WO2022139289A1 - 양극 활물질 및 이를 포함하는 리튬 이차 전지 - Google Patents
양극 활물질 및 이를 포함하는 리튬 이차 전지 Download PDFInfo
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- WO2022139289A1 WO2022139289A1 PCT/KR2021/018829 KR2021018829W WO2022139289A1 WO 2022139289 A1 WO2022139289 A1 WO 2022139289A1 KR 2021018829 W KR2021018829 W KR 2021018829W WO 2022139289 A1 WO2022139289 A1 WO 2022139289A1
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- Prior art keywords
- active material
- mol
- doping
- secondary battery
- lithium secondary
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- 239000006182 cathode active material Substances 0.000 title claims abstract description 16
- 229910001416 lithium ion Inorganic materials 0.000 title description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 135
- 239000002245 particle Substances 0.000 claims abstract description 70
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 44
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 38
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 37
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 28
- 239000010941 cobalt Substances 0.000 claims abstract description 28
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 28
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 25
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 19
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 19
- 239000007774 positive electrode material Substances 0.000 claims description 116
- 239000011572 manganese Substances 0.000 claims description 49
- 238000009792 diffusion process Methods 0.000 claims description 19
- 229910052758 niobium Inorganic materials 0.000 claims description 18
- 229910052726 zirconium Inorganic materials 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- 229910052796 boron Inorganic materials 0.000 claims description 15
- 238000002441 X-ray diffraction Methods 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
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- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
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- 238000003991 Rietveld refinement Methods 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
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- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052795 boron group element Inorganic materials 0.000 description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- 229910018626 Al(OH) Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 102100021202 Desmocollin-1 Human genes 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 101000968043 Homo sapiens Desmocollin-1 Proteins 0.000 description 1
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- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
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- 229910008859 Sn—Y Inorganic materials 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- RLTFLELMPUMVEH-UHFFFAOYSA-N [Li+].[O--].[O--].[O--].[V+5] Chemical compound [Li+].[O--].[O--].[O--].[V+5] RLTFLELMPUMVEH-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
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- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
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- 229910021450 lithium metal oxide Inorganic materials 0.000 description 1
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Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present embodiments relate to a cathode active material and a lithium secondary battery including the same.
- the nickel-cobalt-manganese-based positive electrode active material having a high nickel content results in 1) a decrease in efficiency due to a decrease in capacity as a result of an increase in the nickel content, 2) formation of a NiO rock salt structure and deterioration of cycle characteristics due to surface oxygen generation, and 3) resistance There are problems such as increase.
- the positive active material for a lithium secondary battery according to an embodiment may include metal oxide particles including nickel, cobalt, manganese, and aluminum, and three kinds of doping elements doped into the metal oxide particles.
- the three doping elements may be Nb, B, and Zr.
- the doping amount of Nb may range from 0.00001 mole to 0.03 mole based on 1 mole of the total of nickel, cobalt, manganese, aluminum and doping elements.
- the doping amount of B may be in the range of 0.001 mol to 0.02 mol based on 1 mol of the total of nickel, cobalt, manganese, aluminum, and doping elements.
- the doping amount of Zr may range from 0.001 mol to 0.007 mol based on 1 mol of the total of nickel, cobalt, manganese, aluminum, and doping elements.
- the doping amounts of Nb and Zr may satisfy the relationship of Equation 1 below.
- the doping amounts of Nb and B may satisfy the relationship of Equation 2 below.
- the positive electrode active material may be represented by the following formula (1).
- X is one or more elements selected from the group comprising F, N, and P, and Zr
- a 0.8 ⁇ a ⁇ 1.3
- t is 0.0061 ⁇ t ⁇ 0.057
- h may be in the range of 0.005 ⁇ h ⁇ 0.025.
- the initial diffusion coefficient of the positive active material may be in the range of 7.30*10 -9 m 2 /sec to 8.10*10 -9 m 2 /sec.
- the grain size of the metal oxide particles may be in the range of 1,000 ⁇ to 1,560 ⁇ .
- the full width at half maximum (FWHM) for the (110) plane of the metal oxide particles may be in the range of 0.1901 to 0.27.
- I(003)/I(104) which is the ratio of the peak intensity of the (003) plane to the peak intensity of the (104) plane, may be in the range of 1.2350 to 1.2410.
- the content of nickel in the metal oxide particles may be 0.8 mol or more based on 1 mol of the total of nickel, cobalt, manganese, and aluminum.
- a lithium secondary battery according to another embodiment may include a positive electrode including the positive electrode active material according to an embodiment, a negative electrode, and a non-aqueous electrolyte.
- the cathode active material according to the present embodiment is applied by doping at least two kinds of elements to metal oxide particles including NCMA, room temperature and high temperature lifespan characteristics, initial efficiency, initial resistance, resistance while increasing the capacity of a lithium secondary battery
- the increase rate and thermal stability can be significantly improved.
- first, second and third are used to describe, but are not limited to, various parts, components, regions, layers and/or sections. These terms are used only to distinguish one part, component, region, layer or section from another part, component, region, layer or section. Accordingly, a first part, component, region, layer or section described below may be referred to as a second part, component, region, layer or section without departing from the scope of the present invention.
- the positive active material for a lithium secondary battery according to an embodiment may include metal oxide particles including nickel, cobalt, manganese, and aluminum, and two types of doping elements doped into the metal oxide particles.
- the three kinds of doping elements may be Nb, Zr, and B.
