WO2015012487A1 - 가스 투과막을 포함하는 리튬 이차전지 - Google Patents
가스 투과막을 포함하는 리튬 이차전지 Download PDFInfo
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- WO2015012487A1 WO2015012487A1 PCT/KR2014/005107 KR2014005107W WO2015012487A1 WO 2015012487 A1 WO2015012487 A1 WO 2015012487A1 KR 2014005107 W KR2014005107 W KR 2014005107W WO 2015012487 A1 WO2015012487 A1 WO 2015012487A1
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- WIPO (PCT)
- Prior art keywords
- case
- secondary battery
- lithium secondary
- permeable membrane
- battery
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000012528 membrane Substances 0.000 title claims abstract description 35
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- 150000004820 halides Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
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- 150000003949 imides Chemical class 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
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- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- QEXMICRJPVUPSN-UHFFFAOYSA-N lithium manganese(2+) oxygen(2-) Chemical group [O-2].[Mn+2].[Li+] QEXMICRJPVUPSN-UHFFFAOYSA-N 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- VROAXDSNYPAOBJ-UHFFFAOYSA-N lithium;oxido(oxo)nickel Chemical group [Li+].[O-][Ni]=O VROAXDSNYPAOBJ-UHFFFAOYSA-N 0.000 description 1
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 1
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
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- 235000020638 mussel Nutrition 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 150000005181 nitrobenzenes Chemical class 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
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- 229910000077 silane Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
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- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 235000015041 whisky Nutrition 0.000 description 1
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Images
Classifications
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- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M50/10—Primary casings; Jackets or wrappings
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- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- 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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Definitions
- the present invention relates to a lithium secondary battery comprising a gas permeable membrane.
- a secondary battery is composed of an electrode assembly composed of a positive electrode, a negative electrode, and a separator interposed between the positive electrode and the negative electrode, in a stacked or wound state, embedded in a battery case of a metal can or laminate sheet, and then injected or impregnated with an electrolyte.
- one of the main research problems in a pouch type secondary battery including a high voltage battery cell is to prevent performance degradation of the battery due to gas leakage during activation and use of the battery.
- the secondary battery generates a large amount of gas during the activation process, and the generated gas damages the sealing portion of the battery case and leaks to the outside. Subsequently, the electrolyte leaks to the damaged sealing site, thereby causing a problem of deterioration of the performance of the battery.
- the gas is generated while the electrolyte is decomposed due to abnormal operation of the battery such as an overcharge state exceeding the allowable current and voltage, exposure to high temperature, and the like, the battery may be damaged as described above. Occurs.
- the present invention aims to solve the problems of the prior art as described above and the technical problems that have been requested from the past.
- An object of the present invention is to provide a lithium secondary battery that can discharge the gas generated during the activation process and use of the battery to the outside of the battery, and prevent the electrolyte from leaking.
- a battery case including a space portion in which the electrolyte and the electrode laminate are embedded, and a sealing portion surrounding the space portion;
- the lithium secondary battery according to the present invention includes a gas permeable membrane, thereby discharging the gas generated during the activation process and use of the battery to the outside of the battery and preventing the electrolyte from leaking.
- the gas permeable membrane may be provided in the space part.
- the gas permeable membrane may be liquid impermeable. Thus, leakage of the electrolyte can be prevented.
- the gas permeable membrane may have a pore size within a range of 2.0 kPa or more and 10 kPa or less.
- the pore size is less than 2.0 mm 3, the gas may not be sufficiently discharged to the outside.
- the pore size exceeds 10 mm 3, the electrolyte may leak. Therefore, the appropriate pore size of the gas permeable membrane may be in the above range.
- the gas permeable membrane may be a selective gas permeable membrane that selectively permeates oxygen (O 2 ) and carbon dioxide (CO 2 ).
- the selective gas permeable membrane may have a pore size within a range of 2.0 kPa or more and 10 kPa or less.
- the pore size is less than 2.0 mm 3, oxygen and carbon dioxide may not be sufficiently discharged to the outside.
- the pore size exceeds 10 kPa, the electrolyte may leak in addition to oxygen and carbon dioxide. Therefore, the appropriate pore size of the selective gas permeable membrane may be in the above range.
- the gas permeable membrane may be made of polyethylene terephthalate (PET), but is not limited thereto.
- the gas permeable membrane may be provided between the electrode stack and the sealing part in a vertical cross section.
