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“Negative Electrode Comprising Mesh Type Current Collector, Lithium Secondary Battery Comprising The Same, And Manufacturing Method Thereof”

Abstract: The present disclosure relates to a negative electrode for a lithium secondary battery comprising a mesh-type current collector and a lithium thin film, and in particular, to a negative electrode in which a lithium thin film is inserted to an opening of a current collector and empty space is formed, a lithium secondary battery comprising the same, and a manufacturing method thereof. The present disclosure is capable of enhancing safety of the lithium secondary battery by preventing lithium dendrite growth. In addition, the present disclosure is capable of preventing stripping of the negative electrode current collector and the lithium thin film while charging and discharging the battery since adhesion efficiency increases between the negative electrode and the current collector.

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Patent Information

Application #
Filing Date
24 July 2017
Publication Number
04/2018
Publication Type
INA
Invention Field
ELECTRICAL
Status
Email
Parent Application
Patent Number
Legal Status
Grant Date
2022-05-04
Renewal Date

Applicants

LG CHEM, LTD.
128, Yeoui-daero, Yeongdeungpo-gu, Seoul 07336, Republic of Korea

Inventors

1. OH, Hyunjin
LG Chem Research Park, 188 Munji-ro, Yuseong-gu, Daejeon 34122, Republic of Korea
2. CHO, Jin Hyun
LG Chem Research Park, 188 Munji-ro, Yuseong-gu, Daejeon 34122, Republic of Korea
3. YUN, Hyunwoong
LG Chem Research Park, 188 Munji-ro, Yuseong-gu, Daejeon 34122, Republic of Korea

