbon composite material surface functional layer modified ultrathin cellulose diaphragm on zinc dendrites. The electrolyte is 2mol/L zinc sulfate aqueous solution, the assembled battery is stood for 6 hours at room temperature, so that the electrolyte is fully soaked in the copper/carbon composite material surface functional layer modified ultrathin cellulose diaphragm, and then the electrochemical performance test is carried out.
(3) At 1mA/cm2Current density of 0.5mAh/cm2Cut-off capacity of 5mA/cm2Current density of 2.5mAh/cm2The cut-off capacity of (d) was used as a test condition to perform a constant current charge/discharge test, and the charge/discharge curve thereof is shown in fig. 8. The zinc-zinc symmetrical battery adopting the copper/carbon composite material surface functional layer modified ultrathin cellulose diaphragm still has no short circuit phenomenon after 1517 hours of charge and discharge behaviors under the conditions of lower current density and cut-off capacity, and the overpotential in the charge and discharge process is 51mV (the overpotential is less than and the cycle life is longer than that of the unmodified ultrathin cellulose diaphragm in the embodiment 1); and no short circuit phenomenon still occurs after 551 hours of normal charge and discharge under relatively large current density and cut-off capacity, and the overpotential in the charge and discharge process is 93mV (the overpotential is less than and the cycle life is better than that of the unmodified cellulose diaphragm in the example 1). Compared with the unmodified ultrathin cellulose diaphragm in the embodiment 1, the copper/carbon composite material surface functional layer modified ultrathin cellulose diaphragm is more beneficial to realizing a stable zinc negative electrode, especially under relatively higher current density and cut-off capacity.
Example 7
Preparation of candle ash surface functional layer modified ultrathin cellulose diaphragm
(1) 12.6mg of hydroxyl cellulose nano-fiber (CNF-H2, purchased from Jinhao Green nano-materials GmbH, Zhejiang) is dispersed in deionized water to prepare a dispersion with the concentration of the hydroxyl cellulose nano-fiber of 0.5mg/mL, 6.3mg of candle ash (with the particle size of 40-50nm) is dispersed in ethanol to prepare a dispersion with the concentration of the candle ash of 0.5mg/mL, and the two suspensions are uniformly dispersed by ultrasound. Sequentially filtering the two dispersions by a vacuum filtration method to obtain a nylon filter membrane (type: Tianjin Jinteng microporous organic filter membrane, aperture is 0.2 μm) substrate, drying at room temperature for 8 hours, and stripping off the filter membrane substrate to obtain the candle ash surface functional layer modified ultrathin cellulose diaphragm. Because the test adopts a zinc-zinc symmetrical battery, two candle ash surface functional layer modified ultrathin cellulose diaphragms are needed to be overlapped for use, and the candle ash surface functional layer surfaces of the two diaphragms respectively face the two zinc foils to protect two zinc-zinc electrodes. Therefore, the surface work of the candle ashThe total loading capacity of the energy layer modified ultrathin cellulose diaphragm hydroxyl cellulose nano-fiber is 2mg/cm2The total loading capacity of the candle ash is 1mg/cm2Wherein the total loading amount refers to the total loading amount in the two candle ash surface functional layer modified ultrathin cellulose diaphragms.
(2) A zinc sheet with the diameter of 10mm and a candle ash surface function modified ultrathin cellulose diaphragm with the diameter of 16mm are assembled into a zinc-zinc symmetrical battery (wherein the surface of a functional layer faces a zinc cathode) by adopting a CR2032 type button battery case to carry out electrochemical performance test so as to discuss the inhibition effect of the candle ash surface functional layer modified ultrathin cellulose diaphragm on zinc dendrites. The electrolyte is 2mol/L zinc sulfate aqueous solution, the assembled battery is stood for 6 hours at room temperature, so that the electrolyte fully infiltrates the candle ash surface functional layer modified ultrathin cellulose diaphragm, and then an electrochemical performance test is carried out.