- the gas permeable membrane may be divided into a space portion in a vertical cross section.
- the gas permeable membrane may penetrate the sealing part.
- the battery case may include a first case and a second case coupled to the first case to seal the battery case, and the gas permeable membrane may be interposed on a joining surface of the first case and the second case. have.
- the present invention also includes a first case and a second case coupled to the first case to seal the battery case, wherein the first case and the second case include an inner sealant layer, a barrier layer, and an outer coating layer. It is made of a laminate sheet, wherein at least one of the first case and the second case, a battery case, characterized in that all or part of the laminate sheet made of porous.
- the porous laminate sheet may include a porous inner sealant layer, a porous barrier layer, and a porous outer coating layer, and the pore size may be in a range of 2.0 GPa or more and 10 GPa or less.
- the inner sealant layer is made of unstretched polypropylene
- the barrier layer is made of metal
- the outer coating layer may be made of polyethylene terephthalate, but is not limited thereto.
- the porous inner sealant layer is made of porous unstretched polypropylene
- the porous barrier layer is made of porous metal
- the porous outer coating layer may be made of porous polyethylene terephthalate, but these It is not limited only.
- the second case may extend from a portion of the first case.
- the first case and the second case may be formed of independent members separated from each other.
- the present invention also provides a battery case
- An electrode laminate including one or more anodes, one or more cathodes, and one or more separators, wherein the anode, separator, and cathode include a stacked structure in which a separator is interposed between the anode and the cathode;
- the lithium secondary battery may include, as a cathode active material, at least one lithium transition metal oxide selected from a compound represented by the following Formula (1) and a compound represented by the following Formula (2).
- M is at least one element selected from the group consisting of Al, Mg, Ni, Co, Fe, Cr, V, Ti, Cu, B, Ca, Zn, Zr, Nb, Mo, Sr, Sb, W, Ti and Bi Is;
- A is -1 or -divalent one or more anions.
- M is at least one selected from the group consisting of Ni, Ti, Co, Al, Cu, Fe, Mg, B, Cr, Zr, Zn and bicycle transition metals;
- A is at least one selected from the group consisting of anions of PO 4 , BO 3 , CO 3 , F and NO 3 ,
- the lithium secondary battery may include a carbon-based material and / or Si as a negative electrode active material.
- the lithium secondary battery may be a lithium ion battery, may be a lithium ion polymer battery, may be a lithium polymer battery.
- the electrode may be an anode or a cathode, and may be manufactured by a manufacturing method including the following processes.
- Preparing a binder solution by dispersing or dissolving the binder in a solvent
- Preparing an electrode slurry by mixing the binder solution with an electrode active material and a conductive material;
- the method may further include drying the rolled electrode.
- the binder solution manufacturing process is a process of preparing a binder solution by dispersing or dissolving a binder in a solvent.
- the binder may be all binders known in the art, and specifically, a fluororesin binder, styrene-butadiene, including polyvinylidene fluoride (PVdF) or polytetrafluoroethylene (PTFE) Rubber, acrylonitrile-butadiene rubber, rubber-based binder including styrene-isoprene rubber, carboxymethylcellulose (CMC), starch, hydroxypropyl cellulose, cellulose-based binder including regenerated cellulose, poly It may be a mixture or copolymer of one or two or more binders selected from the group consisting of alcohol-based binders, polyethylene, polyolefin-based binders including polypropylene, polyimide-based binders, polyester-based binders, mussel adhesives, and silane-based binders. .
- the solvent may be selectively used according to the type of the binder.
- an organic solvent such as isopropyl alcohol, N-methylpyrrolidone (NMP), acetone, water, and the like may be used.
- PVdF may be dispersed / dissolved in NMP (N-methyl pyrrolidone) to prepare a binder solution for the positive electrode, and SBR (Styrene-Butadiene Rubber) / CMC (Carboxy Methyl Cellulose) may be used. It is also possible to prepare a binder solution for the negative electrode by dispersing / dissolving in.
- NMP N-methyl pyrrolidone
- SBR Styrene-Butadiene Rubber
- CMC Carboxy Methyl Cellulose
- An electrode slurry may be prepared by mixing / dispersing an electrode active material and a conductive material in the binder solution.
- the electrode slurry thus prepared may be transferred to a storage tank and stored until the coating process.
- an electrode slurry can be stirred continuously.
