CN114094273B - Thermal battery isolation layer with overflow prevention function and preparation method thereof - Google Patents
Thermal battery isolation layer with overflow prevention function and preparation method thereof Download PDFInfo
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- 238000002955 isolation Methods 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 230000002265 prevention Effects 0.000 title abstract description 6
- 239000003792 electrolyte Substances 0.000 claims abstract description 68
- 150000003839 salts Chemical class 0.000 claims abstract description 39
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 27
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 25
- 150000002500 ions Chemical class 0.000 claims abstract description 12
- 238000001179 sorption measurement Methods 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 17
- 239000012528 membrane Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000002791 soaking Methods 0.000 claims description 12
- 159000000003 magnesium salts Chemical class 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000012266 salt solution Substances 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 6
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 6
- 235000011285 magnesium acetate Nutrition 0.000 claims description 6
- 239000011654 magnesium acetate Substances 0.000 claims description 6
- 229940069446 magnesium acetate Drugs 0.000 claims description 6
- 229940074358 magnesium ascorbate Drugs 0.000 claims description 6
- AIOKQVJVNPDJKA-ZZMNMWMASA-L magnesium;(2r)-2-[(1s)-1,2-dihydroxyethyl]-4-hydroxy-5-oxo-2h-furan-3-olate Chemical compound [Mg+2].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] AIOKQVJVNPDJKA-ZZMNMWMASA-L 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 230000005540 biological transmission Effects 0.000 abstract description 7
- 230000009471 action Effects 0.000 abstract description 5
- 239000003463 adsorbent Substances 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 12
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Inorganic materials [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 230000005496 eutectics Effects 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 4
- 229910001508 alkali metal halide Inorganic materials 0.000 description 4
- 150000008045 alkali metal halides Chemical class 0.000 description 4
- -1 aluminum ions Chemical class 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 229910001425 magnesium ion Inorganic materials 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 229910013489 LiCl-LiBr-KBr Inorganic materials 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 229910013618 LiCl—KCl Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000012938 design process Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/417—Polyolefins
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Cell Separators (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a thermal battery isolation layer with an overflow preventing function and a preparation method thereof. The thermal battery isolating layer is characterized by comprising a bi-pass directional vertical array film, magnesium oxide and molten salt electrolyte; the bi-pass directional vertical array film is used as an adsorption carrier, and the mass content is 20-40%; the magnesium oxide is filled as particles, and the mass content is 10-30%; the molten salt electrolyte is used as an ion conducting medium, and the mass content is 40-70%. According to the thermal battery isolation layer with the overflow prevention function, the mechanical strength of the isolation layer is enhanced, molten salt electrolyte is adsorbed inside the pipeline structure through capillary action of the oriented vertically arranged pipeline structure, the adsorption capacity of the adsorbent to the thermal battery electrolyte during the operation of the thermal battery is greatly improved, and the overflow phenomenon of the electrolyte is inhibited. Meanwhile, the thickness of the isolating layer is 50-200 mu m, which is thinner than that of the common thermal battery isolating layer, so that the ion transmission distance can be obviously reduced, and the rapid transmission of ions in the isolating layer can be realized.
Description
Technical Field
The invention belongs to the field of material chemistry, and particularly relates to a thermal battery isolation layer with an anti-overflow function and a preparation method thereof.
Background
The thermal battery is a primary reserve battery which uses self-contained heating materials to heat and melt solid salt electrolyte which is not conductive at normal temperature into ionic conductors to output electric energy, and is characterized in that the working temperature can reach 500-600 ℃, and the battery has the unique performance of normal working at-60 ℃ to +60 ℃.
The common electrolyte of the thermal battery is a eutectic salt system of alkali metal halide, such as LiF-LiCl-LiBr eutectic salt system, liCl-LiBr-KBr eutectic salt system, liCl-KCl eutectic salt system and the like. Although the ionic conductivity of the molten salt electrolyte is high at high temperatures, the flow of the liquid molten salt electrolyte can have a significant impact on the performance of the thermal battery and, in severe cases, can cause shorting of the battery. Therefore, in the conventional thermal battery system, magnesium oxide is added as an inhibitor to the electrolyte to inhibit the flow of the liquid electrolyte, and the electrolyte after the addition of magnesium oxide is collectively called a separator in the field of thermal batteries.
