Secondary Battery Comprising Gas Scavenging Member

Abstract

The present disclosure provides a secondary battery in which an electrode assembly is sealed together with an electrolyte solution within a pouch type battery case, wherein a gas scavenging member is disposed on at least one surface of an inner surface of the battery case. The gas scavenging member defining a pouch containing a mixed solution of an ionic liquid and an amine-based compound.

Claims

1. A secondary battery comprising: an electrode assembly sealed together with an electrolyte solution within a pouch type battery case, and a gas scavenging member defines a pouch disposed on at least one inner surface of the battery case, wherein the gas scavenging member includes a mixed solution of an ionic liquid and an amine-based compound in the pouch.

2. The secondary battery of claim 1, wherein the pouch is composed of a gas permeable polymer.

3. The secondary battery of claim 2, wherein the gas permeable polymer is a poly[4,5-difluoro-2,2-bis(trifluoromethyl)-1,3-dioxole-co-tetrafluoroethylene]-based material.

4. The secondary battery of claim 2, wherein the gas permeable polymer is Teflon AF 2400.

5. The secondary battery of claim 1, wherein the amine-based compound is an alkanol amine.

6. The secondary battery of claim 1, wherein a volume of the mixed solution in the pouch is 50 ml to 200 ml.

7. The secondary battery of claim 1, wherein the amine-based compound is contained in an amount of 5% to 30% by weight based on a total weight of the mixed solution.

8. The secondary battery of claim 1, wherein the ionic liquid is a combination of one or more selected from the group consisting of bis(trifluoromethane)sulfoneimide (Tf.sub.2N.sup.−), [CF.sub.3SO.sub.2].sup.−, and [CF.sub.3CO.sub.2].sup.− [PF.sub.6].sup.− as anions, and one or more selected from the group consisting of 1-butyl-3-methylimidazolium (bmim), 1-butyl-1-methyl pyrrolidinium (bmpyr), and butyltrimethylammonium (btmamm) as cations.

9. The secondary battery of claim 1, wherein the pouch includes an injection hole to receive the mixed solution, the injection hole being sealable after receiving the mixed solution within the pouch.

10. The secondary battery of claim 1, wherein the gas scavenging member is disposed on an inner surface of an upper end of the battery case along a stacking direction of the electrode assembly.

11. The secondary battery of claim 1, wherein the gas scavenging member defines a footprint smaller than an area of an upper end of the electrode assembly along a stacking direction of the electrode assembly.

12. The secondary battery of claim 1, wherein the electrode assembly comprises a positive electrode, a negative electrode, and a separator interposed therebetween, the positive electrode including a positive electrode mixture containing a positive electrode active material formed on at least one surface of a positive electrode current collector, the positive active material comprising a lithium nickel-based-transition metal oxide containing 80 mol % or more of Ni in the total moles of transition metals excluding lithium.

13. The secondary battery of claim 12, wherein the lithium nickel-based-transition metal oxide is represented by the following Chemical Formula:
Li.sub.1+xNi.sub.aCo.sub.bM.sub.cO.sub.2 wherein, 0≤x≤0.5, 0.8≤a≤1, 0≤b≤0.2, 0≤c≤0.2, and the M is at least one selected from the group consisting of Mn, Al, Ti, Mg, Zr, W, Y, Sr, F, Si, Na, Cu, Fe, Ca, S and B.

14. The secondary battery of claim 13, wherein the lithium nickel-based-transition metal oxide is LiNi.sub.0.8Co.sub.0.1 Mn.sub.0.1O.sub.2, LiNi.sub.aCo.sub.b(Mn.sub.yA.sub.z).sub.cO.sub.2, LiNi.sub.aCo.sub.bA.sub.cO.sub.2, wherein a, b and c are as defined above, and the A is at least one selected from the group consisting of Al, Ti, Mg, Zr, W, Y, Sr, F, Si, Na, Cu, Fe, Ca, S and B.

