TWI497802B - Lithium battery separators - Google Patents

Lithium battery separators Download PDF

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TWI497802B
TWI497802B TW102138397A TW102138397A TWI497802B TW I497802 B TWI497802 B TW I497802B TW 102138397 A TW102138397 A TW 102138397A TW 102138397 A TW102138397 A TW 102138397A TW I497802 B TWI497802 B TW I497802B
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Taiwan
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pore
film
pore film
polypropylene
polyethylene
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TW102138397A
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Chinese (zh)
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TW201517357A (en
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Chih Hung Lee
Li Han Chung
Dan Cheng Kong
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Ind Tech Res Inst
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Priority to TW102138397A priority Critical patent/TWI497802B/en
Priority to CN201310637460.0A priority patent/CN104577007A/en
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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
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • 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)
  • Materials Engineering (AREA)
  • Cell Separators (AREA)
  • Secondary Cells (AREA)

Description

鋰電池隔離膜Lithium battery separator

本揭露係有關於一種鋰電池隔離膜，特別是有關於一種具備熱閉孔性、耐穿刺及熱穩定性之鋰電池隔離膜。The present disclosure relates to a lithium battery separator, and more particularly to a lithium battery separator having thermal obscuration, puncture resistance and thermal stability.

鋰離子電池已經廣泛地應用在可攜式電子產品上，未來，隨著電動車的發展，相關材料的需求也備受矚目。鋰離子電池具有高能量密度的優勢，符合車用動力鋰電池的需求，但也因為其輸出功率大，以及電池尺寸增加，在運作的同時也伴隨著大量的熱能產生，若無有效的防護機制很容易造成熱失控(thermal runaway)導致電池燃燒***。隔離膜在鋰電池安全上扮演極重要的角色，其位於兩極之間，負責離子傳導使電化學反應可以進行，因此，隔離膜需要具有良好的離子傳導性，並擁有足夠的機械強度與耐穿刺度，以防止反應中析出的鋰金屬刺破隔離膜造成短路，在異常升溫時，隔離膜的熱閉孔特性可以阻斷離子的傳導使反應終止避免持續地放熱。Lithium-ion batteries have been widely used in portable electronic products. In the future, with the development of electric vehicles, the demand for related materials has also attracted attention. Lithium-ion batteries have the advantage of high energy density and meet the needs of automotive power lithium batteries. However, because of their large output power and increased battery size, they are also accompanied by a large amount of heat energy. If there is no effective protection mechanism. It is easy to cause thermal runaway to cause the battery to explode. The separator plays a very important role in the safety of lithium batteries. It is located between the two poles and is responsible for ion conduction, so that the electrochemical reaction can be carried out. Therefore, the separator needs to have good ion conductivity and has sufficient mechanical strength and puncture resistance. In order to prevent the lithium metal precipitated in the reaction from piercing the separator to cause a short circuit, the thermal closed pore property of the separator can block the conduction of ions during the abnormal temperature rise, so that the reaction is terminated to avoid continuous heat release.

本揭露之一實施例，提供一種鋰電池隔離膜，包括：一聚烯烴複合孔隙膜，包括至少一聚乙烯孔隙膜與至少一聚丙烯孔隙膜；以及一紫外光固化或熱固化高分子孔隙膜，形成於該聚烯烴複合孔隙膜之至少一側。An embodiment of the present disclosure provides a lithium battery separator, comprising: a polyolefin composite pore film comprising at least one polyethylene pore film and at least one polypropylene pore film; and an ultraviolet curing or heat curing polymer pore film Formed on at least one side of the polyolefin composite pore film.

為讓本發明之上述目的、特徵及優點能更明顯易懂，下文特舉一較佳實施例，並配合所附的圖式，作詳細說明如下。The above described objects, features and advantages of the present invention will become more apparent and understood.

10‧‧‧鋰電池隔離膜10‧‧‧Lithium battery separator

12、12’、120‧‧‧聚乙烯(PE)孔隙膜12, 12', 120‧‧‧ Polyethylene (PE) pore film

14、14’、140、140’‧‧‧聚丙烯(PP)孔隙膜14, 14', 140, 140' ‧ ‧ polypropylene (PP) pore film

16、16’‧‧‧紫外光固化或熱固化高分子孔隙膜16, 16'‧‧‧UV-cured or thermally cured polymer pore film

18、18’、19、19’、190‧‧‧聚烯烴複合孔隙膜18, 18', 19, 19', 190‧‧ ‧ polyolefin composite pore film

20、200‧‧‧聚偏二氟乙烯(PVDF)(衍生物)孔隙膜20,200‧‧‧Polyvinylidene fluoride (PVDF) (derivative) pore film

第1圖係根據本揭露之一實施例，一種鋰電池隔離膜之剖面示意圖。1 is a schematic cross-sectional view of a lithium battery separator according to an embodiment of the present disclosure.

第2圖係根據本揭露之一實施例，一種鋰電池隔離膜之剖面示意圖。2 is a schematic cross-sectional view of a lithium battery separator according to an embodiment of the present disclosure.

第3圖係根據本揭露之一實施例，一種鋰電池隔離膜之剖面示意圖。3 is a schematic cross-sectional view of a lithium battery separator according to an embodiment of the present disclosure.

第4圖係根據本揭露之一實施例，一種鋰電池隔離膜之剖面示意圖。4 is a schematic cross-sectional view of a lithium battery separator according to an embodiment of the present disclosure.

第5圖係根據本揭露之一實施例，一種鋰電池隔離膜之剖面示意圖。Figure 5 is a schematic cross-sectional view of a lithium battery separator according to an embodiment of the present disclosure.

第6圖係根據本揭露之一實施例，一種鋰電池隔離膜之剖面示意圖。Figure 6 is a schematic cross-sectional view of a lithium battery separator according to an embodiment of the present disclosure.

第7圖係根據本揭露之一實施例，一種鋰電池隔離膜之剖面示意圖。Figure 7 is a schematic cross-sectional view of a lithium battery separator according to an embodiment of the present disclosure.

第8圖係根據本揭露之一實施例，一種鋰電池隔離膜之剖面示意圖。Figure 8 is a schematic cross-sectional view of a lithium battery separator according to an embodiment of the present disclosure.

第9圖係根據本揭露之一實施例，一種鋰電池隔離膜之剖面示意圖。Figure 9 is a schematic cross-sectional view of a lithium battery separator according to an embodiment of the present disclosure.

第10圖係根據本揭露之一實施例，一種鋰電池隔離膜之剖 面示意圖。Figure 10 is a cross-sectional view of a lithium battery separator according to an embodiment of the present disclosure Schematic diagram.

第11圖係根據本揭露之一實施例，一種鋰電池隔離膜之剖面示意圖。11 is a schematic cross-sectional view of a lithium battery separator according to an embodiment of the present disclosure.

第12圖係一種傳統鋰電池隔離膜之剖面示意圖。Figure 12 is a schematic cross-sectional view of a conventional lithium battery separator.

第13圖係一種傳統鋰電池隔離膜之剖面示意圖。Figure 13 is a schematic cross-sectional view of a conventional lithium battery separator.

本揭露之一實施例，提供一種鋰電池隔離膜，包括：一聚烯烴複合孔隙膜，包括至少一聚乙烯孔隙膜與至少一聚丙烯孔隙膜；以及一紫外光固化或熱固化高分子孔隙膜，形成於聚烯烴複合孔隙膜之至少一側。An embodiment of the present disclosure provides a lithium battery separator, comprising: a polyolefin composite pore film comprising at least one polyethylene pore film and at least one polypropylene pore film; and an ultraviolet curing or heat curing polymer pore film Formed on at least one side of the polyolefin composite pore film.

上述聚乙烯孔隙膜可為一高密度聚乙烯(high density polyethylene,HDPE)孔隙膜，其樹酯密度約介於0.95g/cc~0.975g/cc。The polyethylene pore film may be a high density polyethylene (HDPE) pore film having a resin density of about 0.95 g/cc to 0.975 g/cc.

上述聚丙烯孔隙膜之樹脂等規性(m-pentad)約介於90%~99%或92%~99%。The resin isotacticity (m-pentad) of the above polypropylene pore film is about 90% to 99% or 92% to 99%.

上述紫外光固化或熱固化高分子孔隙膜可包括聚三丙二醇二丙烯酸酯(poly(tripropylene glycol diacrylate),PTPGDA)、聚1,6-己二醇二丙烯酸酯(poly(1,6-hexanediol diacrylate),PHDDA)、聚三甲醇基丙基三丙烯酸酯(poly(trimethylolpropane triacrylate),PTMPTA)或聚二新戊四醇六丙烯酸酯(poly(dipentaerythritol hexylacrylate),PDPHA)。The above UV-curable or thermally curable polymer pore film may include poly(tripropylene glycol diacrylate) (PTPGDA), poly(1,6-hexanediol diacrylate) (poly(1,6-hexanediol diacrylate) ), PHDDA), poly(trimethylolpropane triacrylate, PTMPTA) or poly(dipentaerythritol hexylacrylate, PDPHA).

本揭露鋰電池隔離膜可更包括一聚偏二氟乙烯(PVDF)衍生物孔隙膜，形成於聚烯烴複合孔隙膜與紫外光固化 或熱固化高分子孔隙膜之間。上述聚偏二氟乙烯(PVDF)衍生物孔隙膜可包括聚偏二氟乙烯(PVDF)、聚偏二氟乙烯-六氟丙烯(PVDF-HFP)共聚物、聚偏二氟乙烯-三氟氯乙烯(PVDF-CTFE)共聚物或其組合，其熔點約介於160℃~180℃。The lithium battery separator may further comprise a polyvinylidene fluoride (PVDF) derivative pore film formed on the polyolefin composite pore film and ultraviolet curing Or thermally curing between the polymer pore membranes. The porous film of the polyvinylidene fluoride (PVDF) derivative may include polyvinylidene fluoride (PVDF), polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) copolymer, polyvinylidene fluoride-chlorotrifluorochloride. Ethylene (PVDF-CTFE) copolymer or a combination thereof having a melting point of from about 160 ° C to 180 ° C.

本揭露鋰電池隔離膜可為一微孔性隔離膜。The lithium battery separator can be a microporous separator.

本揭露鋰電池隔離膜之Gurley約小於80(s/10cc)，熱閉孔溫度約小於135℃，以及耐熱溫度約大於165℃。The lithium battery separator has a Gurley of less than about 80 (s/10 cc), a heat closed cell temperature of less than about 135 ° C, and a heat resistant temperature of about 165 ° C.

上述聚乙烯孔隙膜與聚丙烯孔隙膜可由共押出製程製作。The polyethylene pore film and the polypropylene pore film can be produced by a co-extrusion process.

根據第1~11圖，本揭露鋰電池隔離膜可包括以下多種結構態樣：請參閱第1圖，一鋰電池隔離膜10包括一聚乙烯孔隙膜12、一聚丙烯孔隙膜14與一紫外光固化或熱固化高分子孔隙膜16。聚丙烯孔隙膜14位於聚乙烯孔隙膜12上，紫外光固化或熱固化高分子孔隙膜16位於聚丙烯孔隙膜14上。聚乙烯孔隙膜12與聚丙烯孔隙膜14構成一聚烯烴複合孔隙膜18。在一實施例中，紫外光固化或熱固化高分子孔隙膜16可包括聚三丙二醇二丙烯酸酯(poly(tripropylene glycol diacrylate),PTPGDA)、聚1,6-己二醇二丙烯酸酯(poly(1,6-hexanediol diacrylate),PHDDA)、聚三甲醇基丙基三丙烯酸酯(poly(trimethylolpropane triacrylate),PTMPTA)或聚二新戊四醇六丙烯酸酯(poly(dipentaerythritol hexylacrylate),PDPHA)。According to the first to the eleventh, the lithium battery separator can include the following structural aspects: Referring to FIG. 1, a lithium battery separator 10 includes a polyethylene pore film 12, a polypropylene pore film 14 and an ultraviolet film. The photo-cured or thermally cured polymer pore film 16. The polypropylene pore film 14 is located on the polyethylene pore film 12, and the ultraviolet light curing or heat curing polymer pore film 16 is located on the polypropylene pore film 14. The polyethylene pore film 12 and the polypropylene pore film 14 constitute a polyolefin composite pore film 18. In one embodiment, the ultraviolet curable or thermally curable polymeric pore film 16 may comprise poly(tripropylene glycol diacrylate) (PTPGDA), poly(1,6-hexanediol diacrylate) (poly( 1,6-hexanediol diacrylate), PHDDA), poly(trimethylolpropane triacrylate, PTMPTA) or poly(dipentaerythritol hexylacrylate, PDPHA).

鋰電池隔離膜10的製作方法如下：首先，以例如一共押出製程及延伸造孔製程製作聚烯烴複合孔隙膜18。在共押 出製程中，押出溫度可介於190℃~250℃，共押出製程後所得的聚烯烴雙層前驅膜其總厚度可介於20μm~70μm，而聚丙烯層的厚度可佔上述總厚度的5%~50%。之後，以例如100℃~120℃對聚烯烴雙層前驅膜進行一退火製程。之後，對聚烯烴雙層前驅膜進行一延伸造孔製程，例如先於室溫下進行20%~40%單軸延伸，再於100℃~120℃下進行50%~200%單軸延伸。延伸造孔製程後所得的聚烯烴複合孔隙膜18其總厚度可介於10μm~50μm。之後，塗佈一固含量介於1~10%的紫外光固化或熱固化高分子溶液於聚丙烯孔隙膜14表面。以紫外光照射或加熱進行固化後，即可獲得本揭露包含聚乙烯孔隙膜12、聚丙烯孔隙膜14與紫外光固化或熱固化高分子孔隙膜16的三層隔離膜結構。The lithium battery separator 10 is produced as follows: First, the polyolefin composite pore film 18 is produced by, for example, a co-extrusion process and an extended pore-forming process. Co-in In the process, the extrusion temperature can be between 190 ° C and 250 ° C. The total thickness of the polyolefin double-layer precursor film obtained after the co-extrusion process can be between 20 μm and 70 μm, and the thickness of the polypropylene layer can account for 5 of the total thickness. %~50%. Thereafter, the polyolefin double-layer precursor film is subjected to an annealing process at, for example, 100 ° C to 120 ° C. Thereafter, the polyolefin double-layer precursor film is subjected to an extended pore-forming process, for example, 20% to 40% uniaxial stretching at room temperature, and 50% to 200% uniaxial stretching at 100 ° C to 120 ° C. The polyolefin composite pore film 18 obtained after the extension of the pore-forming process may have a total thickness of from 10 μm to 50 μm. Thereafter, a UV curable or thermally curable polymer solution having a solid content of 1 to 10% is coated on the surface of the polypropylene pore film 14. After curing by ultraviolet light irradiation or heating, the three-layer isolation film structure including the polyethylene pore film 12, the polypropylene pore film 14 and the ultraviolet light curing or heat curing polymer pore film 16 can be obtained.