- Doping elements known to date include, for example, mono-valent ions such as Ag + , Na + , Co 2+ , Cu 2+ , Mg 2+ , Zn 2+ , Ba 2+ , Al 3+ , Fe 3+ , Cr 3+ , Ga 3+ , Zr 4+ , and a multivalent ion (multi-valent) having a divalent or higher value, such as Ti 4+ .
- mono-valent ions such as Ag + , Na + , Co 2+ , Cu 2+ , Mg 2+ , Zn 2+ , Ba 2+ , Al 3+ , Fe 3+ , Cr 3+ , Ga 3+ , Zr 4+
- multivalent ion (multi-valent) having a divalent or higher value
- Zr 4+ acts as a kind of filler because Zr ions occupy the Li site and stabilizes the layered structure by relaxing the contraction of the lithium ion path during the charging and discharging process. will come This phenomenon, that is, reduces cation mixing and increases the lithium diffusion coefficient (lithium diffusion coefficient) may increase the cycle life.
- Nb may improve initial capacity and initial efficiency.
- the initial resistance may be reduced by reducing the grain size during sintering of the cathode active material.
- life characteristics and thermal decomposition temperature can be increased.
- the doping amount of Nb is 0.00001 mole to 0.03 mole, more specifically, 0.0001 mole to 0.01 mole, 0.00005 mole to 0.03 mole, or It may range from 0.0005 moles to 0.0025 moles.
- the doping amount of Nb satisfies the above range, a very advantageous effect can be realized in that all of the room temperature life, high temperature life, resistance increase rate, and average leakage current value of the lithium secondary battery can be improved.
- the diffusion coefficient of the lithium secondary battery can be increased and the resistance increase rate can be effectively reduced during impedance analysis.
- the doping amount of B may be in the range of 0.001 mol to 0.02 mol, more specifically 0.005 mol to 0.02 mol, more specifically, 0.005 mol to 0.015 mol with respect to 1 mol of the total of nickel, cobalt, manganese, aluminum and doping elements. .
- the doping amount of B satisfies the above range, since the grain size is reduced during sintering of the positive active material, the initial resistance value may be reduced, and the room temperature and high temperature life characteristics and the thermal decomposition temperature may be increased.
- the doping amount of Zr may be in the range of 0.001 mole to 0.007 mole, more specifically, 0.002 mole to 0.005 mole or 0.0035 mole to 0.005 mole, based on 1 mole of the total of nickel, cobalt, manganese, aluminum and doping element. .
- the Zr doping amount satisfies the above range, high-temperature lifespan and room-temperature lifespan characteristics of the lithium secondary battery may be remarkably improved.
- the doping amounts of Nb and Zr may satisfy the relation of Equation 1 below.
- Equation 1 [Nb] and [Zr] mean doping amounts of each element based on 1 mole of the total of nickel, cobalt, manganese, aluminum, and doping elements.
- Equation 1 may be in the range of 0.6 or more and 9 or less, or 0.7 or more and 7 or less.
- Equation 1 When Equation 1 satisfies the above range, the resistance increase rate can be improved and cycle characteristics are excellent. .
- Nb and B may satisfy the relationship of Equation 2 below.
- Equation 2 [Nb] and [B] mean doping amounts of each element based on 1 mole of the total of nickel, cobalt, manganese, aluminum, and doping elements.
- Equation 2 may be in the range of 0.2 or more and 25 or less, or 0.4 or more and 20 or less.
- Equation 2 satisfies the above range, stability is improved, DSC temperature is increased, and cycle characteristics are improved.
- the positive active material for a lithium secondary battery according to this embodiment may be represented by the following Chemical Formula 1.
- X is one or more elements selected from the group comprising F, N, and P, and Zr
- a 0.8 ⁇ a ⁇ 1.3
- t is 0.0061 ⁇ t ⁇ 0.057
- the content range h of Al may be in the range of 0.008 to 0.029, and more specifically, in the range of 0.005 ⁇ h ⁇ 0.025.
- Al 3+ inhibits the deterioration of the layered structure to the spinel structure due to the movement of Al ions to the tetragonal lattice site.
- the layered structure facilitates removal and insertion of Li ions, but the spinel structure does not facilitate the movement of Li ions. Therefore, when the content of Al in the positive electrode active material of the present embodiment satisfies the above range, it is possible to realize a lithium secondary battery having excellent initial efficiency and thermal stability, and significantly improved room temperature life and high temperature life.
- the content of nickel in this embodiment may be 0.8 mol or more based on 1 mol of the total of nickel, cobalt, manganese, and aluminum, and more specifically, 0.8 mol to 0.99 mol, 0.82 mol to 0.95 mol, or It may range from 0.83 moles to 0.92 moles.
- the content of nickel is 0.8 or more based on 1 mole of the total of nickel, cobalt, manganese, and aluminum in the metal oxide, a positive active material having high output characteristics can be implemented. Since the positive active material of the present embodiment having such a composition has a higher energy density per volume, the capacity of a battery to which it is applied can be improved, and it is also suitable for use in electric vehicles.
- the initial diffusion coefficient of the positive active material according to the present embodiment is 7.30*10 -9 m 2 /sec to 8.10*10 -9 m 2 /sec, more specifically 8.01*10 -9 m 2 /sec to 8.06*10 -9 m 2 /sec range, 8.01*10 -9 m 2 /sec to 8.04*10 -9 m 2 /sec, or 8.01*10 -9 m 2 /sec to 8.03*10 -9 m 2 /sec range can
- the initial diffusion coefficient is from 8.01*10 -9 m 2 /sec to 8.06*10 -9 m 2 /sec, the movement of Li ions in the cathode material is effective, and thus the initial capacity and rate-limiting characteristics of the cathode material are high.
