CN116790024B - Nanocellulose composite aerogel, preparation method thereof and photovoltaic power generation device - Google Patents
Nanocellulose composite aerogel, preparation method thereof and photovoltaic power generation device Download PDFInfo
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- CN116790024B CN116790024B CN202310711747.7A CN202310711747A CN116790024B CN 116790024 B CN116790024 B CN 116790024B CN 202310711747 A CN202310711747 A CN 202310711747A CN 116790024 B CN116790024 B CN 116790024B
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- 239000004964 aerogel Substances 0.000 title claims abstract description 184
- 239000002131 composite material Substances 0.000 title claims abstract description 165
- 229920001046 Nanocellulose Polymers 0.000 title claims abstract description 133
- 238000010248 power generation Methods 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 239000006185 dispersion Substances 0.000 claims abstract description 114
- 238000000034 method Methods 0.000 claims abstract description 91
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 72
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 70
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 70
- 239000007788 liquid Substances 0.000 claims abstract description 62
- 229920002678 cellulose Polymers 0.000 claims abstract description 52
- 239000001913 cellulose Substances 0.000 claims abstract description 52
- 238000001035 drying Methods 0.000 claims abstract description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical class CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 28
- 230000008014 freezing Effects 0.000 claims abstract description 21
- 238000007710 freezing Methods 0.000 claims abstract description 21
- 238000004132 cross linking Methods 0.000 claims abstract description 18
- 238000010008 shearing Methods 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 239000012266 salt solution Substances 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 10
- 239000011240 wet gel Substances 0.000 claims abstract description 10
- 238000013329 compounding Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 122
- 239000008367 deionised water Substances 0.000 claims description 32
- 229910021641 deionized water Inorganic materials 0.000 claims description 32
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000004033 plastic Substances 0.000 claims description 25
- 230000003647 oxidation Effects 0.000 claims description 24
- 238000007254 oxidation reaction Methods 0.000 claims description 24
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 22
- 230000008569 process Effects 0.000 claims description 16
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 238000003466 welding Methods 0.000 claims description 10
- 238000001723 curing Methods 0.000 claims description 9
- 239000012286 potassium permanganate Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 7
- 239000011121 hardwood Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 claims description 6
- 239000005060 rubber Substances 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 239000011122 softwood Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 4
- 238000002715 modification method Methods 0.000 claims description 4
- XTAKVLHYTSGUGS-UHFFFAOYSA-M sodium nitric acid nitrite Chemical compound [Na+].[O-]N=O.O[N+]([O-])=O XTAKVLHYTSGUGS-UHFFFAOYSA-M 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 claims description 3
- 230000021523 carboxylation Effects 0.000 claims description 2
- 238000006473 carboxylation reaction Methods 0.000 claims description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims 1
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 16
- 239000002904 solvent Substances 0.000 abstract description 10
- 239000000523 sample Substances 0.000 description 29
- 238000010257 thawing Methods 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 21
- 239000011148 porous material Substances 0.000 description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 15
- 238000012360 testing method Methods 0.000 description 15
- 239000011888 foil Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 230000009471 action Effects 0.000 description 11
- 229910052782 aluminium Inorganic materials 0.000 description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 229910021645 metal ion Inorganic materials 0.000 description 11
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000004108 freeze drying Methods 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 9
- 238000011010 flushing procedure Methods 0.000 description 8
- 108091006146 Channels Proteins 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000010668 complexation reaction Methods 0.000 description 6
- 239000011889 copper foil Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
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- 239000000047 product Substances 0.000 description 6
- 239000003575 carbonaceous material Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 5
- 230000007774 longterm Effects 0.000 description 5
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- 238000012986 modification Methods 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 5
- 241001397809 Hakea leucoptera Species 0.000 description 4
- 239000005708 Sodium hypochlorite Substances 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- -1 aldehyde ketones Chemical class 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000012520 frozen sample Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000002090 nanochannel Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 229920000554 ionomer Polymers 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 description 1
- 108090000862 Ion Channels Proteins 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229960001149 dopamine hydrochloride Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- 238000000352 supercritical drying Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/009—Use of pretreated compounding ingredients
-
- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02N—ELECTRIC MACHINES NOT OTHERWISE PROVIDED FOR
- H02N3/00—Generators in which thermal or kinetic energy is converted into electrical energy by ionisation of a fluid and removal of the charge therefrom
-
- 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
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/04—Oxycellulose; Hydrocellulose
Abstract
The invention relates to a nano-cellulose composite aerogel, a preparation method thereof and a photovoltaic power generation device. The method comprises the following steps: modifying cellulose to contain carboxyl, mechanically treating to obtain modified nano cellulose, and preparing into modified nano cellulose aqueous dispersion; preparing carboxylated carbon nano-tubes into carboxylated carbon nano-tube aqueous dispersion liquid; compounding the modified nano cellulose aqueous dispersion with the carboxylated carbon nanotube aqueous dispersion, and maintaining under high-speed shearing condition to uniformly mix the modified nano cellulose aqueous dispersion and the carboxylated carbon nanotube aqueous dispersion to obtain modified nano cellulose and carboxylated carbon nanotube composite dispersion; standing the composite dispersion liquid, defoaming, freezing, immersing in absolute ethyl alcohol/metal salt solution after freezing, dissolving and crosslinking to obtain wet gel; washing the wet gel with absolute ethyl alcohol, and drying at normal temperature to obtain the nano cellulose composite aerogel. The invention obtains the nano cellulose composite aerogel through simple mechanical treatment and normal pressure solvent exchange drying, is used for the photovoltaic power generation, and realizes the high-efficiency conversion of electric energy.
Description
Technical Field
The invention belongs to the technical field of aerogel preparation, and particularly relates to a nano-cellulose composite aerogel, a preparation method thereof and a photovoltaic power generation device.
Background
The water resource maintains the energy circulation of the earth, the water energy utilization efficiency can be improved through water energy conversion, and the traditional water energy utilization mode is limited by various aspects such as climate, environment, cost, low conversion efficiency and the like. In the prior researches, environmental energy is absorbed by using a water circulation process through methods such as membrane technology, a mechanical engine, an electrochemical device and the like to construct flowing potential, so that the conversion from water energy to electric energy is realized, but the defects of time consumption, energy consumption and the like are overcome. The water flow flows through the micro-nano structure in the material, positive ions and negative ions form directional transfer, and an electric double layer is generated through capillary action, so that output voltage is generated, water resources are utilized more reasonably, and electric energy conversion is realized.
The solvent exchange drying method has become a research hot spot in recent years, the method is carried out under atmospheric pressure or low vacuum in a wider temperature range, the solvent (especially water) in wet gel is exchanged with low-polarity or nonpolar solvents (such as acetone, ethanol, hexane, pentane and the like), the porous material can be prepared by utilizing the characteristic that the exchanged solvent is easy to volatilize and is dried under normal pressure, no limitation of a specific instrument is needed, the energy consumption and the cost can be reduced, but the method is not applicable to all raw materials, the internal network structure of the material still can collapse to a certain extent due to capillary force in the drying process, and the wet strength is poor, so that the method cannot be well applied to the transformation of hydropower energy.
The prior art discloses a Janus water-based photovoltaic power generation material, which adopts a three-step method of reduction-freeze-drying-tabletting, graphene oxide or graphite oxide powder is firstly dispersed in deionized water to obtain a carbon material dispersion liquid, part of the dispersion liquid is subjected to chemical reduction through dopamine hydrochloride and tris (hydroxymethyl) aminomethane to obtain a reduced carbon material dispersion liquid, the other part of the carbon material dispersion liquid is not treated, the two dispersion liquids are respectively subjected to freeze-drying to obtain a porous material, and the porous material is obtained by tabletting after stacking (see figure 1), wherein the output power generation performance of the porous material can reach 400mV. According to the method, the Janus carbon material is used as a raw material, a freeze-drying mode is adopted to prepare the Janus carbon material, the preparation process is complex, specific instruments and equipment are needed for freeze-drying, the production period is long, time and energy are consumed, and the power generation output performance is still to be improved.
Disclosure of Invention
In view of the above, the main object of the present invention is to provide a nano-cellulose composite aerogel, a preparation method thereof and a photovoltaic power generation device, which aims to solve the technical problems that the nano-cellulose composite aerogel is prepared by simple mechanical treatment and normal pressure solvent exchange drying mode, so as to be used for the photovoltaic power generation and realize the efficient conversion of electric energy; the nano cellulose composite aerogel has higher output voltage and can be kept stable for a long time.