The increase of the content of the magnesium oxide can effectively inhibit the flow of molten salt electrolyte and reduce the leakage amount of the electrolyte, however, the addition of the magnesium oxide can affect the ion transmission efficiency of the electrolyte and increase the resistivity of the electrolyte, so that the content of the magnesium oxide is generally controlled to be 35-60%. When the mass content of magnesium oxide in the isolating layer is 35%, the overall leakage rate of the electrolyte is 6% and the thickness change rate is 24% after the isolating layer is insulated for 30 minutes at 600 ℃. However, since the conventional thermal battery separator is prepared by mixing magnesium oxide with molten salt electrolyte and then using a powder forming process, the mechanical strength of the separator is poor in the preparation process, the separator is easily extruded by the internal pressure of the battery in the discharging process, the electrolyte overflows, and the internal short circuit of the battery is caused, so that serious safety problems are caused.
Disclosure of Invention
In order to solve the problems, the invention provides a thermal battery isolation layer with an anti-overflow function, which is characterized by comprising a bi-pass directional vertical array film, magnesium oxide and molten salt electrolyte; the bi-pass directional vertical array film is used as an adsorption carrier, and the mass content is 20-40%; the magnesium oxide is filled as particles, and the mass content is 10-30%; the molten salt electrolyte is used as an ion conducting medium, and the mass content is 40-70%.
Further, the bi-pass directional vertical array membrane is a bi-pass directional anodic alumina membrane, the aperture range of the bi-pass directional vertical array membrane is 50nm-2000nm, and the aperture depth range is 30 μm-200 μm.
Further, the molten salt electrolyte is an alkali metal halide eutectic salt system.
Further, the alkali metal halide eutectic salt system is any one of LiF-LiCl-LiBr system, liCl-LiBr-KBr system and LiCl-KCl system.
The invention also provides a preparation method of the thermal battery isolation layer with the overflow preventing function, which is characterized by comprising the following preparation steps:
Step 1, cutting a bi-pass directional vertical array membrane with the aperture of 50nm-2000nm and the aperture depth of 30-200 mu m into a required size, cleaning by an organic solvent, and drying;
Step 2, immersing the dried double-pass directional vertical array film in the step1 into a magnesium salt solution with the concentration of 10% -35%, taking out, and placing the immersed film in an oven for drying;
Step 3, placing the double-pass directional vertical array film obtained in the step2 into a muffle furnace, slowly heating to a high temperature, keeping for a certain time, and taking out to obtain the magnesia modified double-pass directional vertical array film, wherein the high temperature is 300-600 ℃, and the certain time is 1-12 hours;
And 4, mixing the modified bi-pass directional vertical array film obtained in the step 3 with molten salt electrolyte with certain mass, placing the mixture into a muffle furnace, keeping the mixture at a second high temperature for a certain time, taking out the mixture, and removing the electrolyte remained on the surface to obtain the thermal battery isolation layer with the anti-overflow function, wherein the second high temperature is 400-700 ℃, and the certain time is 1-6h.
Further, in the step1, the mixture is cut into the required size, then is placed into an acetone solution for soaking for 3 hours, is taken out, and is placed into a 60 ℃ oven for drying for 3 hours.
Further, in step 2, the magnesium salt solution is a magnesium acetate solution or a magnesium ascorbate solution.
Further, in the step 3, the temperature is slowly raised to 500 ℃, and the mixture is taken out after heat preservation for 6 hours.
Further, the bi-pass directional vertical array film is an anodic aluminum oxide film, and in the step 4, the mass ratio of the molten salt electrolyte to the anodic aluminum oxide film is 1.5:1-10:1.
Further, the bi-pass directional vertical array film is an anodic aluminum oxide film, in the step 4, the modified anodic aluminum oxide obtained in the step 3 is mixed with LiF, liCl, liBr with a certain mass and prepared according to a specific proportion, and the mixture is placed into a muffle furnace to be kept at 500 ℃ for 6 hours.
