WO2011136553A2 - 이차전지용 양극 활물질 - Google Patents
이차전지용 양극 활물질 Download PDFInfo
- Publication number
- WO2011136553A2 WO2011136553A2 PCT/KR2011/003075 KR2011003075W WO2011136553A2 WO 2011136553 A2 WO2011136553 A2 WO 2011136553A2 KR 2011003075 W KR2011003075 W KR 2011003075W WO 2011136553 A2 WO2011136553 A2 WO 2011136553A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- active material
- positive electrode
- cathode active
- lithium
- secondary battery
- Prior art date
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- 239000006182 cathode active material Substances 0.000 title claims abstract description 12
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 19
- 150000003624 transition metals Chemical class 0.000 claims abstract description 19
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims description 24
- 239000007774 positive electrode material Substances 0.000 claims description 19
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 229910052748 manganese Inorganic materials 0.000 claims description 8
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- -1 for example Chemical class 0.000 description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 15
- 239000011572 manganese Substances 0.000 description 9
- 230000008859 change Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
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- 239000006258 conductive agent Substances 0.000 description 7
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 239000011149 active material Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 239000007784 solid electrolyte Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
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- 159000000002 lithium salts Chemical class 0.000 description 4
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- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 3
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- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 description 3
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- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 2
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- 239000006229 carbon black Substances 0.000 description 2
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- 239000002388 carbon-based active material Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
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- 229910052731 fluorine Inorganic materials 0.000 description 2
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
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- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229910003480 inorganic solid Inorganic materials 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 150000002642 lithium compounds Chemical class 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 229910021382 natural graphite Inorganic materials 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000011356 non-aqueous organic solvent Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
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- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
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- 239000000843 powder Substances 0.000 description 2
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- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 2
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical compound FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 1
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
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- LECKFEZRJJNBNI-UHFFFAOYSA-N 4-fluoro-5-methyl-1,3-dioxolan-2-one Chemical compound CC1OC(=O)OC1F LECKFEZRJJNBNI-UHFFFAOYSA-N 0.000 description 1
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- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
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- 229910013043 Li3PO4-Li2S-SiS2 Inorganic materials 0.000 description 1
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- 229910012797 Li3PO4—Li2S—SiS2 Inorganic materials 0.000 description 1
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- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
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- 150000003863 ammonium salts Chemical class 0.000 description 1
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- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
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- 238000005096 rolling process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000002409 silicon-based active material Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 229920005608 sulfonated EPDM Polymers 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 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
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 235000015041 whisky Nutrition 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60L—PROPULSION OF ELECTRICALLY-PROPELLED VEHICLES; SUPPLYING ELECTRIC POWER FOR AUXILIARY EQUIPMENT OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRODYNAMIC BRAKE SYSTEMS FOR VEHICLES IN GENERAL; MAGNETIC SUSPENSION OR LEVITATION FOR VEHICLES; MONITORING OPERATING VARIABLES OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRIC SAFETY DEVICES FOR ELECTRICALLY-PROPELLED VEHICLES
- B60L50/00—Electric propulsion with power supplied within the vehicle
- B60L50/50—Electric propulsion with power supplied within the vehicle using propulsion power supplied by batteries or fuel cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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
-
- 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 positive electrode active material for secondary batteries, and more particularly, to a positive electrode active material for secondary batteries having a long life and storage characteristics and excellent safety by a specific element composition.
- lithium secondary batteries used in electric vehicles have high energy density and high power output in a short time, and must be able to be used for 10 years or more under severe conditions. Lifespan characteristics are inevitably required.
- Lithium ion secondary batteries used in conventional small batteries generally use a layered structure of lithium cobalt composite oxide for the positive electrode and a graphite-based material for the negative electrode.
- a lithium manganese composite oxide having a spinel structure composed of manganese having low cost and excellent safety may be suitable as a positive electrode of a lithium ion secondary battery for an electric vehicle.
- LiNi x Mn y Co z O 2 (x + y + z 1), which is a layered mixed metal oxide system, has been used, but it is not yet satisfactory. .
