Aluminum Battery Separator

The breathable aluminum battery separator with specific fiber materials enhances electrolyte penetration and reduces metal deposition, addressing internal resistance issues and improving battery performance and longevity.

JP7758362B2Active Publication Date: 2025-10-22APH EPOWER CO LTD
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Patent Information

Application Number
JP2023119617
Authority / Receiving Office
JP · JP
Patent Type
Patents
Current Assignee / Owner
Priority Date
2023-01-10
Filing Date
2023-07-24
Publication Date
2025-10-22
Estimated Expiration
2043-07-24

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Abstract

To provide an aluminum battery separator which has favorable chemical resistance, and can reduce metal deposition while effectively allowing an electrolyte to penetrate, thereby improving the performance of the aluminum battery and extending the service life of the aluminum battery.SOLUTION: An aluminum battery separator is provided that includes a breathable material, the breathable material having an air permeability of 0.1 sec / 100 ml to 50 sec / 100 ml, and the breathable material includes a fiber material other than glass fiber.SELECTED DRAWING: None
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Description

[Technical Field]

[0001] The present invention relates to battery separators, and more particularly to aluminum battery separators. [Background technology]

[0002] Generally, based on the charge / discharge mechanism of aluminum batteries, if the separator is not fully permeated with electrolyte, the active material in the electrolyte cannot effectively migrate during the charge / discharge process, causing excessive internal resistance in the aluminum battery and affecting its performance. Therefore, how to design an aluminum battery separator that can effectively permeate the electrolyte and improve the performance of the aluminum battery has become a major challenge. Summary of the Invention [Problem to be solved by the invention]

[0003] Based on the charge-discharge mechanism of aluminum batteries, if the separator is not fully permeated with electrolyte, the active material in the electrolyte cannot move effectively during the charge-discharge process, causing excessive internal resistance in the aluminum battery and affecting its performance. [Means for solving the problem]

[0004] The present invention provides an aluminum battery separator that has favorable chemical resistance and can reduce metal deposition while allowing effective electrolyte penetration, thereby improving the performance of aluminum batteries and extending their service life.

[0005] The aluminum battery separator of the present invention includes a breathable material, which has an air permeability of 0.1 seconds / 100 ml to 50 seconds / 100 ml, and includes a fiber material other than glass fiber.

[0006] In one embodiment of the present invention, the fibrous material comprises a fibrous nonwoven material or a fibrous woven material.

[0007] In one embodiment of the present invention, the breathable material includes cellulose, polyacrylonitrile (PAN), cellulose acetate, aramid, polyphenylene sulfide (PPS), and polyvinyl alcohol dimethyl formal.

[0008] In one embodiment of the present invention, the breathable material is comprised of a single material rather than a composite film.

[0009] In one embodiment of the present invention, the single material is cellulose or polyacrylonitrile.

[0010] In one embodiment of the present invention, the fiber diameter of the breathable material is 0.1 μm to 20 μm.

[0011] In one embodiment of the present invention, the areal density of the breathable material is 0.1 g / m 2 ~30g / m 2 is.

[0012] In one embodiment of the present invention, the breathable material is not a pore former.

[0013] In one embodiment of the present invention, the breathable material has a contact angle of 90 degrees or less.

[0014] In one embodiment of the present invention, the breathable material does not include polyethylene (PE) or polypropylene (PP). [Effects of the Invention]

[0015] Based on the above, the aluminum battery separator of the present invention is made of a breathable material with an air permeability of 0.1 seconds / 100 ml to 50 seconds / 100 ml and a fiber material other than glass fiber, depending on the material selection. The aluminum battery separator has good chemical resistance and can effectively penetrate the electrolyte while reducing metal deposition, thereby improving the performance of the aluminum battery and extending its service life.

[0016] To make the features and advantages of the present invention more readily understandable, specific embodiments will now be described in detail in conjunction with the drawings. DETAILED DESCRIPTION OF THE INVENTION

[0017] To facilitate understanding of the present invention, the following provides examples of specific embodiments that can actually implement the present invention. For clarity, many practical details are set forth in the following description. However, it should be understood that the practical details should not be used to limit the present invention. In other words, in some embodiments of the present invention, the practical details are unnecessary.

[0018] Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.

[0019] Unless otherwise specified, the term "between," as used herein to define a range of values, is intended to encompass ranges equal to and between the recited endpoint values. For example, a size range between a first value and a second value means that the size range can encompass the first value, the second value, and any value between the first and second values.

[0020] In the following detailed description, for purposes of explanation and not limitation, exemplary embodiments disclosing specific details are set forth in order to provide a thorough understanding of various principles of the present invention. However, it will be apparent to those skilled in the art that, with the benefit of the present invention, the present invention may be practiced in other embodiments that depart from the specific details disclosed herein. Moreover, descriptions of conventional devices, methods, and materials may be omitted so as not to obscure the description of various principles of the present invention.