The aim and the technical problems of the invention are realized by adopting the following technical proposal. The invention provides a preparation method of nano-cellulose composite aerogel, which comprises the following steps:
1) Modifying cellulose to contain carboxyl, mechanically treating to obtain modified nano cellulose, and preparing into modified nano cellulose aqueous dispersion;
2) Preparing carboxylated carbon nano-tubes into carboxylated carbon nano-tube aqueous dispersion liquid;
3) Compounding the modified nano cellulose aqueous dispersion obtained in the step 1) with the carboxylated carbon nano tube aqueous dispersion obtained in the step 2) in proportion, and keeping the mixture for 0.5 to 2 hours under the high-speed shearing condition to uniformly mix the mixture, so as to obtain modified nano cellulose and carboxylated carbon nano tube composite dispersion;
4) Standing the modified nano cellulose and carboxylated carbon nanotube composite dispersion liquid obtained in the step 3), defoaming, freezing, taking out, soaking in absolute ethyl alcohol/metal salt solution after the modified nano cellulose and carboxylated carbon nanotube composite dispersion liquid are sufficiently frozen, dissolving and crosslinking to obtain wet gel;
5) Washing the wet gel obtained in the step 4), and drying under normal pressure to obtain the nano cellulose composite aerogel with the porous orientation structure.
The aim and the technical problems of the invention can be further realized by adopting the following technical measures.
Preferably, in the aforementioned preparation method of the nanocellulose composite aerogel, in step 1), the carboxyl content of the modified cellulose is 1.3-2.5mmol/g.
Preferably, in the preparation method of the nanocellulose composite aerogel, in the step 1), the mass concentration of the modified nanocellulose aqueous dispersion is 0.8-2%.
Preferably, in the foregoing method for preparing a nanocellulose composite aerogel, in step 1), the nanocellulose raw material is selected from at least one of bleached sulfate softwood pulp, bleached sulfate hardwood pulp, bleached sulfite softwood pulp and bleached sulfite hardwood.
Preferably, in the foregoing method for preparing a nanocellulose composite aerogel, in step 1), the cellulose modification method is selected from one of TEMPO oxidation, periodic acid oxidation, nitric acid-sodium nitrite oxidation, potassium permanganate oxidation and ammonium persulfate oxidation; the diameter of the modified nano cellulose is 15-80nm, the length is more than 1 mu m, and the carboxyl content is 0.3-2.5mmol/g.
Preferably, in the aforementioned method for preparing a nanocellulose composite aerogel, in step 1), the mechanical treatment of the modified cellulose comprises the following steps:
Circularly homogenizing the modified cellulose for 3-5 times under 100-120mPa pressure by using a high-pressure homogenizer.
Preferably, in the foregoing method for preparing a nanocellulose composite aerogel, in step 1), preparing a modified nanocellulose aqueous dispersion includes the following steps:
adding the modified nano cellulose into water for dissolution, and stirring at a rotation speed of 500-1000rpm until no caking exists.
Preferably, in the preparation method of the nanocellulose composite aerogel, in step 1), in step 2), the mass concentration of the carboxylated carbon nanotube aqueous dispersion is 0.8-2%.
Preferably, in the aforementioned preparation method of the nanocellulose composite aerogel, in the step 2), the preparation of the carboxylated carbon nanotube aqueous dispersion liquid includes the following steps: stirring carboxylated carbon nanotubes for 15-35min at 500-800rpm, and dispersing in deionized water.
Preferably, in the aforementioned preparation method of the nanocellulose composite aerogel, in step 2), the diameter of the carboxylated carbon nanotubes is 5-70nm, and the length is 2-40 μm.
Preferably, in the foregoing method for preparing a nanocellulose composite aerogel, in step 3), the high-speed shearing condition is: 5000-10000rpm.
Preferably, in the aforementioned preparation method of the nanocellulose composite aerogel, in the step 3), the absolute dry mass ratio of the modified nanocellulose aqueous dispersion liquid obtained in the step 1) to the carboxylated carbon nanotube aqueous dispersion liquid obtained in the step 2) is (1-4): 1, and the total absolute dry mass of the modified nanocellulose aqueous dispersion liquid and the carboxylated carbon nanotube aqueous dispersion liquid is 0.8-2% of the total dispersion liquid mass.
Preferably, the aforementioned method for preparing a nanocellulose composite aerogel, wherein in step 4), the static defoaming is performed in a plastic, rubber or metal container having a low temperature resistance of at least-80 ℃; the plastic, rubber or metal container has a shape selected from one of a cylinder, a rectangular parallelepiped and a polygonal body.
Preferably, in the aforementioned preparation method of the nanocellulose composite aerogel, in step 4), the freezing temperature is-80 ℃ to-20 ℃; the temperature of the absolute ethyl alcohol/metal salt solution is-20 ℃ to-5 ℃; the crosslinking time is 60-84h.
Preferably, in the aforementioned method for preparing a nanocellulose composite aerogel, in step 4), the solute of the absolute ethanol/metal salt solution is selected from FeCl 3 、CuCl 2 、CaCl 2 、AlCl 3 And MgCl 2 At least one of them, the concentration is 0.5-2wt%.
Preferably, in the aforementioned method for preparing a nanocellulose composite aerogel, in step 4), the washing is performed by using absolute ethanol.
Preferably, in the aforementioned method for preparing a nanocellulose composite aerogel, in step 5), the drying temperature is room temperature to 120 ℃.
The aim of the invention and the technical problems are also achieved by adopting the following technical proposal. According to the nano cellulose composite aerogel provided by the invention, the nano cellulose composite aerogel prepared according to the preparation method has a porous orientation structure, the water adsorption performance reaches more than 48g/g within 3min, the compressive strength of more than 60% under a dry state is maintained under a compressive strain of 60% after the nano cellulose composite aerogel is soaked in water, and the dimensional change rate after the nano cellulose composite aerogel is soaked in water is less than 3%.
The aim of the invention and the technical problems are also achieved by adopting the following technical proposal. According to the manufacturing method of the photovoltaic power generation device provided by the invention, the photovoltaic power generation device is manufactured through the following steps:
(1) Fixing the wires on the upper side and the lower side of the prepared nano cellulose composite aerogel by using a spot welding method through conductive silver paste;
(2) And placing the nano cellulose composite aerogel on a culture dish filled with water, so that the lower end is immersed in the water, and the upper end is not contacted with the water, thus obtaining the photovoltaic power generation device.
The aim and the technical problems of the invention can be further realized by adopting the following technical measures.
Preferably, the method for manufacturing a photovoltaic power generation device, wherein the conductive wire is at least one selected from copper foil, aluminum foil, iron foil, carbon wire and nickel foil.
Preferably, in the foregoing method for manufacturing a photovoltaic power generation device, the fixing the conductive wire on the upper and lower sides of the prepared nanocellulose composite aerogel by using a spot welding method through conductive silver paste specifically includes the following steps: placing two wires on the surfaces of the upper side and the lower side of the composite aerogel, spot-coating conductive silver paste on the contact position of the wires and the composite aerogel, and drying and curing for 15-60min at 70-120 ℃.
The aim of the invention and the technical problems are also achieved by adopting the following technical proposal. According to the photovoltaic power generation device provided by the invention, the photovoltaic power generation device is manufactured according to the preparation method.
By means of the technical scheme, the nano cellulose composite aerogel and the preparation method thereof and the photovoltaic power generation device have at least the following advantages:
the nano cellulose composite aerogel prepared by the normal pressure solvent exchange drying method is crosslinked due to the complexation of metal ions and modified functional groups, and has a porous three-dimensional network structure; has extremely strong hydrophilicity, and the water adsorption performance can reach more than 48g/g within 3 min; has excellent mechanical properties, and can maintain the compressive strength of more than 60% in a dry state under 60% compressive strain in a water-soaked state; has certain dimensional stability, and the dimensional change rate after being soaked in water is less than 3 percent. Through the effective construction of the micro-nano structure of the nano cellulose composite aerogel, the nano cellulose composite aerogel can be applied to the water-borne power generation, the output power generation performance can reach 600mV, can be kept for 12 hours, has certain long-term stability, and can be recycled for more than 6 times.
According to the invention, the nano cellulose composite aerogel is prepared by a normal pressure drying method, and has certain mechanical strength and good hydrophilicity by virtue of the property of hydrophilic groups (hydroxyl and carboxyl) widely existing in aerogel materials and the porous micro-nano structure of the materials, so that the photovoltaic power generation performance is realized. According to the composite gas gel water-voltage power generation device, the dissociated ions are directionally transferred in the porous micro-nano structure of the material through water flow and capillary action by quickly absorbing water molecules, no external force or other energy is needed, ion concentration difference is generated on the material structure, output voltage is generated, high-efficiency electric energy conversion is realized, the power generation mode is less limited by environment, long-term stability is good, and the device can be applied to multiple scenes.