- surface treatment is attempted, but there is a problem in that a price increase, which is one of the biggest problems in the battery market such as an electric vehicle, is caused by the need for an additional manufacturing process.
- an object of the present invention is to solve the problems of the prior art as described above and the technical problems that have been requested from the past.
- the inventors of the present application prepare a positive electrode with a positive electrode active material having a special elemental composition, such as a compound of Formula 1, and including lithium in a transition metal layer, as described later.
- a positive electrode active material having a special elemental composition such as a compound of Formula 1, and including lithium in a transition metal layer, as described later.
- the cathode active material for a secondary battery according to the present invention is composed of one or two or more compounds selected from Chemical Formula 1 including lithium in the transition metal layer.
- M is a stable element in the six coordination structure, and is at least one element selected from one-cycle and two-cycle transition metals;
- the crystal structure is stabilized by the strong bonding force of P contained in the element composition and the oxidation number change of the transition metal by Li in the transition metal layer, thereby improving cycle characteristics and storage characteristics of the active material. It is thought to be.
- the content of P is too large, it may be difficult to improve the performance of the active material by preventing the crystallization of the positive electrode active material, so that it is preferably less than 0.1 as defined above, and more preferably 0 ⁇ x ⁇ 0.05.
- the content of Li in the transition metal layer is too high, a decrease in capacity may be caused, and thus the content range defined above is preferable, and more preferably 0.015 ⁇ 3x ⁇ y ⁇ 0.3.
- the content of oxygen (O) can be varied in the above condition range, i.e., -4x ⁇ z ⁇ 4x.
- M is a transition metal satisfying the above conditions, and may be, for example, one or two or more selected from Ni, Mn, Co, Cr, Fe, V, Zr, and the like, and preferably Ni and Mn. It may be a composition containing as an essential element and containing Co as an optional element. In this case, the content of Ni, Mn and Co may satisfy the conditions of the following formula (2).
- the transition metal (M) may be substituted with a small amount of metal or nonmetal elements, for example, Al, Mg, B, etc., which may have a six-coordination structure, in which case the amount of substitution is M 0.2 mol or less is preferable based on the total amount.
- oxygen (O) may also be substituted with other anions, for example, halogen elements such as F, Cl, Br, I, sulfur, chalcogenide compounds, nitrogen, and the like, in which case the substitution amount is oxygen (O). 0.1 mol or less is preferable based on the total amount.
- the positive electrode active material according to the present invention can be prepared by a method known in the art based on the composition of the formula.
- the mixed transition metal precursor may be prepared by various methods such as coprecipitation, followed by addition of lithium compounds such as lithium hydroxide and lithium carbonate and phosphorus compounds such as diammonium phosphate, followed by firing.
- a phosphorus compound such as diammonium phosphate may be added to prepare a mixed transition metal precursor including a phosphorus (P) component, and then fired together with a lithium compound to prepare the mixed transition metal precursor.
- the present invention also provides a cathode for a secondary battery comprising the cathode active material.
- Such a positive electrode may further include, as a positive electrode active material, a general lithium transition metal oxide that does not satisfy the above conditions in addition to the compound of Formula 1.
- a general lithium transition metal oxide that does not satisfy the above conditions in addition to the compound of Formula 1.
- Examples of such general lithium transition metal oxides include oxides composed of only one type of Ni, Co, and Mn, and oxides including two or more types thereof, and examples thereof include lithium transition metal oxides known in the art.
- the compound of Formula 1 may be included at least 30% by weight or more, preferably 50% by weight or more, based on the total weight of the active material.
- a mixture containing a conductive agent and a binder in the positive electrode active material as described above is mixed with a predetermined solvent such as water and NMP, for example, to form a slurry, and then the slurry is prepared on the positive electrode current collector. It may be prepared by applying to and then drying and rolling.
- the positive electrode mixture may further include at least one material selected from the group consisting of a viscosity modifier and a filler.
- the positive electrode current collector is generally made to a thickness of 3 to 500 ⁇ m. Such a positive electrode current collector is not particularly limited as long as it has conductivity without causing chemical change in the battery.