請參閱第2圖，一鋰電池隔離膜10包括一第一紫外光固化或熱固化高分子孔隙膜16、一聚乙烯孔隙膜12、一聚丙烯孔隙膜14與一第二紫外光固化或熱固化高分子孔隙膜16’。聚乙烯孔隙膜12位於第一紫外光固化或熱固化高分子孔隙膜16上，聚丙烯孔隙膜14位於聚乙烯孔隙膜12上，第二紫外光固化或熱固化高分子孔隙膜16’位於聚丙烯孔隙膜14上。聚乙烯孔隙膜12與聚丙烯孔隙膜14構成一聚烯烴複合孔隙膜18。在一實施例中，第一紫外光固化或熱固化高分子孔隙膜16與第二紫外光固化或熱固化高分子孔隙膜16’可包括聚三丙二醇二丙烯酸酯(poly(tripropylene glycol diacrylate),PTPGDA)、聚1,6-己二醇二丙烯酸酯(poly(1,6-hexanediol diacrylate),PHDDA)、聚三甲醇基丙基三丙烯酸酯(poly(trimethylolpropane triacrylate), PTMPTA)或聚二新戊四醇六丙烯酸酯(poly(dipentaerythritol hexylacrylate),PDPHA)。Referring to FIG. 2, a lithium battery separator 10 includes a first ultraviolet curing or heat curing polymer pore film 16, a polyethylene pore film 12, a polypropylene pore film 14 and a second ultraviolet curing or heat. The polymer pore film 16' is cured. The polyethylene pore film 12 is located on the first ultraviolet light curing or heat curing polymer pore film 16, the polypropylene pore film 14 is located on the polyethylene pore film 12, and the second ultraviolet light curing or heat curing polymer pore film 16' is located in the poly The propylene pore film 14 is on. The polyethylene pore film 12 and the polypropylene pore film 14 constitute a polyolefin composite pore film 18. In one embodiment, the first ultraviolet light curing or heat curing polymer pore film 16 and the second ultraviolet light curing or heat curing polymer pore film 16' may include poly(tripropylene glycol diacrylate). PTPGDA), poly(1,6-hexanediol diacrylate, PHDDA), poly(trimethylolpropane triacrylate), PTMPTA) or poly(dipentaerythritol hexylacrylate, PDPHA).

鋰電池隔離膜10的製作方法如下：首先，以例如一共押出製程製以及延伸造孔製程製作聚烯烴複合孔隙膜18。在共押出製程中，押出溫度可介於190℃~250℃，共押出製程後所得的聚烯烴雙層前驅膜其總厚度可介於20μm~70μm，而聚丙烯層的厚度可佔上述總厚度的5%~50%。之後，以例如100℃~120℃對聚烯烴雙層前驅膜進行一退火製程。之後，對聚烯烴雙層前驅膜進行一延伸造孔製程，例如先於室溫下進行20%~40%單軸延伸，再於100℃~120℃下進行50%~200%單軸延伸。延伸造孔製程後所得的聚烯烴複合孔隙膜18其總厚度可介於10μm~50μm。之後，塗佈一固含量介於1~10%的第一紫外光固化或熱固化高分子溶液於聚乙烯孔隙膜12表面，以及塗佈一固含量介於1~10%的第二紫外光固化或熱固化高分子溶液於聚丙烯孔隙膜14表面。以紫外光照射或加熱進行固化後，即可獲得本揭露包含第一紫外光固化或熱固化高分子孔隙膜16、聚乙烯孔隙膜12、聚丙烯孔隙膜14與第二紫外光固化或熱固化高分子孔隙膜16’的四層隔離膜結構。The lithium battery separator 10 is produced as follows. First, the polyolefin composite pore film 18 is produced by, for example, a co-extrusion process and an extended pore-forming process. In the co-extrusion process, the extrusion temperature can be between 190 ° C and 250 ° C, and the total thickness of the polyolefin double-layer precursor film obtained after the co-extrusion process can be between 20 μm and 70 μm, and the thickness of the polypropylene layer can account for the above total thickness. 5% to 50%. Thereafter, the polyolefin double-layer precursor film is subjected to an annealing process at, for example, 100 ° C to 120 ° C. Thereafter, the polyolefin double-layer precursor film is subjected to an extended pore-forming process, for example, 20% to 40% uniaxial stretching at room temperature, and 50% to 200% uniaxial stretching at 100 ° C to 120 ° C. The polyolefin composite pore film 18 obtained after the extension of the pore-forming process may have a total thickness of from 10 μm to 50 μm. Thereafter, coating a first ultraviolet curing or heat curing polymer solution having a solid content of 1 to 10% on the surface of the polyethylene pore film 12, and coating a second ultraviolet light having a solid content of 1 to 10%. The polymer solution is cured or thermally cured on the surface of the polypropylene pore film 14. After curing by ultraviolet light irradiation or heating, the present disclosure can be obtained by including the first ultraviolet light curing or heat curing polymer pore film 16, the polyethylene pore film 12, the polypropylene pore film 14 and the second ultraviolet light curing or heat curing. Four-layer isolation film structure of polymer pore film 16'.

請參閱第3圖，一鋰電池隔離膜10包括一聚乙烯孔隙膜12、一聚丙烯孔隙膜14、一聚偏二氟乙烯(PVDF)衍生物孔隙膜20與一紫外光固化或熱固化高分子孔隙膜16。聚丙烯孔隙膜14位於聚乙烯孔隙膜12上，聚偏二氟乙烯(PVDF)衍生物孔隙膜20位於聚丙烯孔隙膜14上，紫外光固化或熱固化高分子孔隙膜16位於聚偏二氟乙烯(PVDF)衍生物孔隙膜20上。聚乙烯孔隙 膜12與聚丙烯孔隙膜14構成一聚烯烴複合孔隙膜18。聚偏二氟乙烯(PVDF)衍生物孔隙膜20可包括聚偏二氟乙烯(PVDF)、聚偏二氟乙烯-六氟丙烯(PVDF-HFP)共聚物、聚偏二氟乙烯-三氟氯乙烯(PVDF-CTFE)共聚物或其組合。在一實施例中，紫外光固化或熱固化高分子孔隙膜16可包括聚三丙二醇二丙烯酸酯(poly(tripropylene glycol diacrylate),PTPGDA)、聚1,6-己二醇二丙烯酸酯(poly(1,6-hexanediol diacrylate),PHDDA)、聚三甲醇基丙基三丙烯酸酯(poly(trimethylolpropane triacrylate),PTMPTA)或聚二新戊四醇六丙烯酸酯(poly(dipentaerythritol hexylacrylate),PDPHA)。Referring to FIG. 3, a lithium battery separator 10 includes a polyethylene pore film 12, a polypropylene pore film 14, a polyvinylidene fluoride (PVDF) derivative pore film 20, and a UV curing or heat curing. Molecular pore membrane 16. The polypropylene pore film 14 is located on the polyethylene pore film 12, the polyvinylidene fluoride (PVDF) derivative pore film 20 is located on the polypropylene pore film 14, and the ultraviolet light curing or heat curing polymer pore film 16 is located in the polyvinylidene fluoride. The ethylene (PVDF) derivative is on the pore film 20. Polyethylene pore The film 12 and the polypropylene pore film 14 constitute a polyolefin composite pore film 18. The polyvinylidene fluoride (PVDF) derivative pore film 20 may include polyvinylidene fluoride (PVDF), polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) copolymer, polyvinylidene fluoride-chlorotrifluorochloride. Ethylene (PVDF-CTFE) copolymer or a combination thereof. In one embodiment, the ultraviolet curable or thermally curable polymeric pore film 16 may comprise poly(tripropylene glycol diacrylate) (PTPGDA), poly(1,6-hexanediol diacrylate) (poly( 1,6-hexanediol diacrylate), PHDDA), poly(trimethylolpropane triacrylate, PTMPTA) or poly(dipentaerythritol hexylacrylate, PDPHA).

鋰電池隔離膜10的製作方法如下：首先，以例如一共押出製程以及延伸造孔製程製作聚烯烴複合孔隙膜18。在共押出製程中，押出溫度可介於190℃~250℃，共押出製程後所得的聚烯烴雙層前驅膜其總厚度可介於20μm~70μm，而聚丙烯層的厚度可佔上述總厚度的5%~50%。之後，以例如100℃~120℃對聚烯烴雙層前驅膜進行一退火製程。之後，對聚烯烴雙層前驅膜進行一延伸造孔製程，例如先於室溫下進行20%~40%單軸延伸，再於100℃~120℃下進行50%~200%單軸延伸。延伸造孔製程後所得的聚烯烴複合孔隙膜18其總厚度可介於10μm~50μm。之後，塗佈一固含量介於8wt%~14wt%的聚偏二氟乙烯(PVDF)衍生物溶液於聚丙烯孔隙膜14表面，並以水進行凝固形成聚偏二氟乙烯(PVDF)衍生物孔隙膜20。之後，塗佈一固含量介於1~10%的紫外光固化或熱固化高分子溶液於聚偏二氟乙烯(PVDF)衍生物孔隙膜20表面。以紫外光照射或加熱進 行固化後，即可獲得本揭露包含聚乙烯孔隙膜12、聚丙烯孔隙膜14、聚偏二氟乙烯(PVDF)衍生物孔隙膜20與紫外光固化或熱固化高分子孔隙膜16的四層隔離膜結構。The lithium battery separator 10 is produced as follows: First, the polyolefin composite pore film 18 is produced by, for example, a co-extrusion process and an extended pore-forming process. In the co-extrusion process, the extrusion temperature can be between 190 ° C and 250 ° C, and the total thickness of the polyolefin double-layer precursor film obtained after the co-extrusion process can be between 20 μm and 70 μm, and the thickness of the polypropylene layer can account for the above total thickness. 5% to 50%. Thereafter, the polyolefin double-layer precursor film is subjected to an annealing process at, for example, 100 ° C to 120 ° C. Thereafter, the polyolefin double-layer precursor film is subjected to an extended pore-forming process, for example, 20% to 40% uniaxial stretching at room temperature, and 50% to 200% uniaxial stretching at 100 ° C to 120 ° C. The polyolefin composite pore film 18 obtained after the extension of the pore-forming process may have a total thickness of from 10 μm to 50 μm. Thereafter, a solution of a polyvinylidene fluoride (PVDF) derivative having a solid content of 8 wt% to 14 wt% is coated on the surface of the polypropylene pore film 14 and solidified with water to form a polyvinylidene fluoride (PVDF) derivative. Pore film 20. Thereafter, a UV curable or thermally curable polymer solution having a solid content of 1 to 10% is coated on the surface of the polyvinylidene fluoride (PVDF) derivative pore film 20. Irradiated by ultraviolet light or heated After curing, the four layers including the polyethylene pore film 12, the polypropylene pore film 14, the polyvinylidene fluoride (PVDF) derivative pore film 20 and the ultraviolet light curing or heat curing polymer pore film 16 can be obtained. Isolation membrane structure.

請參閱第4圖，一鋰電池隔離膜10包括一聚丙烯孔隙膜14、一聚乙烯孔隙膜12與一紫外光固化或熱固化高分子孔隙膜16。聚乙烯孔隙膜12位於聚丙烯孔隙膜14上，紫外光固化或熱固化高分子孔隙膜16位於聚乙烯孔隙膜12上。聚丙烯孔隙膜14與聚乙烯孔隙膜12構成一聚烯烴複合孔隙膜18’。在一實施例中，紫外光固化或熱固化高分子孔隙膜16可包括聚三丙二醇二丙烯酸酯(poly(tripropylene glycol diacrylate),PTPGDA)、聚1,6-己二醇二丙烯酸酯(poly(1,6-hexanediol diacrylate),PHDDA)、聚三甲醇基丙基三丙烯酸酯(poly(trimethylolpropane triacrylate),PTMPTA)或聚二新戊四醇六丙烯酸酯(poly(dipentaerythritol hexylacrylate),PDPHA)。Referring to FIG. 4, a lithium battery separator 10 includes a polypropylene pore film 14, a polyethylene pore film 12, and an ultraviolet curing or heat curing polymer pore film 16. The polyethylene pore film 12 is located on the polypropylene pore film 14, and the ultraviolet light curing or heat curing polymer pore film 16 is located on the polyethylene pore film 12. The polypropylene pore film 14 and the polyethylene pore film 12 constitute a polyolefin composite pore film 18'. In one embodiment, the ultraviolet curable or thermally curable polymeric pore film 16 may comprise poly(tripropylene glycol diacrylate) (PTPGDA), poly(1,6-hexanediol diacrylate) (poly( 1,6-hexanediol diacrylate), PHDDA), poly(trimethylolpropane triacrylate, PTMPTA) or poly(dipentaerythritol hexylacrylate, PDPHA).

鋰電池隔離膜10的製作方法如下：首先，以例如一共押出製程以及延伸造孔製程製作聚烯烴複合孔隙膜18’。在共押出製程中，押出溫度可介於190℃~250℃，共押出製程後所得的聚烯烴雙層前驅膜其總厚度可介於20μm~70μm，而聚丙烯層的厚度可佔上述總厚度的5%~50%。之後，以例如100℃~120℃對聚烯烴雙層前驅膜進行一退火製程。之後，對聚烯烴雙層前驅膜進行一延伸造孔製程，例如先於室溫下進行20%~40%單軸延伸，再於100℃~120℃下進行50%~200%單軸延伸。延伸造孔製程後所得的聚烯烴複合孔隙膜18’其總厚度可介於10μm~50μm。之後，塗佈一固含量介於1~10%的紫外光固 化或熱固化高分子溶液於聚乙烯孔隙膜12表面。以紫外光照射或加熱進行固化後，即可獲得本揭露包含聚丙烯孔隙膜14、聚乙烯孔隙膜12與紫外光固化或熱固化高分子孔隙膜16的三層隔離膜結構。The lithium battery separator 10 is produced as follows. First, the polyolefin composite pore film 18' is produced by, for example, a co-extrusion process and an extended pore-forming process. In the co-extrusion process, the extrusion temperature can be between 190 ° C and 250 ° C, and the total thickness of the polyolefin double-layer precursor film obtained after the co-extrusion process can be between 20 μm and 70 μm, and the thickness of the polypropylene layer can account for the above total thickness. 5% to 50%. Thereafter, the polyolefin double-layer precursor film is subjected to an annealing process at, for example, 100 ° C to 120 ° C. Thereafter, the polyolefin double-layer precursor film is subjected to an extended pore-forming process, for example, 20% to 40% uniaxial stretching at room temperature, and 50% to 200% uniaxial stretching at 100 ° C to 120 ° C. The polyolefin composite pore film 18' obtained after the extension of the pore-forming process may have a total thickness of from 10 μm to 50 μm. After that, coating a solid solution with a solid content of 1 to 10% The polymer solution is thermally or thermally cured on the surface of the polyethylene pore film 12. After curing by ultraviolet light irradiation or heating, the three-layer isolation film structure including the polypropylene pore film 14, the polyethylene pore film 12 and the ultraviolet light curing or heat curing polymer pore film 16 can be obtained.