Specification

Field 5 of the Invention The present disclosure relates to a negative electrode for a lithium secondary battery comprising a mesh-type current collector and a lithium thin film, and 10 in particular, to a negative electrode in which a lithium thin film is inserted to an opening of a current collector and empty space is formed, a lithium secondary battery comprising the same, and a manufacturing method thereof. 15 Background of the Invention Interests in energy storage technologies have been increasingly higher recently. As applications are 20 expanded to energy of mobile phones, camcorders and notebook PCs, and furthermore, to electric vehicles, efforts on the research and development of electrochemical devices have been more and more materialized. 25 Electrochemical devices are fields receiving most -2- attentions in such aspects and among these, development of secondary batteries capable of charge and discharge have been the focus of attention, and in developing such batteries, research and development on the design of new electrodes and batteries for enhancing 5 capacity density and energy efficiency have been recently progressed. Among currently used secondary batteries, lithium secondary batteries developed in early 1990s have received attentions with advantages of having high 10 operating voltage and significantly higher energy density compared to conventional batteries such as Ni-MH, Ni-Cd and sulfuric acid-lead batteries using an aqueous liquid electrolyte. A lithium secondary battery is generally formed by 15 an electrode assembly comprising a positive electrode, a negative electrode and a separator provided between the positive electrode and the negative electrode being embedded in a battery case in a laminated or wound structure, and a non-aqueous liquid electrolyte being 20 injected thereinto. As for a lithium electrode as the negative electrode, lithium foil attached on a planar current collector is used. In this case, lithium formation and elimination are irregular when charged and discharged 25 producing lithium dendrite, and this leads to continuous -3- capacity decline. In view of the above, studies introducing a polymer protective layer or inorganic solid protective layer to a lithium metal layer, increasing a salt concentration of a liquid electrolyte, or using proper additives 5 have been progressed. However, effects of suppressing lithium dendrite resulted from such studies are insignificant. Accordingly, solving problems through modifying a form of a lithium metal anode itself or modifying a battery 10 structure may be an effective option. Prior Art Documents Patent Documents Korean Patent No. 10-1621410 “Lithium Electrode and Lithium Secondary Battery comprising the Same” 15 Summary of the Invention As described above, lithium dendrite of a lithium secondary battery is precipitated on a surface of a 20 negative electrode current collector and volume expansion of a cell is sometimes caused therefrom. In view of the above, the inventors of the present disclosure have conducted studies from various angles and, as a result, have found out a method of solving such a problem caused 25 by dendrite through modifying shape and structure of an -4- electrode itself, and have completed the present disclosure. Accordingly, the present disclosure is directed to providing a lithium secondary battery solving a problem of volume expansion of a cell caused by 5 lithium dendrite through modifying shape and structure of an electrode, and having enhanced cell performance. In view of the above, one embodiment of the present disclosure provides a negative electrode for a lithium 10 secondary battery comprising a mesh-type anode current collector formed with a wire rod portion and an opening; and a lithium thin film formed with an inserted portion inserted to the opening of the negative electrode current collector and a non-inserted portion that is not inserted. 15 Another embodiment of the present disclosure provides a method for manufacturing a negative electrode for a lithium secondary battery comprising preparing a mesh-type anode current collector; placing lithium metal foil on the negative electrode current collector; and 20 rolling the lithium metal foil and the negative electrode current collector to insert the lithium metal to an opening of the negative electrode current collector. Still another embodiment of the present disclosure provides a lithium secondary battery comprising the 25 negative electrode. -5- Brief Description of the Drawings Fig. 1 is a cross-sectional view of a negative electrode for a lithium secondary battery 5 comprising a lithium thin film inserted to an opening of a negative electrode current collector according to the present disclosure; Fig. 2 is a perspective view describing a method 10 for manufacturing a negative electrode for a lithium secondary battery according to the present disclosure; Fig. 3 is a step mimetic diagram describing a method for manufacturing a negative electrode for a lithium secondary battery according to the present 15 disclosure; Fig. 4 is an image of a mesh-type anode current collector used in Example 1 of the present disclosure; Fig. 5 is a SEM image of a mesh-type anode current collector used in Example 1 of the present disclosure; 20 Fig. 6 is an image of a negative electrode for a lithium secondary battery according to Example 1 of the present disclosure; Fig. 7 is a SEM image of a negative electrode for a lithium secondary battery according to Example 1 of the 25 present disclosure; -6- Fig. 8 shows initial capacity and efficiency data of lithium secondary batteries using anodes according to Example 1 and Comparative Example 1 of the present disclosure; and Fig. 9 shows data comparing rate 5 performance of lithium secondary batteries using anodes according to Example 1 and Comparative Example 1 of the present disclosure. 