15. A secondary battery comprising: a battery case including an electrode assembly and an electrolyte solution, and a gas scavenging member disposed within the battery case, wherein the gas scavenging member contains a mixed solution of an ionic liquid and an amine-based compound therewithin.

16. The secondary battery of claim 15, wherein the gas scavenging member defines a pouch.

17. A method for assembling a secondary battery, the method comprising the steps of: sealing an electrode assembly with an electrolyte solution within a pouch type battery case, and disposing a gas scavenging member defining a pouch on at least one inner surface of the battery case, wherein the gas scavenging member includes a mixed solution of an ionic liquid and an amine-based compound in the pouch.

18. The method of claim 17, further including a step of providing an injection hole in the pouch to receive the mixed solution, the injection hole being sealable after receiving the mixed solution within the pouch.

19. The method of claim 17, wherein the step of disposing the gas scavenging member includes disposing the gas scavenging member on an inner surface of an upper end of the battery case along a stacking direction of the electrode assembly.

20. The method of claim 17, wherein the gas scavenging member defines a footprint smaller than an area of an upper end of the electrode assembly along a stacking direction of the electrode assembly

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0030] FIG. 1 is a schematic diagram of a secondary battery according to an embodiment of the present disclosure;

[0031] FIGS. 2A-2C are schematic diagrams showing a process of manufacturing a gas scavenging member of the secondary battery of FIG. 1; and

[0032] FIGS. 3A-3C are schematic diagrams showing a process of manufacturing a gas scavenging member according to another embodiment of the present disclosure.

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0033] Hereinafter, the present disclosure will be described in more detail for a better understanding of the present disclosure.

[0034] Terms or words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms, and the present disclosure should be construed with meanings and concepts that are consistent with the technical idea of the present disclosure based on the principle that the inventors may appropriately define concepts of the terms to appropriately describe their own disclosure in the best way.

[0035] The technical terms provided herein is merely used for the purpose of describing particular embodiments, and is not intended to be limiting of the present disclosure. The singular forms “a,” “an,” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise.

[0036] Further, throughout the specification, when a portion is referred to as “including” a certain component, it means that the portion can further include other components, without excluding the other components, unless otherwise stated.

[0037] The secondary battery according to an embodiment of the present disclosure may have a form in which an electrode assembly is sealed together with an electrolyte solution within a pouch type battery case. According to the present embodiment, a gas scavenging member is disposed on at least one surface of the inner surface of the battery case, and the gas scavenging member has a form in which a mixed solution of an ionic liquid and an amine-based compound is contained inside the pouch. At this time, the pouch may be composed of a gas permeable polymer, and the mixed solution may be a mixture of an ionic liquid and an amine-based compound.

[0038] Here, the gas permeable polymer may be, specifically, a poly[4,5-difluoro-2,2-bis(trifluoromethyl)-1,3-dioxole-co-tetrafluoroethylene]-based material, and the gas permeable polymer may be Teflon AF 2400.

[0039] Further, the amine-based compound contained in the pouch made of the gas permeable polymer may be, specifically, an alkanol amine, and more specifically, it may be at least one selected from the group consisting of monoethanol amine, diethanol amine, triethanol amine, methyl diethanol amine, and 2-amino 2-methyl 1-propanol.

[0040] As another component, the ionic liquid may be a combination of one or more selected from the group consisting of bis(trifluoromethane)sulfonimide (Tf.sub.2N.sup.−), [CF.sub.3SO.sub.2].sup.−, and [CF.sub.3CO.sub.2].sup.− [PF.sub.6].sup.− as anions, and one or more selected from the group consisting of 1-butyl-3-methylimidazolium (bmim), 1-butyl-1-methyl pyrrolidinium (bmpyr), and butyltrimethylammonium (btmamm) as cations.

[0041] In this case, the mixed solution containing the amine-based compound and the ionic liquid included in the gas scavenging member varies depending on the size of the pouch in detail, but for example, the mixed solution may be contained in an amount of 50% to 95% of the total volume inside the pouch, and more specifically, it may be contained in an amount of 60% to 80%.

