CN114975878B - Method for preparing large-area thickness controllable ordered porous electrode by tape casting method - Google Patents
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- 238000000034 method Methods 0.000 title claims abstract description 75
- 238000010345 tape casting Methods 0.000 title claims abstract description 26
- 239000004005 microsphere Substances 0.000 claims abstract description 58
- 239000000758 substrate Substances 0.000 claims abstract description 40
- 239000004038 photonic crystal Substances 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 239000006185 dispersion Substances 0.000 claims abstract description 14
- 238000011049 filling Methods 0.000 claims abstract description 14
- 239000007772 electrode material Substances 0.000 claims abstract description 9
- 238000010000 carbonizing Methods 0.000 claims abstract description 6
- 238000002360 preparation method Methods 0.000 claims description 20
- 239000005416 organic matter Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 239000000084 colloidal system Substances 0.000 claims description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 10
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000001179 sorption measurement Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- 239000004642 Polyimide Substances 0.000 claims description 7
- 239000004917 carbon fiber Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 7
- 229920001721 polyimide Polymers 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 238000005266 casting Methods 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 6
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 6
- 238000011065 in-situ storage Methods 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- OTYYBJNSLLBAGE-UHFFFAOYSA-N CN1C(CCC1)=O.[N] Chemical group CN1C(CCC1)=O.[N] OTYYBJNSLLBAGE-UHFFFAOYSA-N 0.000 claims description 5
- 239000004793 Polystyrene Substances 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 229920002223 polystyrene Polymers 0.000 claims description 5
- 238000003892 spreading Methods 0.000 claims description 5
- 230000007480 spreading Effects 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 4
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 4
- 238000003763 carbonization Methods 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- TXDYWJDYXZCRAN-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;prop-2-enoic acid Chemical compound OC(=O)C=C.C=CC1=CC=CC=C1C=C TXDYWJDYXZCRAN-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 claims description 3
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 3
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 3
- 239000011022 opal Substances 0.000 claims description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 230000004927 fusion Effects 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 238000007599 discharging Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 238000007600 charging Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000005357 flat glass Substances 0.000 description 4
- 238000010248 power generation Methods 0.000 description 4
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 239000012621 metal-organic framework Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000001338 self-assembly Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- SMDQFHZIWNYSMR-UHFFFAOYSA-N sulfanylidenemagnesium Chemical compound S=[Mg] SMDQFHZIWNYSMR-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention relates to a method for preparing a large-area thickness controllable ordered porous electrode by a tape casting method, which uses a plurality of porous substrates, uses the tape casting method to disperse colloidal microsphere dispersion liquid with certain concentration into holes of the porous substrates, and leads monodisperse microspheres to be naturally arranged into a photonic crystal structure along with solvent volatilization. And filling organic matters in gaps of the colloidal microsphere photonic crystals, and carbonizing and removing the colloidal microsphere templates at high temperature to obtain the large-area ordered porous sheet. And then filling the electrode active material into the nano holes of the ordered porous sheet to obtain the ordered porous electrode with controllable large area and thickness. Compared with the prior art, the invention realizes the thickness of 20um-600um and the area of 0.1cm by changing the thickness and the area of the base material 2 ‑1000cm 2 Is provided.
Description
Technical Field
The invention relates to a material and a preparation method in the technical field of lithium batteries, in particular to a method for preparing a large-area thickness-controllable ordered porous electrode by a tape casting method.
Background
The new energy battery mainly comprising the lithium battery plays a role in the development of the current society, is widely applied to electronic equipment such as power automobiles, computers and mobile phones, and has a wide application prospect in the aspect of storing energy generated by instant power generation equipment such as solar power generation, wind power generation and tidal power generation. Improving the energy density and the service life are two major targets of developing new energy batteries currently, and electrode polarization generated by uneven charge distribution is one of the key problems of influencing the energy density and the service life of the new energy batteries. Studies have shown that constructing three-dimensional ordered porous electrode microstructures is an effective means of solving the above problems.
Constructing ordered porous electrodes often requires the preparation of colloidal photonic crystal templates. At present, a vertical self-assembly method, a spray coating method, a spin coating method and the like are mainly used for preparing the colloid photon crystal. However, these methods have difficulty in preparing colloidal photonic crystals having a large area and a large thickness because they generally employ a substrate (e.g., glass, metal foil, etc.) having a smooth surface, and when the area and thickness are increased, surface stress is generated during drying, thereby generating a large number of cracks or falling off from the substrate.