- the electrode active material may be a positive electrode active material or a negative electrode active material.
- the electrode active material may include a lithium metal oxide having a spinel structure represented by the following formula (1) as a cathode active material.
- M is at least one element selected from the group consisting of Al, Mg, Ni, Co, Fe, Cr, V, Ti, Cu, B, Ca, Zn, Zr, Nb, Mo, Sr, Sb, W, Ti and Bi Is;
- A is -1 or -divalent one or more anions.
- the maximum substitution amount of A may be less than 0.2 mol%, and in a specific embodiment of the present invention, A may be at least one anion selected from the group consisting of halogen, S and N, such as F, Cl, Br, and I.
- the bonding strength with the transition metal is excellent and the structural transition of the compound is prevented, so that the life of the battery can be improved.
- the amount of substitution of the anion A is too large (t0.2), it is not preferable because the life characteristics are lowered due to the incomplete crystal structure.
- the oxide of Formula (1) may be a lithium metal oxide represented by the following Formula (2).
- the lithium metal oxide may be LiNi 0.5 Mn 1.5 O 4 or LiNi 0.4 Mn 1.6 O 4 .
- the negative electrode active material may be, for example, carbon such as hardly graphitized carbon or graphite carbon; Li x Fe 2 O 3 (0 ⁇ x ⁇ 1), Li x WO 2 (0 ⁇ x ⁇ 1), Sn x Me 1-x Me ' y O z (Me: Mn, Fe, Pb, Ge; Me' Metal complex oxides such as Al, B, P, Si, Group 1, Group 2, Group 3 elements of the periodic table, halogen, 0 ⁇ x ⁇ 1; 1 ⁇ y ⁇ 3; 1 ⁇ z ⁇ 8); Lithium metal; Lithium alloys; Silicon-based alloys; Tin-based alloys; SnO, SnO 2 , PbO, PbO 2 , Pb 2 O 3 , Pb 3 O 4 , Sb 2 O 3 , Sb 2 O 4 , Sb 2 O 5 , GeO, GeO 2 , Bi 2 O 3 , Bi 2 O 4 , Metal oxides such as Bi 2 O 5 ;
- the electrode active material may include a lithium metal oxide as a negative electrode active material, and the lithium metal oxide may be represented by the following general formula (3).
- M ' is at least one element selected from the group consisting of Ti, Sn, Cu, Pb, Sb, Zn, Fe, In, Al and Zr;
- a and b are 0.1 ⁇ a ⁇ 4; Determined according to the oxidation number of M 'in the range of 0.2 ⁇ b ⁇ 4;
- c is determined depending on the oxidation number in the range of 0 ⁇ c ⁇ 0.2;
- A is -1 or -divalent one or more anions.
- the oxide of formula (3) may be represented by the following formula (4).
- the lithium metal oxide may be Li 0.8 Ti 2.2 O 4 , Li 2.67 Ti 1.33 O 4 , LiTi 2 O 4 , Li 1.33 Ti 1.67 O 4 , Li 1.14 Ti 1.71 O 4, or the like. However, it is not limited only to these.
- the lithium metal oxide may be Li 1.33 Ti 1.67 O 4 or LiTi 2 O 4 .
- Li 1.33 Ti 1.67 O 4 has a spinel structure with little change in crystal structure during charge and discharge and excellent reversibility.
- the lithium metal oxide can be produced by a production method known in the art, for example, can be produced by a solid phase method, hydrothermal method, sol-gel method and the like.
- the lithium metal oxide may be in the form of secondary particles in which primary particles are aggregated.
- the particle diameter of the secondary particles may be 200 nm to 30 ⁇ m.
- the particle diameter of the secondary particles is less than 200 nm, since a large amount of solvent is required in the negative electrode slurry production process, productivity is lowered and it is not preferable because it is difficult to control the water content. If the particle diameter of the secondary particles is more than 30 ⁇ m, the diffusion rate of lithium ions is low, and thus it is difficult to realize high output, which is not preferable.
- the lithium metal oxide may be included in more than 50% by weight or less than 100% by weight relative to the weight of the entire negative electrode active material.
- the content of the lithium titanium oxide is 100% by weight based on the total weight of the negative electrode active material, it means a case in which the negative electrode active material is composed of only lithium titanium oxide.
- the conductive agent is not particularly limited as long as it has conductivity without causing chemical change in the battery.