Compared with a supercritical drying method and a freeze drying method, the nano cellulose composite aerogel prepared by the normal pressure solvent exchange drying method does not depend on a specific instrument, reduces cost, has simple process, reduces energy consumption and time, and can be prepared in batches; compared with the traditional solvent exchange drying method, the method is constructed by biomass materials, and the adopted exchange solvent is nontoxic and harmless, has simple preparation process and low cost, does not collapse in the aerogel structure, and has certain mechanical strength performance. The prepared composite aerogel photovoltaic power generation performance is excellent, no external force or other energy is needed, the environment limitation is less, the power generation mode is highly spontaneous, the long-term stability is realized, the cyclic utilization is realized, and the application prospect is wide.
The foregoing description is only an overview of the present invention, and is intended to provide a better understanding of the present invention, as it is embodied in the following description, with reference to the preferred embodiments of the present invention and the accompanying drawings.
Drawings
FIG. 1 is a diagram of a preparation method of a Janus photovoltaic power generation material;
FIG. 2 is an SEM image of a composite aerogel of example 1 of the present invention;
FIG. 3 is a graph of the composite aerogel contact angle test of example 1 of the present invention;
FIG. 4 is a graph of the mechanical properties of the composite aerogel of example 1 of the present invention;
FIG. 5a is a graph of wet strength performance of a composite aerogel according to example 1 of the present invention;
FIG. 5b is a graph of the wet strength performance of the composite aerogel of comparative example 4 of the present invention;
FIG. 6a is a graph of the dimensional stability performance of the composite aerogel of example 1 of the present invention;
FIG. 6b is a graph of the dimensional stability performance of the composite aerogel of comparative example 4 of the present invention;
FIG. 7 is a graph of the wet mechanical properties of the composite aerogel of example 1 of the present invention;
FIG. 8 is a schematic diagram of the water-borne power generation of the composite aerogel of example 1 of the present invention;
FIG. 9 is a schematic diagram of the complex cross-linking of the composite aerogel of example 1 of the present invention;
FIG. 10 is a short-time hydropower electrogram of the composite aerogel of example 1 of the present invention;
FIG. 11 is a long-term hydroelectric electrogram of the composite aerogel of example 1 of the present invention;
FIG. 12 shows various ionomer (Fe 3+ 、Cu 2+ 、Ca 2+ 、Al 3+ 、Mg 2+ ) A prepared composite aerogel sample;
FIG. 13a is a graph of a composite aerogel sample of example 1 of the present invention;
FIG. 13b is a graph of a composite aerogel sample of comparative example 1 of the present invention;
FIG. 13c is a graph of a composite aerogel sample of comparative example 3 of the present invention;
FIG. 13d is a graph of a composite aerogel sample of comparative example 4 of the present invention;
FIG. 14 is a composite aerogel photovoltaic power generation diagram of example 1 and comparative example 4 of the present invention;
FIG. 15 is a composite aerogel cyclic electrogram of example 1 of the present invention.
Detailed Description
In order to further describe the technical means and effects adopted by the invention to achieve the preset aim, the following detailed description refers to the specific implementation, structure, characteristics and effects of the nano cellulose composite aerogel, the preparation method thereof and the photovoltaic power generation device according to the invention by combining the accompanying drawings and the preferred embodiment.
According to some embodiments of the present invention, a method for preparing a nanocellulose composite aerogel is provided, comprising the steps of:
step one, cellulose is modified to contain carboxyl groups. When the cellulose raw material is selected, at least one selected from bleached sulfate softwood pulp, bleached sulfate hardwood pulp, bleached sulfite softwood pulp and bleached sulfite hardwood pulp may be selected, and is not particularly limited herein; when cellulose is modified, the main modification method includes converting part of hydroxyl groups of cellulose into carboxyl groups by TEMPO oxidation, periodate oxidation, nitric acid-sodium nitrite oxidation, potassium permanganate oxidation, ammonium persulfate oxidation, and the like. According to the technical scheme, the nanocellulose is subjected to carboxylation treatment, so that part of hydroxyl groups of the nanocellulose are modified into carboxyl groups, and thus carboxyl groups on the modified cellulose and carboxylated carbon nanotubes can be subjected to electrostatic complexation and crosslinking reaction with metal ions to form a stable structure, so that the cellulose network structure is prevented from collapsing in the normal-pressure drying process of the subsequent process. Among them, TEMPO oxidation mechanism: the TEMPO (2, 6-tetramethyl piperidine oxide) reagent has the function of selective oxidation, and free electrons on nitroxyl radicals in TEMPO molecules are activated under the action of NaBr and NaClO, so that the hydroxyl groups at the C6 position on cellulose can be oxidized into carboxyl groups. Periodic acid oxidation mechanism: hydroxy at C2 and C3 positions on cellulose The groups are broken by oxidation under the action of periodic acid and quantitatively converted into the corresponding aldehyde ketones, which are further oxidized to the corresponding carboxyl groups when periodic acid is present in excess. Nitric acid-sodium nitrite oxidation process: by liberating nitronium ions (NO) from nitric acid and nitrite in the presence of excess acid 2+ ) The resulting nitronium ions attack the primary hydroxyl groups of cellulose and produce aldehyde intermediates, which then produce carboxylate groups. The oxidation mechanism of potassium permanganate is that hydroxy group on cellulose C6 leads MnO 4 - Reduction to Mn 2+ . Excess MnO 4 - Continuing to add Mn 2+ Oxidation to MnO 2 MnO2 is used as an auto-catalyst, so that the system has high oxidability, and hydroxyl groups at the position of cellulose are oxidized into carboxyl groups. Ammonium persulfate oxidation process mechanism: s is S 2 O 8 2- Rapidly decomposing to form sulfate radical, and then generating HSO 4 - Peroxy radicals and sulfate radicals oxidize hydroxyl groups at the C6 position of cellulose to carboxyl groups.
Further, the carboxyl group concentration of the modified cellulose is 1.3-2.5mmol/g. When the carboxyl content is within this range, the formed nanofibers can form a relatively high viscosity, transparent gel without clogging the homogenizer. When cellulose is modified, the carboxyl degree of the obtained modified cellulose is different through different modification methods and degrees, the replacement degree in an absolute ethyl alcohol/metal salt solution is different, the fixed crosslinking effect of the modified cellulose on the composite aerogel is also different, and further the application of the modified cellulose in the photovoltaic power generation is influenced, and the carboxyl of the cellulose surface has a key effect on the formation and the subsequent application of the nano cellulose composite aerogel in a subsequent process. The key point is that the nano cellulose composite aerogel holes cannot collapse in the normal pressure drying process and the water-based power generation process in the later period.
In addition, the modified nano cellulose prepared by modification and mechanical treatment is prepared into modified nano cellulose aqueous dispersion; wherein, the mechanical treatment mode of the modified cellulose is as follows: circularly homogenizing the modified cellulose with a high-pressure homogenizer for 3-5 times under a pressure of 100-120 mPa. Wherein, preparing modified nano cellulose aqueous dispersion liquid specifically comprises the following steps: the modified nano cellulose is added into water for dissolution, and is stirred at the rotating speed of 500-1000rpm until no caking exists. If the rotating speed is lower than 500rpm, the stirring is not uniform due to the too small rotating speed; if the rotation speed is higher than 1000rpm, it is difficult to secure safety due to the too high rotation speed. The modified nano cellulose is prepared into modified nano cellulose aqueous dispersion liquid by the steps, and the mass concentration of the modified nano cellulose aqueous dispersion liquid is 0.8-2%. If the mass concentration is less than 0.8%, the mass concentration is too low to affect the balance of the solid content and the like in the formula, so that the formula is difficult to implement; if the mass concentration is more than 2%, the mass concentration is too high to be uniformly dispersed.
Preparing carboxylated carbon nano-tubes into carboxylated carbon nano-tube aqueous dispersion liquid; in selecting carboxylated carbon nanotubes, carboxylated carbon nanotubes having a diameter of 5 to 70nm and a length of 2 to 40 μm may be selected, and are not particularly limited herein. Wherein, preparing carboxylated carbon nano tube aqueous dispersion liquid specifically comprises the following steps: stirring carboxylated carbon nanotubes at 500-800rpm, and dispersing in deionized water. If the rotating speed is lower than 500rpm, the stirring is difficult to be uniform due to the too low rotating speed; if the rotation speed is higher than 800rpm, it is difficult to secure safety due to the too high rotation speed. The carboxylated carbon nano tube is prepared into carboxylated carbon nano tube aqueous dispersion liquid, and the mass concentration of the carboxylated carbon nano tube aqueous dispersion liquid is 0.8-2%. If the mass concentration is less than 0.8%, the mass concentration is too low to affect the balance of the solid content and the like in the formula, so that the formula is difficult to implement; if the mass concentration is more than 2%, the mass concentration is too high to be uniformly dispersed.