The large-area preparation and the flow line production are the basis for practical application of the battery electrode, and the large thickness is the guarantee of the high energy density of the battery electrode. Obviously, those methods described above are difficult to apply to the preparation of large-area and large-thickness ordered porous electrodes.
Chinese patent CN102691106a discloses a preparation method of photonic crystal, in which a colloidal photonic crystal is grown on the surface of a flexible substrate by using a spray coating, spin coating or ink-jet printing method, but the thickness of the photonic crystal obtained by such a method is difficult to exceed 20um.
According to the preparation method of the large-area thick film controllable texture photonic crystal lithium sulfur battery, the monodisperse microspheres are arranged into a photonic crystal structure in the macropores of a base material along with the volatilization of a solvent by using a vertical sedimentation self-assembly method, ordered microporous carbon is synthesized in a template gap by taking the photonic crystal as a template, and the photonic crystal template is removed to obtain the three-dimensional ordered hierarchical porous carbon photonic crystal, so that the large-area thick film controllable texture photonic crystal is formed. And compounding the lithium metal with elemental sulfur to obtain a sulfur anode, and using lithium metal as a counter electrode to assemble the lithium-sulfur battery. The invention realizes the thick film control of the electrode thickness from 10 to 650um by changing the thickness of the base material and the concentration of the suspension, and realizes the electrode area from 0.1 to 400cm by changing the area of the base material 2 Is prepared in large area. In addition, by adjusting the concentration of the organic solution of sulfur, a concentration of from 1 to 15mg cm is achieved -2 High sulfur loading, thereby realizing high surface capacity density and surface energy density of the lithium sulfur battery, and the electrode area obtained by the method is difficult to exceed 400cm 2 。
Therefore, it is essential to develop a method for preparing an ordered porous electrode of large area and thickness.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a method for preparing a large-area thickness-controllable ordered porous electrode by a tape casting method and application thereof.
The aim of the invention can be achieved by the following technical scheme: a method for preparing a large-area thickness controllable ordered porous electrode by a tape casting method adopts a plurality of porous substrates, and uses the tape casting method to disperse colloidal microsphere dispersion liquid with certain concentration into holes of the porous substrates, and the monodisperse microspheres are naturally arranged into a photonic crystal structure along with the volatilization of a solvent. And filling organic matters in gaps of the colloidal microsphere photonic crystals, and carbonizing and removing the colloidal microsphere templates at high temperature to obtain the large-area ordered porous sheet. And then filling the electrode active material into the nano holes of the ordered porous sheet to obtain the ordered porous electrode with controllable large area and thickness. The method comprises the following steps:
preparation of monodisperse colloidal microsphere Dispersion: mixing the monodisperse microspheres with a solvent and performing ultrasonic dispersion to prepare a dispersion liquid with the concentration of 20-80 wt%;
pretreatment of a porous substrate: placing the porous substrate in a solvent, removing impurities and organic matters on the surface of the porous substrate by ultrasonic cleaning, and then placing the porous substrate in an oven for drying;
preparing colloid photon crystal: spreading the pretreated porous substrate on a clean glass plate, dispersing colloid microspheres into holes of the porous substrate by using a tape casting method, and naturally arranging the colloid microspheres into photonic crystal structures in the holes of the porous substrate along with volatilization of a solvent; the casting method is used for coating at a uniform speed of 1cm/min-20 cm/min.
Preparation of inverse opal structure: filling organic matter solution with certain concentration into gaps of the colloid photon crystal by utilizing a tape casting method, carbonizing at high temperature and subsequently removing colloid microspheres to form ordered porous sheets with inverse opal structures; the casting method is used for coating at a uniform speed of 1cm/min-20 cm/min.
Preparation of ordered porous electrode: and filling electrode active materials into the nano holes of the ordered porous sheet with the inverse opal structure by an in-situ growth method, a melt adsorption method or a casting method to form the ordered porous electrode.
The monodisperse microspheres are polystyrene microspheres, silicon dioxide microspheres or polymethyl methacrylate microspheres.
The particle size of the monodisperse microsphere is 100nm-800nm, preferably 200nm-500nm.
The solvent is nitrogen methyl pyrrolidone, alcohol or water.
The base material is a metal woven net, a metal etching net, foam nickel, carbon fiber paper, carbon fiber cloth or an organic silk screen.
The metal woven mesh is a stainless steel mesh, a nickel mesh, a titanium mesh, a copper mesh, an aluminum mesh, a tungsten mesh, a molybdenum mesh, a zirconium mesh or a platinum mesh.