- the positive electrode current collector may be formed on a surface of stainless steel, aluminum, nickel, titanium, calcined carbon, or aluminum or stainless steel. The surface-treated with carbon, nickel, titanium, silver, etc. can be used.
- the current collector may form fine irregularities on its surface to increase the adhesion of the positive electrode active material, and may be in various forms such as a film, a sheet, a foil, a net, a porous body, a foam, and a nonwoven fabric.
- the conductive agent is a component for further improving the conductivity of the electrode active material, and may be added in an amount of 0.01 to 30 wt% based on the total weight of the electrode mixture.
- Such a 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.
- 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
- the binder is a component that assists in bonding the active material and the conductive agent to the current collector, and is generally added in an amount of 1 to 30 wt% based on the total weight of the mixture including the positive electrode active material.
- binders include polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene , Polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, styrene butylene rubber, fluorine rubber, various copolymers and the like.
- the viscosity modifier is a component that adjusts the viscosity of the electrode mixture so that the mixing process of the electrode mixture and the coating process on the current collector thereof can be easily added, up to 30% by weight based on the total weight of the electrode mixture.
- examples of such viscosity modifiers include carboxymethyl cellulose, polyvinylidene fluoride, and the like, but are not limited thereto.
- the solvent described above can serve as a viscosity modifier.
- the filler is optionally used as a component for inhibiting the expansion of the electrode, and is not particularly limited as long as it is a fibrous material without causing chemical change in the battery.
- the filler include olefinic polymers such as polyethylene and polypropylene; Fibrous materials, such as glass fiber and carbon fiber, are used.
- the present invention also provides a lithium secondary battery composed of the positive electrode, the negative electrode, the separator, and a lithium salt-containing nonaqueous electrolyte.
- the negative electrode is manufactured by applying a negative electrode mixture including a negative electrode active material on a negative electrode current collector and then drying the negative electrode mixture.
- the negative electrode mixture may further include components such as a conductive agent and a binder as described above, if necessary. .
- the negative electrode current collector is generally made to a thickness of 3 to 500 ⁇ m.
- a negative electrode current collector is not particularly limited as long as it has high conductivity without causing chemical change in the battery.
- copper, stainless steel, aluminum, nickel, titanium, calcined carbon, copper or stainless steel Surface-treated with carbon, nickel, titanium, silver and the like on the surface, aluminum-cadmium alloy and the like can be used.
- fine concavities and convexities may be formed on the surface to enhance the bonding strength of the negative 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.
- carbon and graphite materials such as natural graphite, artificial graphite, expanded graphite, carbon fiber, non-graphitizable carbon, carbon black, carbon nanotube, fullerene, and activated carbon; Metals such as Al, Si, Sn, Ag, Bi, Mg, Zn, In, Ge, Pb, Pt, Ti which can be alloyed with lithium, and compounds containing these elements; Composites of metals and compounds thereof with carbon and graphite materials; Lithium-containing nitrides; and the like.
- a carbon-based active material, tin-based active material, silicon-based active material, or silicon-carbon-based active material is more preferable, and these may be used alone or in combination of two or more.
- the separator is interposed between the anode and the cathode, and an insulating thin film having high ion permeability and mechanical strength is used.
- the pore diameter of the separator is generally 0.01 to 10 ⁇ m ⁇ m, thickness is generally 5 ⁇ 300 ⁇ m.
- a separator for example, olefin polymers such as chemical resistance and hydrophobic polypropylene; Sheets made of glass fibers or polyethylene, nonwoven fabrics, and the like are used.
- a solid electrolyte such as a polymer
- the solid electrolyte may also serve as a separator.
- the lithium salt-containing non-aqueous electrolyte solution consists of an electrolyte solution and a lithium salt.
- a non-aqueous organic solvent, an organic solid electrolyte, an inorganic solid electrolyte, etc. are used.
