WO2013081228A1 - 셀룰로오스 나노섬유를 포함하는 이차전지용 다공성 분리막 및 그 제조방법 - Google Patents
셀룰로오스 나노섬유를 포함하는 이차전지용 다공성 분리막 및 그 제조방법 Download PDFInfo
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- WO2013081228A1 WO2013081228A1 PCT/KR2011/009468 KR2011009468W WO2013081228A1 WO 2013081228 A1 WO2013081228 A1 WO 2013081228A1 KR 2011009468 W KR2011009468 W KR 2011009468W WO 2013081228 A1 WO2013081228 A1 WO 2013081228A1
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- Prior art keywords
- separator
- secondary battery
- organic solvent
- cellulose nanofibers
- manufacturing
- Prior art date
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- 239000002121 nanofiber Substances 0.000 title claims abstract description 46
- 239000001913 cellulose Substances 0.000 title claims abstract description 45
- 229920002678 cellulose Polymers 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- 239000011148 porous material Substances 0.000 claims abstract description 15
- 239000003960 organic solvent Substances 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000012528 membrane Substances 0.000 claims description 14
- 230000035699 permeability Effects 0.000 claims description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 7
- 150000002500 ions Chemical class 0.000 claims description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- 239000008151 electrolyte solution Substances 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 229910003002 lithium salt Inorganic materials 0.000 claims description 3
- 159000000002 lithium salts Chemical class 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000003660 carbonate based solvent Substances 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 230000007423 decrease Effects 0.000 abstract description 4
- 239000004743 Polypropylene Substances 0.000 description 15
- 230000008859 change Effects 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 239000004698 Polyethylene Substances 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 6
- -1 polypropylene Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000004745 nonwoven fabric Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229920001222 biopolymer Polymers 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 210000003462 vein Anatomy 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/429—Natural polymers
- H01M50/4295—Natural cotton, cellulose or wood
-
- 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
- H01M50/44—Fibrous material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2001/00—Use of cellulose, modified cellulose or cellulose derivatives, e.g. viscose, as moulding material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2007/00—Flat articles, e.g. films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
-
- 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
Definitions
- the present invention relates to a separator for a secondary battery containing cellulose nanofibers and a method of manufacturing the same.
- Secondary batteries are expanding to the electronics industry, such as computers, smart phones, digital cameras, the automotive industry, such as smart cars and hybrid cars, and the energy storage industry. Applications also demand high performance, such as high energy density, high power density and battery stability.
- the separator functions as an separator that prevents shorting by blocking electron conduction while allowing the movement of ions between the positive electrode and the negative electrode in the secondary battery. Since the secondary battery separator has a physical insulation function, it plays an important role in the stability of the battery.
- separators are made from polyolefin-based polymers such as polypropylene or polyethylene.
- polyolefin-based polymers such as polypropylene or polyethylene.
- the membrane using the polyolefin-based polymer has a problem of poor thermal stability, poor porosity and wettability to the electrolyte.
- the present invention is to provide a separator comprising cellulose nanofibers, a method of manufacturing the same, and a secondary battery including the separator.
- One embodiment of the present invention includes a cellulose nanofiber, and a secondary battery separator having a ventilation value of 10 to 1000 sec / 100 cc ⁇ air and a secondary battery including the separator.
- another embodiment of the present invention is a cellulose nanofiber; And manufacturing a sheet using a solution containing an organic solvent or a mixed solution of water and an organic solvent. And removing the organic solvent contained in the sheet to form fine pores.
- the separator for a secondary battery including the cellulose nanofibers according to the present invention and a method for manufacturing the same can produce a separator having excellent thermal stability, dimensional stability, wettability, and electrochemical stability, and a simplified manufacturing process. Can be lowered.
- 1A is an electron scanning microscope (SEM) photograph of a separator for a secondary battery according to one embodiment of the present invention.
- FIG. 1B is an SEM image of a Celgard 2320 PP / PE / PP separator.
- FIG. 2 is an electron scanning microscope (SEM) photograph of a secondary battery separator according to an embodiment of the present invention.
