CN117638401A - Flexible ceramic diaphragm and preparation method and application thereof - Google Patents
Flexible ceramic diaphragm and preparation method and application thereof Download PDFInfo
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- CN117638401A CN117638401A CN202311262191.4A CN202311262191A CN117638401A CN 117638401 A CN117638401 A CN 117638401A CN 202311262191 A CN202311262191 A CN 202311262191A CN 117638401 A CN117638401 A CN 117638401A
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- 229910016467 AlCl 4 Inorganic materials 0.000 description 1
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- 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 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
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- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Cell Separators (AREA)
Abstract
The invention relates to the technical field of diaphragm materials, in particular to a flexible ceramic diaphragm and a preparation method and application thereof. The flexible ceramic diaphragm consists of a base film and a ceramic coating coated on the surface of the base film; the ceramic coating consists of inorganic ceramic particles, a binder and a dispersing agent. The compact ceramic layer coated on the surface of the base film can improve the mechanical strength and the thermal stability of the diaphragm, and the inorganic ceramic particles are fully filled in the large pore canal of the base film, so that the phenomenon of battery short circuit caused by the large pore canal of the base film can be effectively prevented, the ordered accumulation of the inorganic ceramic particles can better absorb electrolyte, the diaphragm has good liquid absorption rate and liquid storage rate, and the uniform bonding effect of the adhesive enables the flexible ceramic diaphragm to have high flexibility and deformation resistance, thereby improving the safety of the aluminum ion battery and realizing the long service life of the aluminum ion battery in stable circulation.
Description
Technical Field
The invention relates to the technical field of diaphragm materials, in particular to a flexible ceramic diaphragm and a preparation method and application thereof.
Background
With the rapid increase of the demands of new generation electronic digital devices, small mobile tools, new energy electric vehicles and the like, higher demands are put on novel electrochemical energy storage devices. Although the traditional lithium ion battery is widely popularized and applied in daily production and life nowadays, the traditional lithium ion battery still faces a plurality of problems which are difficult to solve. First, the cost of lithium ion batteries is not reduced at all times at present due to the distributed dispersion of lithium resources and the relative scarcity of reserves (the abundance of metallic lithium in the crust is only 17 ppm). In addition, the electrolyte used by the lithium ion battery belongs to flammable, toxic and volatile organic solvent electrolyte, and cannot meet the development trend of clean energy storage in the future, and has potential safety problems. Among the new generation of chemical energy storage devices following lithium secondary batteries, batteries using other metal ions, such as sodium, potassium, calcium, magnesium, and aluminum, are considered as reliable alternatives to electrical energy storage systems.
As the most abundant metal element in the crust, the aluminum mineral reserves are abundant, and the cost of exploitation, extraction, processing and purification has incomparable advantages compared with other metal anode materials, so that the metal aluminum is artificially a metal anode material with great application potential. Among all the current metal ion batteries, the aluminum ion battery has a typical multi-electron reaction system and various oxidation-reduction states, so that the aluminum ion battery has the highest volume specific capacity (8040 mAh.cm -3 ) Its theoretical volumetric energy density is about 4 times that of lithium ion battery, and its specific mass capacity (2980 mAh.g -1 ) Also in close proximity to lithium ion batteries. While metallic aluminum has a lower electrode potential,and thus has certain advantages in the new generation of chemical energy storage devices. In addition, the metal aluminum has good stability in air, does not generate spontaneous combustion reaction, is nontoxic and environment-friendly, has extremely high safety, and is a potential metal electrode material meeting the requirement of high safety of an energy storage device in the future. Therefore, aluminum metal is used as an inexpensive, environment-friendly and high-safety energy storage carrier with high specific energy, and aluminum ion batteries are considered as one of ideal choices of future energy storage systems.
The basic components of the aluminum ion battery are the same as those of the lithium ion battery, and the aluminum ion battery consists of a negative electrode, a diaphragm, an electrolyte and a positive electrode. In the construction of aluminum cells, the separator is one of the critical inner layer components. When the aluminum ion battery is charged and discharged, the battery diaphragm can prevent the positive electrode and the negative electrode of the battery from contacting, the battery is prevented from being short-circuited, and meanwhile, the porous structure can ensure quick passing of ions. The performance of the diaphragm determines the interface structure, internal resistance and the like of the battery, directly influences the capacity, circulation, safety performance and other characteristics of the battery, and the diaphragm with excellent performance plays an important role in improving the comprehensive performance of the battery.