100. Anode Current Collector 10 110. Opening 120. Wire Rod Portion 200. Lithium Thin Film 210. Inserted portion 220. Non-Inserted portion 15 300. Pressure Roller Detailed Description of the Embodiments Hereinafter, embodiments of the present disclosure 20 will be described in detail with reference to the accompanying drawings so that those skilled in the art may readily implement the present disclosure. However, the present disclosure may be implemented in various different forms, and is not limited to the embodiments 25 described herein. -7- In the drawings, parts not relevant to the descriptions are not included in order to clearly describe the present disclosure, and like reference numerals are used for like elements throughout the specification. In addition, sizes and 5 relative sizes of constituents shown in the drawings are unrelated to actual scales, and may be reduced or exaggerated for clarity of the descriptions. Fig. 1 is a cross-sectional view of a negative 10 electrode for a lithium secondary battery comprising a lithium thin film inserted to an opening of a negative electrode current collector according to the present disclosure. When referring to Fig. 1, the present disclosure provides a negative electrode for a lithium 15 secondary battery comprising a mesh-type anode current collector (100) formed with a wire rod portion (120) and an opening (110); and a lithium thin film (200) formed with an inserted portion (210) inserted to the opening (110) of the negative electrode current collector (100) 20 and a non-inserted portion (220) that is not inserted. The negative electrode for a lithium secondary battery according to the present disclosure has a structure in which the lithium thin film (200) is inserted while one surface thereof adjoins on an upper 25 surface of the mesh-type anode current collector (100), -8- and this leaves empty space in the opening (110) as a part of the lithium thin film (200) is inserted to the opening (110) of the negative electrode current collector (100). This space induces lithium dendrite formation preventing volume expansion 5 of a cell. In the present disclosure, the electrode material formed on the negative electrode current collector (100) is preferably a lithium thin film (200). Lithium thin film (200) has malleability and ductility, unique 10 properties of a metal film, and changes its form while spreading thinly when applying a pressure, and therefore, may be inserted to the mesh-type anode current collector opening (110) with only a rolling process. However, among materials used as a negative 15 electrode in a lithium secondary battery, a negative electrode active material that comprises lithium in a form that is not a thin film form is normally prepared into a slurry mixture and a coating process coating the slurry mixture on a negative electrode current collector 20 is carried out, and unlike lithium in a thin film form, such a slurry mixture is difficult to be inserted to an opening of a mesh-type anode current collector through a coating film-forming process or a rolling process thereafter, and cracks may also occur due to a pressure 25 applied in the rolling process. Even when the slurry -9- mixture inserted to an opening of a negative electrode current collector by controlling viscosity of the slurry mixture, there is a problem in that controlling the viscosity enough to secure empty space to a target level aimed in the present disclosure 5 is very difficult. Accordingly, a lithium thin film (200) is preferably used as a negative electrode material in the present disclosure, and an inserted portion thickness (d210) of such a lithium thin film (200) is controlled to 10 be 20% to 60% of the thickness of the whole lithium thin film. In other words, space filled with the inserted portion (210) of the lithium thin film is from 20% to 60% of the thickness of the whole lithium thin film, and accordingly, empty space is preserved in the opening 15 (110) space. Dendrite is formed in such remaining space of the opening (110) while gone through charge and discharge, and as a result, volume expansion of a cell may be prevented. Herein, as for a non-inserted portion thickness 20 (d220) of the lithium thin film (200), it is preferred that 40% to 80% of the total lithium thin film thickness (d200) is left and only the rest is inserted. When the lithium thin film (200) is not completely inserted and a part thereof is left, space remains inside the negative 