- FIG. 3 is a photograph showing the results of experiments with thermal stability of the separator for a secondary battery according to another embodiment of the present invention.
- Figure 4 is a graph showing the results of the electrochemical oxidation stability test of the separator for a secondary battery according to another embodiment of the present invention.
- FIG. 5 is a photograph comparing polar electrolyte wetting test results of a secondary battery separator and a celgard (celgard 2320 PP / PE / PP) separator according to one embodiment of the present invention.
- FIG. 6 is a graph comparing the open circuit voltage drop of the secondary battery separator and the Celgard separator (celgard 2320 PP / PE / PP) according to one embodiment of the present invention.
- FIG. 7 is a graph showing a change in discharge capacity according to a current density change of a separator for a secondary battery and a celgard (celgard 2320 PP / PE / PP) separator according to one embodiment of the present invention.
- FIG. 8-a is a graph showing a change in discharge capacity according to a current density change of the separator for secondary batteries of Comparative Example 1.
- FIG. 8-b is a graph showing the change in discharge capacity according to the current density change of the separator for secondary batteries of Example 1.
- the separator for secondary batteries may include cellulose nanofibers.
- Cellulose is one of the most abundant biopolymers on earth and is renewable and has the advantages of high tensile strength, low density and biodegradability.
- cellulose nanofibers have characteristics such as high surface area and high aspect ratio (L / D).
- the separator may have a Gurley value in the range of 10 to 1000 s / 100 cc ⁇ air.
- the air permeability value may be 1000 cc ⁇ air or less, 10 to 1000 cc ⁇ air, 100 to 800 cc ⁇ air or 450 to 700 s / 100 cc ⁇ air.
- the Gurley value is an index relating to the air permeability of the membrane, and is determined according to the standard of the Garay air permeability (JIS P8117). In general, the smaller the air permeability value, the better the air permeability.
- the air permeability value can be described by Equation 1 below.
- tG is a gurley value
- K is a proportional constant
- ⁇ is a curve ratio (average of the path length divided by the film thickness for any curve)
- L is the film thickness
- ⁇ is the porosity
- d represent an average pore diameter, respectively.
- Equation 1 in order to have a high air permeability of the separation membrane, it can be seen that it is advantageous that the thickness of the membrane is thin, and the porosity and the average pore diameter are large.
- the secondary battery separator may include a microporous structure formed between cellulose nanofibers.
- the porous structure has a porosity of 10 to 80% (v / v), 10 to 50% (v / v), 25 to 50% (v / v), or 25 to 50% (v / v). May be). It is possible to realize excellent air permeability and high physical strength in the porosity range.
- the size of the pores forming the porous structure may range from 0.01 to 10 ⁇ m, and in some cases, from 0.01 to 8 ⁇ m, 0.1 to 10 ⁇ m, or 0.1 to 8 ⁇ m.
- the pore size is to form a porous structure that can implement excellent air permeability, when the pore size is too large, the physical strength may be lowered.
- the thickness of the separator may be in the range of 5 to 30 ⁇ m.
- the average thickness of the separator may be 5 to 30 ⁇ m, 5 to 20 ⁇ m, 5 to 20 ⁇ m, 5 to 15 ⁇ m, or 15 to 20 ⁇ m.
- the separator according to the present invention is characterized in that the average thickness is thinner than the separator for a secondary battery including a conventional cellulose.
- the thickness of the separator is to prevent physical stability by reducing the physical strength.
- the thickness of the separator is too thick, the resistance of the separator increases, and air permeability is lowered, thereby lowering battery efficiency.
- the size of the cellulose nanofibers according to the present invention is not particularly limited, and in one embodiment, the average diameter of the cellulose nanofibers may range from 10 to 100 nm.
- the average diameter of cellulose nanofibers may range from 10 to 80 nm, 30 to 100 nm, or 20 to 80 nm, or 20 to 60 nm.