Currently, most of the reported battery separators applicable to AIBs are Glass Fiber (GF) separators, which have been proven to be effective during previous studies and use. However, the Glass Fiber (GF) diaphragm has smooth surface and high brittleness, and the bonding force between the fibers is low, so that the mechanical strength of the Glass Fiber (GF) diaphragm is low, the structural integrity of the Glass Fiber (GF) diaphragm is difficult to ensure when the battery is assembled, and the short circuit or micro short circuit phenomenon of the battery is caused; and the aperture of the diaphragm is too large, thus increasing AlCl 4 - The permeability is also easily affected by the penetration of aluminum dendrite growth through the membrane, so that safety problems such as short circuit and the like are caused; in addition, the Glass Fiber (GF) preparation process is complicated, and has high energy consumption and high cost, which hinders the continuous progress of the industrialization of the aluminum ion battery. For aluminum battery series, because the electrolyte is an ionic liquid system, the development of ionic liquid resistant diaphragm materials is needed, the mechanical strength and flexibility are needed to be considered, and the flexible diaphragm can ensure that the diaphragm and the electrode are well attached together, so that the large contact area and the small polarization are ensured. In addition, flexible pair device assembly (winding, lamination) and preparation of wearable device to offImportant.
The prior art discloses an ionic liquid resistant cellulose/inorganic ceramic diaphragm, a preparation method and application thereof, and application number is 202311106367.7, and the technical scheme is that a flexible diaphragm is obtained, but a commercial cellulose product is taken as a base film, so that the chemical stability of cellulose is obviously improved, but the inherent micropore diameter and thickness of the commercial cellulose product still cannot avoid the problem of local short circuit of a battery caused by volume expansion of a positive electrode material and growth of negative electrode dendrite in long-term circulation of the battery.
Therefore, in the art, there is a need to develop a novel separator which not only has high mechanical strength and certain toughness, but also has good absorption capacity for electrolyte, and simultaneously, the assembled aluminum ion battery has safe and effective long cycle.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the flexible ceramic diaphragm, the preparation method and the application thereof, and the inorganic ceramic coating is coated on the surface of the base film, so that particles on the surface of the flexible ceramic diaphragm are regularly and tightly distributed, the diaphragm can better absorb electrolyte, and the diaphragm has higher mechanical strength and thermal stability due to the introduction of inorganic ceramic, so that the effective long service life of the aluminum ion battery is ensured to a certain extent. In addition, the inorganic ceramic balls in the inorganic ceramic coating have a synergistic effect, so that not only can macropores in the base film be fully filled, but also enough ion channels and liquid absorption and moisture retention are ensured, and the flexible ceramic diaphragm has high flexibility and deformation resistance due to the uniform bonding effect of the adhesive, so that the flexible ceramic diaphragm and the electrode are well attached, the cycle life of the aluminum ion battery is effectively prolonged, and the multiplying power performance of the aluminum ion battery is ensured.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a method for preparing a flexible ceramic diaphragm, comprising the steps of:
(1) Weighing the following raw materials in percentage by mass: 33-66% of ceramic particles, 0.3-0.8% of binder, 16.6-39.7% of dispersing agent and the balance of solvent, wherein the sum of the mass percentages of the raw materials is 100%;
(2) Ceramic particles, a binder, a dispersing agent and a solvent are mixed to obtain ceramic coating slurry;
(3) The ceramic coating slurry is coated on a base film by using a coating method, and then dried to constant weight, so that the flexible ceramic diaphragm is obtained, and only the coating method can be used for preparing the flexible ceramic diaphragm.
Preferably, the dispersing agent in the step (1) is one or more selected from methanol, ethanol, acetone, isopropanol, ethylene glycol, methyl ether, diethyl ether, propylene glycol, glycerol and polyethylene glycol.
Preferably, the binder in the step (1) is at least one selected from acrylic acid polymer, acrylamide polymer, styrene-butadiene rubber, polyvinyl alcohol, acrylonitrile polymer, polyurethane, polytetrafluoroethylene, sodium carboxymethyl cellulose, sodium alginate, methyl hydroxyethyl cellulose, polyethylene oxide and phenolic resin.
Preferably, the average particle diameter of the ceramic particles in the step (1) is 0.1-5 μm, and the morphology is spherical or lamellar.
Preferably, the ceramic particles in the step (1) are at least one selected from barium titanate particles, titanium dioxide particles, silicon dioxide particles, zirconium dioxide particles and aluminum oxide particles.
Preferably, the base film in the step (3) is selected from polyester resin non-woven fabrics or polytetrafluoroethylene non-woven fabrics; the thickness of the base film is 15-200 mu m.
Preferably, the coating method of step (3) is selected from screen printing coating, gravure coating, knife coating, spray coating or anilox roll coating.
Preferably, the thickness of the ceramic coating after drying in the step (3) is 10-30 μm.
The invention also protects the flexible ceramic diaphragm prepared by the preparation method, and the ceramic coating slurry is coated on one or two surfaces of the base diaphragm.
The invention also protects the application of the flexible ceramic diaphragm in preparing the aluminum ion battery diaphragm.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the preparation method of the flexible ceramic diaphragm, the common commercial diaphragm or non-woven fabric is selected as the base film of the composite diaphragm, so that the composite diaphragm has good stability and good infiltration liquid retention property, the liquid retention capacity of the aluminum ion battery diaphragm is improved, the problem that the aluminum ion battery is easy to dry in the middle and later stages of battery circulation is prevented, and the cycle life of the aluminum ion battery is effectively prolonged while the multiplying power performance of the aluminum ion battery is guaranteed.