According to the thermal battery isolation layer with the overflow prevention function, the mechanical strength of the isolation layer is enhanced, molten salt electrolyte is adsorbed inside the pipeline structure through capillary action of the oriented vertically arranged pipeline structure, the adsorption capacity of the adsorbent to the thermal battery electrolyte during the operation of the thermal battery is greatly improved, and the overflow phenomenon of the electrolyte is inhibited. Meanwhile, the thickness of the isolating layer is 50-200 mu m, which is thinner than that of the common thermal battery isolating layer, so that the ion transmission distance can be obviously reduced, and the rapid transmission of ions in the isolating layer can be realized.
Drawings
FIG. 1 is a graph showing a comparison of discharge curves of a thermal battery prepared from a thermal battery separator having an anti-flooding function according to example 1 of the present invention.
Detailed Description
The technical scheme of the invention is described below through specific examples. It is to be understood that the reference to one or more steps of the invention does not exclude the presence of other methods and steps before or after the described combined steps, or that other methods and steps may be interposed between these explicitly mentioned steps. It should also be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Unless otherwise indicated, the numbering of the method steps is for the purpose of identifying the method steps only and is not intended to limit the order of arrangement of the method steps or to limit the scope of the invention, which relative changes or modifications may be regarded as the scope of the invention which may be practiced without substantial technical content modification.
The invention provides a thermal battery isolation layer with an overflow prevention function and a preparation method thereof. The isolating layer uses magnesia modified porous directional anode alumina array film as adsorption carrier and uses the fused electrolyte adsorbed in the pore diameter of the carrier as medium to realize ion transfer. The porous directional anodic aluminum oxide film not only enhances the mechanical strength of the isolation layer, but also adsorbs molten salt electrolyte inside the pipeline structure through the capillary action of the directional vertically arranged pipeline structure, so that the adsorption capacity of the adsorbent to the thermal battery electrolyte during the operation of the thermal battery is greatly improved, and the phenomenon of electrolyte overflow is inhibited. Meanwhile, the thickness of the isolating layer is 50-200 mu m, which is thinner than that of the common thermal battery isolating layer, so that the ion transmission distance can be obviously reduced, and the rapid transmission of ions in the isolating layer can be realized.
Specifically, the thermal battery isolation layer with the anti-overflow function provided by the invention comprises a porous directional vertical array membrane (abbreviated as a bi-pass directional vertical array membrane) conducting in a bi-pass way, magnesium oxide and molten salt electrolyte; the bi-pass directional vertical array film is used as an adsorption carrier, and the mass content is 20-40%; the magnesium oxide is filled as particles, and the mass content is 10-30%; the molten salt electrolyte is used as an ion conducting medium, and the mass content is 40-70%.
Wherein, the bi-pass directional vertical array membrane is preferably a bi-pass directional anodic alumina membrane, the aperture range of the bi-pass directional vertical array membrane can be 50nm-2000nm, and the aperture depth range can be 30 μm-200 μm. The molten salt electrolyte may be an alkali metal halide eutectic salt system, and is preferably any one of a LiF-LiCl-LiBr system, a LiCl-LiBr-KBr system, and a LiCl-KCl system.
The invention also provides a preparation method of the thermal battery isolation layer with the overflow preventing function, which comprises the following steps:
Step 1: cutting a bi-pass directional vertical array membrane with the aperture of 50-2000 nm and the aperture depth of 30-200 mu m into a required size, cleaning by an organic solvent, and drying; in one embodiment, the materials are cut to the required size, placed in an acetone solution, soaked for 3 hours, taken out, and placed in a 60 ℃ oven for 3 hours.
Step 2: immersing the dried double-pass directional vertical array film in the step 1 into a magnesium salt solution with the concentration of 10% -35%, taking out, and placing the film in an oven for low-temperature drying, wherein the low temperature is 10-40 ℃. The soaking time can be 0.5-12h, and the drying time can be 1-12h. In one embodiment, the material is taken out of the 80 ℃ oven and dried for 6 hours after soaking for 6 hours. The magnesium salt solution may be any one of a magnesium acetate solution, a magnesium ascorbate solution and other soluble magnesium salt solutions, and is preferably a magnesium acetate solution or a magnesium ascorbate solution.