- Examples of the conductive agent include graphite such as natural graphite and artificial graphite; Carbon blacks such as carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black, and summer black; Conductive fibers such as carbon fibers and metal fibers; Metal powders such as carbon fluoride powder, aluminum powder and nickel powder; Conductive whiskeys such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; Conductive materials such as polyphenylene derivatives and the like can be used.
- Filler may be selectively added to the electrode slurry as necessary.
- the filler is not particularly limited as long as it is a fibrous material without causing chemical change in the battery.
- examples of the filler include olefinic polymers such as polyethylene and polypropylene; Fibrous materials, such as glass fiber and carbon fiber, etc. can be used.
- the process of coating the electrode slurry on the current collector is a process of coating the electrode slurry on the current collector in a predetermined pattern and a constant thickness by passing through a coater head.
- the method of coating the electrode slurry on the current collector the method of distributing the electrode slurry on the current collector and then uniformly dispersed using a doctor blade, die casting, comma coating ), Screen printing, and the like.
- the electrode slurry may be bonded to the current collector by pressing or lamination after molding on a separate substrate.
- the current collector is not particularly limited as long as it has high conductivity without causing chemical change in the battery.
- the surface of copper, stainless steel, aluminum, nickel, titanium, calcined carbon, copper or stainless steel Surface-treated with carbon, nickel, titanium, silver, and the like, aluminum-cadmium alloy, and the like can be used.
- the positive electrode current collector may form fine concavities and convexities on the surface to strengthen the bonding strength of the positive electrode active material, and may be used in various forms such as a film, a sheet, a foil, a net, a porous body, a foam, and a nonwoven fabric.
- the positive electrode current collector may be a metal current collector including aluminum
- the negative electrode current collector may be a metal current collector including copper.
- the electrode current collector may be a metal foil, and may be an aluminum (Al) foil or a copper (Cu) foil.
- the drying process is a process of removing the solvent and water in the slurry to dry the slurry coated on the metal current collector, in a specific embodiment, is dried within 1 day in a vacuum oven of 50 to 200 °C.
- a cooling process may be further included, and the cooling process may be slow cooling to room temperature so that the recrystallized structure of the binder is well formed.
- the electrode may be compressed into a desired thickness by passing it between two hot-rolled rolls. This process is called a rolling process.
- the preheating process is a process of preheating the electrode before it is introduced into the roll in order to increase the compression effect of the electrode.
- the electrode after the rolling process is completed as described above may be dried within a day in a vacuum oven at 50 to 200 °C as a range satisfying the temperature of the melting point or more of the binder.
- the rolled electrode may be cut to a constant length and then dried.
- a cooling process may be further included, and the cooling process may be slow cooling to room temperature so that the recrystallized structure of the binder is well formed.
- the polymer membrane is a separator that separates between the positive electrode and the negative electrode.
- the solid electrolyte such as a polymer
- the solid electrolyte may also serve as the separator.
- the separator an insulating thin film having high ion permeability and mechanical strength is used.
- the pore diameter of the separator is generally from 0.01 to 10 mu m, and the thickness is generally from 5 to 300 mu m.
- olefin polymers such as chemical resistance and hydrophobic polypropylene; Sheet or nonwoven fabric made of glass fiber or polyethylene; Kraft paper or the like is used.
- Typical examples currently on the market include Celgard series (Celgard R 2400, 2300 (manufactured by Hoechest Celanese Corp.), polypropylene separator (manufactured by Ube Industries Ltd. or Pall RAI), and polyethylene series (Tonen or Entek).
- a gel polymer electrolyte may be coated on the separator to increase battery stability.
- Representative examples of such gel polymers include polyethylene oxide, polyvinylidene fluoride, polyacrylonitrile, and the like.
- the electrode stack may include a jelly-roll electrode assembly (or wound electrode assembly), a stacked electrode assembly (or a stacked electrode assembly), or a stack & folding electrode assembly having a structure known in the art.
- the stack & folding type electrode assembly is a method of folding or winding a separator sheet after arranging unit cells having a structure in which a separator is interposed between an anode and a cathode on a separator sheet. It can be understood as a concept including a stack & folding electrode assembly to be manufactured.
- the electrode laminate may include an electrode laminate having a structure in which any one of an anode and a cathode is laminated by a method such as thermal fusion in a state in which the anode and the cathode are laminated in a structure interposed between the separators.