請參閱第5圖，一鋰電池隔離膜10包括一聚丙烯孔隙膜14、一聚乙烯孔隙膜12、一聚偏二氟乙烯(PVDF)衍生物孔隙膜20與一紫外光固化或熱固化高分子孔隙膜16。聚乙烯孔隙膜12位於聚丙烯孔隙膜14上，聚偏二氟乙烯(PVDF)衍生物孔隙膜20位於聚乙烯孔隙膜12上，紫外光固化或熱固化高分子孔隙膜16位於聚偏二氟乙烯(PVDF)衍生物孔隙膜20上。聚丙烯孔隙膜14與聚乙烯孔隙膜12構成一聚烯烴複合孔隙膜18’。聚偏二氟乙烯(PVDF)衍生物孔隙膜20可包括聚偏二氟乙烯(PVDF)、聚偏二氟乙烯-六氟丙烯(PVDF-HFP)共聚物、聚偏二氟乙烯-三氟氯乙烯(PVDF-CTFE)共聚物或其組合。在一實施例中，紫外光固化或熱固化高分子孔隙膜16可包括聚三丙二醇二丙烯酸酯(poly(tripropylene glycol diacrylate),PTPGDA)、聚1,6-己二醇二丙烯酸酯(poly(1,6-hexanediol diacrylate),PHDDA)、聚三甲醇基丙基三丙烯酸酯(poly(trimethylolpropane triacrylate),PTMPTA)或聚二新戊四醇六丙烯酸酯(poly(dipentaerythritol hexylacrylate),PDPHA)。Referring to FIG. 5, a lithium battery separator 10 includes a polypropylene pore film 14, a polyethylene pore film 12, a polyvinylidene fluoride (PVDF) derivative pore film 20, and a UV curing or heat curing. Molecular pore membrane 16. The polyethylene pore film 12 is located on the polypropylene pore film 14, the polyvinylidene fluoride (PVDF) derivative pore film 20 is located on the polyethylene pore film 12, and the ultraviolet light curing or heat curing polymer pore film 16 is located in the polyvinylidene fluoride film. The ethylene (PVDF) derivative is on the pore film 20. The polypropylene pore film 14 and the polyethylene pore film 12 constitute a polyolefin composite pore film 18'. The polyvinylidene fluoride (PVDF) derivative pore film 20 may include polyvinylidene fluoride (PVDF), polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) copolymer, polyvinylidene fluoride-chlorotrifluorochloride. Ethylene (PVDF-CTFE) copolymer or a combination thereof. In one embodiment, the ultraviolet curable or thermally curable polymeric pore film 16 may comprise poly(tripropylene glycol diacrylate) (PTPGDA), poly(1,6-hexanediol diacrylate) (poly( 1,6-hexanediol diacrylate), PHDDA), poly(trimethylolpropane triacrylate, PTMPTA) or poly(dipentaerythritol hexylacrylate, PDPHA).

鋰電池隔離膜10的製作方法如下：首先，以例如一共押出製程以及延伸造孔製程製作聚烯烴複合孔隙膜18’。在共押出製程中，押出溫度可介於190℃~250℃，共押出製程後所得的聚烯烴雙層前驅膜其總厚度可介於20μm~70μm，而聚丙 烯層的厚度可佔上述總厚度的5%~50%。之後，以例如100℃~120℃對聚烯烴雙層前驅膜進行一退火製程。之後，對聚烯烴雙層前驅膜進行一延伸造孔製程，例如先於室溫下進行20%~40%單軸延伸，再於100℃~120℃下進行50%~200%單軸延伸。延伸造孔製程後所得的聚烯烴複合孔隙膜18’其總厚度可介於10μm~50μm。之後，塗佈一固含量介於8wt%~14wt%的聚偏二氟乙烯(PVDF)衍生物溶液於聚乙烯孔隙膜12表面，並以水進行凝固，形成聚偏二氟乙烯(PVDF)衍生物孔隙膜20。之後，塗佈一固含量介於1~10%的紫外光固化或熱固化高分子溶液於聚偏二氟乙烯(PVDF)衍生物孔隙膜20表面。以紫外光照射或加熱進行固化後，即可獲得本揭露包含聚丙烯孔隙膜14、聚乙烯孔隙膜12、聚偏二氟乙烯(PVDF)衍生物孔隙膜20與紫外光固化或熱固化高分子孔隙膜16的四層隔離膜結構。The lithium battery separator 10 is produced as follows. First, the polyolefin composite pore film 18' is produced by, for example, a co-extrusion process and an extended pore-forming process. In the co-extrusion process, the extrusion temperature can be between 190 ° C and 250 ° C, and the total thickness of the polyolefin bilayer precursor film obtained after the co-extrusion process can be between 20 μm and 70 μm, and the polypropylene The thickness of the olefin layer may be from 5% to 50% of the total thickness described above. Thereafter, the polyolefin double-layer precursor film is subjected to an annealing process at, for example, 100 ° C to 120 ° C. Thereafter, the polyolefin double-layer precursor film is subjected to an extended pore-forming process, for example, 20% to 40% uniaxial stretching at room temperature, and 50% to 200% uniaxial stretching at 100 ° C to 120 ° C. The polyolefin composite pore film 18' obtained after the extension of the pore-forming process may have a total thickness of from 10 μm to 50 μm. Thereafter, a solution of polyvinylidene fluoride (PVDF) derivative having a solid content of 8 wt% to 14 wt% is coated on the surface of the polyethylene pore film 12, and solidified by water to form a polyvinylidene fluoride (PVDF) derivative. Pore film 20. Thereafter, a UV curable or thermally curable polymer solution having a solid content of 1 to 10% is coated on the surface of the polyvinylidene fluoride (PVDF) derivative pore film 20. After curing by ultraviolet light irradiation or heating, the present disclosure includes a polypropylene pore film 14, a polyethylene pore film 12, a polyvinylidene fluoride (PVDF) derivative pore film 20, and an ultraviolet curing or heat curing polymer. A four-layer isolation film structure of the pore film 16.

請參閱第6圖，一鋰電池隔離膜10包括一第一聚丙烯孔隙膜14、一聚乙烯孔隙膜12、一第二聚丙烯孔隙膜14’與一紫外光固化或熱固化高分子孔隙膜16。聚乙烯孔隙膜12位於第一聚丙烯孔隙膜14上，第二聚丙烯孔隙膜14’位於聚乙烯孔隙膜12上，紫外光固化或熱固化高分子孔隙膜16位於第二聚丙烯孔隙膜14’上。第一聚丙烯孔隙膜14、聚乙烯孔隙膜12與第二聚丙烯孔隙膜14’構成一聚烯烴複合孔隙膜19。在一實施例中，紫外光固化或熱固化高分子孔隙膜16可包括聚三丙二醇二丙烯酸酯(poly(tripropylene glycol diacrylate),PTPGDA)、聚1,6-己二醇二丙烯酸酯(poly(1,6-hexanediol diacrylate),PHDDA)、聚三甲醇基丙基三丙烯酸酯(poly(trimethylolpropane triacrylate),PTMPTA)或聚二新戊四醇六丙烯酸酯(poly(dipentaerythritol hexylacrylate),PDPHA)。Referring to FIG. 6, a lithium battery separator 10 includes a first polypropylene pore film 14, a polyethylene pore film 12, a second polypropylene pore film 14' and an ultraviolet curing or heat curing polymer pore film. 16. The polyethylene pore film 12 is located on the first polypropylene pore film 14, the second polypropylene pore film 14' is located on the polyethylene pore film 12, and the ultraviolet light curing or heat curing polymer pore film 16 is located in the second polypropylene pore film 14. 'on. The first polypropylene pore film 14, the polyethylene pore film 12 and the second polypropylene pore film 14' constitute a polyolefin composite pore film 19. In one embodiment, the ultraviolet curable or thermally curable polymeric pore film 16 may comprise poly(tripropylene glycol diacrylate) (PTPGDA), poly(1,6-hexanediol diacrylate) (poly( 1,6-hexanediol diacrylate), PHDDA), polytrimethanol propyl triacrylate (poly(trimethylolpropane) Triacrylate), PTMPTA) or poly(dipentaerythritol hexylacrylate, PDPHA).

鋰電池隔離膜10的製作方法如下：首先，以例如一共押出製程以及延伸造孔製程製作聚烯烴複合孔隙膜19。在共押出製程中，押出溫度可介於190℃~250℃，共押出製程後所得的聚烯烴三層前驅膜其總厚度可介於20μm~70μm，而第一聚丙烯層與第二聚丙烯層的厚度可佔上述總厚度的5%~70%。之後，以例如100℃~120℃對聚烯烴三層前驅膜進行一退火製程。之後，對聚烯烴三層前驅膜進行一延伸造孔製程，例如先於室溫下進行20%~40%單軸延伸，再於100℃~120℃下進行50%~200%單軸延伸。延伸造孔製程後所得的聚烯烴複合孔隙膜19其總厚度可介於10μm~50μm。之後，塗佈一固含量介於1~10%的紫外光固化或熱固化高分子溶液於第二聚丙烯孔隙膜14’表面。以紫外光照射或加熱進行固化後，即可獲得本揭露包含第一聚丙烯孔隙膜14、聚乙烯孔隙膜12、第二聚丙烯孔隙膜14’與紫外光固化或熱固化高分子孔隙膜16的四層隔離膜結構。The lithium battery separator 10 is produced as follows. First, the polyolefin composite pore film 19 is produced by, for example, a co-extrusion process and an extended pore-forming process. In the co-extrusion process, the extrusion temperature can be between 190 ° C and 250 ° C, and the total thickness of the polyolefin three-layer precursor film obtained after the co-extrusion process can be between 20 μm and 70 μm, and the first polypropylene layer and the second polypropylene. The thickness of the layer may range from 5% to 70% of the total thickness described above. Thereafter, the polyolefin three-layer precursor film is subjected to an annealing process at, for example, 100 ° C to 120 ° C. Thereafter, an extended pore-forming process is performed on the polyolefin three-layer precursor film, for example, 20% to 40% uniaxial stretching is performed at room temperature, and then 50% to 200% uniaxial stretching is performed at 100 ° C to 120 ° C. The polyolefin composite pore film 19 obtained after the extension of the pore forming process may have a total thickness of from 10 μm to 50 μm. Thereafter, a UV curable or thermally curable polymer solution having a solid content of 1 to 10% is coated on the surface of the second polypropylene pore film 14'. After curing by ultraviolet light irradiation or heating, the present disclosure can be obtained to include the first polypropylene pore film 14, the polyethylene pore film 12, the second polypropylene pore film 14' and the ultraviolet light curing or heat curing polymer pore film 16 The four-layer isolation membrane structure.

請參閱第7圖，一鋰電池隔離膜10包括一第一紫外光固化或熱固化高分子孔隙膜16、一第一聚丙烯孔隙膜14、一聚乙烯孔隙膜12、一第二聚丙烯孔隙膜14’與一第二紫外光固化或熱固化高分子孔隙膜16’。第一聚丙烯孔隙膜14位於第一紫外光固化或熱固化高分子孔隙膜16上，聚乙烯孔隙膜12位於第一聚丙烯孔隙膜14上，第二聚丙烯孔隙膜14’位於聚乙烯孔隙膜12上，第二紫外光固化或熱固化高分子孔隙膜16’位於第 二聚丙烯孔隙膜14’上。第一聚丙烯孔隙膜14、聚乙烯孔隙膜12與第二聚丙烯孔隙膜14’構成一聚烯烴複合孔隙膜19。在一實施例中，第一紫外光固化或熱固化高分子孔隙膜16與第二紫外光固化或熱固化高分子孔隙膜16’可包括聚三丙二醇二丙烯酸酯(poly(tripropylene glycol diacrylate),PTPGDA)、聚1,6-己二醇二丙烯酸酯(poly(1,6-hexanediol diacrylate),PHDDA)、聚三甲醇基丙基三丙烯酸酯(poly(trimethylolpropane triacrylate),PTMPTA)或聚二新戊四醇六丙烯酸酯(poly(dipentaerythritol hexylacrylate),PDPHA)。Referring to FIG. 7, a lithium battery separator 10 includes a first ultraviolet light curing or heat curing polymer pore film 16, a first polypropylene pore film 14, a polyethylene pore film 12, and a second polypropylene pore. The film 14' is bonded to a second ultraviolet light curing or heat curing polymeric pore film 16'. The first polypropylene pore film 14 is located on the first ultraviolet light curing or heat curing polymer pore film 16, the polyethylene pore film 12 is located on the first polypropylene pore film 14, and the second polypropylene pore film 14' is located in the polyethylene pore. On the film 12, a second ultraviolet light curing or heat curing polymer pore film 16' is located at the first The second polypropylene pore film 14' is on. The first polypropylene pore film 14, the polyethylene pore film 12 and the second polypropylene pore film 14' constitute a polyolefin composite pore film 19. In one embodiment, the first ultraviolet light curing or heat curing polymer pore film 16 and the second ultraviolet light curing or heat curing polymer pore film 16' may include poly(tripropylene glycol diacrylate). PTPGDA), poly(1,6-hexanediol diacrylate, PHDDA), poly(trimethylolpropane triacrylate, PTMPTA) or poly(new) Poly(dipentaerythritol hexylacrylate, PDPHA).