Step 3: and (3) placing the double-pass directional vertical array film obtained in the step (2) into a muffle furnace, slowly heating to a high temperature, keeping for a certain time, and taking out to obtain the double-pass directional vertical array film modified by magnesium oxide. The high temperature is 300-600 ℃, and the certain time is 1-12h. The reason for maintaining the high temperature is to promote the magnesium salt to be decomposed sufficiently at the high temperature, so that nano magnesium oxide particles are formed. In one embodiment, the temperature is slowly raised to 500℃and removed after 6 hours of incubation. When the double-pass directional vertical array film adopts the anodic aluminum oxide, the anodic aluminum oxide modified by the magnesium oxide is obtained.
Step 4: mixing the modified bi-pass directional vertical array film obtained in the step 3 with molten salt electrolyte with certain mass, placing the mixture into a muffle furnace, taking out the mixture after maintaining the mixture at a second high temperature for a certain time, and removing the electrolyte remained on the surface to obtain the thermal battery isolation layer with the anti-overflow function, wherein the second high temperature is 400-700 ℃, and the certain time is 1-6 hours. In one embodiment, the modified anodized aluminum obtained in step 3 is mixed with a mass of LiF, liCl, liBr formulated in a specific ratio, placed in a muffle furnace, and incubated at 500 ℃ for 6 hours. When the bi-pass directional vertical array film is an anodic aluminum oxide film, the mass ratio of the molten salt electrolyte to the anodic aluminum oxide film may be 1.5:1-10:1.
It is to be understood that the reference to one or more steps of the invention does not exclude the presence of other methods and steps before or after the described combined steps, or that other methods and steps may be interposed between these explicitly mentioned steps.
The thermal battery electrolyte with the overflow prevention function has the following advantages:
(1) The invention provides a thermal battery isolation layer prepared by taking a bi-pass porous anodic alumina film as a carrier for the first time, wherein the isolation layer has high mechanical strength, and can relieve extrusion of internal pressure of a battery to electrolyte in a discharging process, thereby inhibiting overflow phenomenon of molten electrolyte; meanwhile, the nanometer pore diameter in the porous anodic alumina membrane structure has strong capillary action, so that the adsorption action of the carrier on the molten electrolyte can be enhanced, and the overflow phenomenon of the electrolyte in the discharging process of the battery is further reduced.
(2) The invention provides a preparation method for modifying an anodic aluminum oxide film by magnesium oxide for the first time. In the modified anodic aluminum oxide film structure, the magnesium oxide particles not only enhance the wettability of the anodic aluminum oxide film to molten salt electrolysis, realize the uniform distribution of molten salt electrolyte in the pores of the anodic aluminum oxide film, but also enhance the adsorption capacity of the anodic aluminum oxide film to the electrolyte, and further reduce the overflow risk.
(3) The thermal battery isolating layer prepared by the method is thin and controllable in thickness, is beneficial to the design process of the thermal battery, has the advantages of simple technical process, no need of complex post-treatment, low energy consumption and the like, has high compatibility with the existing thermal battery production technical process, and has the potential of being truly applied to thermal battery model products.
Examples
The materials and instruments used in the examples of the present invention are not particularly limited in their sources, and may be purchased on the market or prepared according to conventional methods well known to those skilled in the art.
Example 1
Cutting a bi-pass anodic aluminum oxide film with the aperture of 50nm and the aperture depth of 30 mu m into a wafer with the diameter of 5cm, placing the wafer into an acetone solution for soaking for 3 hours, and drying at 60 ℃ for 3 hours. Immersing the dried double-pass anodic aluminum oxide film into a magnesium acetate solution with the concentration of 35%, soaking for 6 hours, taking out, and placing into an oven at 80 ℃ for drying for 6 hours. And (3) placing the dried double-pass anodic aluminum oxide film into a muffle furnace, slowly heating to 500 ℃, preserving heat for 6 hours, cooling to room temperature, and taking out. And (3) mixing the anodic aluminum oxide film prepared in the previous step with 0.5g of LiF (9.6%), liCl (22.0%) and LiBr (68.4%) in an environment with the dew point not more than-36 ℃, placing the mixture into a muffle furnace, heating to 500 ℃, preserving heat for 6 hours, cooling to room temperature, taking out, and removing residual electrolyte on the surface to obtain the thermal battery isolation layer with the anti-overflow function.