Step three, compounding the modified nano cellulose aqueous dispersion obtained in the step one with the carboxylated carbon nano tube aqueous dispersion obtained in the step two in proportion, and keeping the mixture for 0.5 to 2 hours under the high-speed shearing condition to uniformly mix the mixture, so as to obtain modified nano cellulose and carboxylated carbon nano tube composite dispersion; the modified nano-cellulose aqueous dispersion and the carboxylated carbon nano-tube aqueous dispersion are compounded in proportion by controlling high-speed shearing conditions, wherein the high-speed shearing conditions are set as follows: 5000-12000rpm; if the rotation speed is less than 5000rpm, dispersion is difficult due to too low rotation speed; if the rotation speed is higher than 12000rpm, it is difficult to secure safety due to the too high rotation speed. The absolute mass ratio of the modified nano cellulose to the carboxylated carbon nanotube aqueous dispersion liquid is (1-4): 1, for example, may be 1:1, 2:1, 3:1, 4:1, the total amount of both accounting for 0.8-2% of the total dispersion solid content (meaning that the total absolute dry mass of carboxylated carbon nanotubes and modified cellulose accounts for 0.8-2% of the total mass, if less than 0.8%, aerogel cannot be formed due to too low a ratio, and if more than 2%, aerogel prepared due to too high a mass concentration cannot form porous structure, and the structure is dense). If the absolute mass ratio of the modified nano cellulose aqueous dispersion to the carboxylated carbon nanotube aqueous dispersion is less than 1:1, aerogel cannot be formed due to too little nano cellulose content; if the absolute mass ratio of the nano cellulose aqueous dispersion to the carboxylated carbon nanotube aqueous dispersion is greater than 4:1, the aerogel has small pores due to too much nano cellulose, and a network structure cannot be formed for carrying out water molecule transportation so as to generate electricity.
Fourthly, standing the modified nano cellulose and carboxylated carbon nanotube composite dispersion liquid obtained in the third step for defoaming, freezing, taking out the modified nano cellulose and carboxylated carbon nanotube composite dispersion liquid after the modified nano cellulose and carboxylated carbon nanotube composite dispersion liquid are sufficiently frozen, soaking the modified nano cellulose and carboxylated carbon nanotube composite dispersion liquid in an absolute ethyl alcohol/metal salt solution, dissolving and crosslinking the modified nano cellulose and carboxylated carbon nanotube composite dispersion liquid to obtain wet gel; wherein the freezing process is performed in a plastic, rubber or metal container having a low temperature resistance of at least-80 ℃ because the freezing container needs to have a certain low temperature resistance to prevent deformation; the shape of the plastic, rubber or metal container is selected from one of various shapes such as a cylinder, a rectangular parallelepiped, etc., and the shape thereof is not particularly limited herein, but is required to be open. The freezing temperature is-80 ℃ to-20 ℃, samples below-20 ℃ can be rapidly frozen, the minimum temperature which can be set by a common ultralow temperature refrigerator is-80 ℃, and the sample can be hardly realized if the freezing temperature is lower than-80 ℃; the temperature of the absolute ethyl alcohol/metal salt solution is between minus 20 ℃ and minus 5 ℃, the absolute ethyl alcohol can form a solid state when being lower than minus 114.3 ℃, and the full thawing and crosslinking are required to be carried out under the condition of liquid state, so that the temperature is required to be higher than the solid state, and the lowest temperature of a laboratory ultralow temperature refrigerator is minus 80 ℃; the water contained in the frozen sample needs to be mixed with Fe in absolute ethanol 3+ Slowly proceeding solventIn the exchange and crosslinking processes, water becomes liquid at the temperature above 0 ℃, for example, the water in wet gel at the temperature above 0 ℃ is directly melted; therefore, the temperature of the refrigerator is required to be in the range of-20 ℃ to-5 ℃, and the temperature of a refrigerator commonly used in a laboratory is-20 ℃ to-0 ℃, if the refrigerator is lower than-20 ℃, the refrigerator is not easy to realize, and the energy consumption is high, and the refrigerator is set below-5 ℃ to control the thawing time so as to better crosslink. The thawing time is 60-84h, and if the thawing time is less than 60h, the thawing time is too short to be completely thawed; it can be completely thawed within 60-84h after test. The solute of the absolute ethyl alcohol/metal salt solution is selected from FeCl 3 、CuCl 2 、CaCl 2 、AlCl 3 And MgCl 2 The concentration of at least one of (C) is 0.5-2wt%, and the range of the interval is proper concentration which can reach complete structure and excellent performance after experimental trial. If the concentration is less than 0.5wt%, the degree of crosslinking is too small to form a complete structure due to the too low concentration. The type and the concentration of the metal ions are basically matched with the carboxyl content in the modified nanocellulose, so that the modified nanocellulose can form an excellent network structure with stable structure, and subsequent photovoltaic power generation is realized. The dissolving and crosslinking steps are as follows: the electrostatic complexing and crosslinking effect of metal ions and carboxyl is realized in the process of dissolution and solvent exchange.
And fifthly, flushing the wet gel obtained in the step four, and drying under normal pressure to obtain the nano cellulose composite aerogel with the porous orientation structure. The flushing is carried out by adopting absolute ethyl alcohol, the flushing times are multiple times, and the flushing is not finished until the washing liquid is colorless and transparent; the drying temperature is between room temperature and 120 ℃. Above 120 ℃, the energy consumption increases and the aerogel structure may be deformed by heating.
According to some embodiments of the present invention, there is also provided a nanocellulose composite aerogel prepared according to the aforementioned preparation method, which has an oriented porous structure. FIG. 2 is an SEM image of the nano-cellulose composite aerogel prepared in example 1 of the present invention, and it can be confirmed from the SEM image shown in FIG. 2 that the aerogel according to the technical scheme of the present invention is an oriented porous structure; FIG. 3 is a graph showing the contact angle test of the nano-cellulose composite aerogel prepared in example 1 of the present invention; according to the contact angle test chart shown in fig. 3, the aerogel in the technical scheme of the invention has extremely strong hydrophilicity; furthermore, by performing mechanical property test on the nanocellulose composite aerogel, according to fig. 4, 5a, 6a and 7, it can be shown that the aerogel according to the technical scheme of the invention has better mechanical property, wet strength and dimensional stability.
According to some embodiments of the present invention, there is also provided a method for manufacturing a photovoltaic power generation device, the photovoltaic power generation device being manufactured by:
(1) Fixing the wires on the upper side and the lower side of the prepared nanocellulose composite aerogel by using a spot welding method through conductive silver paste, and drying and curing for 15-60min at 70-120 ℃; if the temperature of drying and curing is lower than 70 ℃, the drying and curing cannot be performed due to the fact that the temperature is too low; the temperature of a plurality of drying solidification is higher than 120 ℃, and the aerogel is not stable due to the over high temperature. If the drying and curing time is less than 15 minutes, the drying and curing time is too short to cure; if the drying and curing time is longer than 60 minutes, the aerogel is not stable easily due to overlong drying and curing time. The conductive wire may be at least one selected from copper foil, aluminum foil, iron foil, carbon wire and nickel foil. The method for fixing the conducting wires on the upper side and the lower side of the prepared nanocellulose composite aerogel by using a spot welding method through conductive silver paste specifically comprises the following steps: and placing the lead on the surfaces of the upper side and the lower side of the composite aerogel, and smearing conductive silver paste on the contact position of the lead and the composite aerogel.
(2) And placing the nano cellulose composite aerogel on a culture dish filled with water, so that the lower end is immersed in the water, and the upper end is not contacted with the water, thus obtaining the photovoltaic power generation device. According to the power generation principle, the lower end needs to be contacted with and absorb water, the upper end needs to evaporate water from the surface to generate continuous flow, so that ion directional transmission is realized, and output voltage is realized.