25 electrode current collector (100), and effects described -10- above are secured. In addition, as both surfaces of the lithium thin film (200) are exposed to a liquid electrolyte, a stable SEI membrane is formed on the both surfaces preventing the Li metal surface from being exposed, and as a result, electrolyte 5 decomposition caused from charge and discharge may be prevented. As for a thickness (d200) of the lithium thin film, those having a thickness of 10 μm to 800 μm are selected, and selecting those having a larger thickness than the 10 negative electrode current collector is preferred. The reason is to secure a sufficient non-inserted portion (220) thickness even after the lithium thin film (200) is inserted to the opening (110) of the negative electrode current collector. 15 In addition, as the negative electrode current collector (100), those having a thickness range of 3 μm to 500 μm are used. When the negative electrode current collector has a thickness of less than 3 μm, a current collecting effect decreases, and an opening (110) having 20 a sufficient size to collect lithium dendrite is not secured. Meanwhile, the thickness being greater than 500 μm has a problem of reducing processibility when assembling a cell through folding. An effect of suppressing lithium dendrite growth is 25 excellent as the size of one opening (110) of the -11- negative electrode current collector (100) is smaller and the percentage of the opening (110) is higher. More specifically, as the wire rod portion (120) of the negative electrode current collector (100), those having a line width of 50 μm to 500 μm and line 5 spacing of 100 μm to 1 mm may be selected, and the size of one opening (110) that such a wire rod portion (120) forms is preferably from 10 μm to 300 μm in securing the abovementioned effects. 10 In addition, as for the percentage of the opening (110) in the negative electrode current collector (100), an aperture ratio, the percentage of the area occupied by the opening (110) region, is preferably from 20% to 80% based on the total area 100% of the negative electrode 15 current collector (100). When the aperture ratio is less than 20%, the effect of inducing precipitation and elimination reactions of lithium dendrite, a goal of the present disclosure, may not be secured, and when the aperture ratio is greater than 80%, the area of contact 20 between the negative electrode current collector and the lithium metal layer relatively decreases, which is not proper in performing a role as a negative electrode current collector, and as a result, battery performance declines. 25 The shape of the opening (110) formed by such a -12- wire rod portion (120) of the negative electrode current collector (100) is not limited, and examples thereof may comprise a circular, oval or polygonal shape. The negative electrode current collector (100) is not particularly limited as long 5 as it has high conductivity without inducing chemical changes in a battery, and may be selected from the group consisting of copper, aluminum, stainless steel, zinc, titanium, silver, palladium, nickel, iron, chromium, alloys thereof and 10 combinations thereof. The stainless steel may have its surface treated with carbon, nickel, titanium or silver, and aluminum-cadmium alloys may be used as the alloy, and in addition thereto, baked carbon, nonconductive polymers of which surface is treated with a conductor, conductive 15 polymers or the like may also be used. As the negative electrode current collector, a copper thin plate is generally used. The negative electrode for a lithium secondary battery in which a part of a lithium thin film is 20 inserted to a negative electrode current collector according to the present disclosure is capable of enhancing safety of the lithium secondary battery by increasing a surface area of contact between the lithium thin film and the negative electrode current collector, 25 uniformizing electron distribution inside the lithium -13- electrode, and inducing lithium dendrite precipitation in empty space inside the current collector. Furthermore, the present disclosure provides a negative electrode for a lithium secondary battery comprising a mesh-type anode current 5 collector formed with a wire rod portion and an opening; a lithium thin film formed with an inserted portion inserted to the opening of the negative electrode current collector and a non-inserted portion that is not inserted; and a 10 protection structure formed on a surface opposite to the lithium thin film that the negative electrode current collector faces, wherein the protection structure is formed with an organic polymer portion and an inorganic material portion, and the organic polymer portion is 15 formed on a surface opposite to the lithium thin film that the wire rod portion adjoins and the inorganic material portion is formed on a surface opposite to the lithium thin film corresponding to the opening. The protection structure according to the present 20 disclosure may provide an ion path between a negative electrode and an electrolyte. Such a protection structure has a form of an inorganic material filling space between frames that