The organic matter is metal frame organic Matter (MOFs), acrylic acid-divinylbenzene, polymethyl methacrylate (PMMA), polyacrylonitrile (PAN), phenolic resin (PF) or Polyimide (PI); the preparation method is that the organic matters are dissolved into N, N-dimethylformamide solution to obtain the organic matter solution with the mass concentration of 20-60 percent.
The carbonization temperature is 300-1000 ℃.
The electrode active material comprises elemental sulfur, elemental selenium, elemental tellurium, metallic lithium, metallic sodium, elemental phosphorus, elemental silicon, elemental tin, elemental germanium, elemental zinc, manganese oxide, nickel oxide, cobalt oxide, vanadium pentoxide, molybdenum sulfide, or lithium sulfide.
The thickness of the prepared porous electrode is 20-600 um;
the area of the prepared porous electrode is 0.1cm 2 -1000 cm 2 。
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention adopts polystyrene microsphere, silicon dioxide microsphere or polymethyl methacrylate microsphere to prepare dispersion liquid with concentration of 20wt percent to 80wt percent, the concentration can reach 80wt percent, and the grain diameter is controlled to be 100nm to 800nm. The concentration and microsphere size in this region are selected to help maintain structural order of the microspheres as they self-assemble within the macropores of the substrate.
(2) The invention adopts a tape casting method to disperse the colloidal microspheres into the holes of the porous substrate, and compared with the self-assembly technology in the prior art, the method has the advantages of simple process and quick molding; secondly, the use of dispersion liquid is reduced, and the cost is saved; and thirdly, the preparation can be carried out in a large area, and industrial production is realized.
(3) The method utilizes the tape casting method to fill the organic matter solution with certain concentration into the gaps of the colloid photon crystal through capillary action, and compared with the organic matter filling technology in the prior art, the method firstly reduces the use of the solution and saves the cost; secondly, the distribution of the organic matters is more uniform, and all gaps can be ensured to be filled with the organic matters.
(4) The technical scheme disclosed by the invention has the advantages of simple process, low cost and wide application range, and can realize the preparation of the large-area and large-thickness ordered porous electrode.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications could be made by those skilled in the art without departing from the inventive concept. These are all within the scope of the present invention.
The invention relates to a method for preparing a large-area thickness controllable ordered porous electrode by a tape casting method, which comprises the following steps:
(1) Preparation of monodisperse microsphere Dispersion
Placing silica microspheres, polystyrene microspheres or polymethyl methacrylate microspheres with the particle size of 100-800 nm and the like into a reactor, adding solvents such as nitrogen methyl pyrrolidone, ethanol or water and the like, and performing ultrasonic dispersion to prepare viscous liquid with the particle size of 20-80%;
(2) Pretreatment of substrates
Taking carbon fiber paper, carbon fiber cloth, a metal woven net or etching net, foam nickel and the like as base materials, respectively ultrasonically cleaning the base materials in ethanol, acetone, isopropanol and deionized water, removing impurities and organic matters on the surfaces, and then drying in an oven;
(3) Preparation of colloidal photonic crystals
Spreading the substrate on a clean and flat glass plate, placing a proper amount of colloidal microsphere dispersion liquid at one end of the substrate, dispersing the colloidal microspheres into holes of the substrate by using a tape casting method, and naturally arranging the colloidal microspheres into photonic crystal structures in the holes of the porous substrate along with volatilization of a solvent;
(4) Preparation of inverse opal Structure
Organic matter solution with certain concentration, such as metal frame organic Matters (MOFs), acrylic acid-divinylbenzene, polymethyl methacrylate (PMMA), polyacrylonitrile (PAN), phenolic resin (PF), polyimide (PI) and the like, is filled into gaps of colloid photon crystals through capillary action, and colloid microspheres are removed after carbonization at 300-1000 ℃ at high temperature, so that an ordered porous sheet with an inverse opal structure is formed;
(5) Preparation of ordered porous electrode
Electrode active materials such as elemental sulfur, elemental selenium, elemental tellurium, metallic lithium, metallic sodium, elemental phosphorus, elemental silicon, elemental tin, elemental germanium, elemental zinc, manganese oxide, nickel oxide, cobalt oxide, vanadium pentoxide, molybdenum sulfide, lithium sulfide and the like are filled into the nano holes of the thin sheet by an in-situ growth method or a fusion adsorption method to form the ordered porous electrode.
The in-situ growth, the melt adsorption method or the casting method are all conventional methods in the field, for example, the in-situ growth can be the method reported in the literature of a foam nickel positive electrode current collector for in-situ growth of NiS of a magnesium-sulfur battery, and the melt adsorption method can be the method reported in the literature of Dendrite-Free and Ultra-Long-Life Lithium Metal Anode Enabled via a Three-Dimensional Ordered Porous Nanostructure.