(3) At 1mA/cm2Current density of 0.5mAh/cm2The cut-off capacity of the zinc-zinc symmetric battery is used as a test condition to perform constant current charge and discharge tests, and the zinc-zinc symmetric battery adopting the candle ash surface functional layer modified ultrathin cellulose diaphragm still has no short circuit phenomenon after 1620 hours of charge and discharge behaviors, so that the zinc-zinc symmetric battery is more beneficial to realizing a stable zinc cathode compared with the unmodified cellulose diaphragm in the embodiment 1.
Example 8
Preparation of cellulose nanofiber derived carbon surface functional layer modified ultrathin cellulose diaphragm
(1) Dispersing 12.6mg of hydroxyl cellulose nano-fiber (CNF-H1, purchased from Jinjiahao green nano-material GmbH, Zhejiang) in deionized water to prepare a dispersion with the concentration of the hydroxyl cellulose nano-fiber of 0.5mg/mL, calcining the commercial hydroxyl cellulose nano-fiber in a tubular furnace at 1000 ℃ and in a hydrogen/argon mixed atmosphere (the volume fraction of hydrogen is 5%) for 1 hour, dispersing 6.3mg of cellulose nano-fiber derived carbon prepared at a heating rate of 5 ℃/min and 0.63mg of cellulose nano-fiber binder in the deionized water to prepare a dispersion with the concentration of the cellulose nano-fiber derived carbon of 0.5mg/mL, and uniformly dispersing the two suspensions by ultrasound. Sequentially filtering the dispersion liquid to obtainMixing a cellulose water system filter membrane (type: Tianjin Jinteng microporous water system filter membrane, aperture is 0.8 μm) substrate, drying for 8 hours at room temperature, stripping off the filter membrane substrate, and obtaining the cellulose nano-fiber derived carbon surface function modified ultrathin cellulose diaphragm. Because a zinc-zinc symmetrical battery is adopted in the test, two cellulose nanofiber derived carbon surface functional layer modified ultrathin cellulose diaphragms are needed to be used in a superposed mode, and the cellulose nanofiber derived carbon surface functional layer surfaces of the two diaphragms respectively face the two zinc foils so as to protect two zinc-zinc electrodes. Therefore, the total loading of the cellulose nanofiber-derived carbon surface functional layer-modified ultrathin cellulose diaphragm hydroxyl cellulose nanofiber is 2mg/cm2The total loading of the cellulose nanofiber derived carbon is 1mg/cm2Wherein the total loading refers to the total loading in the two cellulose nano-derived carbon surface functional layer modified ultrathin cellulose diaphragms.
(2) A zinc sheet with the diameter of 10mm and a cellulose nanofiber derived carbon surface functional layer modified ultrathin cellulose diaphragm with the diameter of 16mm are assembled into a zinc-zinc symmetrical battery (wherein the surface of the functional layer faces a zinc cathode) by adopting a CR2032 type button battery case to carry out an electrochemical performance test so as to discuss the inhibition effect of the cellulose nanofiber derived carbon surface functional layer modified ultrathin cellulose diaphragm on zinc dendrites. The electrolyte is 2mol/L zinc sulfate aqueous solution, the assembled battery is stood for 6 hours at room temperature, so that the electrolyte is fully soaked in the cellulose nanofiber derived carbon surface functional layer modified ultrathin cellulose diaphragm, and then the electrochemical performance test is carried out.
(3) At 5mA/cm2Current density of 2.5mAh/cm2The cut-off capacity of (d) was used as a test condition to perform a constant current charge and discharge test, and the charge and discharge curve thereof is shown in fig. 9. The zinc-zinc symmetrical battery adopting the cellulose nanofiber derived carbon surface functional layer modified ultrathin cellulose diaphragm still has no short circuit phenomenon after 815 hours of charging and discharging, the overpotential in the charging and discharging process is 73mV (the overpotential is less than, and the cycle life is longer than that of the unmodified ultrathin cellulose diaphragm in example 1), and the unmodified cellulose diaphragm in comparative example 1 is more beneficial to realizing a stable zinc cathode.