- the grain size of the metal oxide particles may be in the range of 1,000 ⁇ to 1,560 ⁇ , more specifically, may be in the range of 1,090 ⁇ to 1,350 ⁇ , or 1,180 ⁇ to 1,350 ⁇ .
- the high temperature life is improved without reducing the initial capacity.
- the full width at half maximum (FWHM) with respect to the (110) plane of the metal oxide particles may be in the range of 0.1900 to 0.2030, more specifically, 0.1901 to 0.27, or 0.1901 to 0.104.
- the full width at half maximum (FWHM) with respect to the (110) plane satisfies the above range, the high temperature lifespan is greatly improved.
- I(003)/I(104) which is the ratio of the peak intensity of the (003) plane to the peak intensity of the (104) plane, may be in the range of 1.2350 to 1.2410, and more Specifically, it may be in the range of 1.2351 to 1.2407.
- the peak intensity value means a peak height value or an integrated area value obtained by integrating the peak area, and in this embodiment, the peak intensity value means a peak area value.
- the peak intensity ratio I(003)/I(104) is a cation mixing index, and when the value of I(003)/I(104) decreases, the initial capacity and rate-rate characteristics of the positive electrode active material may decrease.
- I(003)/I(104) since I(003)/I(104) satisfies the above range, a positive electrode active material having excellent capacity and rate-rate characteristics may be implemented.
- the positive active material of the present embodiment may have a bi-modal form in which large particle diameter particles and small particle diameter particles are mixed.
- the large particle diameter particles may have an average particle diameter (D50) in the range of 10 ⁇ m to 20 ⁇ m
- the small particle diameter particles may have an average particle diameter (D50) of 3 ⁇ m to 7 ⁇ m.
- the large particle diameter particles and the small particle diameter particles may also be in the form of secondary particles in which at least one primary particle is assembled.
- the mixing ratio of the large particle diameter particles and the small particle diameter particles may be 50 to 80 wt% of the large particle diameter particles based on 100 wt% of the total. Energy density can be improved due to this bimodal particle distribution.
- a lithium secondary battery comprising a positive electrode including the positive electrode active material according to an embodiment of the present invention described above, a negative electrode including a negative electrode active material, and an electrolyte positioned between the positive electrode and the negative electrode do.
- the positive active material layer may include a binder and a conductive material.
- the binder serves to well adhere the positive active material particles to each other and also to adhere the positive active material to the current collector.
- the conductive material is used to impart conductivity to the electrode, and in the configured battery, any electronically conductive material may be used without causing a chemical change.
- the negative electrode includes a current collector and a negative active material layer formed on the current collector, and the negative active material layer includes a negative electrode active material.
- the negative active material includes a material capable of reversibly intercalating/deintercalating lithium ions, lithium metal, an alloy of lithium metal, a material capable of doping and dedoping lithium, or a transition metal oxide.
- the material capable of reversibly intercalating/deintercalating the lithium ions is a carbon material, and any carbon-based negative active material generally used in lithium ion secondary batteries may be used, and a representative example thereof is crystalline carbon. , amorphous carbon or these may be used together.
- the lithium metal alloy includes lithium and Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Si, Sb, Pb, In, Zn, Ba, Ra, Ge, Al and Sn from the group consisting of Alloys of metals of choice may be used.
- Materials capable of doping and dedoping lithium include Si, SiO x (0 ⁇ x ⁇ 2), Si-Y alloy (where Y is an alkali metal, alkaline earth metal, group 13 element, group 14 element, transition metal, An element selected from the group consisting of rare earth elements and combinations thereof, but not Si), Sn, SnO 2 , Sn-Y (wherein Y is an alkali metal, an alkaline earth metal, a group 13 element, a group 14 element, a transition metal, a rare earth) It is an element selected from the group consisting of elements and combinations thereof, and is not Sn) and the like.
- the negative active material layer also includes a binder, and may optionally further include a conductive material.
- the binder serves to well adhere the negative active material particles to each other and also to adhere the negative active material to the current collector.
- the conductive material is used to impart conductivity to the electrode, and in the configured battery, any electronically conductive material may be used without causing a chemical change.
- the current collector one selected from the group consisting of copper foil, nickel foil, stainless steel foil, titanium foil, nickel foam, copper foam, a polymer substrate coated with conductive metal, and combinations thereof may be used.
- the negative electrode and the positive electrode are prepared by mixing an active material, a conductive material, and a binder in a solvent to prepare an active material composition, and applying the composition to a current collector. Since such an electrode manufacturing method is widely known in the art, a detailed description thereof will be omitted herein.
- the solvent may include, but is not limited to, N-methylpyrrolidone.
- the electrolyte includes a non-aqueous organic solvent and a lithium salt.
- the non-aqueous organic solvent serves as a medium through which ions involved in the electrochemical reaction of the battery can move.
- the lithium salt is dissolved in an organic solvent, serves as a source of lithium ions in the battery, enables basic lithium secondary battery operation, and promotes movement of lithium ions between the positive electrode and the negative electrode.
- a separator may exist between the positive electrode and the negative electrode.
- a separator polyethylene, polypropylene, polyvinylidene fluoride, or a multilayer film of two or more layers thereof may be used.
- a polyethylene/polypropylene two-layer separator, a polyethylene/polypropylene/polyethylene three-layer separator, and polypropylene/polyethylene/poly It goes without saying that a mixed multilayer film such as a propylene three-layer separator or the like can be used.