The following are more detailed embodiments, by which the technical solutions of the invention and the technical effects that can be obtained are further illustrated.
Example 1
A method for preparing a large-area thickness controllable ordered porous electrode by a tape casting method comprises the following steps:
placing the silicon dioxide microsphere with the particle size of 300nm into a beaker, adding the nitrogen methyl pyrrolidone, and performing ultrasonic dispersion to prepare 50% viscous liquid. The method comprises the steps of taking carbon fiber paper as a base material, respectively ultrasonically cleaning the base material in ethanol, acetone, isopropanol and deionized water, removing impurities and organic matters on the surface, and then drying in a 100 ℃ oven. The substrate is subjected toSpreading on a clean and flat glass plate, placing 50mL of colloidal microsphere dispersion liquid at one end of the substrate, dispersing the colloidal microspheres into holes of the substrate by using a tape casting method, and naturally arranging the colloidal microspheres into photonic crystal structures in the holes of the porous substrate along with volatilization of the solvent. And filling a metal frame organic Matter (MOFs) solution with the concentration of 30wt% into gaps of the colloidal photonic crystal by utilizing a tape casting method, carbonizing at the high temperature of 800 ℃ and removing the colloidal microspheres subsequently to form an ordered porous sheet with an inverse opal structure. And melting the elemental sulfur at 160 ℃, and filling the elemental sulfur into the nano holes of the thin sheet by a melting adsorption method to form the ordered porous electrode. The prepared electrode has the thickness of 200um and the area of 400cm 2 。
Example 2
A method for preparing a large-area thickness controllable ordered porous electrode by a tape casting method comprises the following steps:
polystyrene microsphere with the particle size of 400nm is placed in a beaker, water is added, ultrasonic dispersion is carried out, and 60% of viscous liquid is prepared. And taking a nickel etching net as a base material, respectively ultrasonically cleaning the base material in ethanol, acetone, isopropanol and deionized water, removing impurities and organic matters on the surface, and then drying in a 100 ℃ oven. Spreading the substrate on a clean and flat glass plate, placing a proper amount of 70mL colloidal microsphere dispersion liquid at one end of the substrate, dispersing the colloidal microspheres into holes of the substrate by using a tape casting method, and naturally arranging the colloidal microspheres into photonic crystal structures in the holes of the porous substrate along with volatilization of the solvent. Polyimide (PI) with the concentration of 45% is filled into gaps of the colloidal photonic crystal by capillary action through a tape casting method, and colloid microspheres are removed subsequently through high-temperature carbonization at 600 ℃ to form ordered porous sheets with inverse opal structures. And melting metal lithium at 380 ℃, and filling simple substance lithium into the nano holes of the thin sheet by a melting adsorption method to form the ordered porous electrode. The prepared electrode has the thickness of 100um and the area of 500 cm 2 。
Example 3
A method for preparing a large-area thickness controllable ordered porous electrode by a tape casting method comprises the following steps:
the particle diameter is 200nmThe polymethyl methacrylate microsphere is placed in a beaker, added with the nitrogen methyl pyrrolidone, dispersed by ultrasonic, and prepared into 30% viscous liquid. Taking a stainless steel woven mesh as a base material, respectively ultrasonically cleaning the base material in ethanol, acetone, isopropanol and deionized water, removing impurities and organic matters on the surface, and then drying in a 100 ℃ oven. Spreading the substrate on a clean and flat glass plate, placing 100mL of colloidal microsphere dispersion liquid at one end of the substrate, dispersing the colloidal microspheres into holes of the substrate by using a tape casting method, and naturally arranging the colloidal microspheres into photonic crystal structures in the holes of the porous substrate along with volatilization of a solvent. And filling Polyacrylonitrile (PAN) with the concentration of 50% into gaps of the colloidal photonic crystal by utilizing a tape casting method, carbonizing at the high temperature of 700 ℃ and subsequently removing colloidal microspheres to form the ordered porous sheet with the inverse opal structure. And melting the elemental selenium at 300 ℃, and filling the elemental sulfur into the nano holes of the thin sheet by a melting adsorption method to form the ordered porous electrode. The prepared electrode has the thickness of 150um and the area of 800cm 2 。
The thickness of the porous electrode prepared by the method can be 20-600 um; the area can be 0.1cm 2 -1000 cm 2 The area and thickness of the electrode are controlled by the area and thickness of the substrate.
The porous electrode obtained by the invention not only can reach an ultra-large area, but also has excellent performance.