- the diameter range of the cellulose nanofibers is to form pores of sufficient size and to realize a uniform surface. For example, when the average diameter of the cellulose nanofibers is too large, the surface of the prepared separator is not uniform, the strength may be weak.
- the secondary battery separator according to the present invention in the state impregnated in the electrolyte solution containing a lithium salt and a carbonate-based solvent, the ion conductivity may be in the range of 0.01 to 10 mS / cm.
- the ion conductivity of the separator may range from 0.01 to 8 mS / cm, 0.1 to 5 mS / cm, 0.1 to 1 mS / cm, 0.5 to 1 mS / cm, or 0.6 to 0.8 mS / cm.
- the separator according to the present invention can implement a relatively excellent ion conductivity compared to the conventional commercially available separator.
- the carbonate-based electrolyte is not particularly limited and may include one or more of ethylene carbonate, propylene carbonate, dimethyl carbonate, ethylmethyl carbonate, and diethyl carbonate.
- the ion conductivity may be measured by impregnating a separator in an electrolyte prepared by adding 1 mol of lithium salt (LiPF 6 ) to a solution in which ethylene carbonate and dimethyl carbonate are mixed at a ratio of 1: 1.
- the present invention provides a method for manufacturing a separator for a secondary battery described above.
- the manufacturing method In one embodiment, the manufacturing method,
- Cellulose nanofibers And manufacturing a sheet using a solution containing an organic solvent or a mixed solution of water and an organic solvent.
- the manufacturing method uses an organic solvent or a mixture of water and an organic solvent as a dispersion solvent for dispersing cellulose nanofibers.
- the mixing ratio of the dispersion solvent may range from 50:50 to 100: 0 (volume ratio).
- the mixing ratio of the organic solvent and water is 100: 0, it means that only the organic solvent is used alone. Therefore, the present invention includes adjusting the organic solvent and water to the above range, or using an organic solvent that does not contain water.
- the organic solvent is not particularly limited as long as the cellulose nanofibers are uniformly dispersed and the cellulose nanofibers are not dissolved in the process of preparing a suspension containing cellulose nanofibers.
- the organic solvent may include, for example, one or more of methyl alcohol, ethyl alcohol, propyl alcohol, acetone, ethyl acetate, methyl ethyl ketone, toluene and heptane.
- Isopropyl alcohol may be used as the organic solvent.
- the sheet can be prepared by dispersing cellulose nanofibers in isopropyl alcohol alone or in a solution in which water and isopropyl alcohol are mixed.
- the prepared sheet forms strong hydrogen bonds between the nanofibers and shows high tensile strength.
- the number of passes through the homogenizer may be at least eight cycles. For example, the number of passes through the homogenizer may be 8 to 20 cycles, 10 to 15 cycles, or 12 cycles.
- the manufacturing method may further include a step of drying the manufactured sheet after the step of forming the fine pores.
- the drying process of the sheet may be performed at a temperature of 40 ° C. to 80 ° C. for 10 hours to 30 hours.
- the process of drying the sheet may be performed at 50 to 70 ° C. for 20 to 30 hours.
- the drying process removes the dispersion contained in the cellulose nanofibers, and the portion from which the dispersion is removed forms voids.
- the drying of the sheet may include a process of dehydration drying using a vacuum filter, but is not limited thereto.
- the present invention provides a secondary battery including the separator described above.
- the structure of the secondary battery is not particularly limited, and may be used in all batteries, such as square, cylindrical, pouch, coin type, and the like.
- the active material used in the positive electrode and the negative electrode is not particularly limited.
- the secondary battery may be a lithium secondary battery using lithium as an active material.
- Cellulose nanofibers were mixed with a dispersion solvent.
- the amount of cellulose used is shown in Table 1 below, and the organic solvent and water were mixed in a ratio of 95: 5 (v / v) as a dispersion solvent.
- a sheet was prepared by passing a mixture of cellulose nanofibers and dispersion veins through a 12 cycles through a homogenizer. Thereafter, the sheet was dried at 60 ° C. for 24 hours to prepare a cellulose nanofiber separator.