According to some embodiments of the present invention, there is also provided a photovoltaic power generation device fabricated according to the aforementioned fabrication method. Fig. 8 is a schematic diagram of the electricity generation of the photovoltaic electricity generation device, in which hydrophilic hydroxyl groups and carboxyl groups are widely present in the composite aerogel, which is a porous structure, the aerogel is easily absorbed when contacting water, and when the bottom contacts water, water molecules are rapidly absorbed and rapidly climb along the pores of the aerogel, forming an Electric Double Layer (EDL) between water-solid interfaces and generating a flow potential. When the water molecules rise to a certain height in the nano channel, the pressure balance of the upper end and the lower end of the water flow is achieved. Water above the water level evaporates along the surface channels, creating a pressure differential across the fluid. The water inside the aerogel will rise to replenish the water evaporated from the surface. Meanwhile, the existence of hydroxyl and carboxyl on the surface of the aerogel enables the aerogel to have negative charge, water absorbed from the solution flows through a channel of the material, hydrogen protons in water molecules are combined with the hydroxyl and the carboxyl after absorbing the water, movable ions are formed in the channel, ion channels are formed through water flow and capillary action, continuous flow is generated, and directional ion transfer is realized, so that output voltage is realized.
The invention will be further described with reference to specific examples, which are not to be construed as limiting the scope of the invention, but rather as falling within the scope of the invention, since numerous insubstantial modifications and adaptations of the invention will now occur to those skilled in the art in light of the foregoing disclosure.
Unless otherwise indicated, materials, reagents, and the like referred to below are commercially available products well known to those skilled in the art; unless otherwise indicated, the methods are all methods well known in the art. Unless otherwise defined, technical or scientific terms used should be given the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs.
Example 1:
(1) Preparing nano cellulose composite aerogel by an atmospheric pressure method: taking 10g of needle wood bleached sulfate pulp, adding 0.1g of TEMPO reagent, 0.7g of sodium bromide and 100mmol of sodium hypochlorite into 100g of deionized water, reacting for 1h under the stirring of a magnetic stirrer at 600rpm, dropwise adding 1mol/L sodium hydroxide solution in the reaction process to keep the pH at 10.0, washing the product with deionized water for many times to be neutral, adding a proper amount of deionized water to disperse the product into a dispersion liquid with the absolute dry mass percentage concentration of 1%, and circularly homogenizing for 5 times under the pressure of 100mPa by using a high-pressure homogenizer to obtain the TEMPO oxidized nanocellulose. Preparing TEMPO oxidized nanocellulose into dispersion with absolute dry mass percentage concentration of 1% in deionized water, and mixing at 80% The treatment was carried out at 0rpm for 40 minutes to obtain a uniform dispersion. 1g of carboxylated carbon nanotubes are taken in 99g of deionized water and treated for 30min at a rotating speed of 500rpm, so as to prepare uniform dispersion with the absolute dry mass percentage concentration of 1%. 75g of TEMPO oxidized nano-cellulose dispersion and 25g of carboxylated carbon nanotube dispersion are taken and stirred for 1h under high-speed shearing condition of 10000rpm, so as to obtain mixed dispersion. Standing for defoaming, collecting 30g of the above mixture, placing into a cylindrical plastic beaker with diameter of 4cm, freezing in a refrigerator at-80deg.C for 5 hr, taking out, and soaking the sample and beaker together in FeCl solution without demolding 3 Absolute ethanol bath (FeCl) 3 0.5 wt%) and thawing for 84h in a refrigerator at-20 deg.C, gradually thawing the sample until it floats on the upper end of liquid surface, taking out after completely thawing, flushing the sample with absolute ethyl alcohol several times, drying at normal temperature and pressure for 24h so as to obtain the invented composite aerogel with porous orientation structure.
(2) Preparation of a photovoltaic power generation device: fixing the aluminum foil on the composite aerogel through conductive silver paste by utilizing a spot welding method to obtain the photovoltaic power generation device, wherein the method comprises the following specific steps of: two aluminum foils with the width of 0.5cm and the length of 15cm are respectively arranged on the surfaces of the upper side and the lower side of the composite aerogel, 0.5g of conductive silver paste is taken, the conductive silver paste is coated on the contact position of the two aluminum foils and the composite aerogel, the coating area is 0.5cm multiplied by 0.5cm, and the composite aerogel is dried in an oven at 80 ℃ for 20min.
(3) Performance test of the photovoltaic power generation device: the method comprises the steps of placing a photovoltaic power generation device on a culture dish filled with water, immersing the lower electrode in the water, enabling the upper electrode not to contact with the water, enabling the device to generate continuous voltage along with capillary action and evaporation of the water through a micro-nano pore canal structure of composite aerogel, and testing the performance of output voltage of the photovoltaic power generation device by adopting an RLGOL DM3068 digital source meter.
Fig. 2 shows an SEM image of the surface morphology of the composite aerogel of this example, and it can be clearly seen that the network structure of the aerogel includes a large number of micro-nano pores, the pore size of which varies from several tens to several hundreds of micrometers, and the channels can be used as channels for water transport, so that ions are dissociated. Fig. 3 shows a contact angle test chart of the composite aerogel of the embodiment, and it can be seen that, since the surface of the composite aerogel contains abundant hydrophilic groups (carboxyl and hydroxyl), 4 mu L of water drops are dripped on the surface of the composite aerogel, the water drops are quickly absorbed by the aerogel, and the water adsorptivity of 48.98g/g can be achieved within 3min after the water drops are completely immersed in water. The nano channel containing carboxyl and hydroxyl is converted into a negatively charged group in the water permeation process, capillary interaction is promoted, water molecules are promoted to rise through the negatively charged nano channel, directional transfer is realized along with water flow and capillary action, and potential difference is generated at two sides, so that the photovoltaic power generation is realized.
Further, the inventors prepared nanocellulose composite aerogels with the same total solid content and different proportions by adopting the process, which all have higher mechanical strength (fig. 4), show the mechanical properties of the composite aerogel when the maximum compressive strain is 60%, and as the compressive strain increases, the three-dimensional voids of the aerogel are crushed, so that the composite aerogel is compactly hardened and the pressure level increases. While exhibiting superior wet strength (fig. 5 a) and dimensional stability (fig. 6 a), the composite aerogel of this example showed rapid moisture absorption after 20ml of water, maintained structural integrity after 15min, and maintained 60.52% compressive strength in the dry state at 60% compressive stress after complete wet out (fig. 7). It can be seen from FIG. 6a that the structure remains intact after 30min,700r/min of continuous mechanical stirring, and the dimensional change rate is only 2.3%, indicating its excellent dimensional stability, which can be attributed to the modified nanocellulose, carboxylated carbon nanotubes and Fe 3+ The principle of the electrostatic complex crosslinking is shown in figure 9.
Through designing the micron-nanometer multi-stage composite structure, the composite aerogel has a three-dimensional network porous structure, excellent hydrophilicity, high mechanical property, high wet strength and high dimensional stability, and the characteristics are all important factors for subsequent application in the field of the photovoltaic power generation. Fig. 10 shows real-time open circuit voltages of different proportions of the photovoltaic generators in a short time when water is used as a water source, the photovoltaic generators have higher output voltages and can be kept stable for a long time, the voltages still tend to be stable after 12 hours, and corresponding data of long-time real-time monitoring curves are shown in fig. 11.
Example 2:
(1) Preparing nano cellulose composite aerogel by an atmospheric pressure method: 10g of broad-leaved wood bleached sulfate pulp is taken to be placed in 1000ml of ammonium persulfate solution with the concentration of 1mol/L, the reaction is carried out for 1.5 hours at the temperature of 60 ℃ at 600rpm of a magnetic stirrer, deionized water is added until the pH value is 4 after the reaction is finished, and a high-pressure homogenizer is used for circularly homogenizing for 4 times under the pressure of 110mPa, so that the ammonium persulfate oxidized nanocellulose is obtained. And (3) preparing dispersion liquid with absolute dry mass percentage concentration of 1.5% by taking ammonium persulfate oxidized nanocellulose in deionized water, and treating for 30min at a rotating speed of 900rpm to obtain uniform dispersion liquid. 1.5g of carboxylated carbon nanotubes were taken in 98.5g of deionized water and treated at 700rpm for 20min to prepare a uniform dispersion having an absolute dry mass percentage concentration of 1.5%. 50g of ammonium persulfate nano-cellulose dispersion and 50g of carboxylated carbon nanotube dispersion are taken and stirred for 2 hours under the high-speed shearing condition of 5000rpm, so as to obtain mixed dispersion. Standing for defoaming, placing 30g of the mixed solution in a cylindrical plastic beaker with diameter of 4cm, freezing in a refrigerator at-60deg.C for 6 hr, taking out, and soaking the sample and beaker together in a solution containing CuCl without demolding 2 Absolute ethanol bath (CuCl) 2 1.5wt percent), thawing for 78 hours in a refrigerator at minus 10 ℃, gradually thawing the sample until the sample floats on the upper end of the liquid level, taking out the sample after complete thawing, flushing the sample with absolute ethyl alcohol for multiple times, and drying the sample at 40 ℃ and normal pressure for 18 hours to obtain the composite aerogel with the porous orientation structure.