鋰電池隔離膜10的製作方法如下：首先，以例如一共押出製程以及延伸造孔製程製作聚烯烴複合孔隙膜19。在共押出製程中，押出溫度可介於190℃~250℃，共押出製程後所得的聚烯烴三層前驅膜其總厚度可介於20μm~70μm，而第一聚丙烯層與第二聚丙烯層的厚度可佔上述總厚度的5%~70%。之後，以例如100℃~120℃對聚烯烴三層前驅膜進行一退火製程。之後，對聚烯烴三層前驅膜進行一延伸造孔製程，例如先於室溫下進行20%~40%單軸延伸，再於100℃~120℃下進行50%~200%單軸延伸。延伸造孔製程後所得的聚烯烴複合孔隙膜19其總厚度可介於10μm~50μm。之後，塗佈一固含量介於1~10%的第一紫外光固化或熱固化高分子溶液於第一聚丙烯孔隙膜14表面，以及塗佈一固含量介於1~10%的第二紫外光固化或熱固化高分子溶液於第二聚丙烯孔隙膜14’表面。以紫外光照射或加熱進行固化後，即可獲得本揭露包含第一紫外光固化或熱固化高分子孔隙膜16、第一聚丙烯孔隙膜14、聚乙烯孔 隙膜12、第二聚丙烯孔隙膜14’與第二紫外光固化或熱固化高分子孔隙膜16’的五層隔離膜結構。The lithium battery separator 10 is produced as follows. First, the polyolefin composite pore film 19 is produced by, for example, a co-extrusion process and an extended pore-forming process. In the co-extrusion process, the extrusion temperature can be between 190 ° C and 250 ° C, and the total thickness of the polyolefin three-layer precursor film obtained after the co-extrusion process can be between 20 μm and 70 μm, and the first polypropylene layer and the second polypropylene. The thickness of the layer may range from 5% to 70% of the total thickness described above. Thereafter, the polyolefin three-layer precursor film is subjected to an annealing process at, for example, 100 ° C to 120 ° C. Thereafter, an extended pore-forming process is performed on the polyolefin three-layer precursor film, for example, 20% to 40% uniaxial stretching is performed at room temperature, and then 50% to 200% uniaxial stretching is performed at 100 ° C to 120 ° C. The polyolefin composite pore film 19 obtained after the extension of the pore forming process may have a total thickness of from 10 μm to 50 μm. Thereafter, coating a first ultraviolet light curing or heat curing polymer solution having a solid content of 1 to 10% on the surface of the first polypropylene pore film 14, and coating a second solid content of 1 to 10%. The UV curable or thermally curable polymer solution is on the surface of the second polypropylene pore film 14'. After curing by ultraviolet light irradiation or heating, the present disclosure can be obtained by including the first ultraviolet light curing or heat curing polymer pore film 16, the first polypropylene pore film 14, and the polyethylene hole. The gap film 12, the second polypropylene pore film 14' and the fifth ultraviolet light-curable or heat-curable polymer pore film 16' have a five-layer separator structure.

請參閱第8圖，一鋰電池隔離膜10包括一第一聚丙烯膜孔隙14、一聚乙烯孔隙膜12、一第二聚丙烯孔隙膜14’、一聚偏二氟乙烯(PVDF)衍生物孔隙膜20與一紫外光固化或熱固化高分子孔隙膜16。聚乙烯孔隙膜12位於第一聚丙烯孔隙膜14上，第二聚丙烯孔隙膜14’位於聚乙烯孔隙膜12上，聚偏二氟乙烯(PVDF)衍生物孔隙膜20位於第二聚丙烯孔隙膜14’上，紫外光固化或熱固化高分子孔隙膜16位於聚偏二氟乙烯(PVDF)衍生物孔隙膜20上。第一聚丙烯孔隙膜14、聚乙烯孔隙膜12與第二聚丙烯孔隙膜14’構成一聚烯烴複合孔隙膜19。聚偏二氟乙烯(PVDF)衍生物孔隙膜20可包括聚偏二氟乙烯(PVDF)、聚偏二氟乙烯-六氟丙烯(PVDF-HFP)共聚物、聚偏二氟乙烯-三氟氯乙烯(PVDF-CTFE)共聚物或其組合。在一實施例中，紫外光固化或熱固化高分子孔隙膜16可包括聚三丙二醇二丙烯酸酯(poly(tripropylene glycol diacrylate),PTPGDA)、聚1,6-己二醇二丙烯酸酯(poly(1,6-hexanediol diacrylate),PHDDA)、聚三甲醇基丙基三丙烯酸酯(poly(trimethylolpropane triacrylate),PTMPTA)或聚二新戊四醇六丙烯酸酯(poly(dipentaerythritol hexylacrylate),PDPHA)。Referring to FIG. 8, a lithium battery separator 10 includes a first polypropylene film pore 14, a polyethylene pore film 12, a second polypropylene pore film 14', and a polyvinylidene fluoride (PVDF) derivative. The pore film 20 is cured with a UV light or heat-cured polymer pore film 16. The polyethylene pore film 12 is located on the first polypropylene pore film 14, the second polypropylene pore film 14' is located on the polyethylene pore film 12, and the polyvinylidene fluoride (PVDF) derivative pore film 20 is located in the second polypropylene pore. On the film 14', the ultraviolet-curable or thermally-curable polymer pore film 16 is positioned on the polyvinylidene fluoride (PVDF) derivative pore film 20. The first polypropylene pore film 14, the polyethylene pore film 12 and the second polypropylene pore film 14' constitute a polyolefin composite pore film 19. The polyvinylidene fluoride (PVDF) derivative pore film 20 may include polyvinylidene fluoride (PVDF), polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) copolymer, polyvinylidene fluoride-chlorotrifluorochloride. Ethylene (PVDF-CTFE) copolymer or a combination thereof. In one embodiment, the ultraviolet curable or thermally curable polymeric pore film 16 may comprise poly(tripropylene glycol diacrylate) (PTPGDA), poly(1,6-hexanediol diacrylate) (poly( 1,6-hexanediol diacrylate), PHDDA), poly(trimethylolpropane triacrylate, PTMPTA) or poly(dipentaerythritol hexylacrylate, PDPHA).

鋰電池隔離膜10的製作方法如下：首先，以例如一共押出製程以及延伸造孔製程製作聚烯烴複合孔隙膜19。在共押出製程中，押出溫度可介於190℃~250℃，共押出製程後所得的聚烯烴三層前驅膜其總厚度可介於20μm~70μm，而第一聚 丙烯層與第二聚丙烯層的厚度可佔上述總厚度的5%~70%。之後，以例如100℃~120℃對聚烯烴三層前驅膜進行一退火製程。之後，對聚烯烴三層前驅膜進行一延伸造孔製程，例如先於室溫下進行20%~40%單軸延伸，再於100℃~120℃下進行50%~200%單軸延伸。延伸造孔製程後所得的聚烯烴複合孔隙膜19其總厚度可介於10μm~50μm。之後，塗佈一固含量介於8wt%~14wt%的聚偏二氟乙烯(PVDF)衍生物溶液於第二聚丙烯孔隙膜14’表面，並以水進行凝固，形成聚偏二氟乙烯(PVDF)衍生物孔隙膜20。之後，塗佈一固含量介於1~10%的紫外光固化或熱固化高分子溶液於聚偏二氟乙烯(PVDF)衍生物孔隙膜20表面。以紫外光照射或加熱進行固化後，即可獲得本揭露包含第一聚丙烯孔隙膜14、聚乙烯孔隙膜12、第二聚丙烯孔隙膜14’、聚偏二氟乙烯(PVDF)衍生物孔隙膜20與紫外光固化或熱固化高分子孔隙膜16的五層隔離膜結構。The lithium battery separator 10 is produced as follows. First, the polyolefin composite pore film 19 is produced by, for example, a co-extrusion process and an extended pore-forming process. In the co-extrusion process, the extrusion temperature can be between 190 ° C and 250 ° C, and the total thickness of the polyolefin three-layer precursor film obtained after the co-extrusion process can be between 20 μm and 70 μm, and the first polymerization The thickness of the propylene layer and the second polypropylene layer may be from 5% to 70% of the total thickness described above. Thereafter, the polyolefin three-layer precursor film is subjected to an annealing process at, for example, 100 ° C to 120 ° C. Thereafter, an extended pore-forming process is performed on the polyolefin three-layer precursor film, for example, 20% to 40% uniaxial stretching is performed at room temperature, and then 50% to 200% uniaxial stretching is performed at 100 ° C to 120 ° C. The polyolefin composite pore film 19 obtained after the extension of the pore forming process may have a total thickness of from 10 μm to 50 μm. Thereafter, a solution of a polyvinylidene fluoride (PVDF) derivative having a solid content of 8 wt% to 14 wt% is coated on the surface of the second polypropylene pore film 14', and solidified by water to form polyvinylidene fluoride ( PVDF) derivative pore film 20. Thereafter, a UV curable or thermally curable polymer solution having a solid content of 1 to 10% is coated on the surface of the polyvinylidene fluoride (PVDF) derivative pore film 20. After curing by ultraviolet light irradiation or heating, the disclosure discloses that the first polypropylene pore film 14, the polyethylene pore film 12, the second polypropylene pore film 14', and the polyvinylidene fluoride (PVDF) derivative pores are obtained. The film 20 has a five-layer isolation film structure of a UV-curable or heat-curable polymer pore film 16.

請參閱第9圖，一鋰電池隔離膜10包括一第一聚乙烯孔隙膜12、一聚丙烯孔隙膜14、一第二聚乙烯孔隙膜12’與一紫外光固化或熱固化高分子孔隙膜16。聚丙烯孔隙膜14位於第一聚乙烯孔隙膜12上，第二聚乙烯孔隙膜12’位於聚丙孔隙烯膜14上，紫外光固化或熱固化高分子孔隙膜16位於第二聚乙烯孔隙膜12’上。第一聚乙烯孔隙膜12、聚丙烯孔隙膜14與第二聚乙烯孔隙膜12’構成一聚烯烴複合孔隙膜19’。在一實施例中，紫外光固化或熱固化高分子孔隙膜16可包括聚三丙二醇二丙烯酸酯(poly(tripropylene glycol diacrylate),PTPGDA)、聚1,6-己二醇二丙烯酸酯(poly(1,6-hexanediol diacrylate), PHDDA)、聚三甲醇基丙基三丙烯酸酯(poly(trimethylolpropane triacrylate),PTMPTA)或聚二新戊四醇六丙烯酸酯(poly(dipentaerythritol hexylacrylate),PDPHA)。Referring to FIG. 9, a lithium battery separator 10 includes a first polyethylene pore film 12, a polypropylene pore film 14, a second polyethylene pore film 12' and an ultraviolet curing or heat curing polymer pore film. 16. The polypropylene pore film 14 is located on the first polyethylene pore film 12, the second polyethylene pore film 12' is located on the polyporous polyolefin film 14, and the ultraviolet light curing or heat curing polymer pore film 16 is located in the second polyethylene pore film 12. 'on. The first polyethylene pore film 12, the polypropylene pore film 14 and the second polyethylene pore film 12' constitute a polyolefin composite pore film 19'. In one embodiment, the ultraviolet curable or thermally curable polymeric pore film 16 may comprise poly(tripropylene glycol diacrylate) (PTPGDA), poly(1,6-hexanediol diacrylate) (poly( 1,6-hexanediol diacrylate), PHDDA), poly(trimethylolpropane triacrylate, PTMPTA) or poly(dipentaerythritol hexylacrylate, PDPHA).

鋰電池隔離膜10的製作方法如下：首先，以例如一共押出製程以及延伸造孔製程製作聚烯烴複合孔隙膜19’。在共押出製程中，押出溫度可介於190℃~250℃，共押出製程後所得的聚烯烴三層前驅膜其總厚度可介於20μm~70μm，而第一聚乙烯層與第二聚乙烯層的厚度可佔上述總厚度的5%~70%。之後，以例如100℃~120℃對聚烯烴三層前驅膜進行一退火製程。之後，對聚烯烴三層前驅膜進行一延伸造孔製程，例如先於室溫下進行20%~40%單軸延伸，再於100℃~120℃下進行50%~200%單軸延伸。延伸造孔製程後所得的聚烯烴複合孔隙膜19’其總厚度可介於10μm~50μm。之後，塗佈一固含量介於1~10%的紫外光固化或熱固化高分子溶液於第二聚乙烯孔隙膜12’表面。以紫外光照射或加熱進行固化後，即可獲得本揭露包含第一聚乙烯孔隙膜12、聚丙烯孔隙膜14、第二聚乙烯孔隙膜12’與紫外光固化或熱固化高分子孔隙膜16的四層隔離膜結構。The lithium battery separator 10 is produced as follows. First, the polyolefin composite pore film 19' is produced by, for example, a co-extrusion process and an extended pore-forming process. In the co-extrusion process, the extrusion temperature can be between 190 ° C and 250 ° C, and the total thickness of the polyolefin three-layer precursor film obtained after the co-extrusion process can be between 20 μm and 70 μm, and the first polyethylene layer and the second polyethylene layer. The thickness of the layer may range from 5% to 70% of the total thickness described above. Thereafter, the polyolefin three-layer precursor film is subjected to an annealing process at, for example, 100 ° C to 120 ° C. Thereafter, an extended pore-forming process is performed on the polyolefin three-layer precursor film, for example, 20% to 40% uniaxial stretching is performed at room temperature, and then 50% to 200% uniaxial stretching is performed at 100 ° C to 120 ° C. The polyolefin composite pore film 19' obtained after the extension of the pore-forming process may have a total thickness of from 10 μm to 50 μm. Thereafter, a UV curable or thermally curable polymer solution having a solid content of from 1 to 10% is applied to the surface of the second polyethylene pore film 12'. After curing by ultraviolet light irradiation or heating, the present disclosure can be obtained to include the first polyethylene pore film 12, the polypropylene pore film 14, the second polyethylene pore film 12' and the ultraviolet light curing or heat curing polymer pore film 16 The four-layer isolation membrane structure.

請參閱第10圖，一鋰電池隔離膜10包括一第一紫外光固化或熱固化高分子孔隙膜16、一第一聚乙烯孔隙膜12、一聚丙烯孔隙膜14、一第二聚乙烯孔隙膜12’與一第二紫外光固化或熱固化高分子孔隙膜16’。第一聚乙烯孔隙膜12位於第一紫外光固化或熱固化高分子孔隙膜16上，聚丙烯孔隙膜14位於第一聚乙烯孔隙膜12上，第二聚乙烯孔隙膜12’位於聚丙烯 孔隙膜14上，第二紫外光固化或熱固化高分子孔隙膜16’位於第二聚乙烯孔隙膜12’上。第一聚乙烯孔隙膜12、聚丙烯孔隙膜14與第二聚乙烯孔隙膜12’構成一聚烯烴複合孔隙膜19’。在一實施例中，第一紫外光固化或熱固化高分子孔隙膜16與第二紫外光固化或熱固化高分子孔隙膜16’可包括聚三丙二醇二丙烯酸酯(poly(tripropylene glycol diacrylate),PTPGDA)、聚1,6-己二醇二丙烯酸酯(poly(1,6-hexanediol diacrylate),PHDDA)、聚三甲醇基丙基三丙烯酸酯(poly(trimethylolpropane triacrylate),PTMPTA)或聚二新戊四醇六丙烯酸酯(poly(dipentaerythritol hexylacrylate),PDPHA)。Referring to FIG. 10, a lithium battery separator 10 includes a first ultraviolet light curing or heat curing polymer pore film 16, a first polyethylene pore film 12, a polypropylene pore film 14, and a second polyethylene pore. The film 12' and a second ultraviolet light cured or thermally cured polymeric pore film 16'. The first polyethylene pore film 12 is on the first ultraviolet light curing or heat curing polymer pore film 16, the polypropylene pore film 14 is on the first polyethylene pore film 12, and the second polyethylene pore film 12' is located in the polypropylene. On the pore film 14, a second ultraviolet-curable or thermally curable polymer pore film 16' is positioned on the second polyethylene pore film 12'. The first polyethylene pore film 12, the polypropylene pore film 14 and the second polyethylene pore film 12' constitute a polyolefin composite pore film 19'. In one embodiment, the first ultraviolet light curing or heat curing polymer pore film 16 and the second ultraviolet light curing or heat curing polymer pore film 16' may include poly(tripropylene glycol diacrylate). PTPGDA), poly(1,6-hexanediol diacrylate, PHDDA), poly(trimethylolpropane triacrylate, PTMPTA) or poly(new) Poly(dipentaerythritol hexylacrylate, PDPHA).