- Lithium secondary batteries can be classified into lithium ion batteries, lithium ion polymer batteries, and lithium polymer batteries depending on the type of separator and electrolyte used, and can be classified into cylindrical, prismatic, coin-type, pouch-type, etc. according to the shape, According to the size, it can be divided into a bulk type and a thin film type. Since the structure and manufacturing method of these batteries are well known in the art, a detailed description thereof will be omitted.
- the cathode active material precursor was prepared by a general co-precipitation method.
- NiSO 4 ⁇ 6H 2 O was used as a raw material for nickel, CoSO 4 ⁇ 7H 2 O as a raw material for cobalt, and MnSO 4 ⁇ H 2 O as a raw material for manganese. These raw materials were dissolved in distilled water to prepare an aqueous metal salt solution.
- N 2 was purged to prevent oxidation of metal ions during the co-precipitation reaction, and the reactor temperature was maintained at 50°C.
- NH 4 (OH) was added as a chelating agent to the co-precipitation reactor, and NaOH was used for pH control.
- the precipitate obtained according to the co-precipitation process was filtered, washed with distilled water, and dried in a cake dryer at 180° C. to prepare a cathode active material precursor.
- the composition of the prepared precursor was (Ni 0.92 Co 0.04 Mn 0.04 )(OH) 2 , the average particle diameter (D50) of the large particle diameter precursor was 14.3 ⁇ m, and the average particle diameter (D50) of the small particle diameter precursor was 4.5 ⁇ m.
- the mixture in which the precursor, lithium raw material, aluminum raw material, and doping raw material prepared in Preparation Example 1 were uniformly mixed was fired in an oxygen atmosphere in a tube furnace. Firing conditions were maintained at 480 o C for 5 hours, then at 740 ⁇ 780 o C for 15 hours, and the temperature increase rate was 5 o C/min.
- LiOH ⁇ H 2 O (Samjeon Chemical, battery grade) was used as the lithium material used, Al(OH) 3 (Aldrich, 3N) was used as the aluminum material, and ZrO 2 (Aldrich, 3N) was used as the doping material. ), H 3 BO 3 (Aldrich, 3N) and Nb 2 O 5 (Aldrich, 3N) were used.
- the total composition of the large and small particle diameter positive electrode active material doped with two elements prepared as described above was Li(M) 0.993 Zr 0.0035 Nb 0.0025 B 0.001 O 2 .
- the calcined large particle diameter and small particle diameter positive electrode active material was uniformly mixed in a weight ratio of 80:20 (large particle diameter: small particle diameter) to prepare the positive electrode active material of Example 1 in a bi-modal form.
- a bimodal positive electrode active material was prepared in the same manner as in Example 1, except that the doping amount was adjusted using the precursor prepared in Preparation Example 1.
- the total composition of the large- and small-diameter positive electrode active material prepared according to Comparative Example 1 was Li(M) 0.9965 Zr 0.0035 O 2 .
- a bimodal positive electrode active material was prepared in the same manner as in Example 1, except that the amount of the doping raw material was adjusted using the precursor prepared in Preparation Example 1.
- the total composition of the positive active material prepared according to Example 2 was Li(M) 0.989 Zr 0.0035 Nb 0.0025 B 0.005 O 2 .
- a bimodal positive electrode active material was prepared in the same manner as in Example 1, except that the amount of the doping raw material was adjusted using the precursor prepared in Preparation Example 1.
- the total composition of the positive active material prepared according to Example 3 was Li(M) 0.984 Zr 0.0035 Nb 0.0025 B 0.01 O 2 .
- a bimodal positive electrode active material was prepared in the same manner as in Example 1, except that the amount of the doping raw material was adjusted using the precursor prepared in Preparation Example 1.
- the total composition of the positive active material prepared according to Example 4 was Li(M) 0.979 Zr 0.0035 Nb 0.0025 B 0.015 O 2 .
- a bimodal positive electrode active material was prepared in the same manner as in Example 1, except that the amount of the doping raw material was adjusted using the precursor prepared in Preparation Example 1.
- the total composition of the positive active material prepared according to Example 5 was Li(M) 0.974 Zr 0.0035 Nb 0.0025 B 0.02 O 2 .
- a bimodal positive electrode active material was prepared in the same manner as in Example 1, except that the amount of the doping raw material was adjusted using the precursor prepared in Preparation Example 1.
- the total composition of the positive active material prepared according to Example 5 was Li(M) 0.9855 Zr 0.002 Nb 0.0025 B 0.01 O 2 .
- a bimodal positive electrode active material was prepared in the same manner as in Example 1, except that the amount of the doping raw material was adjusted using the precursor prepared in Preparation Example 1.
- the total composition of the positive active material prepared according to Example 6 was Li(M) 0.9825 Zr 0.005 Nb 0.0025 B 0.01 O 2 .
- a bimodal positive electrode active material was prepared in the same manner as in Example 1, except that the amount of the doping raw material was adjusted using the precursor prepared in Preparation Example 1.
- the total composition of the positive active material prepared according to Reference Example 2 was Li(M) 0.9795 Zr 0.008 Nb 0.0025 B 0.01 O 2 .
- a bimodal positive electrode active material was prepared in the same manner as in Example 1, except that the amounts of the aluminum raw material and the doping raw material were adjusted using the precursor prepared in Preparation Example 1.
- the total composition of the positive active material prepared according to Example 7 was Li(Ni 0.915 Co 0.04 Mn 0.04 Al 0.005 ) 0.984 Zr 0.0035 Nb 0.0025 B 0.01 .