1G of the prepared thermal battery isolation layer is weighed, immersed into 50ml of hydrochloric acid solution with the concentration of 2mol/L, subjected to ultrasonic treatment for 2 hours, subjected to ICP test after complete reaction, and subjected to analysis on mass fractions of magnesium ions and aluminum ions in the novel isolation layer, so that mass fractions of components in the isolation layer can be deduced. Wherein the content of the double-pass anodic aluminum oxide film is 25%, the content of magnesium oxide is 25%, and the content of the molten salt electrolyte is 50%.
And (3) carrying out electrolyte leakage test on the prepared novel isolation layer at the constant temperature of 600 ℃ for 30min, wherein the leakage rate is less than 2%, and the thickness change rate is less than 5%. The novel isolation layer is assembled with a heating layer, a positive electrode layer, a negative electrode layer and other parts to form a thermal battery, and the thermal battery is subjected to discharge test, and the result is shown in figure 1.
FIG. 1 is a graph showing a comparison of discharge curves of a thermal battery prepared from a thermal battery separator having an anti-flooding function according to example 1 of the present invention. As shown in figure 1, under the same discharge condition, the voltage of the thermal battery adopting the novel isolation layer of the invention under the 16A pulse current is reduced to be lower than that of a conventional thermal battery, and the overall discharge life is longer than that of the conventional thermal battery. After the pile is discharged, disassembly is carried out, and no obvious overflow phenomenon is found in the discharging process.
Example 2
Cutting a bi-pass anodic aluminum oxide film with the aperture of 50nm and the aperture depth of 200 mu m into a wafer with the diameter of 5cm, placing the wafer into an acetone solution for soaking for 3 hours, and drying at 60 ℃ for 3 hours. Immersing the dried double-pass anodic aluminum oxide film into a magnesium acetate solution with the concentration of 35%, soaking for 6 hours, taking out, and placing into an oven at 80 ℃ for drying for 6 hours. And (3) placing the dried double-pass anodic aluminum oxide film into a muffle furnace, slowly heating to 500 ℃, preserving heat for 6 hours, cooling to room temperature, and taking out. And mixing the anodic aluminum oxide film prepared in the previous step with 1g of LiF (9.6%), liCl (22.0%) and LiBr (68.4%) in an environment with the dew point not more than-36 ℃, placing the mixture into a muffle furnace, heating to 500 ℃, preserving heat for 6 hours, cooling to room temperature, taking out, and removing the electrolyte remained on the surface to obtain the thermal battery electrolyte with the anti-overflow function.
1G of the prepared thermal battery isolation layer is weighed, immersed into 50ml of hydrochloric acid solution with the concentration of 2mol/L, subjected to ultrasonic treatment for 2 hours, subjected to ICP test after complete reaction, and subjected to ICP test, so that the mass fractions of magnesium ions and aluminum ions in the novel isolation layer can be analyzed, and further the mass fractions of all components in the novel isolation layer can be deduced. Wherein the content of the double-pass anodic aluminum oxide film is 25%, the content of magnesium oxide is 20%, and the content of the molten salt electrolyte is 55%.
And (3) carrying out electrolyte leakage test on the prepared novel isolation layer at the constant temperature of 600 ℃ for 30min, wherein the leakage rate is less than 2%, and the thickness change rate is less than 5%.