the organic polymer portion forms, and although an inorganic material cell or layer 25 formed with specific ceramic/glassy may comprise pin- 14- holes, cracks and/or crystal grain-based defects that may spread through the whole cell or layer, the presence of a number of ion paths may minimize the influence of defects in any one ion path. Accordingly, when defects are present in the protection structure, 5 this is typically much less fatal compared to when present inside a protection structure comprising one or more continuous ceramic layers. For example, defects may be isolated (for example, at least partly surrounded by polymer 10 materials), and therefore, the defects spreading to other ion paths (for example, inorganic material-filled cavity) may be reduced or avoided. The organic polymer portion provides advantageous mechanical properties such as flexibility and strength of 15 the protection structure. Placing a cell filled with an inorganic material inside a polymer frame may reduce weakness of the inorganic material-filled cavity for crack mechanism. The material is not limited, and for example, may be selected from among polyvinyl alcohol, 20 polyisobutylene, epoxy, polyethylene, polypropylene, polytetrafluoroethylene and combinations thereof as a non-ionic conductive polymer. The inorganic material portion may be a ceramicbased or glassy-based material as a material ionic 25 communicating with the lithium thin film, and for example, -15- may be selected from among Li2O, Li3N, Al2O3, ZrO2, SiO2, CeO2, Al2TiO5, oxy-sulfide glass and combinations thereof. The protection structure may be prepared by, for example, preparing a frame with an organic polymer portion following a wire rod portion 5 that forms a meshform of a negative electrode current collector, and then filling the space therebetween with an inorganic material, and as the method, methods such as electron beam deposition, sputtering and thermal deposition may be used. 10 Fig. 2 and Fig. 3 are a perspective view and a step mimetic diagram describing a method for manufacturing a negative electrode for a lithium secondary battery according to the present disclosure. Inserting a lithium thin film (200) to an opening (110) that a mesh-type 15 anode current collector (100) forms may be accomplished by placing the lithium thin film (200) on the negative electrode current collector (100) and performing a rolling process. More specifically, the present disclosure provides a method for manufacturing a negative 20 electrode for a lithium secondary battery comprising i) preparing a mesh-type anode current collector (100); ii) placing a lithium thin film (200) on the negative electrode current collector (100); and iii) rolling the lithium thin film (200) and the negative electrode 25 current collector (100) to insert the lithium thin film -16- (200) to an opening (110) of the negative electrode current collector (100). The rolling may be carried out using common methods, and for example, the lithium thin film (200) may be inserted to an opening (110) of the 5 negative electrode current collector (100) using a method of compressing with a pressure roller (300) provided in a roll press and the like, or compressing over the whole electrode surface using a plate-like press. 10 Particularly, in such a rolling process, a pressure of 10 kg/cm2 to 100 ton/cm2 may be applied, and heating to a temperature of 100ºC to 200ºC may be carried out. Heat treatment at the above-mentioned temperature includes either heating while carrying out a rolling 15 process, or carrying out a rolling process while being heated before carrying out the rolling process. By controlling temperature and pressure conditions as above, the degree of lithium thin film insertion may be controlled, and preferably, the lithium thin film may be 20 rolled so as to satisfy the inserted portion thickness (d210) range described above. As for a lithium secondary battery according to the present disclosure, constitutions other than the structure and the properties of the negative electrode 25 described above may be prepared through known -17- technologies implemented by those skilled in the art, and will be specifically described below. A positive electrode according to the present disclosure may be prepared into a positive electrode form by forming film on a positive electrode 5 current collector using a composition comprising a positive electrode active material, a conductor and a binder. As the positive electrode active material, any one selected from the group consisting of LiCoO2, LiNiO2, 10 LiMnO2, LiMn2O4, Li(NiaCobMnc)O2 (0 Lithium foil having a thickness of 40 μm was placed on a copper mesh having a thickness of 25 μm (illustrated 15 in Fig. 4 and Fig. 5) as a negative electrode current collector, a pressure was applied so that 50% of the thicknesses of the lithium foil was inserted, and the result was roll pressed to prepare a negative electrode (illustrated in Fig. 6 and Fig. 7). 20 Cathode active material:conductor (carbon black):binder (KF9700) were formed as a film in a composition of 95.5:2.0:2.5 on aluminum foil having a thickness of 12 μm as a positive electrode current collector to prepare a positive electrode. 