- a bimodal positive electrode active material was prepared in the same manner as in Example 1, except that the amount of the doping raw material was adjusted using the precursor prepared in Preparation Example 1.
- the total composition of the positive active material prepared according to Example 8 was Li(Ni 0.91 Co 0.04 Mn 0.04 Al 0.01 ) 0.984 Zr 0.0035 Nb 0.0025 B 0.01 .
- a bimodal positive electrode active material was prepared in the same manner as in Example 1, except that the amount of the aluminum raw material and the amount of the doping raw material were adjusted using the precursor prepared in Preparation Example 1.
- the total composition of the positive active material prepared according to Example 11 was Li(Ni 0.905 Co 0.04 Mn 0.04 Al 0.015 ) 0.984 Zr 0.0035 Nb 0.0025 B 0.01 .
- a bimodal positive electrode active material was prepared in the same manner as in Example 1, except that the amount of the aluminum raw material and the amount of the doping raw material were adjusted using the precursor prepared in Preparation Example 1.
- the total composition of the positive active material prepared according to Example 12 was Li(Ni 0.898 Co 0.04 Mn 0.04 Al 0.022 ) 0.984 Zr 0.0035 Nb 0.0025 B 0.01 .
- a bimodal positive electrode active material was prepared in the same manner as in Example 1, except that the amount of the aluminum raw material and the amount of the doping raw material were adjusted using the precursor prepared in Preparation Example 1.
- the total composition of the positive active material prepared according to Reference Example 3 was Li(Ni 0.895 Co 0.04 Mn 0.04 Al 0.025 ) 0.984 Zr 0.0035 Nb 0.0025 B 0.01 .
- a bimodal positive electrode active material was prepared in the same manner as in Example 1, except that the amount of the doping raw material was adjusted using the precursor prepared in Preparation Example 1.
- the total composition of the positive active material prepared according to Example 11 was Li(M) 0.986 Zr 0.0035 Nb 0.0005 B 0.01 O 2 .
- a bimodal positive electrode active material was prepared in the same manner as in Example 1, except that the amount of the doping raw material was adjusted using the precursor prepared in Preparation Example 1.
- the total composition of the positive active material prepared according to Example 12 was Li(M) 0.9855 Zr 0.0035 Nb 0.0001 B 0.01 O 2 .
- a bimodal positive electrode active material was prepared in the same manner as in Example 1, except that the amount of the doping raw material was adjusted using the precursor prepared in Preparation Example 1.
- the total composition of the positive active material prepared according to Reference Example 4 was Li(M) 0.9815 Zr 0.0035 Nb 0.005 B 0.01 O 2 .
- a bimodal positive electrode active material was prepared in the same manner as in Example 1, except that the amounts of the aluminum raw material and the doping raw material were adjusted using the precursor.
- the total composition of the positive active material prepared according to Comparative Example 2 was Li(Ni 0.78 Co 0.10 Mn 0.10 Al 0.02 ) 0.994 Zr 0.0035 Nb 0.0025 .
- a bimodal positive electrode active material was prepared in the same manner as in Example 1, except that the amount of the doping raw material was adjusted using the precursor.
- the total composition of the positive active material prepared according to Comparative Example 3 was Li(Ni 0.81 Co 0.12 Mn 0.05 Al 0.02 ) 0.994 Zr 0.0035 Nb 0.0025 .
- a bimodal positive electrode active material was prepared in the same manner as in Example 1, except that the amount of the doping raw material was adjusted using the precursor.
- the total composition of the positive active material prepared according to Comparative Example 4 was Li(Ni 0.83 Co 0.07 Mn 0.08 Al 0.02 ) 0.994 Zr 0.0035 Nb 0.0025 .
- a bimodal positive electrode active material was prepared in the same manner as in Example 1, except that the amount of the doping raw material was adjusted using the precursor.
- the total composition of the positive active material prepared according to Comparative Example 5 was Li(Ni 0.84 Co 0.07 Mn 0.07 Al 0.02 ) 0.994 Zr 0.0035 Nb 0.0025 .
- a bimodal positive electrode active material was prepared in the same manner as in Example 1, except that the amount of the doping raw material was adjusted using the precursor.
- the total composition of the positive active material prepared according to Comparative Example 6 was Li(Ni 0.86 Co 0.05 Mn 0.07 Al 0.02 ) 0.994 Zr 0.0035 Nb 0.0025 .
- a bimodal positive electrode active material was prepared in the same manner as in Example 1, except that the precursor was used.
- the total composition of the positive active material prepared according to Reference Example 5 was Li(Ni 0.78 Co 0.01 Mn 0.01 Al 0.02 ) 0.984 Zr 0.0035 Nb 0.0025 B 0.01 .
- a bimodal positive electrode active material was prepared in the same manner as in Example 1, except that the precursor was used.
- the total composition of the positive active material prepared according to Reference Example 6 was Li(Ni 0.81 Co 0.12 Mn 0.05 Al 0.02 ) 0.984 Zr 0.0035 Nb 0.0025 B 0.01 .
- a bimodal positive electrode active material was prepared in the same manner as in Example 1, except that the precursor was used.
- the total composition of the positive active material prepared according to Example 13 was Li(Ni 0.83 Co 0.07 Mn 0.08 Al 0.02 ) 0.984 Zr 0.0035 Nb 0.0025 B 0.01 .
- a bimodal positive electrode active material was prepared in the same manner as in Example 1, except that the precursor was used.
- the total composition of the positive active material prepared according to Example 14 was Li(Ni 0.84 Co 0.07 Mn 0.07 Al 0.02 ) 0.984 Zr 0.0035 Nb 0.0025 B 0.01 .