2. According to the preparation method of the flexible ceramic diaphragm, the ceramic coating slurry is prepared, and the surface of the base film is coated with a layer of ceramic material, so that the mechanical strength and the thermal stability of the composite diaphragm are effectively improved, the phenomenon of diaphragm perforation is avoided, and the safety and the stability of a lithium battery are further improved; the ceramic particles are added to improve the compatibility problem of the base film and the electrolyte, so that each component of the battery has good interface compatibility, and is beneficial to the transmission of ions; the base film is an irregular macroporous film, the aperture is about 10 mu m, the coating of the ceramic slurry further evenly distributes the aperture, so that even pore channels of the diaphragm are realized, the bonding force of ceramic particles on the base film is further enhanced by reasonable proportioning of the slurry, the problem that the traditional coated ceramic is easy to fall off is effectively solved, the preparation of the flexible ceramic diaphragm is realized, the diaphragm and an electrode are further well attached, the large contact area and the small polarization are ensured, and the good assembly of the coiled and laminated battery device is realized.
Compared with the prior art, the preparation method of the aluminum ion battery flexible ceramic diaphragm provided by the invention is extremely simple, can be realized by simple coating, is low in preparation cost, is environment-friendly, has a certain industrialization prospect, and widens a new thought for the application of ceramic particles in the technical field of batteries.
4. Compared with the cellulose/inorganic ceramic diaphragm in the prior art, in the application of the aluminum ion battery, the thickness of the diaphragm is controllable, and the ceramic particles on the non-woven fabric film are fully accumulated, so that the flexible ceramic diaphragm has certain resistance and flexibility, the deformation problem caused by volume expansion of the positive electrode graphite is reduced, the high surface area generated by particle accumulation increases the growth and tortuosity degree of the aluminum negative electrode dendrite, and the local short circuit phenomenon caused by positive and negative electrode contact is avoided, thereby being beneficial to long-term recycling of the battery.
Drawings
In fig. 1, (a) is a PET nonwoven fabric base film micro-morphology chart, (b) is a flexible ceramic separator micro-morphology chart of example 1, and (c) is a cellulose/inorganic ceramic separator micro-morphology chart;
FIG. 2 is a schematic view of the flexibility of the flexible ceramic membrane prepared in example 1;
fig. 3 is a graph of the rate performance of the flexible ceramic separator assembled aluminum ion battery prepared in example 1:
fig. 4 is a long cycle chart of an aluminum ion battery assembled with a flexible ceramic separator prepared in example 1.
Detailed Description
The following detailed description of specific embodiments of the invention is, but it should be understood that the invention is not limited to specific embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The experimental methods described in the examples of the present invention are conventional methods unless otherwise specified.
Example 1
A method for preparing a flexible ceramic diaphragm, comprising the following steps:
preparing 49.5 mass percent of ceramic particles, 0.5 mass percent of binder, 25 mass percent of dispersing agent and the balance of solvent (deionized water);
(1) Uniformly mixing a solvent and a binder to obtain mucilage;
in order to ensure full and even mixing, the specific method of the step is as follows: adding binder powder (polyvinyl alcohol PVA) into solvent (deionized water), and stirring at a rotation speed of 700r/m for 18h to obtain mucilage;
(2) Uniformly mixing the mucilage with a dispersing agent to obtain a bonding slurry precursor;
in order to ensure full and even mixing, the specific method of the step is as follows: adding a dispersing agent (ethanol) into the adhesive liquid, stirring at the stirring speed of 600r/m, and mixing for 12 hours to obtain a bonding slurry precursor;
(3) Bonding slurry precursor and SiO 2 Uniformly mixing ceramic particles (2 mu m) to obtain ceramic coating slurry;
in order to ensure full and even mixing, the specific method of the step is as follows: siO addition to bond paste precursor 2 (2 μm) ceramic particles, then stirring at a stirring speed of 800r/m, and mixing for 3 hours to obtain ceramic coating slurry;
(4) The preparation method of the flexible battery diaphragm comprises the following steps: coating the ceramic coating slurry on the surface of 200 μm PET non-woven fabric base film by using a doctor blade coating mode, wherein the thickness is 20 μm, and then drying for 12 hours by blowing at 60 ℃ to obtain the flexible SiO 2 A ceramic separator.