[0021] The aluminum battery separator of this embodiment includes a breathable material. Furthermore, the aluminum battery separator of this embodiment is composed of a breathable material with an air permeability of 0.1 seconds / 100 ml to 50 seconds / 100 ml and a fiber material other than glass fiber, depending on the material selection. The aluminum battery separator has favorable chemical resistance and can effectively penetrate the electrolyte while reducing metal deposition, thereby improving the performance of the aluminum battery and extending its service life. The electrolyte may be any suitable ionic liquid (e.g., EMIC, BMIC, etc.) that can be applied to aluminum batteries, but the present invention is not limited thereto. The air permeability is expressed as the Gurley value and can be measured using an air permeability tester (Gurley) or the ASTM D726 method. Specifically, the air permeability of an aluminum battery separator can be measured by applying a certain pressure to the aluminum battery separator using an air permeability tester (Gurley) and calculating the time it takes for a certain volume of gas to pass through the aluminum battery separator.

[0022] In some embodiments, the fibrous material includes a fibrous nonwoven material or a fibrous woven material. For example, breathable materials include, but are not limited to, cellulose, polyacrylonitrile, cellulose acetate, aramid, polyphenylene sulfide, and polyvinyl alcohol dimethyl formal. Any suitable breathable material falls within the scope of the present invention as long as its air permeability is between 0.1 seconds / 100 ml and 50 seconds / 100 ml.

[0023] Furthermore, when glass fiber is used as a material for the separator of an aluminum battery, the electrolyte generates metal deposits on the negative electrode and separator due to oxidation and reduction during the continuous charge and discharge process. In severe cases, metal trees may form between the positive and negative electrodes, causing separator damage and affecting the performance and service life of the aluminum battery. Therefore, this embodiment explicitly excludes the use of glass fiber to effectively delay metal tree puncture and reduce metal deposits, thereby preventing conduction between the positive and negative electrodes and improving the service life and performance of the aluminum battery cell.

[0024] In some embodiments, due to their hydrophobic properties, polyethylene or polypropylene materials cannot effectively permeate when used in aluminum batteries. If the separator is not completely permeated, the active materials in the electrolyte cannot effectively migrate during charging and discharging of the aluminum battery, increasing the battery's internal resistance and affecting the performance of the aluminum battery. Therefore, aluminum battery separators that do not contain polyethylene or polypropylene separators, which are commonly used in the lithium battery industry, can more effectively improve the performance of aluminum batteries. Furthermore, aluminum battery separators that do not contain polyethylene or polypropylene separators, which are commonly used in the lithium battery industry, can also prevent separators made of these materials from being dissolved by the aluminum battery's electrolyte (e.g., ionic liquid), but the present invention is not limited thereto.

[0025] In some embodiments, the electrolyte in an aluminum battery system is typically an ionic liquid, which has a relatively high viscosity. When a polymer pore-forming thin film is used as a separator, the separator is not completely permeated, increasing the internal resistance of the aluminum battery and affecting its performance. Therefore, the breathable material does not have to be a pore-forming material to more effectively improve the performance of the aluminum battery, but the present invention is not limited thereto.

[0026] Furthermore, the breathable material is not a composite film but is composed of a single material, which is cellulose or polyacrylonitrile, for better permeability and chemical resistance, as detailed in Tables 1 and 2 below.

[0027] In Table 1, the permeability of a separator can be determined by measuring the contact angle and analyzing the droplet absorption rate. As can be seen from Table 1, separators made of cellulose or polyacrylonitrile materials instantly absorb droplets, making it impossible to measure the contact angle. Therefore, cellulose or polyacrylonitrile materials can be considered hydrophilic materials that promote electrolyte permeation. However, in the case of polyethylene or polypropylene materials, the contact angle is greater than 90 degrees, making them hydrophobic materials that do not promote electrolyte permeation. Therefore, the contact angle of the breathable material of the present invention is less than 90 degrees. Furthermore, Table 1 shows that all fibrous separators have a fast droplet absorption rate and superior permeability to separators made of pore-forming thin film materials.

[0028] [Table 1]

[0029] As shown in Table 2, separators made from different materials were cut into 5cm long, 1cm wide sheets, immersed in ionic liquid electrolyte (EMIC), and left in room temperature (25°C) and high temperature (80°C) environments to observe the chemical resistance of the polymers in the ionic liquid electrolyte. As can be seen from Table 2, polyethylene and polypropylene materials dissolve in the electrolyte at room temperature within four days, making them unsuitable for ionic liquid electrolyte systems. However, cellulose and polyacrylonitrile materials are insoluble in the electrolyte at room temperature, making them advantageous for use in aluminum battery separators.