(2) Preparation of a photovoltaic power generation device: fixing the copper foil on the composite aerogel through conductive silver paste by utilizing a spot welding method to obtain the photovoltaic power generation device, wherein the method comprises the following specific steps of: two copper foils with the width of 0.8cm and the length of 12cm are respectively arranged on the surfaces of the upper side and the lower side of the composite aerogel, 0.6g of conductive silver paste is taken, the conductive silver paste is coated on the contact position of the two copper foils and the composite aerogel, the coating area is 0.6cm multiplied by 0.6cm, and the copper foils are placed in an oven at the temperature of 70 ℃ for drying for 35min.
(3) Performance test of the photovoltaic power generation device: the method comprises the steps of placing a photovoltaic power generation device on a culture dish filled with water, immersing the lower electrode in the water, enabling the upper electrode not to contact with the water, enabling the device to generate continuous voltage along with capillary action and evaporation of the water through a micro-nano pore canal structure of composite aerogel, and testing the performance of output voltage of the photovoltaic power generation device by adopting an RLGOL DM3068 digital source meter.
Example 3:
(1) 10g of bleached sulfite broadleaf wood is prepared by an atmospheric pressure method, dispersed in 100ml of 1wt% dilute sulfuric acid solution, 14g of potassium permanganate is added, the mixture is reacted for 2.5 hours at 50 ℃ at 600rpm by a magnetic stirrer, deionized water is used for washing for many times to be neutral after the reaction is finished, and a high-pressure homogenizer is used for circularly homogenizing for 5 times at 100mPa pressure to obtain the potassium permanganate oxidized nanocellulose. And (3) preparing the potassium permanganate oxidized nanocellulose into a dispersion liquid with the absolute dry mass percentage concentration of 1.2% in deionized water, and processing the dispersion liquid for 40 minutes at the rotating speed of 600rpm to obtain a uniform dispersion liquid. 1.2g of carboxylated carbon nanotubes were taken in 98.8g of deionized water and treated at 500rpm for 30min to prepare a uniform dispersion having an absolute dry mass percentage concentration of 1.2%. 66.67g of potassium permanganate oxidized nanocellulose dispersion and 33.33g of carboxylated carbon nanotube dispersion are taken and stirred for 1.5 hours under high-speed shearing condition at 8000rpm, so as to obtain mixed dispersion. Standing for defoaming, collecting 30g of the above mixture, placing into a circular plastic beaker with diameter of 4cm, freezing in a refrigerator at-25deg.C for 10 hr, taking out, and soaking the sample and beaker together with CaCl without demolding 2 Absolute ethanol bath (CaCl) 2 1.2wt percent), thawing for 96 hours in a refrigerator at minus 5 ℃, gradually thawing the sample until the sample floats on the upper end of the liquid level, taking out the sample after complete thawing, flushing the sample with absolute ethyl alcohol for multiple times, and drying the sample at 60 ℃ and normal pressure for 45 minutes to obtain the composite aerogel with the porous orientation structure.
(2) Preparation of a photovoltaic generator: the nickel foil is fixed on the composite aerogel through conductive silver paste by utilizing a spot welding method, and the photovoltaic power generation device is obtained, and the specific steps comprise: two nickel foils with the width of 0.3cm and the length of 19cm are respectively arranged on the surfaces of the upper side and the lower side of the composite aerogel, 0.5g of conductive silver paste is taken, the conductive silver paste is coated at the contact position of the two nickel foils and the composite aerogel, the coating area is 0.4cm multiplied by 0.4cm, and the composite aerogel is dried in an oven at the temperature of 100 ℃ for 15min.
(3) Performance test of the photovoltaic power generation device: the method comprises the steps of placing a photovoltaic power generation device on a culture dish filled with water, immersing the lower electrode in the water, enabling the upper electrode not to contact with the water, enabling the device to generate continuous voltage along with capillary action and evaporation of the water through a micro-nano pore canal structure of composite aerogel, and testing the performance of output voltage of the photovoltaic power generation device by adopting an RLGOL DM3068 digital source meter.
According to the same preparation procedure, examples 1, 2 and 3 were combined to obtain carboxylated nanocellulose by different cellulose modification means, and different ionomer (Fe 3+ 、Cu 2+ 、Ca 2+ ) Complexation can be made into porous composite aerogels for use in a photovoltaic power generation device, and FIG. 12 is a plurality of composite aerogels crosslinked with different ions. The photovoltaic power generation device is simple to prepare, has certain universality, is good in stability, is easy to prepare in a large scale, can obtain good photovoltaic power generation performance, and realizes the characteristic of directly obtaining energy from environmental water.
Comparative example 1:
(1) Preparing nano cellulose composite aerogel by an atmospheric pressure method: taking 10g of needle wood bleached sulfate pulp, adding 0.1g of TEMPO reagent, 0.7g of sodium bromide and 100mmol of sodium hypochlorite into 100g of deionized water, reacting for 1h under the stirring of 600pm of a magnetic stirrer, dropwise adding 1mol/L sodium oxide solution in the reaction process to keep the pH at 10.0, washing the product with deionized water for many times to be neutral, adding a proper amount of deionized water to disperse into a dispersion liquid with the absolute dry mass percentage concentration of 0.8%, and circularly homogenizing for 5 times under the pressure of 100mPa by using a high-pressure homogenizer to obtain the TEMPO oxidized nanocellulose. Preparing a dispersion liquid with the absolute dry mass percentage concentration of 0.8% by taking TEMPO oxidized nano-cellulose in deionized water, and processing for 40min at the rotating speed of 800rpm to obtain a uniform dispersion liquid. 0.8g of carboxylated carbon nano-tubes are taken in 99.2g of deionized water and treated for 30min at the rotating speed of 500rpm, and uniform dispersion with the absolute dry mass percentage concentration of 0.8% is prepared. 75g of TEMPO oxidized nano-cellulose dispersion and 25g of carboxylated carbon nano-tube dispersion are taken and stirred for 1h under the high-speed shearing condition of 10000rpm, so as to obtain a mixed dispersion. Standing for defoaming, placing 30g of the mixed solution in a cylindrical plastic beaker with a diameter of 4cm, freezing in a refrigerator with a temperature of-80 ℃ for 5 hours, taking out after freezing completely, and demoulding Immersing the sample and beaker together in a solution containing FeCl 3 Thawing in an absolute ethyl alcohol bath (0.5 wt%) for 84 hours at-20 ℃ in a refrigerator, gradually thawing the sample until floating at the upper end of the liquid level, taking out after complete thawing, flushing the sample with absolute ethyl alcohol for multiple times, and drying for 24 hours at normal temperature and normal pressure to obtain the composite aerogel.
As can be seen from fig. 13b, the cellulose of this comparative example was not carboxylated, and although the subsequent process was the same as example 1, it was not possible to form a porous aerogel of similar structural integrity to example 1 (see fig. 13 a). The nano cellulose can be self-assembled into a network structure layer by layer through hydroxyl groups on the surface when the nano cellulose is melted layer by layer, and metal ions can also permeate into the network structure, but the nano cellulose has no carboxyl group with negative charges on the surface, and cannot be complexed with the metal ions, so that a stable aerogel network structure cannot be formed, and the stable aerogel network structure can collapse in the subsequent process, which indicates the importance of carboxylated nano cellulose to the preparation of composite aerogel.