[0042] Further, of course, since the size of the pouch may vary depending on the size of the secondary battery, the absolute amount of the mixed solution may vary accordingly. Since it is possible to scavenge enough gas to contain at least 50 ml or more, it is preferable that the mixed solution is contained in an amount of 50 ml or more. On the other hand, if the content of the mixed solution is too large, the volume occupied by the gas scavenging member in the secondary battery becomes too large, and thus, specifically, it is preferably contained in an amount of 200 ml or less.

[0043] In addition, the amine-based compound contained in the mixed solution may be contained in an amount of 5% to 30% by weight based on the total weight of the mixed solution, and specifically, it may be contained in an amount of 10% by weight to 20% by weight, and more specifically, it may be contained in an amount of 10% to 15% by weight.

[0044] If the content of the amine-based compound is too small outside the above range, the amine-based compound is not enough and so the gas scavenging effect is poor. If the content of the amine-based compound is too large, hydrogen carbonate and free amine, which are carbon dioxide absorption products, may precipitate in an ionic liquid, which is thus not preferable.

[0045] Meanwhile, the gas scavenging member may be disposed on at least one surface of the inner surface of the battery case, specifically, on the inner surface of the upper end of the battery case on the basis of the stacking direction of the electrode assembly.

[0046] At this time, by “it is disposed on the inner surface of the battery case” is meant herein that the gas scavenging member may be attached to the inner surface of the battery case, and subsequently, may be attached to the built-in electrode assembly, and may be formed in a form that is not attached as a separate member. However, it is preferably attached to the inner surface of the battery case or the electrode assembly so that the pouch can be fixed onto the inner surface of the battery case. More specifically, it may be attached to the inner surface of the battery case so as not to interfere with the electrolyte impregnation of the electrode assembly.

[0047] Further, the gas scavenging member may be formed to have a size smaller than the area of the upper end of the electrode assembly on the basis of the stacking direction of the electrode assembly as described above, and specifically, it may be 0.2% to 15% smaller than the area of the upper end of the electrode assembly.

[0048] When the gas scavenging member is formed to be too small outside the above range, the gas generated during the operation of the secondary battery cannot be sufficiently scavenged, which is thus not preferable.

[0049] As an example, a schematic diagram of a secondary battery 100 according to an embodiment of the present disclosure is shown in FIG. 1.

[0050] Referring to FIG. 1, the secondary battery 100 has a structure in which an electrode assembly 110 is sealed together with an electrolyte solution 120 within a pouch type battery case 130, and a gas scavenging member 140 is disposed on the upper surface of the electrode assembly 110 and the upper inner surface of the battery case 130, that is, between the upper surface of the electrode assembly 110 and the upper end of the battery case 130.

[0051] At this time, it may be in the form of being attached to the upper surface of the electrode assembly 110, and may be in the form of being attached to the inner surface of the upper end of the battery case 130, and as a separate member, it may be simply interposed between the upper surface of the electrode assembly 110 and the inner surface of the upper end of the battery case 130.

[0052] At this time, the size of the prepared gas scavenging member 140 may be designed to be smaller than the horizontal and vertical lengths of the upper surface of the electrode assembly 110. Here, the gas scavenging member 140 may be prepared, for example, by the method as shown in FIGS. 2A-2C and 3A-3C.

[0053] Referring to FIG. 2A first, the gas scavenging member can be prepared by sealing three surfaces under high-temperature as so to make a film made of two gas-permeable polymers as a pouch shape, so as to include a three-sided sealing part 141 and a one-sided mixed solution injection port 142. Turning to FIG. 2B, a mixed solution according to the present disclosure is then injected through the mixed solution injection port 142. Finally, as shown in FIG. 2C, the mixed solution injection port 142 is sealed under high-temperature.