25 A separator coating SRS on both surfaces of a 8 μm -26- polyethylene (PE) material each to a thickness of 2.5 μm was used as a separator to prepare a secondary battery. FEC/DEC was used as an electrolyte, and a liquid electrolyte containing 1 M of LiPF6 and 0.5 wt% of additives was used to manufacture a 5 lithium secondary battery. A lithium secondary battery was manufactured in the same manner as in Example 1 except that lithium foil 10 having a thickness of 40 μm was placed on a copper mesh having a thickness of 25 μm (illustrated in Fig. 4 and Fig. 5) as the negative electrode current collector, and the thickness was controlled so that 40% of the thicknesses of the lithium foil was inserted. 15 A lithium secondary battery was manufactured in the same manner as in Example 1 except that lithium foil having a thickness of 40 μm was placed on a copper mesh having a thickness of 25 μm (illustrated in Fig. 4 and 20 Fig. 5) as the negative electrode current collector, and the thickness was controlled so that 30% of the thicknesses of the lithium foil was inserted. A lithium secondary battery was manufactured in the 25 same manner as in Example 1 except that lithium foil -27- having a thickness of 40 μm was placed on a copper mesh having a thickness of 25 μm (illustrated in Fig. 4 and Fig. 5) as the negative electrode current collector, and the thickness was controlled so that 20% of the thicknesses of the lithium 5 foil was inserted. A lithium secondary battery was manufactured in the same manner as in Example 1 except that lithium foil having a thickness of 40 μm was placed on a copper mesh 10 having a thickness of 25 μm (illustrated in Fig. 4 and Fig. 5) as the negative electrode current collector, and the thickness was controlled so that 10% of the thicknesses of the lithium foil was inserted. 15 A lithium secondary battery was manufactured in the same manner as in Example 1 except that copper foil having a thickness of 20 μm was used as the negative electrode current collector, and the rolling process of the negative electrode was not carried out. 20 For the lithium secondary batteries of Examples 1 to 5 and Comparative Example 1, a charge and discharge test was carried out under a condition of 0.1 C charge/0.1 C discharge, and the results are shown in Fig. 25 8 and summarized in the following Table 1. -28- 【Table 1】 Charge Capacity (mAh/g) Discharge Capacity (mAh/g) Efficiency (%) Example 1 225 210 93.22 Example 2 224 209 93.30 Example 3 225 209 92.88 Example 4 226 210 92.92 Example 5 224 209 93.30 Comparative Example 1 226 210 93.14 As shown in Table 1, initial charge and discharge capacity and efficiency of the 5 lithium secondary batteries of Examples 1 to 5 and Comparative Example 1 were similar. Fig. 9 and table 2 shows data comparing rate 10 performance of the lithium secondary batteries using the negative electrodes according to Examples 1 to 5 and Comparative Example 1 of the present disclosure. 【Table 2】 -29- Capacity Retention (%, Compared to 0.1 C) Discharge C-rate Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 0.5 C/0.1 C 92.50 92.30 92.10 91.95 91.80 91.37 1.0 C/0.1 C 85.05 83.55 82.10 80.05 78.05 75.46 2.0 C/0.1 C 66.40 63.35 60.20 55.05 51.05 43.63 3.0 C/0.1 C 44.60 38.66 32.55 27.05 22.10 13.99 The capacity retention rate was identified while fixing the charge rate and increasing the discharge Crate. The results described in the table indicates capacity expression with respect to 0.1 5 C, and the 0.1 C capacity was identically expressed in the lithium secondary batteries of Example 1 and Comparative Example 1. However, when increasing the discharge rate, the lithium secondary batteries of Examples 1 to 5 had a 10 higher capacity retention rate compared to the lithium secondary battery of Comparative Example 1. The difference became larger as the C-rate increased. When discharging with 2.0 C, the lithium secondary battery of Example 1 exhibited a capacity retention rate of 66%, 15 however, the lithium secondary battery of Comparative Example 1 had a capacity retention ratio of 44%, and the difference was approximately 22%. The lithium secondary batteries of Examples 2 to 5 also exhibited a superior -30- capacity retention rate compared to Comparative Example 1. In other words, when using mesh Cu, the contact area between Li metal and Cu increases, and resistance inside a cell is reduced as electrical conductivity becomes superior. Besides, cell performance 5 is enhanced while dendrite formation is induced inside empty space of an opening described above. When using general Cu foil, interfacial resistance between a separator and Li metal increases while dendrite is formed on the Li metal 10 surface touching the separator when charged and discharged, however, when using Mesh Cu, a phenomenon of increasing interfacial resistance between Li metal and a separator may be prevented even after charge and discharge as dendrite formation is induced inside empty 15 space of an opening. The negative electrode for a lithium secondary battery in which a part of a lithium thin film is inserted to a negative electrode current collector according to the