Example 3
Cutting a bi-pass anodic aluminum oxide film with the aperture of 50nm and the aperture depth of 100 mu m into a wafer with the diameter of 5cm, placing the wafer into an acetone solution for soaking for 3 hours, and drying at 60 ℃ for 3 hours. Immersing the dried double-pass anodic aluminum oxide film into 35% magnesium ascorbate solution, soaking for 6 hours, taking out, and placing into an 80 ℃ oven for drying for 6 hours. And (3) placing the dried double-pass anodic aluminum oxide film into a muffle furnace, slowly heating to 500 ℃, preserving heat for 6 hours, cooling to room temperature, and taking out. And mixing the anodic aluminum oxide film prepared in the previous step with 0.5g of LiF (9.6%), liCl (22.0%) and LiBr (68.4%) in an environment with the dew point not more than-36 ℃, placing the mixture into a muffle furnace, heating to 500 ℃, preserving heat for 6 hours, cooling to room temperature, taking out, and removing the electrolyte remained on the surface to obtain the thermal battery electrolyte with the anti-overflow function.
1G of the prepared thermal battery isolation layer is weighed, immersed into 50ml of hydrochloric acid solution with the concentration of 2mol/L, subjected to ultrasonic treatment for 2 hours, subjected to ICP test after complete reaction, and subjected to ICP test, so that the mass fractions of magnesium ions and aluminum ions in the novel isolation layer can be analyzed, and further the mass fractions of all components in the novel isolation layer can be deduced. Wherein the content of the double-pass anodic aluminum oxide film is 30%, the content of magnesium oxide is 30%, and the content of the molten salt electrolyte is 40%.
And (3) carrying out electrolyte leakage test on the prepared novel isolation layer at the constant temperature of 600 ℃ for 30min, wherein the leakage rate is less than 2%, and the thickness change rate is less than 5%.
Example 4
A double-pass anodic aluminum oxide film with the aperture of 100nm and the aperture depth of 200 mu m is cut into a wafer with the diameter of 5cm, and the wafer is placed into an acetone solution for soaking for 3 hours and then dried for 3 hours at the temperature of 60 ℃. Immersing the dried double-pass anodic aluminum oxide film into 35% magnesium ascorbate solution, soaking for 6 hours, taking out, and placing into an 80 ℃ oven for drying for 6 hours. And (3) placing the dried double-pass anodic aluminum oxide film into a muffle furnace, slowly heating to 500 ℃, preserving heat for 6 hours, cooling to room temperature, and taking out. And (3) mixing the anodic aluminum oxide film prepared in the previous step with 0.5g of LiCl (12.1%), LBr (36.5%) and KBr (51.4%) in an environment with the dew point not more than-36 ℃, placing the mixture into a muffle furnace, heating to 500 ℃, preserving heat for 6 hours, cooling to room temperature, taking out, and removing the electrolyte remained on the surface to obtain the thermal battery electrolyte with the anti-overflow function.
1G of the prepared thermal battery isolation layer is weighed, immersed into 50ml of hydrochloric acid solution with the concentration of 2mol/L, subjected to ultrasonic treatment for 2 hours, subjected to ICP test after complete reaction, and subjected to ICP test, so that the mass fractions of magnesium ions and aluminum ions in the novel isolation layer can be analyzed, and further the mass fractions of all components in the novel isolation layer can be deduced. Wherein the content of the double-pass anodic aluminum oxide film is 30%, the content of magnesium oxide is 20%, and the content of the molten salt electrolyte is 50%. And (3) carrying out electrolyte leakage test on the prepared novel isolation layer at the constant temperature of 600 ℃ for 30min, wherein the leakage rate is less than 2%, and the thickness change rate is less than 5%.
From the above examples 1 to 4, it can be seen that the composite separator based on the bi-pass directional anodized aluminum film as a matrix can effectively slow down leakage of the electrolyte and maintain stability of the self structure at high temperature, thereby suppressing overflow phenomenon of the electrolyte in the thermal cell stack.
The above embodiments are merely illustrative of specific embodiments of the present invention and are not intended to limit the scope of the present invention, and those skilled in the art may make various modifications and changes on the basis of the prior art, which should fall within the scope of protection defined by the claims of the present invention without departing from the spirit of the present invention.