鋰電池隔離膜10的製作方法如下：首先，以例如一共押出製程以及延伸造孔製程製作聚烯烴複合孔隙膜19’。在共押出製程中，押出溫度可介於190℃~250℃，共押出製程後所得的聚烯烴三層前驅膜其總厚度可介於20μm~70μm，而第一聚乙烯層與第二聚乙烯層的厚度可佔上述總厚度的5%~70%。之後，以例如100℃~120℃對聚烯烴三層前驅膜進行一退火製程。之後，對聚烯烴三層前驅膜進行一延伸造孔製程，例如先於室溫下進行20%~40%單軸延伸，再於100℃~120℃下進行50%~200%單軸延伸。延伸造孔製程後所得的聚烯烴複合孔隙膜19’其總厚度可介於10μm~50μm。之後，塗佈一固含量介於1~10%的第一紫外光固化或熱固化高分子溶液於第一聚乙烯孔隙膜12表面，以及塗佈一固含量介於1~10%的第二紫外光固化或熱固化高分子溶液於第二聚乙烯孔隙膜12’表面。以紫外光照射或加熱進行固化後，即可獲得本揭露包含第一紫外光固 化或熱固化高分子孔隙膜16、第一聚乙烯孔隙膜12、聚丙烯孔隙膜14、第二聚乙烯孔隙膜12’與第二紫外光固化或熱固化高分子孔隙膜16’的五層隔離膜結構。The lithium battery separator 10 is produced as follows. First, the polyolefin composite pore film 19' is produced by, for example, a co-extrusion process and an extended pore-forming process. In the co-extrusion process, the extrusion temperature can be between 190 ° C and 250 ° C, and the total thickness of the polyolefin three-layer precursor film obtained after the co-extrusion process can be between 20 μm and 70 μm, and the first polyethylene layer and the second polyethylene layer. The thickness of the layer may range from 5% to 70% of the total thickness described above. Thereafter, the polyolefin three-layer precursor film is subjected to an annealing process at, for example, 100 ° C to 120 ° C. Thereafter, an extended pore-forming process is performed on the polyolefin three-layer precursor film, for example, 20% to 40% uniaxial stretching is performed at room temperature, and then 50% to 200% uniaxial stretching is performed at 100 ° C to 120 ° C. The polyolefin composite pore film 19' obtained after the extension of the pore-forming process may have a total thickness of from 10 μm to 50 μm. Thereafter, coating a first ultraviolet light curing or heat curing polymer solution having a solid content of 1 to 10% on the surface of the first polyethylene pore film 12, and coating a second solid content of 1 to 10% The ultraviolet light curing or heat curing polymer solution is on the surface of the second polyethylene pore film 12'. After curing by ultraviolet light irradiation or heating, the present disclosure can be obtained to include the first ultraviolet light solid. Five layers of a chemically or thermally cured polymeric pore membrane 16, a first polyethylene pore membrane 12, a polypropylene pore membrane 14, a second polyethylene pore membrane 12' and a second ultraviolet curable or thermally curable polymeric pore membrane 16' Isolation membrane structure.

請參閱第11圖，一鋰電池隔離膜10包括一第一聚乙烯孔隙膜12、一聚丙烯孔隙膜14、一第二聚乙烯孔隙膜12’、一聚偏二氟乙烯(PVDF)衍生物孔隙膜20與一紫外光固化或熱固化高分子孔隙膜16。聚丙烯孔隙膜14位於第一聚乙烯孔隙膜12上，第二聚乙烯孔隙膜12’位於聚丙烯孔隙膜14上，聚偏二氟乙烯(PVDF)衍生物孔隙膜20位於第二聚乙烯孔隙膜12’上，紫外光固化或熱固化高分子孔隙膜16位於聚偏二氟乙烯(PVDF)衍生物孔隙膜20上。第一聚乙烯孔隙膜12、聚丙烯孔隙膜14與第二聚乙烯孔隙膜12’構成一聚烯烴複合孔隙膜19’。聚偏二氟乙烯(PVDF)衍生物孔隙膜20可包括聚偏二氟乙烯(PVDF)、聚偏二氟乙烯-六氟丙烯(PVDF-HFP)共聚物、聚偏二氟乙烯-三氟氯乙烯(PVDF-CTFE)共聚物或其組合。在一實施例中，紫外光固化或熱固化高分子孔隙膜16可包括聚三丙二醇二丙烯酸酯(poly(tripropylene glycol diacrylate),PTPGDA)、聚1,6-己二醇二丙烯酸酯(poly(1,6-hexanediol diacrylate),PHDDA)、聚三甲醇基丙基三丙烯酸酯(poly(trimethylolpropane triacrylate),PTMPTA)或聚二新戊四醇六丙烯酸酯(poly(dipentaerythritol hexylacrylate),PDPHA)。Referring to FIG. 11, a lithium battery separator 10 includes a first polyethylene pore film 12, a polypropylene pore film 14, a second polyethylene pore film 12', and a polyvinylidene fluoride (PVDF) derivative. The pore film 20 is cured with a UV light or heat-cured polymer pore film 16. The polypropylene pore film 14 is located on the first polyethylene pore film 12, the second polyethylene pore film 12' is located on the polypropylene pore film 14, and the polyvinylidene fluoride (PVDF) derivative pore film 20 is located in the second polyethylene pore. On the film 12', a UV-curable or thermally curable polymer pore film 16 is positioned on the polyvinylidene fluoride (PVDF) derivative pore film 20. The first polyethylene pore film 12, the polypropylene pore film 14 and the second polyethylene pore film 12' constitute a polyolefin composite pore film 19'. The polyvinylidene fluoride (PVDF) derivative pore film 20 may include polyvinylidene fluoride (PVDF), polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) copolymer, polyvinylidene fluoride-chlorotrifluorochloride. Ethylene (PVDF-CTFE) copolymer or a combination thereof. In one embodiment, the ultraviolet curable or thermally curable polymeric pore film 16 may comprise poly(tripropylene glycol diacrylate) (PTPGDA), poly(1,6-hexanediol diacrylate) (poly( 1,6-hexanediol diacrylate), PHDDA), poly(trimethylolpropane triacrylate, PTMPTA) or poly(dipentaerythritol hexylacrylate, PDPHA).

鋰電池隔離膜10的製作方法如下：首先，以例如一共押出製程以及延伸造孔製程製作聚烯烴複合孔隙膜19’。在共押出製程中，押出溫度可介於190℃~250℃，共押出製程後 所得的聚烯烴三層前驅膜其總厚度可介於20μm~70μm，而第一聚乙烯層與第二聚乙烯層的厚度可佔上述總厚度的5%~70%。之後，以例如100℃~120℃對聚烯烴三層前驅膜進行一退火製程。之後，對聚烯烴三層前驅膜進行一延伸造孔製程，例如先於室溫下進行20%~40%單軸延伸，再於100℃~120℃下進行50%~200%單軸延伸。延伸造孔製程後所得的聚烯烴複合孔隙膜19’其總厚度可介於10μm~50μm。之後，塗佈一固含量介於8wt%~14wt%的聚偏二氟乙烯衍生物溶液於第二聚乙烯孔隙膜12’表面，並以水進行凝固，形成聚偏二氟乙烯(PVDF)衍生物孔隙膜20。之後，塗佈一固含量介於1~10%的紫外光固化或熱固化高分子溶液於聚偏二氟乙烯(PVDF)衍生物孔隙膜20表面。以紫外光照射或加熱進行固化後，即可獲得本揭露包含第一聚乙烯孔隙膜12、聚丙烯孔隙膜14、第二聚乙烯孔隙膜12’、聚偏二氟乙烯(PVDF)衍生物孔隙膜20與紫外光固化或熱固化高分子孔隙膜16的五層隔離膜結構。The lithium battery separator 10 is produced as follows. First, the polyolefin composite pore film 19' is produced by, for example, a co-extrusion process and an extended pore-forming process. In the co-extrusion process, the extrusion temperature can be between 190 ° C and 250 ° C, after the total extrusion process The obtained polyolefin three-layer precursor film may have a total thickness of 20 μm to 70 μm, and the first polyethylene layer and the second polyethylene layer may have a thickness of 5% to 70% of the total thickness. Thereafter, the polyolefin three-layer precursor film is subjected to an annealing process at, for example, 100 ° C to 120 ° C. Thereafter, an extended pore-forming process is performed on the polyolefin three-layer precursor film, for example, 20% to 40% uniaxial stretching is performed at room temperature, and then 50% to 200% uniaxial stretching is performed at 100 ° C to 120 ° C. The polyolefin composite pore film 19' obtained after the extension of the pore-forming process may have a total thickness of from 10 μm to 50 μm. Thereafter, a solution of a polyvinylidene fluoride derivative having a solid content of 8 wt% to 14 wt% is coated on the surface of the second polyethylene pore film 12', and solidified by water to form a polyvinylidene fluoride (PVDF) derivative. Pore film 20. Thereafter, a UV curable or thermally curable polymer solution having a solid content of 1 to 10% is coated on the surface of the polyvinylidene fluoride (PVDF) derivative pore film 20. After curing by ultraviolet light irradiation or heating, the disclosure discloses that the first polyethylene pore film 12, the polypropylene pore film 14, the second polyethylene pore film 12', and the polyvinylidene fluoride (PVDF) derivative pores are obtained. The film 20 has a five-layer isolation film structure of a UV-curable or heat-curable polymer pore film 16.

本揭露隔離膜結構中，聚丙烯孔隙膜可作為一抗穿刺層，提供隔離膜足夠的機械強度，聚乙烯孔隙膜可作為一熱閉孔層，於異常升溫時熔融閉孔阻斷電池反應，紫外光固化或熱固化高分子孔隙膜可作為一尺寸安定層，於高溫下維持尺寸穩定性，防止隔離膜受熱收縮，而聚偏二氟乙烯(PVDF)衍生物孔隙膜則作為一耐高溫層，使隔離膜於高溫下維持結構完整。因此，本揭露新型隔離膜結構具有良好機械性質，耐高溫，在高溫下具有良好尺寸穩定性，且具有熱閉孔能力。In the structure of the separator, the polypropylene pore film can be used as an anti-puncture layer to provide sufficient mechanical strength of the separator. The polyethylene pore film can be used as a heat-closed pore layer to block the battery reaction when the temperature is abnormally increased. The UV-curable or thermally-curable polymer pore film can be used as a dimensional stability layer to maintain dimensional stability at high temperatures and prevent the separator from being thermally contracted, while the polyvinylidene fluoride (PVDF) derivative pore film acts as a high temperature resistant layer. To maintain the structural integrity of the separator at high temperatures. Therefore, the novel separator structure has good mechanical properties, high temperature resistance, good dimensional stability at high temperatures, and heat blocking ability.

實施例1Example 1

鋰電池隔離膜之製備(1)(聚乙烯(PE)孔隙膜/聚丙烯(PP)孔隙膜/聚三丙二醇二丙烯酸酯(PTPGDA)孔隙膜)Preparation of lithium battery separator (1) (polyethylene (PE) pore film / polypropylene (PP) pore film / polytripropylene glycol diacrylate (PTPGDA) pore film)

請參閱第1圖，首先，以一共押出製程製作聚烯烴雙層前驅膜(聚乙烯(PE)層/聚丙烯(PP)層)。在共押出製程中，押出溫度為230℃，共押出製程後所得的聚烯烴雙層前驅膜其總厚度為45μm，而聚丙烯層的厚度佔上述總厚度的30%。之後，以120℃對聚烯烴雙層前驅膜進行一退火製程。之後，對聚烯烴雙層前驅膜進行一延伸造孔製程，先於室溫下進行40%單軸延伸，再於120℃下進行60%單軸延伸。延伸造孔製程後所得的聚烯烴複合孔隙膜18其總厚度為20μm。之後，將三丙二醇二丙烯酸酯(tripropylene glycol diacrylate,TPGDA)、聚酯丙烯酸酯(6311-100®，產自Eternal公司)與1-羥基-環己基苯基丙酮(1-hydroxy-cyclohexylpheneyl ketone)以16：4：1的比例混合於甲苯溶劑中，以配製固含量2.5wt%的三丙二醇二丙烯酸酯(TPGDA)溶液。之後，將三丙二醇二丙烯酸酯(TPGDA)溶液塗佈於聚丙烯孔隙膜14表面。以紫外光照射進行交聯固化後，形成聚三丙二醇二丙烯酸酯(PTPGDA)膜(e.g.,紫外光固化或熱固化高分子孔隙膜16)。至此，即獲得本實施例包含聚乙烯(PE)孔隙膜、聚丙烯(PP)孔隙膜與聚三丙二醇二丙烯酸酯(PTPGDA)孔隙膜的三層隔離膜結構。之後，對隔離膜結構進行例如厚度、Gurley、穿刺強度、熱閉孔溫度、耐熱溫度及收縮率等物化特性的量測，結果載於下表1。Referring to Fig. 1, first, a polyolefin double-layer precursor film (polyethylene (PE) layer/polypropylene (PP) layer) is produced by a total extrusion process. In the co-extrusion process, the extrusion temperature was 230 ° C, and the total thickness of the polyolefin double-layer precursor film obtained after the total extrusion process was 45 μm, and the thickness of the polypropylene layer accounted for 30% of the total thickness described above. Thereafter, the polyolefin double-layer precursor film was subjected to an annealing process at 120 °C. Thereafter, the polyolefin double-layer precursor film was subjected to an extended pore-forming process, 40% uniaxial stretching at room temperature, and 60% uniaxial stretching at 120 °C. The polyolefin composite pore film 18 obtained after the extension of the pore forming process had a total thickness of 20 μm. Thereafter, tripropylene glycol diacrylate (TPGDA), polyester acrylate (6311-100®, manufactured by Eternal Corporation) and 1-hydroxy-cyclohexylpheneyl ketone were used. A ratio of 16:4:1 was mixed in a toluene solvent to prepare a solution of a solid content of 2.5% by weight of a tripropylene glycol diacrylate (TPGDA). Thereafter, a solution of tripropylene glycol diacrylate (TPGDA) was applied to the surface of the polypropylene pore film 14. After crosslinking and curing by ultraviolet light irradiation, a polytripropylene glycol diacrylate (PTPGDA) film (e.g., ultraviolet light curing or heat curing polymer pore film 16) is formed. Thus, the three-layer separator structure comprising the polyethylene (PE) pore film, the polypropylene (PP) pore film and the polytripropylene glycol diacrylate (PTPGDA) pore film of the present embodiment was obtained. Thereafter, the separator structure was measured for physical properties such as thickness, Gurley, puncture strength, heat-closed pore temperature, heat-resistant temperature, and shrinkage ratio, and the results are shown in Table 1 below.