- non-aqueous electrolyte a non-aqueous electrolyte, a solid electrolyte, an inorganic solid electrolyte, and the like are used.
- nonaqueous electrolyte examples include N-methyl-2-pyrrolidinone, propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate and ethylmethyl carbonate.
- organic solid electrolyte examples include polyethylene derivatives, polyethylene oxide derivatives, polypropylene oxide derivatives, phosphate ester polymers, polyedgetion lysine, polyester sulfides, polyvinyl alcohols, polyvinylidene fluorides, Polymers containing ionic dissociating groups and the like can be used.
- the lithium salt is a good material to be dissolved in the non-aqueous electrolyte, for example, LiCl, LiBr, LiI, LiClO 4 , LiBF 4 , LiB 10 Cl 10 , LiPF 6 , LiCF 3 SO 3 , LiCF 3 CO 2 , LiAsF 6, LiSbF 6, LiAlCl 4, CH 3 SO 3 Li, CF 3 SO 3 Li, LiSCN, LiC (CF 3 SO 2) 3, (CF 3 SO 2) 2 NLi, chloroborane lithium, lower aliphatic carboxylic acid lithium, 4 phenyl lithium borate, imide and the like can be used.
- LiCl, LiBr, LiI, LiClO 4 , LiBF 4 , LiB 10 Cl 10 LiPF 6 , LiCF 3 SO 3 , LiCF 3 CO 2 , LiAsF 6, LiSbF 6, LiAlCl 4, CH 3 SO 3 Li, CF 3 SO 3 Li, LiSCN, LiC (CF 3 SO 2) 3, (
- pyridine triethyl phosphite, triethanolamine, cyclic ether, ethylene diamine, n-glyme, hexaphosphate triamide, nitro Benzene derivatives, sulfur, quinone imine dyes, N-substituted oxazolidinones, N, N-substituted imidazolidines, ethylene glycol dialkyl ethers, ammonium salts, pyrroles, 2-methoxy ethanol, aluminum trichloride and the like may be added. .
- a halogen-containing solvent such as carbon tetrachloride or ethylene trifluoride may be further included, and in order to improve high temperature storage characteristics, a carbon dioxide gas may be further included, and fluoro-ethylene carbonate), propene sultone (PRS), and fluoro-propylene carbonate (FPC).
- the present invention also provides a battery pack including the lithium secondary battery as a unit cell.
- the present invention also provides a device using the battery pack as an energy source.
- the device may be selected from the group consisting of a mobile phone, a portable computer, a smartphone, a smart pad, a netbook, a light electronic vehicle (LEV), an electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, and a power storage device.
- a mobile phone a portable computer
- smartphone a smartphone
- smart pad a netbook
- a light electronic vehicle LUV
- an electric vehicle a hybrid electric vehicle
- a plug-in hybrid electric vehicle a power storage device.
- FIG. 1 is a schematic view of a lithium secondary battery according to one embodiment of the present invention.
- FIG. 2 is a schematic view of a battery case according to another embodiment of the present invention.
- FIG. 1 is a schematic diagram of a lithium secondary battery according to one embodiment of the present invention.
- the lithium secondary battery 10 includes an electrode stack 100, a battery case 200, a gas permeable membrane 300, and an electrolyte (not shown).
- the battery case 200 includes a space portion 210 and a sealing portion 220, and the electrode stack 100 is embedded in the space portion 210.
- the gas permeable membrane 300 is provided between the electrode stack 100 and the sealing portion 220. Therefore, the gas generated from the electrode stack 100 may be discharged to the gas permeable membrane 300 and then discharged to the outside of the battery through the sealing unit 220.
- the electrolyte since the electrolyte may not pass through the gas permeable membrane 300, the electrolyte may be prevented from leaking.
- FIG. 2 is a schematic view of a battery case according to another embodiment of the present invention.
- the battery case 20 includes a first case 21 and a second case 22.
- the second case 22 has a structure extending from the first case 21.
- the first case 21 and the second case 22 consist of a laminate sheet comprising an inner sealant layer 20A, a barrier layer 20B, and an outer cladding layer 20C, wherein the laminate sheet has a plurality of pores 20D.
- the lithium secondary battery according to the present invention includes a gas permeable membrane, thereby discharging the gas generated during the activation process and use of the battery to the outside of the battery and preventing the electrolyte from leaking.