Example 9
Preparation of nano barium titanate modified ultrathin cellulose diaphragm
(1) 25.2mg of hydroxyl cellulose nano-fiber (CNF-H1, available from Jinjiahao Green nano-materials GmbH, Zhejiang) and 12.6mg of commercial nano-barium titanate (particle size less than 100nm, available from Shanghai Aladdin Biotechnology GmbH) were dispersed in deionized water to prepare a dispersion with a cellulose nano-fiber concentration of 0.5mg/mL and a nano-barium titanate concentration of 0.25mg/mL, and the dispersion was uniformly dispersed by ultrasound. And (3) carrying out vacuum filtration on the mixed dispersion liquid to obtain a mixed cellulose water system filter membrane (type: Tianjin Jinteng microporous water system filter membrane, aperture is 0.8 μm). Drying at room temperature for 8 hours, stripping off the filter membrane substrate to obtain the cellulose nanofiber with the loading of 2mg/cm2The loading amount of the nano barium titanate is 1mg/cm2The nanometer barium titanate modified ultrathin cellulose diaphragm.
(2) A zinc sheet with the diameter of 10mm and a nano barium titanate modified ultrathin cellulose diaphragm with the diameter of 16mm are assembled into a zinc-zinc symmetrical battery by adopting a CR2032 type button battery case to carry out electrochemical performance test so as to discuss the inhibition effect of the nano barium titanate modified ultrathin cellulose diaphragm on zinc dendrites. The electrolyte is 2mol/L zinc sulfate aqueous solution, the assembled battery is stood for 6 hours at room temperature, so that the electrolyte fully infiltrates the nano barium titanate modified ultrathin cellulose diaphragm, and then the electrochemical performance test is carried out.
(3) At 1mA/cm2Current density of 0.5mAh/cm2The cut-off capacity of (d) was used as a test condition to perform a constant current charge and discharge test, and the charge and discharge curve thereof is shown in fig. 10. The zinc-zinc symmetrical battery adopting the nano barium titanate modified ultrathin cellulose diaphragm still has no short circuit phenomenon after 1633 hours of charging and discharging, and is more beneficial to realizing a stable zinc cathode compared with the unmodified ultrathin cellulose diaphragm in the embodiment 1.
Example 10
Preparation of nano strontium titanate modified ultrathin cellulose diaphragm
(1) 25.2mg of carboxyl cellulose nano-fiber (purchased from Zhejiang gold Haoyao green nano-material Co., Ltd., model number)TOCNF) and 12.6mg of nano strontium titanate (with the particle size of 40-100nm) are dispersed in deionized water to prepare a dispersion liquid with the concentration of the carboxyl cellulose nano-fiber of 0.5mg/mL and the concentration of the nano strontium titanate of 0.25mg/mL, and the dispersion liquid is uniformly dispersed by ultrasonic. And (3) carrying out vacuum filtration on the mixed dispersion liquid to obtain a mixed cellulose water system filter membrane (type: Tianjin Jinteng microporous water system filter membrane, aperture is 0.8 μm). Drying at room temperature for 8 hours, stripping off the filter membrane substrate to obtain the carboxyl cellulose nanofiber with the load of 2mg/cm2The loading capacity of the nano strontium titanate is 1mg/cm2The nanometer strontium titanate modified ultrathin cellulose diaphragm.
(2) A zinc sheet with the diameter of 10mm and a nano strontium titanate modified ultrathin cellulose diaphragm with the diameter of 16mm are assembled into a zinc-zinc symmetrical battery by adopting a CR2032 button battery case to carry out electrochemical performance test so as to discuss the inhibition effect of the nano strontium titanate modified ultrathin cellulose diaphragm on zinc dendrites. The electrolyte is 2mol/L zinc sulfate aqueous solution, the assembled battery is stood for 6 hours at room temperature, so that the electrolyte is fully soaked in the nano strontium titanate modified ultrathin cellulose diaphragm, and then the electrochemical performance test is carried out.
(3) At 1mA/cm2Current density of 0.5mAh/cm2The cut-off capacity of the nano strontium titanate modified ultrathin cellulose diaphragm is used as a test condition to carry out a constant current charge and discharge test, and the zinc-zinc symmetrical battery adopting the nano strontium titanate modified ultrathin cellulose diaphragm still has no short circuit phenomenon after 1825 hours of charge and discharge behaviors, so that the zinc-zinc symmetrical battery is more beneficial to realizing a stable zinc cathode compared with the unmodified ultrathin cellulose diaphragm in the embodiment 1.