實施例2Example 2

鋰電池隔離膜之製備(2)(聚三丙二醇二丙烯酸酯Preparation of lithium battery separator (2) (polytripropylene glycol diacrylate (PTPGDA)孔隙膜/聚乙烯(PE)孔隙膜/聚丙烯(PP)孔隙膜/聚三丙二醇二丙烯酸酯(PTPGDA)孔隙膜)(PTPGDA) Pore Membrane/Polyethylene (PE) Pore Membrane/Polypropylene (PP) Pore Membrane/Polytripropylene Glycol Diacrylate (PTPGDA) Pore Membrane)

請參閱第2圖，首先，以一共押出製程製作聚烯烴雙層前驅膜(聚乙烯(PE)層/聚丙烯(PP)層)。在共押出製程中，押出溫度為230℃，共押出製程後所得的聚烯烴雙層前驅膜其總厚度為45μm，而聚丙烯層的厚度佔上述總厚度的30%。之後，以120℃對聚烯烴雙層前驅膜進行一退火製程。之後，對聚烯烴雙層前驅膜進行一延伸造孔製程，先於室溫下進行40%單軸延伸，再於120℃下進行60%單軸延伸。延伸造孔製程後所得的聚烯烴複合孔隙膜18其總厚度為20μm。之後，將三丙二醇二丙烯酸酯(tripropylene glycol diacrylate,TPGDA)、聚酯丙烯酸酯(6311-100®，產自Eternal公司)與1-羥基-環己基苯基丙酮(1-hydroxy-cyclohexylpheneyl ketone)以16：4：1的比例混合於甲苯溶劑中，以配製固含量2.5wt%的三丙二醇二丙烯酸酯(TPGDA)溶液。之後，將三丙二醇二丙烯酸酯(TPGDA)溶液分別塗佈於聚乙烯孔隙膜12與聚丙烯孔隙膜14表面。以紫外光照射進行交聯固化後，形成聚三丙二醇二丙烯酸酯(PTPGDA)膜(e.g.,紫外光固化或熱固化高分子孔隙膜16、16’)。至此，即獲得本實施例包含聚三丙二醇二丙烯酸酯(PTPGDA)孔隙膜、聚乙烯(PE)孔隙膜、聚丙烯(PP)孔隙膜與聚三丙二醇二丙烯酸酯(PTPGDA)孔隙膜的四層隔離膜結構。之後，對隔離膜結構進行例如厚度、Gurley、穿刺強度、熱閉孔溫度、耐熱溫度及收縮率等物化特性的量測，結果載於下表1。Referring to Figure 2, first, a polyolefin double-layer precursor film (polyethylene (PE) layer/polypropylene (PP) layer) was produced by a total extrusion process. In the co-extrusion process, the extrusion temperature was 230 ° C, and the total thickness of the polyolefin double-layer precursor film obtained after the total extrusion process was 45 μm, and the thickness of the polypropylene layer accounted for 30% of the total thickness described above. Thereafter, the polyolefin double-layer precursor film was subjected to an annealing process at 120 °C. Thereafter, the polyolefin double-layer precursor film was subjected to an extended pore-forming process, 40% uniaxial stretching at room temperature, and 60% uniaxial stretching at 120 °C. The polyolefin composite pore film 18 obtained after the extension of the pore forming process had a total thickness of 20 μm. Thereafter, tripropylene glycol diacrylate (TPGDA), polyester acrylate (6311-100®, manufactured by Eternal Corporation) and 1-hydroxy-cyclohexylpheneyl ketone were used. A ratio of 16:4:1 was mixed in a toluene solvent to prepare a solution of a solid content of 2.5% by weight of a tripropylene glycol diacrylate (TPGDA). Thereafter, a solution of tripropylene glycol diacrylate (TPGDA) was applied to the surface of the polyethylene pore film 12 and the polypropylene pore film 14, respectively. After crosslinking and curing by ultraviolet light irradiation, a polytripropylene glycol diacrylate (PTPGDA) film (e.g., ultraviolet light curing or heat curing polymer pore film 16, 16') is formed. So far, four layers of the porous film of polytripropylene glycol diacrylate (PTPGDA), polyethylene (PE) pore film, polypropylene (PP) pore film and polytripropylene glycol diacrylate (PTPGDA) pore film are obtained. Isolation membrane structure. Thereafter, the separator structure was measured for physical properties such as thickness, Gurley, puncture strength, heat-closed pore temperature, heat-resistant temperature, and shrinkage ratio, and the results are shown in Table 1 below.

實施例3Example 3

鋰電池隔離膜之製備(3)(聚乙烯(PE)孔隙膜/聚丙烯孔隙(PP)膜/聚偏二氟乙烯孔隙(PVDF)膜/聚三丙二醇二丙烯酸酯(PTPGDA)孔隙膜)Preparation of lithium battery separator (3) (polyethylene (PE) pore film / polypropylene pore (PP) film / polyvinylidene fluoride pore (PVDF) film / polytripropylene glycol diacrylate (PTPGDA) pore film)

請參閱第3圖，首先，以一共押出製程製作聚烯烴雙層前驅膜(聚乙烯(PE)層/聚丙烯(PP)層)。在共押出製程中，押出溫度為230℃，共押出製程後所得的聚烯烴雙層前驅膜其總厚度為45μm，而聚丙烯層的厚度佔上述總厚度的30%。之後，以120℃對聚烯烴雙層前驅膜進行一退火製程。之後，對聚烯烴雙層前驅膜進行一延伸造孔製程，先於室溫下進行40%單軸延伸，再於120℃下進行60%單軸延伸。延伸造孔製程後所得的聚烯烴複合孔隙膜18其總厚度為20μm。將聚偏二氟乙烯(PVDF)溶於NMP溶劑中，以配製固含量14wt%的聚偏二氟乙烯(PVDF)溶液。之後，將聚偏二氟乙烯(PVDF)溶液塗佈於聚丙烯孔隙膜14表面，並以水進行凝固，形成聚偏二氟乙烯(PVDF)孔隙膜(e.g.,聚偏二氟乙烯(PVDF)衍生物孔隙膜20)。之後，將三丙二醇二丙烯酸酯(tripropylene glycol diacrylate,TPGDA)、聚酯丙烯酸酯(6311-100®，產自Eternal公司)與1-羥基-環己基苯基丙酮(1-hydroxy-cyclohexylpheneyl ketone)以16：4：1的比例混合於甲苯溶劑中，以配製固含量2.5wt%的三丙二醇二丙烯酸酯(TPGDA)溶液。之後，將三丙二醇二丙烯酸酯(TPGDA)溶液塗佈於聚偏二氟乙烯(PVDF)孔隙膜表面。以紫外光照射進行交聯固化後，形成聚三丙二醇二丙烯酸酯(PTPGDA)孔隙膜(e.g.,紫外光固化或熱固化高分子孔隙膜16)。至此，即獲得本實施例包含聚乙烯(PE)孔隙膜、聚丙烯(PP)孔隙膜、聚偏二氟乙烯 (PVDF)孔隙膜與聚三丙二醇二丙烯酸酯(PTPGDA)孔隙膜的四層隔離膜結構。之後，對隔離膜結構進行例如厚度、Gurley、穿刺強度、熱閉孔溫度、耐熱溫度及收縮率等物化特性的量測，結果載於下表1。Referring to Figure 3, first, a polyolefin double-layer precursor film (polyethylene (PE) layer/polypropylene (PP) layer) was produced by a total extrusion process. In the co-extrusion process, the extrusion temperature was 230 ° C, and the total thickness of the polyolefin double-layer precursor film obtained after the total extrusion process was 45 μm, and the thickness of the polypropylene layer accounted for 30% of the total thickness described above. Thereafter, the polyolefin double-layer precursor film was subjected to an annealing process at 120 °C. Thereafter, the polyolefin double-layer precursor film was subjected to an extended pore-forming process, 40% uniaxial stretching at room temperature, and 60% uniaxial stretching at 120 °C. The polyolefin composite pore film 18 obtained after the extension of the pore forming process had a total thickness of 20 μm. Polyvinylidene fluoride (PVDF) was dissolved in a NMP solvent to prepare a 14 wt% solution of polyvinylidene fluoride (PVDF). Thereafter, a polyvinylidene fluoride (PVDF) solution is applied to the surface of the polypropylene pore film 14 and solidified with water to form a polyvinylidene fluoride (PVDF) pore film (eg, polyvinylidene fluoride (PVDF)). Derivative pore film 20). Thereafter, tripropylene glycol diacrylate (TPGDA), polyester acrylate (6311-100®, manufactured by Eternal Corporation) and 1-hydroxy-cyclohexylpheneyl ketone were used. A ratio of 16:4:1 was mixed in a toluene solvent to prepare a solution of a solid content of 2.5% by weight of a tripropylene glycol diacrylate (TPGDA). Thereafter, a solution of tripropylene glycol diacrylate (TPGDA) was applied to the surface of the polyvinylidene fluoride (PVDF) pore membrane. After crosslinking and curing by ultraviolet light irradiation, a polytripropylene glycol diacrylate (PTPGDA) pore film (e.g., ultraviolet curing or heat curing polymer pore film 16) is formed. So far, the present embodiment includes a polyethylene (PE) pore film, a polypropylene (PP) pore film, and a polyvinylidene fluoride. (PVDF) Four-layer separator structure of pore film and polytripropylene glycol diacrylate (PTPGDA) pore film. Thereafter, the separator structure was measured for physical properties such as thickness, Gurley, puncture strength, heat-closed pore temperature, heat-resistant temperature, and shrinkage ratio, and the results are shown in Table 1 below.

實施例4Example 4

鋰電池隔離膜之製備(4)(聚丙烯(PP)孔隙膜/聚乙烯(PE)孔隙膜/聚三丙二醇二丙烯酸酯(PTPGDA)孔隙膜)Preparation of lithium battery separator (4) (polypropylene (PP) pore film / polyethylene (PE) pore film / polytripropylene glycol diacrylate (PTPGDA) pore film)

請參閱第4圖，首先，以一共押出製程製作聚烯烴雙層前驅膜(聚丙烯(PP)層/聚乙烯(PE)層)。在共押出製程中，押出溫度為230℃，共押出製程後所得的聚烯烴雙層前驅膜’其總厚度為45μm，而聚丙烯層的厚度佔上述總厚度的30%。之後，以120℃對聚烯烴雙層前驅膜進行一退火製程。之後，對聚烯烴雙層前驅膜進行一延伸造孔製程，先於室溫下進行40%單軸延伸，再於120℃下進行60%單軸延伸。延伸造孔製程後所得的聚烯烴複合孔隙膜18’其總厚度為20μm。之後，將三丙二醇二丙烯酸酯(tripropylene glycol diacrylate,TPGDA)、聚酯丙烯酸酯(6311-100®，產自Eternal公司)與1-羥基-環己基苯基丙酮(1-hydroxy-cyclohexylpheneyl ketone)以16：4：1的比例混合於甲苯溶劑中，以配製固含量2.5wt%的三丙二醇二丙烯酸酯(TPGDA)溶液。之後，將三丙二醇二丙烯酸酯(TPGDA)溶液塗佈於聚乙烯孔隙膜12表面。以紫外光照射進行交聯固化後，形成聚三丙二醇二丙烯酸酯(PTPGDA)孔隙膜(e.g.,紫外光固化或熱固化高分子孔隙膜16)。至此，即獲得本實施例包含聚丙烯(PP)孔隙膜、聚乙烯(PE)孔隙膜與聚三丙二醇二丙烯酸酯 (PTPGDA)孔隙膜的三層隔離膜結構。之後，對隔離膜結構進行例如厚度、Gurley、穿刺強度、熱閉孔溫度、耐熱溫度及收縮率等物化特性的量測，結果載於下表1。Referring to Figure 4, first, a polyolefin double-layer precursor film (polypropylene (PP) layer/polyethylene (PE) layer) is produced by a total extrusion process. In the co-extrusion process, the extrusion temperature was 230 ° C, and the polyolefin double-layer precursor film obtained after the total extrusion process had a total thickness of 45 μm, and the thickness of the polypropylene layer accounted for 30% of the total thickness described above. Thereafter, the polyolefin double-layer precursor film was subjected to an annealing process at 120 °C. Thereafter, the polyolefin double-layer precursor film was subjected to an extended pore-forming process, 40% uniaxial stretching at room temperature, and 60% uniaxial stretching at 120 °C. The polyolefin composite pore film 18' obtained after the extension of the pore-forming process had a total thickness of 20 μm. Thereafter, tripropylene glycol diacrylate (TPGDA), polyester acrylate (6311-100®, manufactured by Eternal Corporation) and 1-hydroxy-cyclohexylpheneyl ketone were used. A ratio of 16:4:1 was mixed in a toluene solvent to prepare a solution of a solid content of 2.5% by weight of a tripropylene glycol diacrylate (TPGDA). Thereafter, a solution of tripropylene glycol diacrylate (TPGDA) was applied to the surface of the polyethylene pore film 12. After crosslinking and curing by ultraviolet light irradiation, a polytripropylene glycol diacrylate (PTPGDA) pore film (e.g., ultraviolet curing or heat curing polymer pore film 16) is formed. So far, the present embodiment comprises a polypropylene (PP) pore film, a polyethylene (PE) pore film and a polytripropylene glycol diacrylate. (PTPGDA) Three-layer separator structure of the pore film. Thereafter, the separator structure was measured for physical properties such as thickness, Gurley, puncture strength, heat-closed pore temperature, heat-resistant temperature, and shrinkage ratio, and the results are shown in Table 1 below.