- the Gurley value decreases as the amount of cellulose nanofibers decreases from 0.20 g to 0.15 g.
- the smaller the Gurley value the higher the air permeability. Therefore, it can be seen that the air permeability increases significantly as the amount of cellulose nanofibers decreases.
- the separator made using 0.15 g of cellulose nanofibers has a thickness of 17 ⁇ m, and thus a separator thinner than the Celgard 2320 PP / PE / PP separator could be manufactured.
- FIG. 1A shows a large difference in structure from commercially available Celgard (FIG. 1B).
- FIG. 1B shows a large difference in structure from commercially available Celgard (FIG. 1B).
- the separation membrane shown in Figure 1a can be seen that the size of the pores formed between the cellulose nanofibers is large, and formed relatively uniformly.
- FIG. 2 shows the enlarged observation result of the separator shown in FIG. 1A.
- Example 1 the secondary battery separator prepared in Example 1 and the Celgard (celgard 2320 PP / PE / PP) separator were each exposed at 150 ° C. for 30 minutes.
- the photographs taken before and after exposing each separator to 150 ° C. are shown in FIG. 3.
- the Celgard separator was exposed at a temperature of 150 ° C., it was found that the dimensions of about 36% decreased. On the other hand, almost no dimensional change was observed in the separator of Example 1.
- the wettability of the separator for secondary batteries is one of the characteristics that greatly affects battery productivity and battery efficiency. Electrolytic solution wettability of the separator according to Example 1 and the Celgard separator was measured. After dropping the propylene carbonate electrolyte solution having high polarity to each separator by using a micro syringe, the result was observed. 5 is a result of observing the time point 2 seconds after dropping the propylene carbonate electrolyte. The Celgard separator was not wet with the electrolyte, but the separator according to Example 1 was found to be immediately wet when the electrolyte was dropped.
- the open circuit voltage drop of the coin cell prepared by mounting the separator was measured.
- the low voltage characteristic provides information on self discharge that can predict an internal short between two electrodes of a secondary battery.
- the coin cell was completely charged with a current density of 0.5 C and a voltage of 4.2 V, and then observed change over time.
- the results are shown in FIG. Referring to FIG. 6, the low voltage characteristics of the separator according to Example 1 and the Celgard separator were nearly similar. Through this, the separator according to the present invention was confirmed that the low voltage characteristics do not fall compared to the conventional separator.
- the change in discharge capacity according to the change in current density was measured for the separators for secondary batteries of Examples 1 and 2 and Comparative Examples 1 and 4 described above.
- Coin cells equipped with each separator were charged at a voltage of 3.0V and 4.2V at a current density of 0.2C. Then, when discharged while varying the current density from 0.1C to 2.0C, the change in the discharge capacity of the coin cell was measured.
- Example 1 Similar discharge characteristics were shown at low current densities (0.1C, 0.2C, 0.5C) compared to Comparative Example 4 (CellGuard). However, it was confirmed that Example 1 exhibited a discharge characteristic superior to Comparative Example 4 (CellGuard) at a high current density (1C, 2C). In the case of Example 2, the discharge capacity tends to be somewhat lower than that of Comparative Example 4 in the 0.5C and 1C sections, but similar or superior discharge characteristics are shown in the other sections. In addition, Comparative Example 1 is a case where the thickness of the separation membrane is formed in comparison with Examples 1 and 2. In addition, Comparative Example 1 confirmed that the discharge characteristics were significantly reduced over the entire period.
- FIG. 8A and 8B are graphs comparing the results of measuring charge and discharge characteristics of secondary batteries including the separators according to Comparative Example 1 and Example 1, respectively. Compared with Example 1 (FIG. 8B), in Comparative Example 1 (FIG. 8A), it can be seen that the inclination of the charge and discharge curves is significantly different depending on the current density.
- the separator for a secondary battery including the cellulose nanofibers according to the present invention and a method of manufacturing the same can be used in various ways.