Example 2
A method for preparing a flexible ceramic diaphragm, comprising the following steps:
preparing 49.5 mass percent of ceramic particles, 0.5 mass percent of binder, 25 mass percent of dispersing agent and the balance of solvent (deionized water);
(1) Uniformly mixing a solvent and a binder to obtain mucilage;
in order to ensure full and even mixing, the specific method of the step is as follows: adding binder powder (polyvinyl alcohol PVA) into solvent (deionized water), and stirring at a rotation speed of 700r/m for 18h to obtain mucilage;
(2) Uniformly mixing the mucilage with a dispersing agent to obtain a bonding slurry precursor;
in order to ensure full and even mixing, the specific method of the step is as follows: adding a dispersing agent (ethanol) into the adhesive liquid, stirring at the stirring speed of 600r/m, and mixing for 12 hours to obtain a bonding slurry precursor;
(3) Bonding slurry precursor and TiO 2 Uniformly mixing ceramic particles (2 mu m) to obtain ceramic coating slurry;
in order to ensure full and even mixing, the specific method of the step is as follows: to the bonding paste precursorTiO is added into the body 2 (2 μm) ceramic particles, then stirring at a stirring speed of 800r/m, and mixing for 3 hours to obtain ceramic coating slurry;
(4) The preparation method of the flexible battery diaphragm comprises the following steps: coating the ceramic coating slurry on the surface of 200 μm PET non-woven fabric base film by using a doctor blade coating mode, wherein the thickness is 20 μm, and then drying for 12 hours by blowing at 60 ℃ to obtain flexible TiO 2 A ceramic separator.
Example 3
A method for preparing a flexible ceramic diaphragm, comprising the following steps:
preparing 49.5 mass percent of ceramic particles, 0.5 mass percent of binder, 25 mass percent of dispersing agent and the balance of solvent (deionized water);
(1) Uniformly mixing a solvent and a binder to obtain mucilage;
in order to ensure full and even mixing, the specific method of the step is as follows: adding binder powder (polyvinyl alcohol PVA) into solvent (deionized water), and stirring at a rotation speed of 700r/m for 18h to obtain mucilage;
(2) Uniformly mixing the mucilage with a dispersing agent to obtain a bonding slurry precursor;
in order to ensure full and even mixing, the specific method of the step is as follows: adding a dispersing agent (ethanol) into the adhesive liquid, stirring at the stirring speed of 600r/m, and mixing for 12 hours to obtain a bonding slurry precursor;
(3) Bonding slurry precursor and ZrO 2 Uniformly mixing ceramic particles (2 mu m) to obtain ceramic coating slurry;
in order to ensure full and even mixing, the specific method of the step is as follows: adding ZrO to a bonding paste precursor 2 (2 μm) ceramic particles, then stirring at a stirring speed of 800r/m, and mixing for 3 hours to obtain ceramic coating slurry;
(4) The preparation method of the flexible battery diaphragm comprises the following steps: coating the ceramic coating slurry on the surface of 200 μm PET non-woven fabric base film by using a doctor blade coating mode, wherein the thickness is 20 μm, and then drying for 12h by blowing at 60 ℃ to obtain the flexible ZrO 2 A ceramic separator.
Example 4
A method for preparing a flexible ceramic diaphragm, comprising the following steps:
preparing 49.5 mass percent of ceramic particles, 0.5 mass percent of binder, 25 mass percent of dispersing agent and the balance of solvent (deionized water);
(1) Uniformly mixing a solvent and a binder to obtain mucilage;
in order to ensure full and even mixing, the specific method of the step is as follows: adding binder powder (polyvinyl alcohol PVA) into solvent (deionized water), and stirring at a rotation speed of 700r/m for 18h to obtain mucilage;
(2) Uniformly mixing the mucilage with a dispersing agent to obtain a bonding slurry precursor;
in order to ensure full and even mixing, the specific method of the step is as follows: adding a dispersing agent (ethanol) into the adhesive liquid, stirring at the stirring speed of 600r/m, and mixing for 12 hours to obtain a bonding slurry precursor;
(3) Bonding slurry precursor and Al 2 O 3 Uniformly mixing ceramic particles (2 mu m) to obtain ceramic coating slurry;
in order to ensure full and even mixing, the specific method of the step is as follows: adding Al to a bond paste precursor 2 O 3 (2 μm) ceramic particles, then stirring at a stirring speed of 800r/m, and mixing for 3 hours to obtain ceramic coating slurry;
(4) The preparation method of the flexible battery diaphragm comprises the following steps: coating the ceramic coating slurry on the surface of 200 μm PET non-woven fabric base film by using a doctor blade coating mode, wherein the thickness is 20 μm, and then drying for 12h by blowing at 60 ℃ to obtain flexible Al 2 O 3 A ceramic separator.
Example 5
A method for preparing a flexible ceramic diaphragm, comprising the following steps:
preparing 49.5 mass percent of ceramic particles, 0.5 mass percent of binder, 25 mass percent of dispersing agent and the balance of solvent (deionized water);
(1) Uniformly mixing a solvent and a binder to obtain mucilage;
in order to ensure full and even mixing, the specific method of the step is as follows: adding binder powder (polyvinyl alcohol PVA) into solvent (deionized water), and stirring at a rotation speed of 700r/m for 18h to obtain mucilage;
(2) Uniformly mixing the mucilage with a dispersing agent to obtain a bonding slurry precursor;
in order to ensure full and even mixing, the specific method of the step is as follows: adding a dispersing agent (ethanol) into the adhesive liquid, stirring at the stirring speed of 600r/m, and mixing for 12 hours to obtain a bonding slurry precursor;
(3) Bonding slurry precursor and BaTiO 3 Uniformly mixing ceramic particles (2 mu m) to obtain ceramic coating slurry;
in order to ensure full and even mixing, the specific method of the step is as follows: addition of BaTiO to bond paste precursor 3 (2 μm) ceramic particles, then stirring at a stirring speed of 800r/m, and mixing for 3 hours to obtain ceramic coating slurry;
(4) The preparation method of the flexible battery diaphragm comprises the following steps: coating the ceramic coating slurry on the surface of 200 μm PET non-woven fabric base film by using a doctor blade coating mode, wherein the thickness is 20 μm, and then drying for 12 hours by blowing at 60 ℃ to obtain the flexible BaTiO 3 A ceramic separator.