Comparative example 2:
(1) Preparing nano cellulose aerogel by an atmospheric pressure method: taking 10g of needle wood bleached sulfate pulp, adding 0.1g of TEMPO reagent, 0.7g of sodium bromide and 100mmol of sodium hypochlorite into 100g of deionized water, reacting for 1h under the stirring of a magnetic stirrer at 600rpm, dropwise adding 1mol/L sodium hydroxide solution in the reaction process to keep the pH at 10.0, washing the product with deionized water for many times to be neutral, adding a proper amount of deionized water to disperse into a dispersion liquid with the absolute dry mass percentage concentration of 1%, and circularly homogenizing for 5 times under the pressure of 100mPa by using a high-pressure homogenizer to obtain the TEMPO oxidized nanocellulose. Preparing a dispersion liquid with the absolute dry mass percentage concentration of 1% by taking TEMPO oxidized nano-cellulose in deionized water, and processing for 40min at the rotating speed of 800rpm to obtain a uniform dispersion liquid. Taking 20g of TEMPO oxidized nanocellulose dispersion, standing for defoaming, placing in a cylindrical plastic beaker with the diameter of 4cm, freezing in a refrigerator at the temperature of minus 20 ℃ for 12 hours, taking out after the freezing is completed, and immersing a sample and the beaker together in a solution containing FeCl without demoulding 3 Thawing in absolute ethanol bath (0.5 wt%) at-20deg.C for 84 hr, thawing the sample gradually until it floats on the upper end of liquid surface, taking out after complete thawing, and usingWashing the sample with absolute ethyl alcohol for multiple times, and drying for 24 hours at normal temperature and normal pressure to obtain the composite aerogel.
(2) Preparing a photovoltaic power generation device: fixing the aluminum foil on the composite aerogel through conductive silver paste by utilizing a spot welding method to obtain the photovoltaic power generation device, wherein the method comprises the following specific steps of: two aluminum foils with the width of 0.5cm and the length of 15cm are respectively arranged on the surfaces of the upper side and the lower side of the composite aerogel, 0.5g of conductive silver paste is taken, the conductive silver paste is coated on the contact position of the two aluminum foils and the composite aerogel, the coating area is 0.5cm multiplied by 0.5cm, and the composite aerogel is dried in an oven at 80 ℃ for 20min.
(3) Performance test of the photovoltaic power generation device: the method comprises the steps of placing a photovoltaic power generation device on a culture dish filled with water, immersing the lower electrode in the water, enabling the upper electrode not to contact with the water, enabling the device to generate continuous voltage along with capillary action and evaporation of the water through a micro-nano pore canal structure of composite aerogel, and testing the performance of output voltage of the photovoltaic power generation device by adopting an RLGOL DM3068 digital source meter.
The comparative example, in which carboxylated carbon nanotubes were not added during the preparation of the composite aerogel, and the subsequent process was completely consistent with example 1, can form a porous aerogel with complete structure, but as can be seen from fig. 11, the output voltage test result of the composite aerogel of the comparative example is 250mv, and the output voltage of the aerogel is reduced compared with that of the aerogel in which carboxylated carbon nanotubes are added in the example. The addition of the carboxylated carbon nano-tube can influence the microstructure of the aerogel, the modified nano-cellulose prepared by a TEMPO oxidation method, an ammonium persulfate method and a potassium permanganate method is gel-like and has certain viscosity, the carboxylated carbon nano-tube is powdery, the stability and the strength of the aerogel structure are facilitated by the nano-cellulose, and the micro-pore channels of the aerogel can be changed by adding the carboxylated carbon nano-tube in different contents, so that the performance of the photovoltaic power generation is influenced.
Comparative example 3:
(1) Preparing nano cellulose composite aerogel by an atmospheric pressure method: 10g of broad-leaved wood bleached sulfate pulp is placed in 1000ml of 1mol/L ammonium persulfate solution, a magnetic stirrer is used for 600rpm and reacting for 1.5 hours at 60 ℃, deionized water is added until the pH value is 4 after the reaction, and a high-pressure homogenizer is used for circularly homogenizing for 4 times under the pressure of 110mPa to obtain the ammonium persulfate oxidized nanocellulose. And (3) preparing dispersion liquid with the absolute dry mass percentage concentration of 2% by taking ammonium persulfate oxidized nanocellulose in deionized water, and treating for 30min at the rotating speed of 900rpm to obtain uniform dispersion liquid. 2g of carboxylated carbon nanotubes are taken in 98g of deionized water and treated for 20min at the rotating speed of 700rpm, and uniform dispersion with the absolute dry mass percentage concentration of 2% is prepared. 75g of ammonium persulfate nano-cellulose dispersion and 25g of carboxylated carbon nanotube dispersion are taken and stirred for 2 hours under the high-speed shearing condition of 5000rpm, so as to obtain mixed dispersion. Placing 30g of the mixed solution after standing and defoaming in a cylindrical plastic beaker with the diameter of 4cm, putting the cylindrical plastic beaker into a refrigerator with the temperature of-80 ℃ for freezing for 5 hours, taking out the cylindrical plastic beaker after the cylindrical plastic beaker is completely frozen, immersing a sample and the beaker in an absolute ethyl alcohol bath without demoulding, thawing the cylindrical plastic beaker in the refrigerator with the temperature of-15 ℃ for 80 hours, gradually thawing the sample until the cylindrical plastic beaker floats on the upper end of the liquid level, taking out the cylindrical plastic beaker after the cylindrical plastic beaker is completely thawed, and drying the cylindrical plastic beaker at normal temperature and normal pressure for 30 hours to obtain aerogel.
As can be seen in FIG. 13c, in sharp contrast, the composite frozen sample of this comparative example did not incorporate metal ions during thawing and did not form a structurally complete porous aerogel. The method is characterized in that when the composite frozen sample is melted layer by layer, no metal ions can form complexation with carboxyl groups, a network structure cannot be formed, collapse occurs in the preparation process, and the cross-linking complexation of the metal ions on the composite aerogel is described, which is necessary for preparing the porous composite aerogel.
Comparative example 4:
(1) Preparing nano cellulose composite aerogel by an atmospheric pressure method: taking 10g of needle wood bleached sulfate pulp, adding 0.1g of TEMPO reagent, 0.7g of sodium bromide and 100mmol of sodium hypochlorite into 100g of deionized water, reacting for 1h under the stirring of a magnetic stirrer at 600rpm, dropwise adding 1mol/L sodium hydroxide solution in the reaction process to keep the pH at 10.0, washing the product with deionized water for many times to be neutral, adding a proper amount of deionized water to disperse into a dispersion liquid with the absolute dry mass percentage concentration of 1%, and circularly homogenizing for 5 times under the pressure of 100mPa by using a high-pressure homogenizer to obtain the TEMPO oxidized nanocellulose. Preparing a dispersion liquid with the absolute dry mass percentage concentration of 1% by taking TEMPO oxidized nano-cellulose in deionized water, and processing for 40min at the rotating speed of 800rpm to obtain a uniform dispersion liquid. 1g of carboxylated carbon nanotubes are taken in 99g of deionized water and treated for 30min at a rotating speed of 500rpm, and a uniform dispersion with an absolute dry mass percentage concentration of 1% is prepared. 80g of TEMPO oxidized nano cellulose dispersion and 20g of carboxylated carbon nano tube dispersion are taken and stirred for 1h under the high-speed shearing condition of 10000rpm, so as to obtain mixed dispersion. And (3) standing for defoaming, then placing a certain amount of the mixed solution into a cylindrical plastic beaker with the diameter of 4cm, putting the cylindrical plastic beaker into a refrigerator with the temperature of minus 80 ℃ for freezing for 5 hours, taking out the cylindrical plastic beaker after the cylindrical plastic beaker is frozen completely, and drying the cylindrical plastic beaker by a freeze drying method (freeze drying for 60 hours at the temperature of minus 45 ℃ by using a freeze dryer) to obtain the composite aerogel.
(2) Preparation of a photovoltaic power generation device: fixing the aluminum foil on the composite aerogel through conductive silver paste by utilizing a spot welding method to obtain the photovoltaic power generation device, wherein the method comprises the following specific steps of: two aluminum foils with the width of 0.5cm and the length of 15cm are respectively arranged on the surfaces of the upper side and the lower side of the composite aerogel, 0.5g of conductive silver paste is taken, the conductive silver paste is coated on the contact position of the two aluminum foils and the composite aerogel, the coating area is 0.5cm multiplied by 0.5cm, and the composite aerogel is dried in an oven at the temperature of 100 ℃ for 15min.
(3) Performance test of the photovoltaic power generation device: the method comprises the steps of placing a photovoltaic power generation device on a culture dish filled with water, immersing the lower electrode in the water, enabling the upper electrode not to contact with the water, enabling the device to generate continuous voltage along with capillary action and evaporation of the water through a micro-nano pore canal structure of composite aerogel, and testing the performance of output voltage of the photovoltaic power generation device by adopting an RLGOL DM3068 digital source meter.