- non-aqueous organic solvent examples include N-methyl-2-pyrrolidinone, propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, and gamma Butyl lactone, 1,2-dimethoxy ethane, tetrahydroxy franc, 2-methyl tetrahydrofuran, dimethyl sulfoxide, 1,3-dioxorone, formamide, dimethylformamide, dioxolon , Acetonitrile, nitromethane, methyl formate, methyl acetate, phosphate triester, trimethoxy methane, dioxorone derivatives, sulfolane, methyl sulfolane, 1,3-dimethyl-2-imidazolidinone, propylene carbo Aprotic organic solvents such as nate derivatives, tetrahydrofuran derivatives, ethers, methyl pyroionate and ethyl propionate can be
- organic solid electrolyte examples include polyethylene derivatives, polyethylene oxide derivatives, polypropylene oxide derivatives, phosphate ester polymers, polyedgetion lysine, polyester sulfides, polyvinyl alcohols, polyvinylidene fluorides, Polymerizers containing ionic dissociating groups and the like can be used.
- Examples of the inorganic solid electrolyte include Li 3 N, LiI, Li 5 NI 2 , Li 3 N-LiI-LiOH, LiSiO 4 , LiSiO 4 -LiI-LiOH, Li 2 SiS 3 , Li 4 SiO 4 , Nitrides, halides, sulfates, and the like of Li, such as Li 4 SiO 4 —LiI-LiOH, Li 3 PO 4 —Li 2 S-SiS 2 , and the like, may 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, (CF 3 SO 2) 2 NLi, chloroborane lithium, lower aliphatic carboxylic acid lithium, lithium tetraphenyl borate and imide have.
- 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 carbon dioxide gas may be further included to improve high temperature storage characteristics, and FEC (Fluoro-Ethylene) may be further included.
- carbonate), PRS (propene sultone), FPC (Fluoro-Propylene carbonate) may be further included.
- the secondary battery according to the present invention may be used as a unit cell of a battery module which is a power source of medium and large devices requiring high temperature safety and long cycle characteristics.
- the medium to large device comprises: a power tool driven by an electric motor; Electric vehicles including electric vehicles (EVs), hybrid electric vehicles (HEVs), plug-in hybrid electric vehicles (PHEVs), and the like; Electric motorcycles including electric bicycles (E-bikes) and electric scooters (E-scooters); Electric golf carts, and the like, but are not limited thereto.
- Electric vehicles including electric vehicles (EVs), hybrid electric vehicles (HEVs), plug-in hybrid electric vehicles (PHEVs), and the like
- Electric motorcycles including electric bicycles (E-bikes) and electric scooters (E-scooters); Electric golf carts, and the like, but are not limited thereto.
- the present invention provides a medium-large battery pack having the secondary battery as a unit battery. Since the general structure and manufacturing method of the medium-large battery pack are known in the art, a detailed description thereof is omitted herein.
- FIG. 1 is a graph showing discharge profiles at 5 th cycles and 25 th cycles for the battery of Example 1 and Comparative Example 1 in Experimental Example 2.
- FIG. 1 is a graph showing discharge profiles at 5 th cycles and 25 th cycles for the battery of Example 1 and Comparative Example 1 in Experimental Example 2.
- the synthesized positive electrode active material was mixed with NMP such that the ratio of active material: conductive agent: binder was 95: 2.5: 2.5 (weight ratio), and coated on 20 ⁇ m thick Al foil to prepare a positive electrode.
- the positive electrode was rolled to have an internal porosity of 25%, and then manufactured as a coin type battery.
- batteries using the positive electrode active material containing P have a significantly lower capacity deterioration rate as the number of charge / discharge cycles increases, compared to batteries using the positive electrode active material (Comparative Example 1). It can be seen. Specifically, at 30 th cycle capacity compared to 1 st cycle capacity, it can be seen that the cells of Examples 1-4 exhibited at least 4% higher capacity than the cells of Comparative Example 1. This difference is expressed as a difference of several tens of percent at 300 cycles or more, and as described above, in the case of automotive batteries, the difference is greater than 1000 cycles, and thus becomes larger under such conditions.