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Abstract
Description
Claims (23)
- 전해질;전극 적층체;상기 전해질과 상기 전극 적층체를 내장하는 공간부와 상기 공간부를 둘러싸고 있는 밀봉부를 포함하는 전지 케이스; 및가스 투과막;을 포함하는 것을 특징으로 하는 리튬 이차전지.
- 제 1 항에 있어서, 상기 가스 투과막은, 상기 공간부에 설치되는 것을 특징으로 하는 리튬 이차전지.
- 제 1 항에 있어서, 상기 가스 투과막은, 액체 비 투과성인 것을 특징으로 하는 리튬 이차전지.
- 제 3 항에 있어서, 상기 가스 투과막은, 기공의 크기가 2.0 Å 이상 내지 10 Å 이하의 범위 내인 것을 특징으로 하는 리튬 이차전지.
- 제 1 항에 있어서, 상기 가스 투과막은, 산소(O2)와 이산화탄소(CO2)를 선택적으로 투과하는 선택적 가스 투과막인 것을 특징으로 하는 리튬 이차전지.
- 제 5 항에 있어서, 상기 선택적 가스 투과막은, 기공의 크기가 2.0 Å 이상 내지 10 Å 이하의 범위 내인 것을 특징으로 하는 리튬 이차전지.
- 제 1 항에 있어서, 상기 가스 투과막은, 폴리에틸렌테레프탈레이트(PET)로 이루어진 것을 특징으로 하는 리튬 이차전지.
- 제 2 항에 있어서, 상기 가스 투과막은, 수직 단면상으로, 상기 전극 적층체와 밀봉부 사이에 설치되는 것을 특징으로 하는 리튬 이차전지.
- 제 8 항에 있어서, 상기 가스 투과막은, 수직 단면상으로, 공간부를 분할하는 것을 특징으로 하는 리튬 이차전지.
- 제 9 항에 있어서, 상기 가스 투과막은, 상기 밀봉부를 관통하는 것을 특징으로 하는 리튬 이차전지.
- 제 10 항에 있어서, 전지 케이스는, 제 1 케이스와 상기 제 1 케이스와 결합하여 전지 케이스를 밀봉하는 제 2 케이스를 포함하고, 상기 가스 투과막은, 상기 제 1 케이스와 상기 제 2 케이스의 접합면에 개재되는 것을 특징으로 하는 리튬 이차전지.
- 제 1 케이스와 상기 제 1 케이스와 결합하여 전지 케이스를 밀봉하는 제 2 케이스를 포함하고, 상기 제 1 케이스와 상기 제 2 케이스는, 내부 실란트 층, 베리어 층, 및 외부 피복층을 포함하는 라미네이트 시트로 이루어지며, 상기 제 1 케이스와 상기 제 2 케이스 중 하나 이상은, 전부 또는 일부가 다공성의 라미네이트 시트로 이루어진 것을 특징으로 하는 전지 케이스.
- 제 12 항에 있어서, 상기 다공성의 라미네이트 시트는, 다공성의 내부 실란트 층, 다공성의 베리어 층,및 다공성의 외부 피복층을 포함하고, 기공의 크기가 2.0 Å 이상 내지 10 Å 이하의 범위 내인 것을 특징으로 하는 전지 케이스.
- 제 12 항에 있어서, 상기 내부 실란트 층은, 무연신 폴리프로필렌으로 이루어지고, 상기 베리어 층은, 금속으로 이루어지며, 상기 외부 피복층은, 폴리에틸렌테레프탈레이트로 이루어지는 것을 특징으로 하는 전지 케이스.
- 제 13 항에 있어서, 상기 다공성의 내부 실란트 층은, 다공성의 무연신 폴리프로필렌으로 이루어지고, 상기 다공성의 베리어 층은, 다공성 금속으로 이루어지며, 상기 다공성의 외부 피복층은, 다공성의 폴리에틸렌테레프탈레이트로 이루어지는 것을 특징으로 하는 전지 케이스.
- 제 12 항에 있어서, 상기 제 2 케이스는, 상기 1 케이스의 일부로부터 연장되는 것을 특징으로 하는 전지 케이스.
- 제 12 항에 있어서, 상기 제 1 케이스와 상기 제 2 케이스는, 서로 분리된 독립된 부재인 것을 특징으로 하는 전지 케이스.