[0054] Alternatively, referring to FIGS. 3A-3C, the gas scavenging member can be prepared by folding a film made of a gas permeable polymer in half so as to include the two-sided sealing part 141′ and the one-sided mixed solution injection port 142′, and high-temperature sealing the two side surfaces of the folded part as shown in FIG. 3A. A mixed solution according to the present disclosure is then injected through the mixed solution injection port 142 as shown in FIG. 3B. Finally, the mixed solution inlet or port 142 is sealed using high-temperature as shown in FIG. 3C.

[0055] Therefore, the gas scavenging member according to the present disclosure has a pouch structure, which has a form in which a mixed solution injection hole is formed on one side of the gas scavenging member, and the mixed solution injection hole is sealed in a state where the mixed solution is injected.

[0056] Meanwhile, the electrode assembly includes a positive electrode, a negative electrode, and a separator interposed between the positive electrode and the negative electrode. The positive electrode has a positive electrode mixture containing a positive electrode active material formed on at least one surface of a positive electrode current collector, and the positive active material may include a lithium nickel-based-transition metal oxide containing 80 mol % or more of Ni in the total moles of transition metals excluding lithium.

[0057] Here, the lithium nickel-based-transition metal oxide may be represented by the following Chemical Formula.

Li.sub.1+xNi.sub.aCo.sub.bM.sub.cO.sub.2

wherein, 0≤x≤0.5, 0.8≤a≤1, 0≤b≤0.2, 0≤c≤0.2, and the M is at least one selected from the group consisting of Mn, Al, Ti, Mg, Zr, W, Y, Sr, F, Si, Na, Cu, Fe, Ca, S and B.

[0058] More specifically, the lithium nickel-based-transition metal oxide may be LiNi.sub.0.8Co.sub.0.1 Mn.sub.0.1O.sub.2, LiNi.sub.aCo.sub.b(Mn.sub.yA.sub.z).sub.cO.sub.2, LiNi.sub.aCo.sub.bA.sub.cO.sub.2, wherein a, b and c are as defined above, and the A is at least one selected from the group consisting of Al, Ti, Mg, Zr, W, Y, Sr, F, Si, Na, Cu, Fe, Ca, S and B.

[0059] When the lithium nickel-based transition metal oxide, that is, an oxide having 80 mol % or more of a nickel content in the total moles of transition metals excluding lithium, is included as a positive electrode active material, it is suitable for high energy and high output requirements, but a large amount of CO.sub.2 is generated at high temperature, performance deteriorates due to gas traps and the incidence of venting issues is high. Thereby, since the gas control requirement is higher, the secondary battery including the gas scavenging member according to the present disclosure can operate efficiently.

[0060] Meanwhile, the positive active material may further include, for example, lithium manganese oxides such as chemical formulae Li.sub.1+x Mn.sub.2−xO.sub.4 (where, x is 0 to 0.33), LiMnO.sub.3, LiMn.sub.2O.sub.3, LiMnO.sub.2; lithium copper oxide (Li.sub.2CuO.sub.2); vanadium oxides such as LiV.sub.3O.sub.8, LiFe.sub.3O.sub.4, V.sub.2O.sub.5, and Cu.sub.2V.sub.2O.sub.7 lithium manganese composite oxide represented by chemical formulae LiMn.sub.2−xM.sub.xO.sub.2 (where, M=Co, Ni, Fe, Cr, Zn or Ta, and x=0.01 to 0.1) or Li.sub.2Mn.sub.3MO.sub.8 (where, M=Fe, Co, Ni, Cu or Zn); LiMn.sub.2O.sub.4 with a Li portion of chemical formula substituted with an alkaline earth metal ion; a disulfide compound; Fe.sub.2(MoO.sub.4).sub.3, and the like. As long as it has a configuration of a conventionally known positive active material, it is not limited thereto and may be further included.

[0061] The positive electrode mixture may further include a conductive material and a binder together with the positive electrode active material described above.