- Example 1 The batteries produced in Example 1 and Comparative Example 1 were charged and discharged at a 5 th cycle and a 25 th cycle under a charge and discharge condition of 0.5C, and the discharge profile at such a cycle is shown in FIG. 1.
- the battery of Example 1 is significantly reduced in the degree of degeneration at the end of the discharge, in particular, the voltage drop, when compared with the battery of Comparative Example 1. This means that the degradation due to the structural change of the anode is lowered. This deterioration of the discharge end is the most important cause of the sudden drop in power in the battery for an electric vehicle or hybrid electric vehicle, more important than the meaning of a simple capacity can be measured in a typical battery.
- the positive electrode active material of the present invention can significantly reduce the deterioration of the discharge end, and as shown in FIG. 1, it can be seen that this phenomenon becomes larger as the number of cycles increases. That is, the degradation of the discharge end than at the 25 th 5 th differences are larger.
- the positive electrode active material according to the present invention can greatly improve the life characteristics by a special element composition, in particular, it can be preferably used in devices that require long-term use by excellent cycle characteristics.
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Abstract
Description
Claims (9)
- 하기 화학식 1로부터 선택된 하나 또는 둘 이상의 화합물로서 전이금속층에 리튬을 포함하는 것으로 구성되어 있는 이차전지용 양극 활물질:Li(Li3x±yM1-yPx)O2+z (1)상기 식에서,M은 6배위 구조에 안정한 원소로서, 1주기 및 2주기 전이금속 중에서 선택된 1종 이상의 원소이고;0<x<0.1;0<y<0.3; 및-4x<z≤4x이고,3x-y일 때, 3x>y의 조건을 만족한다.
- 제 1 항에 있어서, 상기 P의 함량은 0<x≤0.05의 조건을 만족하는 것을 특징으로 하는 양극 활물질.
- 제 1 항에 있어서, 전이금속층의 상기 Li 함량은 0.015≤3x≤y≤0.3의 조건을 만족하는 것을 특징으로 하는 양극 활물질.
- 제 1 항에 있어서, 상기 M은 Ni, Mn, Co, Cr, Fe, V 및 Zr로 이루어진 군에서 선택되는 하나 또는 둘 이상인 것을 특징으로 하는 양극 활물질.
- 제 4 항에 있어서, 상기 M은 Ni과 Mn을 필수 원소로서 포함하고 Co를 선택적 원소로서 포함하는 조성으로 이루어진 것을 특징으로 하는 양극 활물질.
- 제 5 항에 있어서, 상기 M은 하기 화학식 2의 조성을 갖는 것을 특징으로 하는 양극 활물질:M = NiaMnbCoc (2)상기 식에서, 0.10<a<0.85, 0.10<b<0.85, 0≤c<0.5이다.
- 제 1 항 내지 제 7 항 중 어느 하나에 따른 양극 활물질을 포함하는 이차전지용 양극.
- 제 7 항에 따른 양극을 포함하는 것을 특징으로 하는 리튬 이차전지.