[0030] [Table 2]

[0031] In some embodiments, the fiber diameter of the breathable material is between 0.1 μm and 20 μm, and the areal density of the breathable material is 0.1 g / m 2 to 30.0 g / m 2 However, the present invention is not limited thereto. Here, the fiber diameter can be measured by a scanning electron microscope (SEM), and the areal density can be measured by any suitable technique.

[0032] The effects of applying the aluminum battery separator of the present invention to an aluminum battery will be described more specifically below with reference to Example 1 and Comparative Example 1. Note that, although Example 1 will be described below, details such as the materials used and the process can be changed as appropriate without departing from the spirit of the present invention, and the present invention should not be construed as being limited to the following example.

[0033] <Comparative Example 1>

[0034] First, aluminum foil was cut to prepare a negative electrode (thickness 0.05 mm, size 88 mm × 148 mm). Graphite slurry was applied to nickel foil (thickness 0.03 mm, size 85 mm × 145 mm) to obtain a positive electrode. Next, glass fiber filter paper (manufactured by Lifeng Industrial Co., Ltd., product name: YF100, air permeability 4.3 seconds / 100 ml) was cut to prepare a separator. Next, the negative electrode, separator, and positive electrode were arranged in this order. An aluminum plastic film was placed, and an electrolyte (aluminum chloride / 1-ethyl-3-methylimidazolium chloride, molar ratio 1.8:1) was poured in and sealed. An aluminum battery of Comparative Example 1 was obtained.

[0035] <Comparative Example 2>

[0036] The aluminum battery of Comparative Example 2 was produced using the same method as in Comparative Example 1, except that the separator was replaced with a separator containing a polypropylene material (manufactured by Foresight Energy Technologies, Inc., product name: multilayer composite separator, air permeability 210 seconds / 100 ml).

[0037] <Comparative Example 3>

[0038] The aluminum battery of Comparative Example 3 was produced using the same method as in Comparative Example 1, except that the separator was replaced with a separator made of polyethylene terephthalate (PET) (manufactured by Teijin Limited, product name: 012TH-10, air permeability: 0.05 seconds / 100 ml).

[0039] Example 1

[0040] The aluminum battery of Example 1 was produced using the same method as in Comparative Example 1, except that the separator was replaced with a cellulose separator (manufactured by Nippon Kodoshi Kogyo Co., Ltd., product name: TF4850, air permeability 20 seconds / 100 ml).

[0041] The coulombic efficiencies of Example 1 and Comparative Example 1 were tested, and the number of cycles at which the coulombic efficiency fell below 80% was calculated. Using a BioLogic electrochemical workstation (BioLogic BCS-815), charge / discharge tests were conducted on the aluminum batteries obtained in Example 1, Comparative Example 1, and Comparative Example 2. The maximum discharge capacity was measured at a charge / discharge rate of 4C. The results are shown in Table 3. The following conclusions can be drawn from the results in Table 3. Comparing Example 1 and Comparative Example 1, the cycle life is substantially extended by approximately six times. However, Comparative Example 2 cannot be charged / discharged normally because the electrolyte cannot penetrate. Furthermore, although charge / discharge is possible in Comparative Example 3, the pore size of the separator is too large and the air permeability value is low (less than 0.1 seconds / 100 ml), resulting in too low an impedance between the positive and negative electrodes and preventing the coulombic efficiency from reaching 80%.

[0042] [Table 3]

[0043] It should be noted that in the above content, other unspecified compositions and specifications of the aluminum battery can be obtained by a person skilled in the art of the present invention according to any content that covers the spirit and scope included in the appended claims, and as long as a separator is disposed between the positive electrode and the negative electrode of the aluminum battery, it falls within the protection scope of the present invention.

[0044] In summary, the aluminum battery separator of the present invention is made of a breathable material with a breathability of 0.1 seconds / 100 ml to 50 seconds / 100 ml and a fiber material other than glass fiber, depending on the material selection. The aluminum battery separator has favorable chemical resistance and can effectively penetrate the electrolyte while reducing metal deposition, thereby improving the performance and extending the service life of the aluminum battery.

[0045] Although the present invention has been disclosed in the above embodiments, these embodiments are not intended to limit the present invention. Those skilled in the art can make some changes and modifications without departing from the spirit and scope of the present invention. Therefore, the protection scope of the present invention is defined by the appended claims. [Industrial Applicability]

[0046] The aluminum battery separator of the present invention can be applied to aluminum batteries.

Claims

1. 1. An aluminum battery separator for immersion in an electrolyte comprising 1-ethyl-3-methylimidazolium chloride, a breathable material having breathability of 20 seconds / 100 ml to 50 seconds / 100 ml and made of a single material, the single material being cellulose; The surface density of the breathable material is 0.1 g / m 2 ~30g / m 2 Aluminum battery separator.

2. 2. The aluminum battery separator according to claim 1, wherein the fiber diameter of the breathable material is 0.1 μm to 20 μm.

Citation Information

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