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Abstract
Description
나노섬유 함량(g) | 유기용매: 물 비율 | 통기도값(Gurley value) | 두께(㎛) | 저항(Ω) | 이온전도도 (mS/cm) | |
실시예 1 | 0.15 | 95:5 | 496.4 | 17 | 1.127 | 0.750 |
실시예 2 | 0.2 | 95:5 | 549.8 | 18 | 1.344 | 0.666 |
실시예 3 | 0.25 | 100:0 | 680.4 | 18 | 1.598 | 0.694 |
비교예 1 | 0.5 | 70:30 | 4749.1 | 26 | 7.330 | 0.151 |
비교예 2 | 0.5 | 90:10 | 1045.8 | 22 | 4.603 | 0.280 |
비교예 3 | 0.5 | 100:0 | 1003.5 | 21 | 1.361 | 0.410 |
비교예 4 | 셀가드(celgard 2320) | 500 | 20 | 1.356 | 0.734 |
Claims (14)
- 셀룰로오스 나노섬유를 포함하며, 통기도값이 10 내지 1000 sec/100cc·air인 이차전지용 분리막.
- 제 1 항에 있어서,셀룰로오스 나노섬유들 사이에 형성된 미세 다공성 구조를 포함하고, 다공성 구조는 기공도가 10 내지 80%(v/v)이고, 기공의 크기는 0.01 내지 10 ㎛인 이차전지용 분리막.
- 제 1 항에 있어서,분리막의 두께는 5 내지 30 ㎛인 이차전지용 분리막.
- 제 1 항에 있어서,셀룰로오스 나노섬유의 평균 직경은 10 내지 100 nm인 이차전지용 분리막.
- 제 1 항에 있어서,리튬염 및 카보네이트 계열 용매를 포함하는 전해액에 함침된 상태에서, 이온 전도도가 0.01 내지 10 mS/cm인 이차전지용 분리막.
- 셀룰로오스 나노섬유; 및 유기용매 혹은 물과 유기용매의 혼합액을 포함하는 용액을 사용하여 시트를 제조하는 공정; 및시트 내에 포함된 유기용매 제거하여 미세 다공을 형성하는 공정을 포함하는 이차전지용 분리막의 제조방법.
- 제 6 항에 있어서,유기용매와 물의 혼합 비율은 50:50 내지 100:0(부피비)인 이차전지용 분리막의 제조방법.
- 제 6 항에 있어서,유기용매는 메틸알코올, 에틸알코올, 프로필알코올, 아세톤, 에틸아세테이트, 메틸에틸케톤, 톨루엔 및 헵탄 중 1 종 이상을 포함하는 이차전지용 분리막의 제조방법.
- 제 6 항에 있어서,유기용매는 이소프로필알코올인 이차전지용 분리막의 제조방법.
- 제 6 항에 있어서,시트를 제조하는 공정은,셀룰로오스 나노섬유; 및 유기용매 혹은 물과 유기용매의 혼합액을 포함하는 용액을 호모지나이저에 통과시켜 현탁액을 제조하고, 이를 감압하여 시트로 제조하는 과정을 포함하는 이차전지용 분리막의 제조방법.
- 제 10 항에 있어서,셀룰로오스 나노섬유; 및 유기용매 혹은 물과 유기용매의 혼합액을 포함하는 용액을 호모지나이저에 8 싸이클(cycle) 이상 통과시키는 이차전지용 분리막의 제조방법.
- 제 6 항에 있어서,미세 다공을 형성하는 공정 이후에,제조된 시트를 건조하는 과정을 더 포함하는 이차전지용 분리막의 제조방법.
- 제 1 항 내지 제 5 항 중 어느 한 항에 따른 분리막을 포함하는 이차전지.