- 제 12 항에 따른 전지 케이스; 하나 이상의 양극, 하나 이상의 음극, 및 하나 이상의 분리막을 포함하고, 양극, 분리막, 음극이, 양극과 음극 사이에 분리막이 개재되도록 적층되어 있는 적층 구조를 포함하는 전극 적층체; 및 전해질;을 포함하는 것을 특징으로 하는 리튬 이차전지.
- 제 1 항 또는 제 18 항에 있어서, 양극 활물질로서, 하기 화학식 (1)로 표현되는 화합물 및 하기 화학식 (2)로 표현되는 화합물 중에서 선택된 하나 이상의 리튬 전이금속 산화물을 포함하고 있는 것을 특징으로 하는 리튬 이차전지:LixMyMn2-yO4-zAz (1)상기 식에서,0.9≤x≤1.2, 0<y<2, 0≤z<0.2이고;M은 Al, Mg, Ni, Co, Fe, Cr, V, Ti, Cu, B, Ca, Zn, Zr, Nb, Mo, Sr, Sb, W, Ti 및 Bi로 이루어진 군에서 선택되는 하나 이상의 원소이며;A는 -1 또는 -2가의 하나 이상의 음이온이다.(1-x)LiM'O2-yAy -xLi2MnO3-y'Ay' (2)상기 식에서,M'은 MnaMb이고;M은 Ni, Ti, Co, Al, Cu, Fe, Mg, B, Cr, Zr, Zn 및 2주기 전이금속들로 이루어진 군에서 선택되는 하나 이상이며;A는 PO4, BO3, CO3, F 및 NO3의 음이온으로 이루어진 군에서 선택되는 하나 이상이고,0<x<1; 0<y≤0.02; 0<y'≤0.02; 0.5≤a≤1.0; 0≤b≤0.5; a + b = 1 이다.
- 제 19 항에 있어서, 음극 활물질로서, 탄소계 물질, 및/또는 Si을 포함하는 것을 특징으로 하는 리튬 이차전지.
- 제 19 항에 있어서, 상기 리튬 이차전지는, 리튬 이온 전지, 리튬 이온 폴리머 전지, 또는 리튬 폴리머 전지인 것을 특징으로 하는 리튬 이차전지.
- 제 1 항 또는 제 18항에 따른 리튬 이차전지를 포함하는 것을 특징으로 하는 전지팩.
- 제 22 항에 따른 전지팩을 에너지원으로 사용하는 디바이스.
Priority Applications (4)
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US14/769,348 US10103372B2 (en) | 2013-07-25 | 2014-06-11 | Lithium secondary battery including gas permeable membrane |
CN201480019723.4A CN105122534B (zh) | 2013-07-25 | 2014-06-11 | 包含气体透过膜的锂二次电池 |
JP2015560127A JP6430410B2 (ja) | 2013-07-25 | 2014-06-11 | ガス透過膜を含むリチウム二次電池 |
EP14830351.4A EP2945214B1 (en) | 2013-07-25 | 2014-06-11 | Lithium secondary battery including gas permeable membrane |
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KR10-2013-0088011 | 2013-07-25 | ||
KR1020130088011A KR101595740B1 (ko) | 2013-07-25 | 2013-07-25 | 가스 투과막을 포함하는 리튬 이차전지 |
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JP (2) | JP6430410B2 (ko) |
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KR102033746B1 (ko) * | 2015-09-15 | 2019-10-17 | 주식회사 엘지화학 | 다공성 나노 소재를 포함하는 내부 실란트층을 포함하는 이차전지용 케이스 및 이를 포함하는 리튬 이차전지 |
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JP2017010946A (ja) | 2017-01-12 |
CN105122534A (zh) | 2015-12-02 |
JP6509179B2 (ja) | 2019-05-08 |
CN105122534B (zh) | 2018-09-18 |
KR101595740B1 (ko) | 2016-02-22 |
KR20150012469A (ko) | 2015-02-04 |
JP2016511930A (ja) | 2016-04-21 |
US20160156007A1 (en) | 2016-06-02 |
US10103372B2 (en) | 2018-10-16 |
EP2945214B1 (en) | 2021-04-07 |
EP2945214A4 (en) | 2017-02-15 |
JP6430410B2 (ja) | 2018-11-28 |
EP2945214A1 (en) | 2015-11-18 |
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