Example 11
Preparation of lead titanate modified ultrathin cellulose diaphragm
(1) 25.2mg of carboxyl cellulose nano-fiber (purchased from Jinjiahao green nano-material GmbH, Zhejiang, model number: TOCNF) and 12.6mg of lead titanate (particle size less than 1 μm) are dispersed in deionized water to prepare a dispersion liquid with the concentration of the carboxyl cellulose nano-fiber of 0.5mg/mL and the concentration of the lead titanate of 0.25mg/mL, and the dispersion liquid is uniformly dispersed by ultrasonic. Vacuum filtering to obtain mixed cellulose water system filter membrane (type: Tianjin Jinteng microporous water system filter membrane)Pore size 0.8 μm). Drying at room temperature for 8 hours, stripping off the filter membrane substrate to obtain the carboxyl cellulose nanofiber with the load of 2mg/cm2The lead titanate loading amount is 1mg/cm2The lead titanate modified ultrathin cellulose diaphragm.
(2) A zinc sheet with the diameter of 10mm and a lead titanate modified ultrathin cellulose diaphragm with the diameter of 16mm are assembled into a zinc-zinc symmetrical battery by adopting a CR2032 type button battery case to carry out electrochemical performance test so as to discuss the inhibition effect of the lead titanate modified ultrathin cellulose diaphragm on zinc dendrites. The electrolyte is 2mol/L zinc sulfate aqueous solution, the assembled battery is stood for 6 hours at room temperature, so that the electrolyte is fully soaked in the lead titanate modified ultrathin cellulose diaphragm, and then the electrochemical performance test is carried out.
(3) At 1mA/cm2Current density of 0.5mAh/cm2The cut-off capacity of the lead titanate modified ultrathin cellulose diaphragm is used as a test condition to carry out a constant current charge and discharge test, and the zinc-zinc symmetrical battery adopting the lead titanate modified ultrathin cellulose diaphragm still has no short circuit phenomenon after 1652 hours of charge and discharge behaviors, so that the lead titanate modified ultrathin cellulose diaphragm is more beneficial to realizing a stable zinc cathode compared with the unmodified ultrathin cellulose diaphragm in the embodiment 1.
Example 12
Preparation of nano lead zirconate modified ultrathin cellulose diaphragm
(1) Adding carboxylated cellulose nano-fiber purchased from Jinhao NanoTanjiao, Zhejiang, with the model of TOCNF, into an ethanol solution with the mass fraction of polyetherimide of 10%, reacting at 30 ℃ for 24 hours to prepare 25.2mg of amino cellulose nano-fiber and 12.6mg of nano-lead zirconate (with the particle size of 10-50nm), dispersing in deionized water to prepare a dispersion with the concentration of the amino cellulose nano-fiber of 0.5mg/mL and the concentration of the nano-lead zirconate of 0.25mg/mL, and uniformly dispersing by ultrasound. And (3) carrying out suction filtration on the mixed dispersion liquid to a substrate of a mixed cellulose water system filter membrane (type: a Tianjin Jinteng microporous water system filter membrane, the aperture is 0.8 mu m) by a vacuum suction filtration method. Drying at room temperature for 8 hours, stripping off the filter membrane substrate to obtain the amino cellulose nanofiber with the loading of 2mg/cm2The loading amount of the nano lead zirconate is 1mg/cm2The nanometer lead zirconate modified ultrathin cellulose diaphragm.
(2) A zinc sheet with the diameter of 10mm and a nano lead zirconate modified ultrathin cellulose diaphragm with the diameter of 16mm are assembled into a zinc-zinc symmetrical battery by adopting a CR2032 button battery case to carry out electrochemical performance test so as to discuss the inhibition effect of the nano lead zirconate modified ultrathin cellulose diaphragm on zinc dendrite. The electrolyte is 2mol/L zinc sulfate aqueous solution, the assembled battery is stood for 6 hours at room temperature, so that the electrolyte fully infiltrates the nano lead zirconate modified ultrathin cellulose diaphragm, and then the electrochemical performance test is carried out.