- 제 8 항에 따른 리튬 이차전지를 단위전지로 하는 것을 특징으로 하는 중대형 전지팩.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP11775258.4A EP2565967B1 (en) | 2010-04-30 | 2011-04-27 | Cathode active material for secondary battery |
CN201180021842.XA CN102870257B (zh) | 2010-04-30 | 2011-04-27 | 二次电池用正极活性材料 |
US13/534,816 US8632694B2 (en) | 2010-04-30 | 2012-06-27 | Cathode active material for secondary battery |
Applications Claiming Priority (2)
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KR1020100041052A KR101098193B1 (ko) | 2010-04-30 | 2010-04-30 | 이차전지용 양극 활물질 |
KR10-2010-0041052 | 2010-04-30 |
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US13/534,816 Continuation US8632694B2 (en) | 2010-04-30 | 2012-06-27 | Cathode active material for secondary battery |
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WO2011136553A2 true WO2011136553A2 (ko) | 2011-11-03 |
WO2011136553A3 WO2011136553A3 (ko) | 2012-04-19 |
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PCT/KR2011/003075 WO2011136553A2 (ko) | 2010-04-30 | 2011-04-27 | 이차전지용 양극 활물질 |
Country Status (5)
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US (1) | US8632694B2 (ko) |
EP (1) | EP2565967B1 (ko) |
KR (1) | KR101098193B1 (ko) |
CN (1) | CN102870257B (ko) |
WO (1) | WO2011136553A2 (ko) |
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KR101954119B1 (ko) | 2013-10-31 | 2019-03-06 | 주식회사 엘지화학 | 리튬 이차전지용 양극 활물질 조성물 및 그 제조방법 |
CN104575687B (zh) * | 2014-10-28 | 2017-11-17 | 天津工业大学 | 一种强附着力的碳纳米管柔性透明导电薄膜及其制备方法 |
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JP4383681B2 (ja) * | 2000-02-28 | 2009-12-16 | 三星エスディアイ株式会社 | リチウム二次電池用正極活物質及びその製造方法 |
KR100519011B1 (ko) | 2003-03-12 | 2005-10-06 | 대주전자재료 주식회사 | 복합재료 고체 고분자 전해질막, 이의 제조방법 및 이를이용한 연료전지 |
DE102004009287A1 (de) | 2004-02-26 | 2005-09-15 | Institut Für Neue Materialien Gem. Gmbh | Amphiphile Nanopartikel |
KR100657951B1 (ko) * | 2005-02-18 | 2006-12-14 | 삼성에스디아이 주식회사 | 양극 활물질, 그 제조 방법 및 이를 채용한 양극과 리튬 전지 |
KR20070014679A (ko) | 2005-07-29 | 2007-02-01 | 삼성에스디아이 주식회사 | 연료 전지용 고분자 전해질 막, 이의 제조방법 및 이를포함하는 연료 전지 시스템 |
CN101300696A (zh) * | 2006-05-10 | 2008-11-05 | 株式会社Lg化学 | 用于高性能锂二次电池的材料 |
KR101306230B1 (ko) | 2006-09-07 | 2013-09-09 | 주식회사 동진쎄미켐 | 유기-무기 복합체 고분자 및 이를 이용한 고분자 전해질막 |
KR100834053B1 (ko) * | 2006-09-29 | 2008-06-02 | 한양대학교 산학협력단 | 양극, 이를 포함하는 리튬 이차 전지, 및 이를 포함하는 하이브리드 커패시터 |
KR100800313B1 (ko) | 2006-11-07 | 2008-02-01 | 한양대학교 산학협력단 | 설폰산기를 갖는 폴리실세스퀴옥산 나노입자를 함유한직접메탄올 연료전지용 유무기 하이브리드 분리막 |
TWI397506B (zh) * | 2008-04-03 | 2013-06-01 | Lg Chemical Ltd | 鋰過渡金屬氧化物製備用之前驅物 |
KR101077869B1 (ko) * | 2010-04-30 | 2011-10-28 | 주식회사 엘지화학 | 이차전지용 양극 |
-
2010
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2011
- 2011-04-27 WO PCT/KR2011/003075 patent/WO2011136553A2/ko active Application Filing
- 2011-04-27 CN CN201180021842.XA patent/CN102870257B/zh active Active
- 2011-04-27 EP EP11775258.4A patent/EP2565967B1/en active Active
-
2012
- 2012-06-27 US US13/534,816 patent/US8632694B2/en active Active
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See also references of EP2565967A4 |
Also Published As
Publication number | Publication date |
---|---|
CN102870257A (zh) | 2013-01-09 |
EP2565967A4 (en) | 2016-01-20 |
WO2011136553A3 (ko) | 2012-04-19 |
EP2565967A2 (en) | 2013-03-06 |
CN102870257B (zh) | 2015-02-11 |
US8632694B2 (en) | 2014-01-21 |
US20130119323A1 (en) | 2013-05-16 |
KR20110121452A (ko) | 2011-11-07 |
EP2565967B1 (en) | 2017-11-01 |
KR101098193B1 (ko) | 2011-12-23 |
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