- 제 13 항에 있어서,상기 전지는 리튬 이차전지인 것을 특징으로 하는 이차전지.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP11876415.8A EP2787561A4 (en) | 2011-11-30 | 2011-12-08 | POROUS SEPARATOR FOR SECONDARY BATTERY COMPRISING CELLULOSE NANOFIBERS AND METHOD FOR MANUFACTURING THE SAME |
CN201180075259.7A CN103999260A (zh) | 2011-11-30 | 2011-12-08 | 用于二次电池的含纤维素纳米纤维的多孔隔板及其制造方法 |
US14/361,196 US20140335424A1 (en) | 2011-11-30 | 2011-12-08 | Porous Separator for a Secondary Battery Including Cellulose Nanofibers and Method For Manufacturing Same |
JP2014544637A JP2014534603A (ja) | 2011-11-30 | 2011-12-08 | セルロースナノファイバを有する二次電池用多孔性セパレータ及びその製造方法 |
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KR1020110126752A KR101164650B1 (ko) | 2011-11-30 | 2011-11-30 | 셀룰로오스 나노섬유를 포함하는 이차전지용 다공성 분리막 및 그 제조방법 |
KR10-2011-0126752 | 2011-11-30 |
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US (1) | US20140335424A1 (ko) |
EP (1) | EP2787561A4 (ko) |
JP (1) | JP2014534603A (ko) |
KR (1) | KR101164650B1 (ko) |
CN (1) | CN103999260A (ko) |
WO (1) | WO2013081228A1 (ko) |
Cited By (3)
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US20150364739A1 (en) * | 2014-06-13 | 2015-12-17 | The Regents Of The University Of California | Flexible porous aluminum oxide films |
EP2860791B1 (en) | 2013-10-08 | 2017-01-11 | Johns Manville | Battery electrode plate reinforcement mat having improved wettability characteristics and methods of use therefor |
US10164230B2 (en) | 2015-05-27 | 2018-12-25 | Samsung Electronics Co., Ltd. | Separator including microbial cellulose, method of producing the separator, and use of the separator |
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JP5846449B2 (ja) * | 2012-11-12 | 2016-01-20 | 北越紀州製紙株式会社 | 電池用セパレータの製造方法及び電池用セパレータ |
KR101423296B1 (ko) * | 2012-12-05 | 2014-07-24 | 대한민국 | 셀룰로오스 섬유와 실리카를 포함하는 이차전지용 다공성 분리막 및 그 제조방법 |
KR101618218B1 (ko) * | 2014-09-26 | 2016-05-09 | 대한민국 | 셀룰로오스 나노섬유 분리막을 포함하는 전기화학소자 및 이의 제조방법 |
US10033213B2 (en) * | 2014-09-30 | 2018-07-24 | Johnson Controls Technology Company | Short circuit wake-up system and method for automotive battery while in key-off position |
KR101912017B1 (ko) * | 2016-11-21 | 2018-10-25 | 한국생산기술연구원 | 분리막, 이를 포함한 에너지 저장 장치 및 이들의 제조 방법 |
EP4023436A1 (en) * | 2020-12-29 | 2022-07-06 | Renata AG | Multilayer separator for a battery |
CN114597580B (zh) * | 2022-03-14 | 2023-03-21 | 华南农业大学 | 钠离子电池用全纤维素复合隔膜及其原位制备方法和应用 |
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- 2011-12-08 EP EP11876415.8A patent/EP2787561A4/en not_active Withdrawn
- 2011-12-08 WO PCT/KR2011/009468 patent/WO2013081228A1/ko active Application Filing
- 2011-12-08 CN CN201180075259.7A patent/CN103999260A/zh active Pending
- 2011-12-08 JP JP2014544637A patent/JP2014534603A/ja active Pending
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US10164230B2 (en) | 2015-05-27 | 2018-12-25 | Samsung Electronics Co., Ltd. | Separator including microbial cellulose, method of producing the separator, and use of the separator |
Also Published As
Publication number | Publication date |
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KR101164650B1 (ko) | 2012-07-27 |
EP2787561A1 (en) | 2014-10-08 |
CN103999260A (zh) | 2014-08-20 |
EP2787561A4 (en) | 2015-07-22 |
JP2014534603A (ja) | 2014-12-18 |
US20140335424A1 (en) | 2014-11-13 |
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