- a bimodal positive electrode active material was prepared in the same manner as in Example 1, except that the precursor was used.
- the total composition of the positive active material prepared according to Example 15 was Li(Ni 0.86 Co 0.05 Mn 0.07 Al 0.02 ) 0.984 Zr 0.0035 Nb 0.0025 B 0.01 .
- the lattice constants of the positive active materials prepared according to Examples 1 to 4, Reference Example 1, and Comparative Example 1 were obtained by X-ray diffraction measurement using CuK ⁇ ray.
- the measured a-axis length, b-axis length, and c-axis length are shown in Table 1 below.
- the intensity (peak area) of the (003) and (104) planes and the intensity of the (110) plane were measured using XRD equipment (X'pert3 powder diffraction, manufactured by Panalytical) at a scan speed (°/s) of 0.328. From this result, the full width at half maximum (FWHM) of the I(003)/I(104) and (110) planes was calculated and shown in Table 1.
- the (003) plane was well developed as the main peak near 18.7 o , the (006)/(102) peak between 37.5 o and 38.5 o , and (108)/(110) between 63.5 o and 35.5 o
- the peak splitting appeared it was confirmed that the hexagonal layer had a good crystalline ordering, and it was found to represent a typical ⁇ -NaFeO 2 (space group R-3m) structure.
- the doping amount of B may be in the range of 0.005 mol to 0.02 mol, and preferably in the range of 0.001 mol to 0.015 mol.
- a positive active material a conductive material (Denka Black), and a polyvinylidene fluoride binder (trade name: KF1100) are mixed in a weight ratio of 92.5:3.5:4, and the mixture is mixed with N-methyl so that the solid content is about 30% by weight.
- -2-pyrrolidone N-Methyl-2-pyrrolidone was added to a solvent to prepare a cathode active material slurry.
- the slurry was coated on an aluminum foil (thickness: 15 ⁇ m) as a positive electrode current collector using a doctor blade, dried and rolled to prepare a positive electrode.
- the loading amount of the positive electrode was about 14.6 mg/cm 2 , and the rolling density was about 3.1 g/cm 3 .
- a 2032 coin-type half-cell was manufactured in a conventional manner using the positive electrode, lithium metal negative electrode (thickness 300 ⁇ m, MTI), electrolyte, and a polypropylene separator.
- 205 mAh/g was used as a reference capacity, and a constant current (CC) / constant voltage (CV) 2.5V to 4.25V, 1/20C cut-off was applied as a charge/discharge condition.
- CC constant current
- CV constant voltage
- the initial capacity was measured by measuring the discharge capacity after 0.1C charge/0.1C discharge, and after performing 0.2C charge/0.2C discharge, the initial efficiency was calculated, and the results are shown in Table 2 below.
- Room temperature cycle life characteristics were measured 30 times at room temperature (25 o C), and high temperature cycle life characteristics at 0.3 C charge/0.3 C discharge conditions at high temperature (45 o C).
- Room temperature initial resistance (Direct current internal resistance: DC-IR (Direct current internal resistance)) is a constant current-constant voltage 2.5V to 4.25V, 1/20C cut-off condition at 25°C, 0.2C charge and 0.2C discharge discharge. It was carried out once, and after measuring the voltage value 60 seconds after applying the discharge current at 100% of the 4.25V charge, it was calculated.
- the resistance increase rate was measured in the same manner as the initial resistance measurement method after 30 cycles of cycle life compared to the resistance (room temperature initial resistance) measured initially at room temperature (25° C.), and the rate of increase was converted into a percentage (%).
- Average leakage current was measured by measuring the current generation during 120 hours when the half-cell was maintained at 4.7V at a high temperature of 45°C, and obtaining the average value of the values.
- DSC differential scanning calorimetry
- Table 4 below shows the electrochemical property evaluation results performed by the method of Experimental Example 2 for the positive active materials prepared according to Examples 1 to 7 and Comparative Example 1.
- Examples 1 to 4 are results of measuring electrochemical properties according to the doping amount when Al raw material is mixed with a precursor having a Ni content of 90 mol% or more and Zr, Nb and B are doped together.
- the doping amount of B is nickel, cobalt, manganese, Based on 1 mol of the total of aluminum and doping elements, it may be in the range of 0.001 mol to 0.02 mol, and it can be confirmed that the range is preferably 0.005 mol to 0.015 mol.
- Table 5 shows the electrochemical characteristics evaluation results performed by the method of Experimental Example 2 for the positive active materials prepared according to Examples 5 to 6 and Reference Example 2. For comparison, the results of Example 3 are also shown.
- Example 5 219.6 94.3 93.9 94.4 29.8 61.4 0.31 228.0
- Example 3 219.6 94.4 97.6 97.3 25.4 36.4 0.17 231.0
- Example 6 216.5 92.9 97.6 97.2 33.7 38.5 0.18 232.0
- a suitable doping amount of Zr in this embodiment is in the range of 0.001 mole to 0.007 mole, specifically 0.002 mole to 0.005 mole or 0.0035 mole to 0.005 mole, based on 1 mole of the total of nickel, cobalt, manganese and doping elements.
- Table 6 below shows the electrochemical characteristics evaluation results performed by the method of Experimental Example 2 for the positive active materials prepared according to Examples 7 to 10 and Reference Example 3. For comparison, the results of Example 3 are also shown.