Claims (6)
1. The preparation method of the thermal battery isolation layer with the anti-overflow function is characterized by comprising the following preparation steps:
Step 1, cutting a bi-pass directional vertical array membrane with the aperture of 50nm-2000nm and the aperture depth of 30-200 mu m into a required size, cleaning the membrane by an organic solvent, and drying the membrane, wherein the bi-pass directional vertical array membrane is an anodic alumina membrane;
Step 2, immersing the anode aluminum oxide film dried in the step 1 into a magnesium salt solution with the concentration of 10% -35%, taking out, placing the immersed anode aluminum oxide film in an oven, drying at a low temperature of 10-40 ℃ for 0.5-12h, and drying for 1-12h, wherein the magnesium salt solution is a magnesium acetate solution or a magnesium ascorbate solution;
Step 3, placing the anodic aluminum oxide film obtained in the step 2 into a muffle furnace, slowly heating to a high temperature, keeping for a certain time, and taking out to obtain the anodic aluminum oxide film modified by magnesium oxide, wherein the high temperature is 300-600 ℃, and the certain time is 1-12 hours;
And 4, mixing the modified anodic aluminum oxide film obtained in the step 3 with a molten salt electrolyte with a certain mass, placing the mixture into a muffle furnace, taking out the mixture after keeping the mixture at a second high temperature for a certain time, and removing the electrolyte remained on the surface to obtain the thermal battery isolation layer with an anti-overflow function, wherein the second high temperature is 400-700 ℃, the certain time is 1-6h, the mass ratio of the molten salt electrolyte to the anodic aluminum oxide film is 1.5:1-10:1, and the molten salt electrolyte comprises the following components in percentage by mass: liF 9.6%, liCl 22.0%, liBr 68.4%, or LiCl 12.1%, LBr 36.5.5%, KBr 51.4%.
2. The method for preparing a thermal battery isolation layer with an anti-overflow function according to claim 1, wherein in the step 1, the thermal battery isolation layer is cut into a required size, then the thermal battery isolation layer is placed in an acetone solution for soaking for 3 hours, then the thermal battery isolation layer is taken out, and is placed in a 60 ℃ oven for drying for 3 hours.
3. The method for producing a thermal battery separator with an anti-overflow function according to claim 1, wherein in step 3, the temperature is slowly raised to 500 ℃, and the thermal battery separator is taken out after heat preservation for 6 hours.
4. The method for preparing a thermal battery isolation layer with an anti-overflow function according to claim 1, wherein in the step 4, the second high temperature is kept at 500 ℃ for a certain period of time for 6 hours.
5. A thermal battery isolation layer with an anti-overflow function obtained by the preparation method of any one of claims 1 to 4, which is characterized by comprising a bi-pass directional vertical array film, magnesium oxide and molten salt electrolyte; the bi-pass directional vertical array film is used as an adsorption carrier, and the mass content is 20-40%; the magnesium oxide is filled as particles, and the mass content is 10-30%; the molten salt electrolyte is used as an ion conducting medium, and the mass content of the molten salt electrolyte is 40-70%.
6. The thermal battery isolation layer with anti-overflow function according to claim 5, wherein the aperture range of the bi-pass directional vertical array membrane is 50nm-2000nm, and the aperture depth range is 30 μm-200 μm.
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| CN110690397A (en) * | 2019-09-17 | 2020-01-14 | 厦门大学 | Fused salt composite electrolyte diaphragm, preparation method and application |
| CN111559740A (en) * | 2020-05-29 | 2020-08-21 | 河南大学 | Preparation method of solid electrolyte with air gap |
| CN111740151A (en) * | 2020-07-07 | 2020-10-02 | 河南大学 | All-solid-state composite electrolyte taking V-shaped AAO template as framework and lithium ion battery |
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| CN107010649A (en) * | 2017-04-20 | 2017-08-04 | 中国药科大学 | A kind of method for preparing aluminate nano-wire array |
| CN110690397A (en) * | 2019-09-17 | 2020-01-14 | 厦门大学 | Fused salt composite electrolyte diaphragm, preparation method and application |
| CN111559740A (en) * | 2020-05-29 | 2020-08-21 | 河南大学 | Preparation method of solid electrolyte with air gap |
| CN111740151A (en) * | 2020-07-07 | 2020-10-02 | 河南大学 | All-solid-state composite electrolyte taking V-shaped AAO template as framework and lithium ion battery |
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