[0062] The negative electrode may be prepared in a form in which a negative electrode mixture including a negative electrode active material is coated onto a negative electrode current collector, and the negative electrode mixture may further include the conductive material and binder as described above together with the negative electrode active material.

[0063] Since the positive electrode current collector, the negative electrode active material, the negative electrode current collector, the conductive material, the binder, and the like are well known in the art, a detailed description thereof is omitted herein.

[0064] In addition, since the separator included in the electrode assembly of the secondary battery, the electrolyte solution built-in together with the electrode assembly in the secondary battery, and the laminate sheet configuration of the battery case are known in the art, a detailed description thereof is omitted herein.

[0065] Hereinafter, preferred examples of the present disclosure, comparative examples for comparing them, and experimental examples for evaluating them are described. However, it will be obvious to those skilled in the art that these examples are for illustrative purposes only and various changes and modifications can be made without deviating from the scope and spirit of the present description, and it goes without saying that such modifications and modifications fall within the scope of the appended claims.

Production Example 1

[0066] Preparation of Gas Scavenging Member

[0067] Two Teflon AF 2400 films were prepared, and three surfaces of them were sealed to prepare a pouch equipped with a liquid injection port.

[0068] Monoethanolamine (MEA) as an amine-based compound was dissolved in bis(trifluoromethane)sulfoneimide (Tf.sub.2N) as an ionic liquid so as to contain 10% by weight based on the total weight of the mixed solution, thereby preparing a mixed solution.

[0069] 50 ml of the mixed solution was injected into the pouch, and the injection port was sealed to prepare a gas scavenging member 1.

Preparation Example 2

[0070] Preparation of Gas Scavenging Member

[0071] A gas scavenging member 2 was prepared in the same manner as in Preparation Example 1, except that diethanolamine (DEA) was used as an amine-based compound.

Preparation Example 3

[0072] Preparation of Gas Scavenging Member

[0073] A gas scavenging member 3 was prepared in the same manner as in Preparation Example 1, except that monoethanolamine was dissolved as the amine-based compound, so as to contain 30% by weight based on the total weight of the mixed solution.

Preparation Example 4

[0074] Preparation of Gas Scavenging Member

[0075] A gas scavenging member 4 was prepared in the same manner as in Preparation Example 1, except that monoethanolamine was dissolved as the amine-based compound, so as to contain 5% by weight based on the total weight of the mixed solution.

Preparation Example 5

[0076] Preparation of Gas Scavenging Member

[0077] A gas scavenging member 5 was prepared in the same manner as in Preparation Example 1, except that only 30 ml of the mixed solution was injected into the pouch.

Preparation Example 6

[0078] Preparation of Gas Scavenging Member

[0079] A gas scavenging member 6 was prepared in the same manner as in Preparation Example 1, except that 50 ml of a liquid electrolyte in which LiPF.sub.6 was dissolved at 1 M in a mixed solvent of ethylene carbonate and ethylmethyl carbonate in a ratio of 3:7 (volume ratio) was injected instead of the mixed solution into the pouch.

Example 1

[0080] LiNi.sub.0.8Co.sub.0.1 Mn.sub.0.1O.sub.2 was used as a positive electrode active material. 96 wt. % of the positive electrode active material, 2.0 wt. % of Super-P (conductive material), and 2.0 wt. % of PVdF (binder) were added to NMP (N-methyl-2-pyrrolidone) as a solvent to prepare a positive electrode active material slurry.

[0081] The positive electrode mixture slurry was coated to a thickness of 50 μm onto aluminum foil. For NMP drying, it was dried and rolled at a speed of 0.2 m/min (about 5 minutes) in a dryer at 130° C. to prepare a positive electrode.

[0082] Artificial graphite was used as a negative electrode active material. 96.3 wt. % of artificial graphite, 1.0 wt. % of Super-P (conductive agent), and 2.7 wt. % of PVdF (binder) were added to NMP as a solvent to prepare a negative electrode active material slurry, and then, the resulting slurry was coated to 70 μm onto a copper foil, dried at a speed of 0.2 m/min (about 5 minutes) in a dryer at 130° C., and rolled to prepare a negative electrode.