- Example 7 222.3 94.8 91.0 90.9 37.0 73.9 0.45 223.0
- Example 8 221.3 94.6 94.5 94.9 27.2 49.5 0.27 228.0
- Example 3 219.6 94.4 97.6 97.3 25.4 36.4 0.18 231.0
- Example 10 217.6 93.5 99.2 98.8 23.9 33.1 0.17 234.4 Reference Example 3 209.6 86.1 99.0 99.7 22.9 32.1 0.15 236.1
- the amount of the aluminum raw material may be in the range of 0.008 moles to 0.029 moles, more specifically, 0.005 moles to 0.025 moles, based on 1 mole of the total of nickel, cobalt, manganese, aluminum and doping elements.
- Table 7 below shows the electrochemical property evaluation results performed by the method of Experimental Example 2 for the positive active materials prepared according to Examples 11 to 12 and Reference Example 4. For comparison, the results of Example 3 are also shown.
- Example 11 218.1 93.7 96.5 96.4 27.8 42.5 0.23 229.0
- Example 12 218.8 94.1 97.0 96.1 27.3 40.3 0.20 231.0
- Example 3 219.6 94.4 97.6 97.3 25.4 36.4 0.17 231.0
- Reference Example 4 214.7 91.7 96.7 96.6 30.0 65.5 0.17 231.0
- a suitable doping amount of Nb in this embodiment is in the range of 0.00005 mole to 0.03 mole, and specifically 0.0001 mole to 0.01 mole or 0.0005 mole to 0.0025 mole based on 1 mole of the total of nickel, cobalt, manganese, aluminum and doping elements. It can be a range.
- Table 8 below shows the electrochemical property evaluation results performed by the method of Experimental Example 2 for the positive active materials prepared according to Comparative Examples 2 to 6, Reference Examples 5 to 6, and Examples 13 to 15. For comparison, the results of Comparative Examples 1 and 3 are also shown.
- Example 2 (Ni78%) 198.43 86.80 96.9 95.3 16.2 42.8 0.21 233 Reference Example 5 198.32 86.75 97.3 97.1 17.1 35.7 0.17 236 Comparative Example 3 (Ni81%) 203.84 87.60 94.5 94.3 19.9 48.7 0.24 224 Reference Example 6 202.74 88.69 97.1 96.0 21.4 41.3 0.19 228 Comparative Example 4 (Ni83%) 210.5 89.50 95.5 95.4 21.9 44.9 0.21 222 Example 13 209.8 91.77 98.3 98.1 23.2 37.8 0.16 227 Comparative Example 5 (Ni84%) 211.7 91.80 95.3 95.1 22.2 47.9 0.23 223 Example 14 210.7 92.17 98.0 97.8 23.7 40.1 0.17 229 Comparative Example 2 (Ni84%) 211.7 91.80 95.3 95.1 22.2 47.9 0.23 223 Example 14 210.7 92.17 98.0 97.8 23.7 40.1 0.17
- Comparative Examples 2 to 6 are positive electrode active materials in which NCMA is doped with Zr and Nb
- Reference Examples 5 to 6 and Examples 13 to 15 are positive electrode active materials prepared by mixing NCMA with Zr, Nb, and B doped raw materials.
- the diffusion coefficient was measured by the GITT method, and after 30 minutes of charging, 50 minutes of maintenance was carried out, and the data obtained at this time were analyzed using Equation 3 below.
- V M Molar volume of positive active material
- the molar volume of the positive active material was calculated using the unit volume analyzed through the XRD measurement result.
- A is the electrode area when the diffusion coefficient is measured. In the case of the coin cell used for the diffusion coefficient measurement, the area has a size of 1.538 cm 2 .
- I o means 0.1C current value.
- X can be calculated assuming that the entire charge/discharge section is 100%. For example, x corresponding to the initial 30-minute charging section can be expressed as 0.05, the x value corresponding to the second 30-minute charging section can be expressed as 0.1, and x corresponding to the middle section can be expressed as 0.5.
- Impedance analysis was performed using the obtained impedance graph at 3.7V, and the same as the diffusion coefficient is shown in Table 9 below.
- the obtained impedance value was divided into real and imaginary axes and Nyquist plot was performed, and the obtained figure was divided into two semicircle shapes and fitted to obtain R sei and R ct .
- R sei the resistance value obtained by the semicircle generated in the high frequency region
- Rct the resistance value obtained by the semicircle generated in the low frequency region
- the suppression of the increase in Rsei resistance means that the reaction with the electrolyte is suppressed
- the suppression of the increase in Rct resistance means that the deterioration of the electrode activity of the cathode material is suppressed. It can be understood that the initial output improvement and deterioration phenomenon can be suppressed when doping of B is appropriate.