present disclosure is capable of 20 enhancing performance of the lithium secondary battery by increasing a surface area of contact between the lithium thin film and the negative electrode current collector, and is capable of enhancing safety of the lithium secondary battery by preventing lithium dendrite growth 25 when driving the lithium secondary battery through -31- uniformizing electron distribution inside the lithium electrode. In addition, volume expansion of a cell can be prevented as lithium dendrite formation is induced in empty space left while a part of the lithium 5 thin film is inserted to an opening of the negative electrode current collector. Furthermore, when compared to existing simple joint structures, an inserted portion of the lithium thin film 10 and an opening of the negative electrode current collector are connected in a fitted manner and adhesion efficiency can be enhanced therefrom, and therefore, stripping of the negative electrode current collector and the lithium thin film can be prevented while charging and 15 discharging the battery. What is claimed is: 1. A negative electrode for a lithium secondary battery comprising: a mesh-type anode current collector 5 formed with a wire rod portion and an opening; and a lithium thin film formed with an inserted portion inserted to the opening of the negative electrode current collector and a non-inserted portion that is not inserted. 10 2. The negative electrode for a lithium secondary battery of Claim 1, wherein a thickness of the inserted portion of the lithium thin film is 20% to 60% of a thickness of the whole lithium thin film. 15 3. The negative electrode for a lithium secondary battery of Claim 1, wherein a thickness of the noninserted portion of the lithium thin film is 40% to 80% of a thickness of the whole lithium thin film. 20 4. The negative electrode for a lithium secondary battery of Claim 1, wherein a thickness of the lithium thin film is from 10 μm to 800 μm. 25 5. The negative electrode for a lithium secondary -33- battery of Claim 1, wherein the wire rod portion of the negative electrode current collector has a line width of 50 μm to 500 μm and line spacing of 100 μm to 1 mm. 6. The negative electrode for a 5 lithium secondary battery of Claim 1, wherein a shape of the opening of the negative electrode current collector is circular, oval or polygonal. 10 7. The negative electrode for a lithium secondary battery of Claim 1, wherein an aperture ratio of the negative electrode current collector is from 20% to 80%. 8. The negative electrode for a lithium secondary 15 battery of Claim 1, wherein a thickness of the negative electrode current collector is from 3 μm to 500 μm. 9. The negative electrode for a lithium secondary battery of Claim 1, wherein the negative electrode 20 current collector is one or more types selected from the group consisting of copper, aluminum, stainless steel, zinc, titanium, silver, palladium, nickel, iron, chromium, alloys thereof and combinations thereof. 25 10. A negative electrode for a lithium secondary -34- battery comprising: a mesh-type anode current collector formed with a wire rod portion and an opening; a lithium thin film formed with an inserted portion inserted to the opening of the negative 5 electrode current collector and a non-inserted portion that is not inserted; and a protection structure formed on a surface opposite to the lithium thin film that the negative electrode 10 current collector faces, wherein the protection structure is formed with an organic polymer portion and an inorganic material portion, and the organic polymer portion is formed on a surface opposite to the lithium thin film that the wire rod 15 portion adjoins and the inorganic material portion is formed on a surface opposite to the lithium thin film corresponding to the opening. 11. The negative electrode for a lithium secondary 20 battery of Claim 10, wherein the organic polymer portion is selected from among polyvinyl alcohol, polyisobutylene, epoxy, polyethylene, polypropylene, polytetrafluoroethylene and combinations thereof. 25 12. The negative electrode for a lithium secondary -35- battery of Claim 10, wherein the inorganic material portion is selected from among Li2O, Li3N, Al2O3, ZrO2, SiO2, CeO2, Al2TiO5, oxy-sulfide glass and combinations thereof. 5 13. A method for manufacturing a negative electrode for a lithium secondary battery comprising: i) preparing a mesh-type anode current collector; ii) placing lithium thin film on the negative electrode current 10 collector; and iii) rolling the lithium thin film and the negative electrode current collector to insert the lithium thin film to an opening of the negative electrode current collector. 15 14. The method for manufacturing the negative electrode for a lithium secondary battery of Claim 13, wherein the rolling in iii) is applying a pressure of 10 kg/cm2 to 100 ton/cm2. 20 15. The method for manufacturing the negative electrode for a lithium secondary battery of Claim 13, wherein the rolling in iii) is heating to a temperature of 100ºC to 200 ºC. 25 16. A lithium secondary battery comprising the negative electrode of any one of Claims 1 to 12.