[0083] An electrode assembly was prepared using the above-prepared positive electrode and negative electrode, and a polyethylene film (Celgard, thickness: 20 μm) as a separator.

[0084] The gas scavenging member 1 of Preparation Example 1 was disposed on the upper end of the electrode assembly, which was built into a battery case, and injected and sealed using a liquid electrolyte in which LiPF.sub.6 was dissolved at 1 M in a mixed solvent of ethylene carbonate, dimethylene carbonate and diethyl carbonate in a ratio of 1:2:1 (volume ratio), thereby preparing the secondary battery.

Example 2

[0085] A secondary battery was prepared in the same manner as in Example 1, except that as the gas scavenging member, the gas scavenging member 2 was used instead of the gas scavenging member 1.

Example 3

[0086] A secondary battery was prepared in the same manner as in Example 1, except that as the gas scavenging member, the gas scavenging member 3 was used instead of the gas scavenging member 1.

Example 4

[0087] A secondary battery was prepared in the same manner as in Example 1, except that as the gas scavenging member, the gas scavenging member 4 was used instead of the gas scavenging member 1.

Example 5

[0088] A secondary battery was prepared in the same manner as in Example 1, except that as the gas scavenging member, the gas scavenging member 5 was used instead of the gas scavenging member 1.

Comparative Example 1

[0089] A secondary battery was prepared in the same manner as in Example 1, except that the gas scavenging member was not used.

Comparative Example 2

[0090] A secondary battery was prepared in the same manner as in Example 1, except that the gas scavenging member 6 was disposed instead of the gas scavenging member 1.

Experimental Example 1

[0091] The secondary batteries prepared in Examples 1-5 to Comparative Examples 1-2 were charged up to 4.2V at 0.1 C and 5 mA, stored in a convection oven at 60° C. for 2 weeks, and then the amount of gas generated in the secondary battery was measured by GC-mass analysis, and the results are shown in Table 1 below.

TABLE-US-00001 TABLE 1 Amount of gas generated (CO.sub.2 content, ) Example 1 267 Example 2 375 Example 3 106 Example 4 1032 Example 5 633 Comparative 1619 Example 1 Comparative 1465 Example 2

[0092] Referring to Table 1, it can be confirmed that when a gas scavenging member containing an ionic liquid and an amine-based compound was prepared and formed as in the present disclosure the amount of gas generated was significantly reduced as compared with the case where this was not formed or the general electrolyte composition was added.

Experimental Example 2

[0093] A sample was charged to 4.2V at 0.5 C and then charged to 0.05 C under constant voltage at 45° C., and then discharged to 2.5V at 0.5 C. This was repeatedly carried out up to 800 cycles at a temperature of 45° C., then the discharge capacity retention rate (discharge capacity @ 800 cycles/initial capacity×100) was calculated, and the occurrence of venting was confirmed. The results are shown in Table 2 below.

TABLE-US-00002 TABLE 2 Capacity retention rate (%) Pouch venting Example 1 82.2 No Example 2 81.9 No Example 3 82.1 No Example 4 78.6 No Example 5 81.7 No Comparative 68.5 Yes Example 1 Comparative 72.3 Yes Example 2

[0094] Referring to Table 2, it can be confirmed that according to the present disclosure, venting did not occur and the capacity retention rate was significantly improved.

[0095] Based on the above disclosure, various applications and modifications can be carried out by those of ordinary skill in the art without deviating from the spirit and scope of the present disclosure.

INDUSTRIAL APPLICABILITY

[0096] As described above, the secondary battery according to an embodiment of the present disclosure includes a gas scavenging member containing a mixed solution of an ionic liquid and an amine-based compound, and therefore, can effectively scavenge the gas generated during the operation of the secondary battery, improve the lifetime characteristics, do not cause issues such as packaging venting, and secure the safety.