Performance detection is carried out under the constant current condition, and the detection method and the detection result are as follows:
specific capacity: and placing the assembled battery on a battery tester, setting a charge-discharge voltage interval and constant current parameters, testing the capacity of the battery in a constant current charge-discharge mode, and calculating the specific capacity of the battery according to the quality of the electrode active material.
Area capacity: and placing the assembled battery on a battery tester, setting a charge-discharge voltage interval and constant current parameters, testing the battery capacity in a constant current charge-discharge mode, and calculating the surface capacity of the electrode according to the electrode area.
Cycle life: and placing the assembled battery on a battery tester, setting a charging and discharging voltage interval and constant current parameters, and testing the capacity of the battery in a constant current charging and discharging mode. And (3) circularly running in the same mode, and counting all the circulation times of normal running of the battery and the capacity retention rate relative to the initial running.
Rate capability: and placing the assembled battery on a battery tester, setting a charging and discharging voltage interval, and simultaneously setting gradually-increased current parameters, and obtaining the rate performance of the battery according to the charging and discharging capacity and the quality of electrode active materials under different charging and discharging currents.
| Example 1 | Example 2 | Example 3 | |
| Specific capacity of | 1120mAh/g | 3160mAh/g | 630mAh/g |
| Area capacity | 8.96mAh/cm 2 | 47.4mAh/cm 2 | 6.3mAh/cm 2 |
| Capacity of | 3.6Ah | 23.7Ah | 50.4 |
| Cycle life | 300 weeks | 200 weeks | 300 weeks |
| Rate capability | 2C,810mAh/g | 2C,2490mAh/g | 2C,500mAh/g |
As can be seen from the above table, the method of the present invention can produce a surface area exceeding 400cm 2 And the resulting material has good properties.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (2)
1. A method for preparing a large-area thickness controllable ordered porous electrode by a tape casting method, which is characterized by comprising the following steps:
preparation of monodisperse colloidal microsphere Dispersion: mixing the monodisperse microspheres with a solvent and performing ultrasonic dispersion to prepare a dispersion liquid with the concentration of 20-80 wt%; the monodisperse microspheres are polystyrene microspheres, silicon dioxide microspheres or polymethyl methacrylate microspheres;
pretreatment of a porous substrate: ultrasonically cleaning a porous substrate, and then drying in an oven;
preparing colloid photon crystal: spreading the pretreated porous substrate on a clean glass plate, placing colloidal microsphere dispersion liquid at one end of the substrate, dispersing the colloidal microspheres into holes of the porous substrate by using a tape casting method, and naturally arranging the colloidal microspheres into photonic crystal structures in the holes of the porous substrate along with volatilization of a solvent;
preparation of inverse opal structure: filling organic matter solution with the mass concentration of 20% -60% into gaps of the colloidal photonic crystal by utilizing a tape casting method, carbonizing at high temperature and subsequently removing colloidal microspheres to form ordered porous sheets with inverse opal structures; the organic matter is metal frame organic matter, acrylic acid-divinylbenzene, polymethyl methacrylate, polyacrylonitrile, phenolic resin or polyimide; the preparation method of the organic matter solution comprises the steps of dissolving the organic matter into N, N-dimethylformamide solution to obtain the organic matter solution; the carbonization temperature is 300-1000 ℃;
preparation of ordered porous electrode: filling electrode active materials into the nano holes of the ordered porous sheet with the inverse opal structure by an in-situ growth method, a fusion adsorption method or a casting method to form an ordered porous electrode;
the particle size of the monodisperse microsphere is 100nm-800 nm;
the base material is a metal woven mesh, carbon fiber paper and carbon fiber cloth;
the metal woven mesh is a stainless steel mesh, a nickel mesh, a titanium mesh, a copper mesh, an aluminum mesh, a tungsten mesh, a molybdenum mesh, a zirconium mesh or a platinum mesh;
the electrode active material comprises elemental sulfur, elemental selenium, elemental tellurium, metallic lithium, metallic sodium, elemental phosphorus, elemental silicon, elemental tin, elemental germanium, elemental zinc, manganese oxide, nickel oxide, cobalt oxide, vanadium pentoxide, molybdenum sulfide or lithium sulfide;
the thickness of the prepared porous electrode is 20um-600um;
the area of the prepared porous electrode is 500 cm 2 -1000 cm 2 。
2. The method for preparing the large-area thickness-controllable ordered porous electrode by using the casting method according to claim 1, wherein the solvent is nitrogen methyl pyrrolidone, alcohol or water.
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