實施例5Example 5

鋰電池隔離膜之製備(5)(聚丙烯(PP)孔隙膜/聚乙烯(PE)孔隙膜/聚偏二氟乙烯(PVDF)孔隙膜/聚三丙二醇二丙烯酸酯(PTPGDA)孔隙膜)Preparation of lithium battery separator (5) (polypropylene (PP) pore film / polyethylene (PE) pore film / polyvinylidene fluoride (PVDF) pore film / polytripropylene glycol diacrylate (PTPGDA) pore film)

請參閱第5圖，首先，以一共押出製程製作聚烯烴雙層前驅膜(聚丙烯(PP)層/聚乙烯(PE)層)。在共押出製程中，押出溫度為230℃，共押出製程後所得的聚烯烴雙層前驅膜其總厚度為45μm，而聚丙烯層的厚度佔上述總厚度的30%。之後，以120℃對聚烯烴雙層前驅膜進行一退火製程。之後，對聚烯烴雙層前驅膜進行一延伸造孔製程，先於室溫下進行40%單軸延伸，再於120℃下進行60%單軸延伸。延伸造孔製程後所得的聚烯烴複合孔隙膜18’其總厚度為20μm。將聚偏二氟乙烯(PVDF)溶於NMP溶劑中，以配製固含量14wt%的聚偏二氟乙烯(PVDF)溶液。之後，將聚偏二氟乙烯(PVDF)溶液塗佈於聚乙烯孔隙膜12表面，並以水進行凝固，形成聚偏二氟乙烯(PVDF)孔隙膜(e.g.,聚偏二氟乙烯(PVDF)衍生物孔隙膜20)。之後，將三丙二醇二丙烯酸酯(tripropylene glycol diacrylate,TPGDA)、聚酯丙烯酸酯(6311-100®，產自Eternal公司)與1-羥基-環己基苯基丙酮(1-hydroxy-cyclohexylpheneyl ketone)以16：4：1的比例混合於甲苯溶劑中，以配製固含量2.5wt%的三丙二醇二丙烯酸酯(TPGDA)溶液。之後，將三丙二醇二丙烯酸酯 (TPGDA)溶液塗佈於聚偏二氟乙烯(PVDF)孔隙膜表面。以紫外光照射進行交聯固化後，形成聚三丙二醇二丙烯酸酯(PTPGDA)孔隙膜(e.g.,紫外光固化或熱固化高分子孔隙膜16)。至此，即獲得本實施例包含聚丙烯(PP)孔隙膜、聚乙烯(PE)孔隙膜、聚偏二氟乙烯(PVDF)孔隙膜與聚三丙二醇二丙烯酸酯(PTPGDA)孔隙膜的四層隔離膜結構。之後，對隔離膜結構進行例如厚度、Gurley、穿刺強度、熱閉孔溫度、耐熱溫度及收縮率等物化特性的量測，結果載於下表1。Referring to Figure 5, first, a polyolefin double-layer precursor film (polypropylene (PP) layer/polyethylene (PE) layer) is produced by a total extrusion process. In the co-extrusion process, the extrusion temperature was 230 ° C, and the total thickness of the polyolefin double-layer precursor film obtained after the total extrusion process was 45 μm, and the thickness of the polypropylene layer accounted for 30% of the total thickness described above. Thereafter, the polyolefin double-layer precursor film was subjected to an annealing process at 120 °C. Thereafter, the polyolefin double-layer precursor film was subjected to an extended pore-forming process, 40% uniaxial stretching at room temperature, and 60% uniaxial stretching at 120 °C. The polyolefin composite pore film 18' obtained after the extension of the pore-forming process had a total thickness of 20 μm. Polyvinylidene fluoride (PVDF) was dissolved in a NMP solvent to prepare a 14 wt% solution of polyvinylidene fluoride (PVDF). Thereafter, a polyvinylidene fluoride (PVDF) solution is applied to the surface of the polyethylene pore film 12 and solidified with water to form a polyvinylidene fluoride (PVDF) pore film (eg, polyvinylidene fluoride (PVDF)). Derivative pore film 20). Thereafter, tripropylene glycol diacrylate (TPGDA), polyester acrylate (6311-100®, manufactured by Eternal Corporation) and 1-hydroxy-cyclohexylpheneyl ketone were used. A ratio of 16:4:1 was mixed in a toluene solvent to prepare a solution of a solid content of 2.5% by weight of a tripropylene glycol diacrylate (TPGDA). After that, tripropylene glycol diacrylate The (TPGDA) solution was applied to the surface of a polyvinylidene fluoride (PVDF) pore membrane. After crosslinking and curing by ultraviolet light irradiation, a polytripropylene glycol diacrylate (PTPGDA) pore film (e.g., ultraviolet curing or heat curing polymer pore film 16) is formed. So far, the four layers of the porous film including the polypropylene (PP) pore film, the polyethylene (PE) pore film, the polyvinylidene fluoride (PVDF) pore film and the polytripropylene glycol diacrylate (PTPGDA) pore film are obtained. Membrane structure. Thereafter, the separator structure was measured for physical properties such as thickness, Gurley, puncture strength, heat-closed pore temperature, heat-resistant temperature, and shrinkage ratio, and the results are shown in Table 1 below.

實施例6Example 6

鋰電池隔離膜之製備(6)(聚丙烯(PP)孔隙膜/聚乙烯(PE)孔隙膜/聚丙烯(PP)孔隙膜/聚三丙二醇二丙烯酸酯(PTPGDA)孔隙膜)Preparation of lithium battery separator (6) (polypropylene (PP) pore film / polyethylene (PE) pore film / polypropylene (PP) pore film / polytripropylene glycol diacrylate (PTPGDA) pore film)

請參閱第6圖，首先，以一共押出製程製作聚烯烴三層前驅膜(聚丙烯(PP)層/聚乙烯(PE)層/聚丙烯(PP)層)。在共押出製程中，押出溫度為230℃，共押出製程後所得的聚烯烴三層前驅膜其總厚度為45μm，而上下兩個聚丙烯層的厚度佔上述總厚度的60%。之後，以120℃對聚聚烯烴三層前驅膜進行一退火製程。之後，對聚烯烴三層前驅膜進行一延伸造孔製程，先於室溫下進行40%單軸延伸，再於120℃下進行60%單軸延伸。延伸造孔製程後所得的聚烯烴複合孔隙膜19其總厚度為20μm。之後，將三丙二醇二丙烯酸酯(tripropylene glycol diacrylate,TPGDA)、聚酯丙烯酸酯(6311-100®，產自Eternal公司)與1-羥基-環己基苯基丙酮(1-hydroxy-cyclohexylpheneyl ketone)以16：4：1的比例混合於甲苯溶劑中，以配製固含量2.5wt%的三丙 二醇二丙烯酸酯(TPGDA)溶液。之後，將三丙二醇二丙烯酸酯(TPGDA)溶液塗佈於聚丙烯孔隙膜14’表面。以紫外光照射進行交聯固化後，形成聚三丙二醇二丙烯酸酯(PTPGDA)孔隙膜(e.g.,紫外光固化或熱固化高分子孔隙膜16)。至此，即獲得本實施例包含聚丙烯(PP)孔隙膜、聚乙烯(PE)孔隙膜、聚丙烯(PP)孔隙膜與聚三丙二醇二丙烯酸酯(PTPGDA)孔隙膜的四層隔離膜結構。之後，對隔離膜結構進行例如厚度、Gurley、穿刺強度、熱閉孔溫度、耐熱溫度及收縮率等物化特性的量測，結果載於下表1。Referring to Fig. 6, first, a polyolefin three-layer precursor film (polypropylene (PP) layer/polyethylene (PE) layer/polypropylene (PP) layer) was produced by a total extrusion process. In the co-extrusion process, the extrusion temperature was 230 ° C, and the total thickness of the polyolefin three-layer precursor film obtained after the total extrusion process was 45 μm, and the thickness of the upper and lower polypropylene layers accounted for 60% of the total thickness. Thereafter, the polyolefin three-layer precursor film was subjected to an annealing process at 120 °C. Thereafter, the polyolefin three-layer precursor film was subjected to an extended pore-forming process, 40% uniaxial stretching at room temperature, and 60% uniaxial stretching at 120 °C. The polyolefin composite pore film 19 obtained after the extension of the pore forming process had a total thickness of 20 μm. Thereafter, tripropylene glycol diacrylate (TPGDA), polyester acrylate (6311-100®, manufactured by Eternal Corporation) and 1-hydroxy-cyclohexylpheneyl ketone were used. a ratio of 16:4:1 is mixed with toluene solvent to prepare a solid content of 2.5% by weight of tripropylene Diol diacrylate (TPGDA) solution. Thereafter, a solution of tripropylene glycol diacrylate (TPGDA) was applied to the surface of the polypropylene pore film 14'. After crosslinking and curing by ultraviolet light irradiation, a polytripropylene glycol diacrylate (PTPGDA) pore film (e.g., ultraviolet curing or heat curing polymer pore film 16) is formed. Thus, the four-layer separator structure comprising the polypropylene (PP) pore film, the polyethylene (PE) pore film, the polypropylene (PP) pore film and the polytripropylene glycol diacrylate (PTPGDA) pore film of the present embodiment was obtained. Thereafter, the separator structure was measured for physical properties such as thickness, Gurley, puncture strength, heat-closed pore temperature, heat-resistant temperature, and shrinkage ratio, and the results are shown in Table 1 below.

實施例7Example 7

鋰電池隔離膜之製備(7)(聚三丙二醇二丙烯酸酯(PTPGDA)孔隙膜/聚丙烯(PP)孔隙膜/聚乙烯(PE)孔隙膜/聚丙烯(PP)孔隙膜/聚三丙二醇二丙烯酸酯(PTPGDA)孔隙膜)Preparation of lithium battery separator (7) (polytripropylene glycol diacrylate (PTPGDA) pore film / polypropylene (PP) pore film / polyethylene (PE) pore film / polypropylene (PP) pore film / polytripropylene glycol II Acrylate (PTPGDA) pore film)

請參閱第7圖，首先，以一共押出製程製作聚烯烴三層前驅膜(聚丙烯(PP)層/聚乙烯(PE)層/聚丙烯(PP)層)。在共押出製程中，押出溫度為230℃，共押出製程後所得的聚烯烴三層前驅膜其總厚度為45μm，而上下兩個聚丙烯層的厚度佔上述總厚度的60%。之後，以120℃對聚烯烴三層前驅膜進行一退火製程。之後，對聚烯烴三層前驅膜進行一延伸造孔製程，先於室溫下進行40%單軸延伸，再於120℃下進行60%單軸延伸。延伸造孔製程後所得的聚烯烴複合孔隙膜19其總厚度為20μm。之後，將三丙二醇二丙烯酸酯(tripropylene glycol diacrylate,TPGDA)、聚酯丙烯酸酯(6311-100®，產自Eternal公司)與1-羥基-環己基苯基丙酮(1-hydroxy-cyclohexylpheneyl ketone)以 16：4：1的比例混合於甲苯溶劑中，以配製固含量2.5wt%的三丙二醇二丙烯酸酯(TPGDA)溶液。之後，將三丙二醇二丙烯酸酯(TPGDA)溶液分別塗佈於聚丙烯孔隙膜14、14’表面。以紫外光照射進行交聯固化後，形成聚三丙二醇二丙烯酸酯(PTPGDA)孔隙膜(e.g.,紫外光固化或熱固化高分子孔隙膜16、16’)。至此，即獲得本實施例包含聚三丙二醇二丙烯酸酯(PTPGDA)孔隙膜、聚丙烯(PP)孔隙膜、聚乙烯(PE)孔隙膜、聚丙烯(PP)孔隙膜與聚三丙二醇二丙烯酸酯(PTPGDA)孔隙膜的五層隔離膜結構。之後，對隔離膜結構進行例如厚度、Gurley、穿刺強度、熱閉孔溫度、耐熱溫度及收縮率等物化特性的量測，結果載於下表1。Referring to Figure 7, first, a polyolefin three-layer precursor film (polypropylene (PP) layer/polyethylene (PE) layer/polypropylene (PP) layer) is produced by a total extrusion process. In the co-extrusion process, the extrusion temperature was 230 ° C, and the total thickness of the polyolefin three-layer precursor film obtained after the total extrusion process was 45 μm, and the thickness of the upper and lower polypropylene layers accounted for 60% of the total thickness. Thereafter, the polyolefin three-layer precursor film was subjected to an annealing process at 120 °C. Thereafter, the polyolefin three-layer precursor film was subjected to an extended pore-forming process, 40% uniaxial stretching at room temperature, and 60% uniaxial stretching at 120 °C. The polyolefin composite pore film 19 obtained after the extension of the pore forming process had a total thickness of 20 μm. Thereafter, tripropylene glycol diacrylate (TPGDA), polyester acrylate (6311-100®, manufactured by Eternal Corporation) and 1-hydroxy-cyclohexylpheneyl ketone were used. A ratio of 16:4:1 was mixed in a toluene solvent to prepare a solution of a solid content of 2.5% by weight of a tripropylene glycol diacrylate (TPGDA). Thereafter, a solution of tripropylene glycol diacrylate (TPGDA) was applied to the surfaces of the polypropylene pore films 14, 14', respectively. After crosslinking and curing by ultraviolet light irradiation, a polytripropylene glycol diacrylate (PTPGDA) pore film (e.g., ultraviolet curable or thermally curable polymer pore film 16, 16') is formed. So far, the present embodiment comprises a polytripropylene glycol diacrylate (PTPGDA) pore film, a polypropylene (PP) pore film, a polyethylene (PE) pore film, a polypropylene (PP) pore film and a polytripropylene glycol diacrylate. (PTPGDA) Five-layer isolation membrane structure of the pore film. Thereafter, the separator structure was measured for physical properties such as thickness, Gurley, puncture strength, heat-closed pore temperature, heat-resistant temperature, and shrinkage ratio, and the results are shown in Table 1 below.