Example 6
A method for preparing a flexible ceramic diaphragm, comprising the following steps:
preparing materials according to the mass percent of 19.8 percent of ceramic particles, 0.8 percent of binder, 39.7 percent of dispersing agent and the balance of solvent (deionized water);
(1) Uniformly mixing a solvent and a binder to obtain mucilage;
in order to ensure full and even mixing, the specific method of the step is as follows: adding binder powder (polyvinyl alcohol PVA) into solvent (deionized water), and stirring at 800r/m for 24h to obtain mucilage;
(2) Uniformly mixing the mucilage with a dispersing agent to obtain a bonding slurry precursor;
in order to ensure full and even mixing, the specific method of the step is as follows: adding a dispersing agent (ethanol) into the adhesive liquid, stirring at a stirring speed of 800r/m, and mixing for 18 hours to obtain a bonding slurry precursor;
(3) Bonding slurry precursor and SiO 2 Uniformly mixing ceramic particles (0.2 mu m) to obtain ceramic coating slurry;
in order to ensure full and even mixing, the specific method of the step is as follows: siO addition to bond paste precursor 2 (0.2 mu m) ceramic particles, stirring at 800r/m, and mixing for 3 hours to obtain ceramic coating slurry;
(4) The preparation method of the flexible battery diaphragm comprises the following steps: coating the ceramic coating slurry on the surface of 200 μm PET non-woven fabric base film by using a doctor blade coating mode, wherein the thickness is 20 μm, and then drying for 12 hours by blowing at 60 ℃ to obtain the flexible SiO 2 A ceramic separator.
Example 7
A method for preparing a flexible ceramic diaphragm, comprising the following steps:
preparing materials according to 33 mass percent of ceramic particles, 0.7 mass percent of binder, 33 mass percent of dispersing agent and the balance of solvent (deionized water);
(1) Uniformly mixing a solvent and a binder to obtain mucilage;
in order to ensure full and even mixing, the specific method of the step is as follows: adding binder powder (polyvinyl alcohol PVA) into solvent (deionized water), and stirring at 800r/m for 20h to obtain mucilage;
(2) Uniformly mixing the mucilage with a dispersing agent to obtain a bonding slurry precursor;
in order to ensure full and even mixing, the specific method of the step is as follows: adding a dispersing agent (ethanol) into the adhesive liquid, stirring at a stirring speed of 800r/m, and mixing for 18 hours to obtain a bonding slurry precursor;
(3) Bonding slurry precursor and SiO 2 Uniformly mixing ceramic particles (0.5 mu m) to obtain ceramic coating slurry;
in order to ensure full and even mixing, the specific method of the step is as follows: siO addition to bond paste precursor 2 (0.5 μm) ceramic particles, stirring at 800r/m, and mixing for 3 hr to obtain ceramicCeramic coating slurry;
(4) The preparation method of the flexible battery diaphragm comprises the following steps: coating the ceramic coating slurry on the surface of 200 μm PET non-woven fabric base film by using a doctor blade coating mode, wherein the thickness is 20 μm, and then drying for 12 hours by blowing at 60 ℃ to obtain the flexible SiO 2 A ceramic separator.
Example 8
A method for preparing a flexible ceramic diaphragm, comprising the following steps:
preparing materials according to 66% of ceramic particles, 0.3% of binder, 16.6% of dispersing agent and the balance of solvent (deionized water) by mass percent;
(1) Uniformly mixing a solvent and a binder to obtain mucilage;
in order to ensure full and even mixing, the specific method of the step is as follows: adding binder powder (polyvinyl alcohol PVA) into solvent (deionized water), and stirring at 600r/m for 12h to obtain mucilage;
(2) Uniformly mixing the mucilage with a dispersing agent to obtain a bonding slurry precursor;
in order to ensure full and even mixing, the specific method of the step is as follows: adding a dispersing agent (ethanol) into the adhesive liquid, stirring at the stirring speed of 600r/m, and mixing for 12 hours to obtain a bonding slurry precursor;
(3) Bonding slurry precursor and SiO 2 Uniformly mixing (5 mu m) ceramic particles to obtain ceramic coating slurry;
in order to ensure full and even mixing, the specific method of the step is as follows: siO addition to bond paste precursor 2 (5 μm) ceramic particles, then stirring at a stirring speed of 800r/m, and mixing for 3 hours to obtain ceramic coating slurry;
(4) The preparation method of the flexible battery diaphragm comprises the following steps: coating the ceramic coating slurry on the surface of 200 μm PET non-woven fabric base film by using a doctor blade coating mode, wherein the thickness is 20 μm, and then drying for 12 hours by blowing at 60 ℃ to obtain the flexible SiO 2 A ceramic separator.