As can be seen from fig. 13d, the composite aerogel of the comparative example, which was prepared by the freeze-drying method, can form a structurally complete aerogel structure similar to that of example 1, and its mechanical properties in a dry state are similar to those of example 1 (fig. 4), whereas the wet strength and dimensional stability of the composite aerogel prepared by the freeze-drying method of the comparative example are far inferior to those of example 1, and the composite aerogel of the comparative example, after being immersed in 20ml of water for 15min, is structurally soft and has collapsed in its internal structure (fig. 5 b), and after being mechanically stirred for the same degree and time as in example 1, the composite aerogel of the comparative example is broken and cannot be kept intact (fig. 6 b), and cannot be well applied to the subsequent photovoltaic power generation. The wet strength and the dimensional stability are key characteristics of the photovoltaic power generation device in subsequent applications, and can be attributed to the cross-linking complexation generated between the modified nanocellulose, the carboxylated carbon nanotubes and the metal ions, so that the composite aerogel forms an excellent structure.
As can be seen from the output voltage test, the composite aerogel of this comparative example has a reduced output voltage (see fig. 14), and has a severe collapse of the structure after one test and air drying, and does not have long-term stability, because although the freeze-drying method can form a porous network structure, which can be used as a channel for transporting water, sufficient water is provided during evaporation, but there is no cross-linking of metal ions, after water molecules enter the pore structure, the wet strength and mechanical stability of the aerogel are deteriorated, the internal pore structure collapses, breaks, and there is no water molecule transport channel, resulting in a smaller output voltage than the examples.
As can be seen from fig. 14, after the composite aerogel of this comparative example was subjected to the output voltage for 10 hours, the aerogel structure collapsed after natural air drying, and the output voltage could not be performed again, whereas compared with the composite aerogel of example 1, after the output voltage was performed for 10 hours, the dried aerogel structure remained intact, no significant recess occurred, and the cyclic output power generation of more than six times could be performed (see fig. 15).
From the test data of the above examples and comparative examples, it can be seen that each of the process steps of the present invention are endless rather than isolated. Only the technical steps in the technical scheme are included, and the technical purpose can be completely realized only by the sequential occurrence of the technical steps, so that the technical effect is achieved.
The technical features of the claims and/or the description of the present invention may be combined in a manner not limited to the combination of the claims by the relation of reference. The technical scheme obtained by combining the technical features in the claims and/or the specification is also the protection scope of the invention.
The above description is only of the preferred embodiments of the present invention, and is not intended to limit the present invention in any way, but any simple modification, equivalent variation and modification made to the above embodiments according to the technical substance of the present invention still fall within the scope of the technical solution of the present invention.
Claims (11)
1. The preparation method of the nano-cellulose composite aerogel is characterized by comprising the following steps of:
1) Modifying cellulose to contain carboxyl, mechanically treating to obtain modified nano cellulose, and preparing into modified nano cellulose aqueous dispersion;
2) Preparing carboxylated carbon nano-tubes into carboxylated carbon nano-tube aqueous dispersion liquid;
3) Compounding the modified nano cellulose aqueous dispersion obtained in the step 1) with the carboxylated carbon nano tube aqueous dispersion obtained in the step 2) in proportion, and keeping the mixture for 0.5 to 2 hours under the high-speed shearing condition to uniformly mix the mixture, so as to obtain modified nano cellulose and carboxylated carbon nano tube composite dispersion; the absolute dry mass ratio of the modified nano cellulose to the carboxylated carbon nanotube aqueous dispersion liquid is (1-4): 1, a step of;
4) Standing the modified nano cellulose and carboxylated carbon nanotube composite dispersion liquid obtained in the step 3), defoaming, freezing, taking out, soaking in absolute ethyl alcohol/metal salt solution after the modified nano cellulose and carboxylated carbon nanotube composite dispersion liquid are sufficiently frozen, dissolving and crosslinking to obtain wet gel;
5) Washing the wet gel obtained in the step 4) with absolute ethyl alcohol, and drying under normal pressure to obtain the nano cellulose composite aerogel with the porous orientation structure.
2. The method for preparing a nanocellulose composite aerogel as claimed in claim 1 wherein in step 1), the nanocellulose raw material is selected from at least one of bleached sulfate softwood pulp, bleached sulfate hardwood pulp, bleached sulfite softwood pulp, and bleached sulfite hardwood; the cellulose carboxylation modification method is selected from one of a TEMPO oxidation method, a periodic acid oxidation method, a nitric acid-sodium nitrite oxidation method, a potassium permanganate oxidation method and an ammonium persulfate oxidation method; the mass concentration of the modified nano cellulose aqueous dispersion is 0.8-2%; the diameter of the modified nano-cellulose is 15-80nm, the length is more than 1 mu m, and the carboxyl content is 1.3-2.5mmol/g.
3. The method for preparing a nanocellulose composite aerogel as claimed in claim 1 wherein in step 1), preparing the modified nanocellulose aqueous dispersion comprises the steps of:
Adding the modified nano cellulose into water for dispersion, and stirring at 500-1000rpm until no caking exists.
4. The method for preparing a nano-cellulose composite aerogel according to claim 1, wherein in the step 2), the mass concentration of the carboxylated carbon nanotube aqueous dispersion is 0.8-2%; the preparation of the carboxylated carbon nanotube aqueous dispersion comprises the following steps: stirring carboxylated carbon nanotubes for 15-35min at 500-800rpm, and dispersing in deionized water.
5. The method for preparing a nano-cellulose composite aerogel according to claim 1, wherein in the step 2), the carboxylated carbon nanotubes have a diameter of 5-70nm and a length of 2-40 μm.
6. The method of claim 1, wherein in step 3), the high-speed shearing conditions are: 5000-10000rpm; the total absolute dry mass of the modified nano cellulose aqueous dispersion liquid obtained in the step 1) and the carboxylated carbon nanotube aqueous dispersion liquid obtained in the step 2) accounts for 0.8-2% of the total dispersion liquid mass.
7. The method of preparing a nanocellulose composite aerogel as claimed in claim 1 wherein in step 4) the freezing process is performed in a plastic, rubber or metal container having a low temperature resistance of at least-80 ℃; the shape of the plastic, rubber or metal container is selected from one of a cylinder, a cuboid and a polygonal body; the freezing temperature is-80 ℃ to-20 ℃; the temperature of the absolute ethyl alcohol/metal salt solution is-20 ℃ to-5 ℃; the crosslinking time is 60-84h.
8. The method of claim 1, wherein in step 4), the solute of the absolute ethanol/metal salt solution is selected from FeCl 3 、CuCl 2 、CaCl 2 、AlCl 3 And MgCl 2 At least one of the components, the concentration is 0.5-2wt%; in the step 5), the drying temperature is room temperature to 120 ℃.
9. The nanocellulose composite aerogel is prepared by the preparation method according to any one of claims 1 to 8, and has a porous orientation structure, water adsorption performance reaches more than 48g/g in 3min, compressive strength of more than 60% in a dry state under 60% compressive strain after being soaked in water, and dimensional change rate after being soaked in water is less than 3%.
10. The manufacturing method of the photovoltaic power generation device is characterized in that the photovoltaic power generation device is manufactured through the following steps:
(1) Fixing wires on the upper side and the lower side of the nanocellulose composite aerogel in claim 9 through conductive silver paste by using a spot welding method, and drying and curing for 15-60min at 70-120 ℃;
(2) And placing the nano cellulose composite aerogel on a culture dish filled with water, so that the lower end is immersed in the water, and the upper end is not contacted with the water, thus obtaining the photovoltaic power generation device.
11. A photovoltaic power generation device, characterized in that the photovoltaic power generation device is manufactured according to the manufacturing method of claim 10.
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| CN105566659A (en) * | 2015-12-25 | 2016-05-11 | 郑州轻工业学院 | Graphene oxide/nano cellulose aerogel and preparation method and application thereof |
| KR20190137377A (en) * | 2018-06-01 | 2019-12-11 | 이성균 | A. (hydrophobic) nano cellulose aerogels for water and air purification and hydrogen production. outside |
| WO2021056851A1 (en) * | 2019-09-27 | 2021-04-01 | 中国科学院深圳先进技术研究院 | Mxene/metal composite aerogel, preparation method therefor and use thereof, and thermal interface material containing same |
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| CN105566659A (en) * | 2015-12-25 | 2016-05-11 | 郑州轻工业学院 | Graphene oxide/nano cellulose aerogel and preparation method and application thereof |
| KR20190137377A (en) * | 2018-06-01 | 2019-12-11 | 이성균 | A. (hydrophobic) nano cellulose aerogels for water and air purification and hydrogen production. outside |
| WO2021056851A1 (en) * | 2019-09-27 | 2021-04-01 | 中国科学院深圳先进技术研究院 | Mxene/metal composite aerogel, preparation method therefor and use thereof, and thermal interface material containing same |
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