實施例8Example 8

鋰電池隔離膜之製備(8)(聚丙烯(PP)孔隙膜/聚乙烯(PE)孔隙膜/聚丙烯(PP)孔隙膜/聚偏二氟乙烯(PVDF)孔隙膜/聚三丙二醇二丙烯酸酯(PTPGDA)孔隙膜)Preparation of lithium battery separator (8) (polypropylene (PP) pore film / polyethylene (PE) pore film / polypropylene (PP) pore film / polyvinylidene fluoride (PVDF) pore film / polytripropylene glycol diacrylic acid Ester (PTPGDA) pore film)

請參閱第8圖，首先，以一共押出製程製作聚烯烴三層前驅膜(聚丙烯(PP)層/聚乙烯(PE)層/聚丙烯(PP)層)。在共押出製程中，押出溫度為230℃，共押出製程後所得的聚烯烴三層前驅膜其總厚度為45μm，而上下兩個聚丙烯層的厚度佔上述總厚度的60%。之後，以120℃對聚烯烴三層前驅膜進行一退火製程。之後，對聚烯烴三層前驅膜進行一延伸造孔製程，先於室溫下進行40%單軸延伸，再於120℃下進行60%單軸延伸。延伸造孔製程後所得的聚烯烴複合孔隙膜19其總厚度為20μm。將聚偏二氟乙烯(PVDF)溶於NMP溶劑中，以配製固含量14wt% 的聚偏二氟乙烯(PVDF)溶液。之後，將聚偏二氟乙烯(PVDF)溶液塗佈於聚丙烯孔隙膜14’表面，並以水進行凝固，形成聚偏二氟乙烯(PVDF)孔隙膜(e.g.,聚偏二氟乙烯(PVDF)衍生物孔隙膜20)。之後，將三丙二醇二丙烯酸酯(tripropylene glycol diacrylate,TPGDA)、聚酯丙烯酸酯(6311-100®，產自Eternal公司)與1-羥基-環己基苯基丙酮(1-hydroxy-cyclohexylpheneyl ketone)以16：4：1的比例混合於甲苯溶劑中，以配製固含量2.5wt%的三丙二醇二丙烯酸酯(TPGDA)溶液。之後，將三丙二醇二丙烯酸酯(TPGDA)溶液塗佈於聚偏二氟乙烯(PVDF)孔隙膜表面。以紫外光照射進行交聯固化後，形成聚三丙二醇二丙烯酸酯(PTPGDA)孔隙膜(e.g.,紫外光固化或熱固化高分子孔隙膜16)。至此，即獲得本實施例包含聚丙烯(PP)孔隙膜、聚乙烯(PE)孔隙膜、聚丙烯(PP)孔隙膜、聚偏二氟乙烯(PVDF)孔隙膜與聚三丙二醇二丙烯酸酯(PTPGDA)孔隙膜的五層隔離膜結構。之後，對隔離膜結構進行例如厚度、Gurley、穿刺強度、熱閉孔溫度、耐熱溫度及收縮率等物化特性的量測，結果載於下表1。Referring to Fig. 8, first, a polyolefin three-layer precursor film (polypropylene (PP) layer/polyethylene (PE) layer/polypropylene (PP) layer) was produced by a total extrusion process. In the co-extrusion process, the extrusion temperature was 230 ° C, and the total thickness of the polyolefin three-layer precursor film obtained after the total extrusion process was 45 μm, and the thickness of the upper and lower polypropylene layers accounted for 60% of the total thickness. Thereafter, the polyolefin three-layer precursor film was subjected to an annealing process at 120 °C. Thereafter, the polyolefin three-layer precursor film was subjected to an extended pore-forming process, 40% uniaxial stretching at room temperature, and 60% uniaxial stretching at 120 °C. The polyolefin composite pore film 19 obtained after the extension of the pore forming process had a total thickness of 20 μm. Dissolving polyvinylidene fluoride (PVDF) in NMP solvent to prepare a solid content of 14wt% Polyvinylidene fluoride (PVDF) solution. Thereafter, a polyvinylidene fluoride (PVDF) solution is applied to the surface of the polypropylene pore film 14' and solidified with water to form a polyvinylidene fluoride (PVDF) pore film (eg, polyvinylidene fluoride (PVDF). ) Derivative pore film 20). Thereafter, tripropylene glycol diacrylate (TPGDA), polyester acrylate (6311-100®, manufactured by Eternal Corporation) and 1-hydroxy-cyclohexylpheneyl ketone were used. A ratio of 16:4:1 was mixed in a toluene solvent to prepare a solution of a solid content of 2.5% by weight of a tripropylene glycol diacrylate (TPGDA). Thereafter, a solution of tripropylene glycol diacrylate (TPGDA) was applied to the surface of the polyvinylidene fluoride (PVDF) pore membrane. After crosslinking and curing by ultraviolet light irradiation, a polytripropylene glycol diacrylate (PTPGDA) pore film (e.g., ultraviolet curing or heat curing polymer pore film 16) is formed. So far, the present embodiment comprises a polypropylene (PP) pore film, a polyethylene (PE) pore film, a polypropylene (PP) pore film, a polyvinylidene fluoride (PVDF) pore film and a polytripropylene glycol diacrylate ( PTPGDA) Five-layer separator structure of the pore film. Thereafter, the separator structure was measured for physical properties such as thickness, Gurley, puncture strength, heat-closed pore temperature, heat-resistant temperature, and shrinkage ratio, and the results are shown in Table 1 below.

比較實施例1Comparative Example 1

傳統鋰電池隔離膜之製備(1)(聚丙烯(PP)孔隙膜/聚乙烯(PE)孔隙膜/聚丙烯(PP)孔隙膜)Preparation of traditional lithium battery separator (1) (polypropylene (PP) pore film / polyethylene (PE) pore film / polypropylene (PP) pore film)

請參閱第12圖，首先，以一共押出製程製作聚烯烴三層前驅膜(聚丙烯(PP)層/聚乙烯(PE)層/聚丙烯(PP)層)。在共押出製程中，押出溫度為230℃，共押出製程後所得的聚烯烴三層前驅膜其總厚度為45μm，而上下兩個聚丙烯層的厚度佔 上述總厚度的60%。之後，以120℃對聚烯烴三層前驅膜進行一退火製程。之後，對聚烯烴三層前驅膜進行一延伸造孔製程，先於室溫下進行40%單軸延伸，再於120℃下進行60%單軸延伸。延伸造孔製程後所得的聚烯烴複合孔隙膜190其總厚度為20μm。至此，即獲得本比較實施例包含聚丙烯(PP)孔隙膜140、聚乙烯(PE)孔隙膜120與聚丙烯(PP)孔隙膜140’的三層隔離膜結構。之後，對隔離膜結構進行例如厚度、Gurley、穿刺強度、熱閉孔溫度、耐熱溫度及收縮率等物化特性的量測，結果載於下表1。Referring to Fig. 12, first, a polyolefin three-layer precursor film (polypropylene (PP) layer/polyethylene (PE) layer/polypropylene (PP) layer) was produced by a total extrusion process. In the co-extrusion process, the extrusion temperature is 230 ° C, and the total thickness of the polyolefin three-layer precursor film obtained after the total extrusion process is 45 μm, while the thickness of the upper and lower polypropylene layers accounts for 45 μm. 60% of the above total thickness. Thereafter, the polyolefin three-layer precursor film was subjected to an annealing process at 120 °C. Thereafter, the polyolefin three-layer precursor film was subjected to an extended pore-forming process, 40% uniaxial stretching at room temperature, and 60% uniaxial stretching at 120 °C. The polyolefin composite pore film 190 obtained after the extension of the pore forming process had a total thickness of 20 μm. Thus, the three-layer isolating film structure of the comparative embodiment comprising the polypropylene (PP) pore film 140, the polyethylene (PE) pore film 120 and the polypropylene (PP) pore film 140' was obtained. Thereafter, the separator structure was measured for physical properties such as thickness, Gurley, puncture strength, heat-closed pore temperature, heat-resistant temperature, and shrinkage ratio, and the results are shown in Table 1 below.

比較實施例2Comparative Example 2

傳統鋰電池隔離膜之製備(2)(聚乙烯(PE)孔隙膜/聚偏二氟乙烯(PVDF)孔隙膜)Preparation of traditional lithium battery separator (2) (polyethylene (PE) pore film / polyvinylidene fluoride (PVDF) pore film)

請參閱第13圖，首先，以一押出製程製作聚乙烯(PE)單層前驅膜。在押出製程中，押出溫度為230℃，押出製程後所得的聚乙烯單層前驅膜其厚度為45μm。之後，以120℃對聚乙烯單層前驅膜進行一退火製程。之後，對聚乙烯單層前驅膜進行一延伸造孔製程，先於室溫下進行40%單軸延伸，再於120℃下進行60%單軸延伸。延伸造孔製程後所得的聚乙烯(PE)孔隙膜120其厚度為20μm。將聚偏二氟乙烯(PVDF)溶於NMP溶劑中，以配製固含量14wt%的聚偏二氟乙烯(PVDF)溶液。之後，將聚偏二氟乙烯(PVDF)溶液塗佈於聚乙烯孔隙膜120表面，並以水進行凝固，形成聚偏二氟乙烯(PVDF)孔隙膜200。至此，即獲得本比較實施例包含聚乙烯(PE)孔隙膜與聚偏二氟乙烯(PVDF)孔隙膜的二層隔離膜結構。之後，對隔離膜結構進 行例如厚度、Gurley、穿刺強度、熱閉孔溫度、耐熱溫度及收縮率等物化特性的量測，結果載於下表1。Referring to Figure 13, first, a polyethylene (PE) single-layer precursor film is produced by an extrusion process. In the extrusion process, the extrusion temperature was 230 ° C, and the polyethylene single-layer precursor film obtained after the extrusion process had a thickness of 45 μm. Thereafter, the polyethylene monolayer precursor film was subjected to an annealing process at 120 °C. Thereafter, an extended pore-forming process was performed on the polyethylene single-layer precursor film, 40% uniaxial stretching was performed at room temperature, and 60% uniaxial stretching was performed at 120 °C. The polyethylene (PE) pore film 120 obtained after the extension of the pore forming process has a thickness of 20 μm. Polyvinylidene fluoride (PVDF) was dissolved in a NMP solvent to prepare a 14 wt% solution of polyvinylidene fluoride (PVDF). Thereafter, a polyvinylidene fluoride (PVDF) solution is applied onto the surface of the polyethylene pore film 120 and solidified with water to form a polyvinylidene fluoride (PVDF) pore film 200. Thus far, a two-layer separator structure comprising a polyethylene (PE) pore film and a polyvinylidene fluoride (PVDF) pore film of the comparative example was obtained. After that, the structure of the isolation membrane Measurements of physical and chemical properties such as thickness, Gurley, puncture strength, heat-closed pore temperature, heat-resistant temperature, and shrinkage were measured, and the results are shown in Table 1 below.

雖然本發明已以數個較佳實施例揭露如上，然其並非用以限定本發明，任何所屬技術領域中具有通常知識者，在不脫離本發明之精神和範圍內，當可作任意之更動與潤飾，因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。While the invention has been described above in terms of several preferred embodiments, it is not intended to limit the scope of the present invention, and any one of ordinary skill in the art can make any changes without departing from the spirit and scope of the invention. And the scope of the present invention is defined by the scope of the appended claims.

10‧‧‧鋰電池隔離膜10‧‧‧Lithium battery separator

12‧‧‧聚乙烯(PE)孔隙膜12‧‧‧ Polyethylene (PE) pore film

14、14’‧‧‧聚丙烯(PP)孔隙膜14, 14' ‧ ‧ polypropylene (PP) pore film

16‧‧‧紫外光固化或熱固化高分子孔隙膜16‧‧‧UV-cured or thermally cured polymer pore film

19‧‧‧聚烯烴複合孔隙膜19‧‧‧Polyolefin composite pore film

20‧‧‧聚偏二氟乙烯(PVDF)衍生物孔隙膜20‧‧‧Polyvinylidene fluoride (PVDF) derivative pore film

Claims (9)

一種鋰電池隔離膜，包括：一聚烯烴複合孔隙膜，包括至少一聚乙烯孔隙膜與至少一聚丙烯孔隙膜，其中該聚乙烯孔隙膜為一高密度聚乙烯孔隙膜；以及一紫外光固化或熱固化高分子孔隙膜，形成於該聚烯烴複合孔隙膜之至少一側。 A lithium battery separator comprising: a polyolefin composite pore film comprising at least one polyethylene pore film and at least one polypropylene pore film, wherein the polyethylene pore film is a high density polyethylene pore film; and an ultraviolet curing Or a thermally curable polymer pore film formed on at least one side of the polyolefin composite pore film. 如申請專利範圍第1項所述之鋰電池隔離膜，其中該高密度聚乙烯孔隙膜之樹脂密度介於0.95g/cc~0.975g/cc。 The lithium battery separator according to claim 1, wherein the high density polyethylene pore film has a resin density of from 0.95 g/cc to 0.975 g/cc. 如申請專利範圍第1項所述之鋰電池隔離膜，其中該聚丙烯孔隙膜之樹脂等規性(m-pentad)介於90%~99%。 The lithium battery separator according to claim 1, wherein the polypropylene pore film has a resin m-pentad of 90% to 99%. 如申請專利範圍第1項所述之鋰電池隔離膜，其中該紫外光固化或熱固化高分子孔隙膜包括聚三丙二醇二丙烯酸酯(poly(tripropylene glycol diacrylate),PTPGDA)、聚1,6-己二醇二丙烯酸酯(poly(1,6-hexanediol diacrylate),PHDDA)、聚三甲醇基丙基三丙烯酸酯(poly(trimethylolpropane triacrylate),PTMPTA)或聚二新戊四醇六丙烯酸酯(poly(dipentaerythritol hexylacrylate),PDPHA)。 The lithium battery separator according to claim 1, wherein the ultraviolet light curing or heat curing polymer pore film comprises poly(tripropylene glycol diacrylate, PTPGDA), poly 1,6- Poly(1,6-hexanediol diacrylate, PHDDA), poly(trimethylolpropane triacrylate, PTMPTA) or polydipentaerythritol hexaacrylate (poly (dipentaerythritol hexylacrylate), PDPHA). 如申請專利範圍第1項所述之鋰電池隔離膜，更包括一聚偏二氟乙烯(PVDF)衍生物孔隙膜，形成於該聚烯烴複合孔隙膜與該紫外光固化或熱固化高分子孔隙膜之間。 The lithium battery separator as described in claim 1, further comprising a polyvinylidene fluoride (PVDF) derivative pore film formed on the polyolefin composite pore film and the ultraviolet light curing or heat curing polymer pore Between the membranes. 如申請專利範圍第5項所述之鋰電池隔離膜，其中 該聚偏二氟乙烯(PVDF)衍生物孔隙膜包括聚偏二氟乙烯(PVDF)、聚偏二氟乙烯-六氟丙烯(PVDF-HFP)共聚物、聚偏二氟乙烯-三氟氯乙烯(PVDF-CTFE)共聚物或其組合。 A lithium battery separator as described in claim 5, wherein The polyvinylidene fluoride (PVDF) derivative pore film comprises polyvinylidene fluoride (PVDF), polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) copolymer, polyvinylidene fluoride-chlorotrifluoroethylene (PVDF-CTFE) copolymer or a combination thereof. 如申請專利範圍第5項所述之鋰電池隔離膜，其中該聚偏二氟乙烯(PVDF)衍生物孔隙膜之熔點介於160℃~180℃。 The lithium battery separator according to claim 5, wherein the polyvinylidene fluoride (PVDF) derivative pore film has a melting point of from 160 ° C to 180 ° C. 如申請專利範圍第1項所述之鋰電池隔離膜，其中該鋰電池隔離膜之Gurley小於80(s/10cc)，熱閉孔溫度小於135℃，以及耐熱溫度大於165℃。 The lithium battery separator according to claim 1, wherein the lithium battery separator has a Gurley of less than 80 (s/10 cc), a heat closed cell temperature of less than 135 ° C, and a heat resistant temperature of more than 165 ° C. 如申請專利範圍第1項所述之鋰電池隔離膜，其中該聚乙烯孔隙膜與該聚丙烯孔隙膜係由共押出製程製作。The lithium battery separator according to claim 1, wherein the polyethylene pore film and the polypropylene pore film are produced by a co-extrusion process.
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TW200710135A (en) * 2005-08-03 2007-03-16 Asahi Kasei Chemicals Corp Polyolefin microporous film
TW200933960A (en) * 2008-01-16 2009-08-01 Ind Tech Res Inst Separators utilized in lithium battery and method of fabricating the same

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