Example 9
A method for preparing a flexible ceramic diaphragm, comprising the following steps:
preparing 49.5 mass percent of ceramic particles, 0.5 mass percent of binder, 25 mass percent of dispersing agent and the balance of solvent (deionized water);
(1) Uniformly mixing a solvent and a binder to obtain mucilage;
in order to ensure full and even mixing, the specific method of the step is as follows: adding binder powder (polyacrylamide PAM) into solvent (deionized water), and stirring at 600r/m for 18h to obtain mucilage;
(2) Uniformly mixing the mucilage with a dispersing agent to obtain a bonding slurry precursor;
in order to ensure full and even mixing, the specific method of the step is as follows: adding a dispersing agent (ethanol) into the adhesive liquid, stirring at the stirring speed of 600r/m, and mixing for 18 hours to obtain a bonding slurry precursor;
(3) Bonding slurry precursor and SiO 2 Uniformly mixing ceramic particles (2 mu m) to obtain ceramic coating slurry;
in order to ensure full and even mixing, the specific method of the step is as follows: siO addition to bond paste precursor 2 (2 μm) ceramic particles, then stirring at a stirring speed of 800r/m, and mixing for 3 hours to obtain ceramic coating slurry;
(4) The preparation method of the flexible battery diaphragm comprises the following steps: coating the ceramic coating slurry on the surface of 200 μm PET non-woven fabric base film by using a doctor blade coating mode, wherein the thickness is 20 μm, and then drying for 12 hours by blowing at 60 ℃ to obtain the flexible SiO 2 A ceramic separator.
Example 10
A method for preparing a flexible ceramic diaphragm, comprising the following steps:
preparing 49.5 mass percent of ceramic particles, 0.5 mass percent of binder, 25 mass percent of dispersing agent and the balance of solvent (deionized water);
(1) Uniformly mixing a solvent and a binder to obtain mucilage;
in order to ensure full and even mixing, the specific method of the step is as follows: adding binder powder (polytetrafluoroethylene (PTFE)) into solvent (deionized water), and stirring at 600r/m for 12 hr to obtain mucilage;
(2) Uniformly mixing the mucilage with a dispersing agent to obtain a bonding slurry precursor;
in order to ensure full and even mixing, the specific method of the step is as follows: adding a dispersing agent (ethanol) into the adhesive liquid, stirring at the stirring speed of 600r/m, and mixing for 12 hours to obtain a bonding slurry precursor;
(3) Bonding slurry precursor and SiO 2 Uniformly mixing ceramic particles (2 mu m) to obtain ceramic coating slurry;
in order to ensure full and even mixing, the specific method of the step is as follows: siO addition to bond paste precursor 2 (2 μm) ceramic particles, then stirring at a stirring speed of 800r/m, and mixing for 3 hours to obtain ceramic coating slurry;
(4) The preparation method of the flexible battery diaphragm comprises the following steps: coating the ceramic coating slurry on the surface of 200 μm PET non-woven fabric base film by using a doctor blade coating mode, wherein the thickness is 20 μm, and then drying for 12 hours by blowing at 60 ℃ to obtain the flexible SiO 2 A ceramic separator.
Example 11
A method for preparing a flexible ceramic diaphragm, comprising the following steps:
preparing 49.5 mass percent of ceramic particles, 0.5 mass percent of binder, 25 mass percent of dispersing agent and the balance of solvent (N, N dimethylformamide);
(1) Uniformly mixing a solvent and a binder to obtain mucilage;
in order to ensure full and even mixing, the specific method of the step is as follows: adding binder powder (polyacrylonitrile PAN) into solvent (N, N dimethylformamide), and stirring at a rotation speed of 700r/m for 12h to obtain mucilage;
(2) Uniformly mixing the mucilage with a dispersing agent to obtain a bonding slurry precursor;
in order to ensure full and even mixing, the specific method of the step is as follows: adding a dispersing agent (ethanol) into the adhesive liquid, stirring at the stirring speed of 600r/m, and mixing for 10 hours to obtain a bonding slurry precursor;
(3) Bonding slurry precursorSiO 2 Uniformly mixing ceramic particles (2 mu m) to obtain ceramic coating slurry;
in order to ensure full and even mixing, the specific method of the step is as follows: siO addition to bond paste precursor 2 (2 μm) ceramic particles, stirring at 800r/m, and mixing for 3 hr to obtain SiO 2 Ceramic coating slurry;
(4) The preparation method of the flexible ceramic battery diaphragm comprises the following steps: coating the ceramic coating slurry on the surface of 200 μm PET non-woven fabric base film by using a doctor blade coating mode, wherein the thickness is 20 μm, and then drying for 12 hours by blowing at 60 ℃ to obtain the flexible SiO 2 A ceramic separator.