(3) At 1mA/cm2Current density of 0.5mAh/cm2The cut-off capacity of the nano lead zirconate ultrathin cellulose diaphragm is used as a test condition to carry out constant current charge and discharge tests, the zinc-zinc symmetrical battery adopting the nano lead zirconate modified ultrathin cellulose diaphragm still has no short circuit phenomenon after 1536 hours of charge and discharge behaviors, and compared with the unmodified ultrathin cellulose diaphragm in the embodiment 1, the zinc-zinc symmetrical battery is more beneficial to realizing a stable zinc cathode.
Example 13
Preparation of polyvinylidene fluoride modified ultrathin cellulose diaphragm
(1) 25.2mg of carboxyl cellulose nano-fiber (TOCNF, model, purchased from Jinjiahao Green nano materials GmbH, Zhejiang) was dispersed in deionized water to prepare a dispersion with a concentration of 0.5mg/mL of carboxyl cellulose nano-fiber, 12.6mg of polyvinylidene fluoride (average weight average molecular weight 400000) was dispersed in ethanol to prepare a dispersion with a concentration of 0.5mg/mL of polyvinylidene fluoride, and the two suspensions were uniformly dispersed by ultrasound. Sequentially filtering the two dispersions by vacuum filtration method to obtain nylon filter membrane (type: Tianjin Jinteng microporous organic filter membrane, pore diameter is 0.2 μm), drying at room temperature for 8 hr, and stripping off the filter membrane substrate to obtain carboxyl cellulose nanofiber with loading of 2mg/cm2The load capacity of the polyvinylidene fluoride is 1mg/cm2The polyvinylidene fluoride modified ultrathin cellulose diaphragm.
(2) A zinc sheet with the diameter of 10mm and a polyvinylidene fluoride modified ultrathin cellulose diaphragm with the diameter of 16mm are assembled into a zinc-zinc symmetrical battery by adopting a CR2032 type button battery case to carry out electrochemical performance test so as to discuss the inhibition effect of the polyvinylidene fluoride modified ultrathin cellulose diaphragm on zinc dendrites. The electrolyte is 2mol/L zinc sulfate aqueous solution, the assembled battery is stood for 6 hours at room temperature, so that the electrolyte is fully soaked in the polyvinylidene fluoride modified ultrathin cellulose diaphragm, and then the electrochemical performance test is carried out.
(3) At 1mA/cm2Current density of 0.5mAh/cm2The cut-off capacity of the polyvinylidene fluoride modified ultrathin cellulose diaphragm is used as a test condition to carry out constant current charge and discharge tests, and the zinc-zinc symmetrical battery adopting the polyvinylidene fluoride modified ultrathin cellulose diaphragm still has no short circuit phenomenon after 1687 hours of charge and discharge behaviors, so that the zinc-zinc symmetrical battery is more beneficial to realizing a stable zinc cathode compared with the unmodified ultrathin cellulose diaphragm in the embodiment 1.
Example 14
Preparation of polyethylene oxide modified ultrathin cellulose diaphragm
(1) 25.2mg of hydroxycellulose nanofibers (purchased from jinghanhao green nano materials ltd., zhejiang, No., model number CNF-H2) were dispersed in deionized water to prepare a dispersion with a hydroxycellulose nanofiber concentration of 0.5mg/mL, 12.6mg of polyethylene oxide (average viscosity average molecular weight 2000000) was dispersed in ethanol to prepare a dispersion with a polyethylene oxide concentration of 0.5mg/mL, and the two suspensions were uniformly dispersed by ultrasound. Sequentially filtering the two dispersions by vacuum filtration method to obtain nylon filter membrane (type: Tianjin Jinteng microporous organic filter membrane, pore diameter is 0.2 μm), drying at room temperature for 8 hr, and stripping off the filter membrane substrate to obtain hydroxyl cellulose nanofiber with loading of 2mg/cm2The loading amount of the polyethylene oxide is 1mg/cm2The polyethylene oxide modified ultrathin cellulose diaphragm.