Documents

Application Documents

# Name Date
1 201714026257-ASSIGNMENT WITH VERIFIED COPY [01-12-2022(online)].pdf 2022-12-01
1 201714026257-STATEMENT OF UNDERTAKING (FORM 3) [24-07-2017(online)].pdf 2017-07-24
2 201714026257-FORM-16 [01-12-2022(online)].pdf 2022-12-01
2 201714026257-POWER OF AUTHORITY [24-07-2017(online)].pdf 2017-07-24
3 201714026257-POWER OF AUTHORITY [01-12-2022(online)].pdf 2022-12-01
3 201714026257-FORM 1 [24-07-2017(online)].pdf 2017-07-24
4 201714026257-IntimationOfGrant04-05-2022.pdf 2022-05-04
4 201714026257-FIGURE OF ABSTRACT [24-07-2017(online)].pdf 2017-07-24
5 201714026257-PatentCertificate04-05-2022.pdf 2022-05-04
5 201714026257-DRAWINGS [24-07-2017(online)].pdf 2017-07-24
6 201714026257-Written submissions and relevant documents [30-03-2022(online)].pdf 2022-03-30
6 201714026257-DRAWINGS [24-07-2017(online)].pdf 2017-07-24
7 201714026257-DECLARATION OF INVENTORSHIP (FORM 5) [24-07-2017(online)].pdf 2017-07-24
7 201714026257-Correspondence to notify the Controller [10-03-2022(online)].pdf 2022-03-10
8 201714026257-FORM-26 [10-03-2022(online)].pdf 2022-03-10
8 201714026257-COMPLETE SPECIFICATION [24-07-2017(online)].pdf 2017-07-24
9 201714026257-US(14)-HearingNotice-(HearingDate-17-03-2022).pdf 2022-02-16
9 abstract.jpg 2017-07-28
10 201714026257-FORM 3 [21-04-2020(online)].pdf 2020-04-21
10 201714026257-Power of Attorney-040817.pdf 2017-08-16
11 201714026257-ABSTRACT [14-04-2020(online)].pdf 2020-04-14
11 201714026257-Correspondence-040817.pdf 2017-08-16
12 201714026257-CLAIMS [14-04-2020(online)].pdf 2020-04-14
12 201714026257-Proof of Right (MANDATORY) [09-01-2018(online)].pdf 2018-01-09
13 201714026257-Certified Copy of Priority Document (MANDATORY) [10-01-2018(online)].pdf 2018-01-10
13 201714026257-COMPLETE SPECIFICATION [14-04-2020(online)].pdf 2020-04-14
14 201714026257-CORRESPONDENCE [14-04-2020(online)].pdf 2020-04-14
14 201714026257-FORM 3 [16-01-2018(online)].pdf 2018-01-16
15 201714026257-DRAWING [14-04-2020(online)].pdf 2020-04-14
15 201714026257-OTHERS-120118.pdf 2018-01-18
16 201714026257-Correspondence-120118.pdf 2018-01-18
16 201714026257-FER_SER_REPLY [14-04-2020(online)].pdf 2020-04-14
17 201714026257-OTHERS-120118..pdf 2018-02-13
17 201714026257-OTHERS [14-04-2020(online)].pdf 2020-04-14
18 201714026257-Correspondence-120118..pdf 2018-02-13
18 201714026257-FER.pdf 2019-12-24
19 201714026257-FORM 18 [12-10-2018(online)].pdf 2018-10-12
19 201714026257-RELEVANT DOCUMENTS [16-07-2018(online)].pdf 2018-07-16
20 201714026257-Changing Name-Nationality-Address For Service [16-07-2018(online)].pdf 2018-07-16
21 201714026257-FORM 18 [12-10-2018(online)].pdf 2018-10-12
21 201714026257-RELEVANT DOCUMENTS [16-07-2018(online)].pdf 2018-07-16
22 201714026257-Correspondence-120118..pdf 2018-02-13
22 201714026257-FER.pdf 2019-12-24
23 201714026257-OTHERS [14-04-2020(online)].pdf 2020-04-14
23 201714026257-OTHERS-120118..pdf 2018-02-13
24 201714026257-FER_SER_REPLY [14-04-2020(online)].pdf 2020-04-14
24 201714026257-Correspondence-120118.pdf 2018-01-18
25 201714026257-OTHERS-120118.pdf 2018-01-18
25 201714026257-DRAWING [14-04-2020(online)].pdf 2020-04-14
26 201714026257-CORRESPONDENCE [14-04-2020(online)].pdf 2020-04-14
26 201714026257-FORM 3 [16-01-2018(online)].pdf 2018-01-16
27 201714026257-Certified Copy of Priority Document (MANDATORY) [10-01-2018(online)].pdf 2018-01-10
27 201714026257-COMPLETE SPECIFICATION [14-04-2020(online)].pdf 2020-04-14
28 201714026257-CLAIMS [14-04-2020(online)].pdf 2020-04-14
28 201714026257-Proof of Right (MANDATORY) [09-01-2018(online)].pdf 2018-01-09
29 201714026257-ABSTRACT [14-04-2020(online)].pdf 2020-04-14
29 201714026257-Correspondence-040817.pdf 2017-08-16
30 201714026257-FORM 3 [21-04-2020(online)].pdf 2020-04-21
30 201714026257-Power of Attorney-040817.pdf 2017-08-16
31 201714026257-US(14)-HearingNotice-(HearingDate-17-03-2022).pdf 2022-02-16
31 abstract.jpg 2017-07-28
32 201714026257-COMPLETE SPECIFICATION [24-07-2017(online)].pdf 2017-07-24
32 201714026257-FORM-26 [10-03-2022(online)].pdf 2022-03-10
33 201714026257-Correspondence to notify the Controller [10-03-2022(online)].pdf 2022-03-10
33 201714026257-DECLARATION OF INVENTORSHIP (FORM 5) [24-07-2017(online)].pdf 2017-07-24
34 201714026257-DRAWINGS [24-07-2017(online)].pdf 2017-07-24
34 201714026257-Written submissions and relevant documents [30-03-2022(online)].pdf 2022-03-30
35 201714026257-DRAWINGS [24-07-2017(online)].pdf 2017-07-24
35 201714026257-PatentCertificate04-05-2022.pdf 2022-05-04
36 201714026257-FIGURE OF ABSTRACT [24-07-2017(online)].pdf 2017-07-24
36 201714026257-IntimationOfGrant04-05-2022.pdf 2022-05-04
37 201714026257-POWER OF AUTHORITY [01-12-2022(online)].pdf 2022-12-01
37 201714026257-FORM 1 [24-07-2017(online)].pdf 2017-07-24
38 201714026257-POWER OF AUTHORITY [24-07-2017(online)].pdf 2017-07-24
38 201714026257-FORM-16 [01-12-2022(online)].pdf 2022-12-01
39 201714026257-STATEMENT OF UNDERTAKING (FORM 3) [24-07-2017(online)].pdf 2017-07-24
39 201714026257-ASSIGNMENT WITH VERIFIED COPY [01-12-2022(online)].pdf 2022-12-01

Search Strategy

1 2019-12-2315-32-50_23-12-2019.pdf

ERegister / Renewals

3rd: 30 May 2022

From 24/07/2019 - To 24/07/2020

4th: 30 May 2022

From 24/07/2020 - To 24/07/2021

5th: 30 May 2022

From 24/07/2021 - To 24/07/2022

6th: 30 May 2022

From 24/07/2022 - To 24/07/2023

7th: 28 Jun 2023

From 24/07/2023 - To 24/07/2024

8th: 02 Jul 2024

From 24/07/2024 - To 24/07/2025

9th: 27 Jun 2025

From 24/07/2025 - To 24/07/2026