Example 12
A method for preparing a flexible ceramic diaphragm, comprising the following steps:
preparing 49.5 mass percent of ceramic particles, 0.5 mass percent of binder, 25 mass percent of dispersing agent and the balance of solvent (deionized water);
(1) Uniformly mixing a solvent and a binder to obtain mucilage;
in order to ensure full and even mixing, the specific method of the step is as follows: adding binder powder (polyvinyl alcohol PVA) into solvent (deionized water), and stirring at a rotation speed of 700r/m for 18h to obtain mucilage;
(2) Uniformly mixing the mucilage with a dispersing agent to obtain a bonding slurry precursor;
in order to ensure full and even mixing, the specific method of the step is as follows: adding a dispersing agent (ethanol) into the adhesive liquid, stirring at the stirring speed of 600r/m, and mixing for 12 hours to obtain a bonding slurry precursor;
(3) The mass ratio of the bonding slurry precursor is 1:1 SiO of 1 2 And TiO 2 Uniformly mixing ceramic particles (2 mu m) to obtain ceramic coating slurry;
in order to ensure full and even mixing, the specific method of the step is as follows: adding the following components in percentage by mass into a bonding slurry precursor: 1 SiO of 1 2 And TiO 2 (2 μm) ceramic particles, then stirring at a stirring speed of 800r/m, and mixing for 3 hours to obtain ceramic coating slurry;
(4) The preparation method of the flexible battery diaphragm comprises the following steps: coating the ceramic coating slurry on the surface of 200 μm PET non-woven fabric base film by using a doctor blade coating mode, wherein the thickness is 20 μm, and then drying for 12 hours by blowing at 60 ℃ to obtain the flexible SiO 2 And TiO 2 Is provided.
Example 13
A method for preparing a flexible ceramic diaphragm, comprising the following steps:
preparing 49.5 mass percent of ceramic particles, 0.5 mass percent of binder, 25 mass percent of dispersing agent and the balance of solvent (deionized water);
(1) Uniformly mixing a solvent and a binder to obtain mucilage;
in order to ensure full and even mixing, the specific method of the step is as follows: adding binder powder (polyvinyl alcohol PVA) into solvent (deionized water), and stirring at a rotation speed of 700r/m for 18h to obtain mucilage;
(2) Uniformly mixing the mucilage with a dispersing agent to obtain a bonding slurry precursor;
in order to ensure full and even mixing, the specific method of the step is as follows: adding a dispersing agent (ethanol) into the adhesive liquid, stirring at the stirring speed of 600r/m, and mixing for 12 hours to obtain a bonding slurry precursor;
(3) The mass ratio of the bonding slurry precursor is 1:1 SiO of 1 2 (2 μm) ceramic particles and SiO 2 Uniformly mixing ceramic particles (0.2 mu m) to obtain ceramic coating slurry;
in order to ensure full and even mixing, the specific method of the step is as follows: adding the following components in percentage by mass into a bonding slurry precursor: 1 SiO of 1 2 (2 mu m, 0.2 mu m) ceramic particles, stirring at 800r/m, and mixing for 3 hours to obtain ceramic coating slurry;
(4) The preparation method of the flexible battery diaphragm comprises the following steps: coating the ceramic coating slurry on the surface of a 200 mu m PET non-woven fabric base film in a doctor blade coating mode, wherein the thickness is 20 mu m, and then drying the PET non-woven fabric base film in a blowing mode at 60 ℃ for 12 hours to obtain the SiO with flexible mixed particle size 2 A ceramic separator.
Inventive examples 1-13 were all madeThe flexible ceramic diaphragm with simple process and long cycle service life is obtained, the effect is parallel, and the flexible SiO prepared in the following example 1 2 The diaphragm was studied as an example, and the specific study method and results are as follows:
preparation of a positive plate:
the positive electrode active material adopts Flake Graphite (FG), and the preparation process is as follows:
s1, compounding and stirring: according to Flake Graphite (FG), conductive agent, CMC=80:10:10, and stirring to obtain viscous slurry;
s2, coating the slurry on a current collector molybdenum foil (AIBs) to manufacture a pole piece, rolling after coating, and baking at 70 ℃ for 12 hours;
s3, cutting into pieces by a cutting machine to obtain a circular piece with the diameter of 12mm, so as to obtain a positive plate;
assembling an aluminum ion battery:
the obtained flexible SiO 2 The diaphragm is cut into a circular sheet with the diameter of 16mm, a customized polytetrafluoroethylene Shiwei roc battery (with the inner diameter of 14.8 mm) is assembled, the battery is assembled in a glove box, the shaped polytetrafluoroethylene is used as a shell, two molybdenum electrodes with the diameter of 14.8 mm are used as two poles, and two rubber rings are respectively arranged at two ends, so that the inside of the device is isolated and sealed from the external environment. Placing negative aluminum foil and flexible SiO 2 Diaphragm and ionic liquid electrolyte AlCl 3 /Et 3 NHCl (1.5:1) and positive plate (FG), and finally sealing the schweilok cell mold completely with sealing film to isolate air; and (3) evaluating the electrochemical performance of the material by adopting a Prins ston electrochemical workstation and a voltage range of 0.5-2.5V.