(2) A zinc sheet with the diameter of 10mm and a polyethylene oxide modified ultrathin cellulose diaphragm with the diameter of 16mm are assembled into a zinc-zinc symmetrical battery by adopting a CR2032 type button battery case to carry out electrochemical performance test so as to discuss the inhibition effect of the polyethylene oxide modified ultrathin cellulose diaphragm on zinc dendrites. The electrolyte is 2mol/L zinc sulfate aqueous solution, the assembled battery is stood for 6 hours at room temperature, so that the electrolyte is fully soaked in the polyethylene oxide modified ultrathin cellulose diaphragm, and then the electrochemical performance test is carried out.
(3) Is based on 1mAcm2Current density of 0.5mAh/cm2The cut-off capacity of the zinc-zinc battery is used as a test condition to perform constant current charge and discharge tests, and the zinc-zinc symmetrical battery adopting the polyethylene oxide modified ultrathin cellulose diaphragm still has no short circuit phenomenon after 1468 hours of charge and discharge behaviors, so that the zinc-zinc symmetrical battery is more beneficial to realizing a stable zinc cathode compared with the unmodified ultrathin cellulose diaphragm in the embodiment 1.
Comparative example 1
(1) A zinc sheet with the diameter of 10mm and a non-woven fabric diaphragm with the diameter of 16mm (the thickness is 200 mu m, the aperture is 10-200 mu m) which are punched by a punching machine are assembled into a zinc-zinc symmetrical battery by adopting a CR2032 type button battery case for carrying out electrochemical performance test. The electrolyte adopts 2mol/L zinc sulfate aqueous solution, and the assembled battery is stood for 6 hours at room temperature to enable the electrolyte to fully infiltrate the non-woven fabric diaphragm for electrochemical performance test.
(2) At 1mA/cm2Current density of 0.5mAh/cm2The cut-off capacity of (d) was used as a test condition to perform a constant current charge and discharge test, and the charge and discharge curve thereof is shown in fig. 11. After 6 hours of charge and discharge, the zinc-zinc symmetrical battery using the non-woven fabric as the diaphragm has short circuit.
Comparative example 2
(1) A zinc sheet with the diameter of 10mm and a commercial cellulose paper diaphragm with the diameter of 16mm (the manufacturer is Mitsubishi, Japan, the thickness is 36 μm, and the aperture is 0.5-2 μm) which are punched by a punching machine are assembled into a zinc-zinc symmetrical battery by adopting a CR2032 type button battery case for carrying out electrochemical performance test. The electrolyte is 2mol/L zinc sulfate aqueous solution, and the assembled battery is stood for 6 hours at room temperature to enable the electrolyte to fully infiltrate the non-woven fabric diaphragm for electrochemical performance test.
(2) At 1mA/cm2Current density of 0.5mAh/cm2The cut-off capacity of (d) was used as a test condition to perform a constant current charge and discharge test, and the charge and discharge curve thereof is shown in fig. 12. After a zinc-zinc symmetrical battery adopting commercial cellulose paper as a diaphragm is subjected to charge-discharge behavior for 2 hours, a short circuit phenomenon occurs.
Comparative example 3
(1) A zinc sheet with the diameter of 10mm and a glass fiber diaphragm (the model is Whatman GF/A, the thickness is 260 mu m, and the pore diameter is about 1-100 mu m) with the diameter of 16mm, which are punched by a punching machine, are assembled into a zinc-zinc symmetrical battery by a CR2032 type button battery case for electrochemical performance test. The electrolyte is 2mol/L zinc sulfate aqueous solution, and the assembled battery is stood for 6 hours at room temperature to enable the electrolyte to fully infiltrate the commercial glass fiber diaphragm for electrochemical performance test.
(2) At 1mA/cm2Current density of 0.5mAh/cm2The cut-off capacity of (d) was used as a test condition to perform a constant current charge and discharge test, and the charge and discharge curve thereof is shown in fig. 13. After a zinc-zinc symmetrical battery adopting commercial glass fiber as a diaphragm is subjected to charging and discharging behaviors for 40 hours, a short circuit phenomenon occurs.
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 modifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of a modified ultrathin cellulose diaphragm is characterized by comprising the following steps:
(1) uniformly dispersing cellulose nano-fibers in water to obtain a cellulose water system suspension; dispersing the functional material into a solvent to obtain a suspension 2;
(2) the step is the following step (2.1) or step (2.2):
(2.1) blending the cellulose aqueous suspension and the suspension 2, then carrying out suction filtration on the mixture to obtain a filter membrane substrate, drying the filter membrane substrate at room temperature, and stripping off the filter membrane substrate to obtain a modified ultrathin cellulose diaphragm;
or (2.2) filtering the cellulose water system suspension onto the filter membrane substrate to obtain an ultrathin cellulose diaphragm substrate, and filtering the suspension 2 onto the obtained ultrathin cellulose diaphragm substrate to obtain a modified ultrathin cellulose diaphragm;
the functional material in the step (1) comprises at least one of zirconium hydrogen phosphate nanosheets, silica nanofibers, nano zinc oxide, nano aluminum oxide, halloysite nanotubes, nano tin, copper nanowires, copper/carbon composite materials, candle ash, cellulose nanofiber derived carbon, barium titanate, strontium titanate, barium strontium titanate, bismuth titanate, lead zirconate, sodium bismuth titanate, barium strontium titanate, cadmium niobate, polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate and polyethylene oxide.
2. The method for preparing the modified ultrathin cellulose membrane as claimed in claim 1, wherein the method comprises the following steps:
the cellulose nano-fiber in the step (1) contains at least one of carboxyl, hydroxyl and amino functional groups;
the diameter of the cellulose nano-fiber in the step (1) is 5-200nm, and the length is 0.5-20 μm.
3. The method for preparing the modified ultrathin cellulose membrane as claimed in claim 1, wherein the method comprises the following steps:
the solvent used for dispersing the functional material in the step (1) is one of water, an organic solvent or a water/organic solvent mixture;
the dosage of the functional material and the solvent in the step (1) meets the following requirements: the concentration of the functional material in the solvent is 0.05-10 mg/mL;
the concentration of the cellulose dispersion liquid in the step (1) is 0.5-1 mg/mL.
4. The method for preparing the modified ultrathin cellulose membrane as claimed in claim 1, characterized in that:
the cellulose water-based suspension and the suspension 2 described in the step (2.1) and the step (2.2) are used in amounts satisfying: the loading capacity of the cellulose nano-fiber is 0.5-10mg/cm2Preferably 1 to 6mg/cm2(ii) a The loading capacity of the functional material is 0.1-9mg/cm2Preferably 0.3 to 5mg/cm2(ii) a The mass fraction of the functional material in the modified ultrathin cellulose diaphragm is 0-90%, preferably 5-50%.
5. The method for preparing the modified ultrathin cellulose membrane as claimed in claim 1, wherein the method comprises the following steps:
and (3) mixing a certain proportion of cellulose nanofibers into the suspension 2 in the step (2.2) to play a role of a binder, wherein the mixed cellulose nanofibers account for 0-20% of the functional material by mass percent.
6. The method for preparing the modified ultrathin cellulose membrane as claimed in claim 1, wherein the method comprises the following steps:
the filter membrane substrate in the step (2.1) and the step (2.2) is a mixed cellulose water system filter membrane or a nylon filter membrane, and the aperture is 0.01-2 mu m; the mixed cellulose water system filter membrane is suitable for the case that the solvent in the step (1) is water, and the nylon filter membrane is suitable for the case that the solvent in the step (1) is an organic solvent or water or a mixture of the organic solvent and the water.
7. A modified ultrathin cellulose membrane prepared according to the method of any one of claims 1-6.
8. The modified ultrathin cellulose membrane of claim 7, characterized in that: the thickness of the modified ultrathin cellulose diaphragm is 3-80 μm, and preferably 5-40 μm.
9. Use of the modified ultrathin cellulose membrane of claim 7 or 8 in an aqueous zinc-based energy storage system.
10. An aqueous zinc-based energy storage system characterized by comprising the modified ultrathin cellulose membrane of claim 7 or 8.
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| CN112332026A (en) * | 2020-11-19 | 2021-02-05 | 宿迁德特材料科技有限公司 | Zinc ion battery diaphragm for inhibiting zinc dendrite and preparation method thereof |
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