TABLE 1 cutting the required base film 19X 19mm, weighing after 12h treatment at 120deg.C in vacuum oven, transferring into glove box, soaking in AlCl 3 /Et 3 Transferring the mixture out of the glove box 7 days after NHCl (1.5:1), weighing again after soaking and washing the mixture by clear water, calculating the quality difference before and after soaking, and calculating the quality loss ratio.
Wherein m is 1 Represents the mass before soaking, m 2 Representing the mass after soaking.
Table 1 comparison of chemical stability of base film in ionic liquid electrolyte
As can be seen from the data in table 1, the base film was different in chemical stability in the ionic liquid electrolyte, so that the commercial PET and PTFE nonwoven fabric films were first selected when the base film was selected.
FIG. 1 shows a PET nonwoven fabric base film, flexible SiO 2 SEM images of ceramic membranes and cellulose/ceramic membranes, FIG. 2 is a flexible SiO 2 A flexible representation of a ceramic diaphragm. As can be seen from fig. 1, the coarse fibers and the large pore diameter of the PET non-woven fabric base film are very easy to generate the short circuit phenomenon of the battery, and the cellulose/inorganic ceramic diaphragm is improved in the large pore diameter compared with the PET non-woven fabric base film, but still presents the micron pore diameter, and still has the hidden trouble of local micro short circuit; with reference to FIGS. 1 and 2, the flexible SiO produced in example 1 of the present application 2 In the ceramic diaphragm, ceramic particles are uniformly distributed on the fiber surface and in the large pore canal of the PET non-woven fabric base film, and the base film and the ceramic particles have good compatibility, so that the ceramic diaphragm integrally shows high flexibility and deformation resistance due to uniform adhesion of ceramic particles.
The results of fig. 3 and 4 show that when the flexible ceramic diaphragm is assembled into an Aluminum Ion Battery (AIBs), the battery can be stably charged and discharged under different current densities, the coulomb efficiency is kept above 98%, the rapid charging and discharging of the battery can be realized, further, the flexible ceramic diaphragm has good ion conductivity and porosity, and the stable long-cycle result of 700 circles under the current density of 500mA/g also proves that the flexible ceramic diaphragm has good electrochemical stability, and can meet the charging and discharging requirements of the Aluminum Ion Battery (AIBs).
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (10)
1. A method for preparing a flexible ceramic diaphragm, comprising the steps of:
weighing the following raw materials in percentage by mass: 33-66% of ceramic particles, 0.3-0.8% of binder, 16.6-39.7% of dispersing agent and the balance of solvent, wherein the sum of the mass percentages of the raw materials is 100%;
ceramic particles, a binder, a dispersing agent and a solvent are mixed to obtain ceramic coating slurry;
the ceramic coating slurry is coated on a base film by using a coating method, and then dried to constant weight, thereby obtaining the flexible ceramic diaphragm.
2. The method for preparing the flexible ceramic membrane according to claim 1, wherein the dispersing agent is one or more selected from methanol, ethanol, acetone, isopropanol, ethylene glycol, methyl ether, diethyl ether, propylene glycol, glycerol and polyethylene glycol.
3. The method for preparing a flexible ceramic membrane according to claim 1, wherein the binder is at least one selected from the group consisting of acrylic polymers, acrylamide polymers, styrene-butadiene rubber, polyvinyl alcohol, acrylonitrile polymers, polyurethane, polytetrafluoroethylene, sodium carboxymethyl cellulose, sodium alginate, methyl hydroxyethyl cellulose, polyethylene oxide, and phenolic resins.
4. The method for preparing the flexible ceramic membrane according to claim 1, wherein the average particle size of the ceramic particles is 0.1-5 μm, and the morphology is spherical or lamellar.
5. The method for producing a flexible ceramic separator according to claim 1, wherein the ceramic particles are at least one selected from the group consisting of barium titanate particles, titanium dioxide particles, silicon dioxide particles, zirconium dioxide particles, and aluminum oxide particles.
6. The method for preparing a flexible ceramic membrane according to claim 1, wherein the base membrane is selected from polyester resin nonwoven fabric or polytetrafluoroethylene nonwoven fabric; the thickness of the base film is 15-200 mu m.
7. The method of claim 1, wherein the coating method is selected from screen printing, gravure, knife coating, spray coating, and anilox roll coating.
8. The method for preparing a flexible ceramic membrane according to claim 1, wherein the thickness of the ceramic coating after drying is 10-30 μm.
9. A flexible ceramic separator membrane made by the method of any one of claims 1-8 wherein the ceramic coating slurry is applied to one or both surfaces of the base membrane.
10. Use of the flexible ceramic separator of claim 9 in the preparation of an aluminum ion battery separator.
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