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Abstract
Description
구분 | Al | 도핑 원소 | 양극 활물질 전체 조성 | ||
Zr | Nb | B | |||
실시예 1 | 0.02 | 0.0035 | 0.0025 | 0.001 | Li(M)0.993Zr0.0035Nb0.0025 B0.001O2 |
비교예 1 | 0.02 | 0.0035 | 0 | 0 | Li(M)0.9965Zr0.0035O2 |
실시예 2 | 0.02 | 0.0035 | 0.0025 | 0.005 | Li(M)0.989Zr0.0035Nb0.0025B0.005O2 |
실시예 3 | 0.02 | 0.0035 | 0.0025 | 0.01 | Li(M)0.984Zr0.0035Nb0.0025B0.01O2 |
실시예 4 | 0.02 | 0.0035 | 0.0025 | 0.015 | Li(M)0.979Zr0.0035Nb0.0025B0.015O2 |
참고예 1 | 0.02 | 0.0035 | 0.0025 | 0.02 | Li(M)0.974Zr0.0035Nb0.0025B0.02O2 |
실시예 5 | 0.02 | 0.002 | 0.0025 | 0.01 | Li(M)0.9855Zr0.002Nb0.0025B0.01O2 |
실시예 6 | 0.02 | 0.005 | 0.0025 | 0.01 | Li(M)0.9825Zr0.005Nb0.0025B0.01O2 |
참고예 2 | 0.02 | 0.008 | 0.0025 | 0.01 | Li(M)0.9795Zr0.008Nb0.0025B0.01O2 |
실시예 7 | 0.005 | 0.0035 | 0.0025 | 0.01 | Li(Ni0.915Co0.04Mn0.04Al0.005)0.984Zr0.0035Nb0.0025B0.01 |
실시예 8 | 0.01 | 0.0035 | 0.0025 | 0.01 | Li(Ni0.91Co0.04Mn0.04Al0.01)0.984Zr0.0035Nb0.0025B0.01 |
실시예 9 | 0.015 | 0.0035 | 0.0025 | 0.01 | Li(Ni0.905Co0.04Mn0.04Al0.015)0.984Zr0.0035Nb0.0025B0.01 |
실시예 10 | 0.022 | 0.0035 | 0.0025 | 0.01 | Li(Ni0.898Co0.04Mn0.04Al0.022)0.984Zr0.0035Nb0.0025B0.01 |
참고예 3 | 0.025 | 0.0035 | 0.0025 | 0.01 | Li(Ni0.895Co0.04Mn0.04Al0.025)0.984Zr0.0035Nb0.0025B0.01 |
실시예 11 | 0.02 | 0.0035 | 0.0005 | 0.01 | Li(M)0.986Zr0.0035Nb0.0005B0.01O2 |
실시예 12 | 0.02 | 0.0035 | 0.001 | 0.01 | Li(M)0.9855Zr0.0035Nb0.0001B0.01O2 |
참고예 4 | 0.02 | 0.0035 | 0.005 | 0.01 | Li(M)0.9815Zr0.0035Nb0.005B0.01O2 |
구분 | 도핑 원소 | 양극 활물질 전체 조성 | ||
Zr | Nb | B | ||
비교예 2 | 0.0035 | 0.0025 | 0 | Li(Ni0.78Co0.10Mn0.10Al0.02)0.994Zr0.0035Nb0.0025 |
비교예 3 | 0.0035 | 0.0025 | 0 | Li(Ni0.81Co0.12Mn0.05Al0.02)0.994Zr0.0035Nb0.0025 |
비교예 4 | 0.0035 | 0.0025 | 0 | Li(Ni0.83Co0.07Mn0.08Al0.02)0.994Zr0.0035Nb0.0025 |
비교예 5 | 0.0035 | 0.0025 | 0 | Li(Ni0.84Co0.07Mn0.07Al0.02)0.994Zr0.0035Nb0.0025 |
비교예 6 | 0.0035 | 0.0025 | 0 | Li(Ni0.86Co0.05Mn0.07Al0.02)0.994Zr0.0035Nb0.0025 |
참고예 5 | 0.0035 | 0.0025 | 0.01 | Li(Ni0.78Co0.01Mn0.01Al0.02)0.984Zr0.0035Nb0.0025B0.01 |
참고예 6 | 0.0035 | 0.0025 | 0.01 | Li(Ni0.81Co0.12Mn0.05Al0.02)0.984Zr0.0035Nb0.0025B0.01 |
실시예 13 | 0.0035 | 0.0025 | 0.01 | Li(Ni0.83Co0.07Mn0.08Al0.02)0.984Zr0.0035Nb0.0025B0.01 |
실시예 14 | 0.0035 | 0.0025 | 0.01 | Li(Ni0.84Co0.07Mn0.07Al0.02)0.984Zr0.0035Nb0.0025B0.01 |
실시예 15 | 0.0035 | 0.0025 | 0.01 | Li(Ni0.86Co0.05Mn0.07Al0.02)0.984Zr0.0035Nb0.0025B0.01 |
a | b | c | 단위셀 부피 | I(003)/I(104) (강도기준) |
(110)면 FWHM | 결정립 크기(Å) | |
비교예1 | 2.8721 | 2.8721 | 14.2046 | 101.4829 | 1.2408 | 0.1886 | 1592 |
실시예1 | 2.8737 | 2.8737 | 14.2046 | 101.4970 | 1.2407 | 0.1901 | 1350 |
실시예2 | 2.8736 | 2.8736 | 14.2047 | 101.5120 | 1.2391 | 0.1916 | 1270 |
실시예3 | 2.8734 | 2.8734 | 14.2049 | 101.5210 | 1.2383 | 0.2014 | 1180 |
실시예4 | 2.8732 | 2.8732 | 14.2051 | 101.5360 | 1.2351 | 0.2017 | 1090 |
참고예 1 | 2.8722 | 2.8722 | 14.2046 | 101.4810 | 1.2408 | 0.1886 | 1576 |
방전용량 (mAh/g) |
초기효율 (%) |
상온수명 (%) |
고온수명 (%) |
상온초기저항 (Ω) |
저항증가율 (%) |
평균 누설전류 (mA) |
DSC peak 온도 (oC) |
|
비교예1 | 213.7 | 90.9 | 92.4 | 92.1 | 29.3 | 79.8 | 0.37 | 228 |
실시예1 | 220.3 | 94.7 | 95.2 | 95.1 | 23.1 | 40.7 | 0.20 | 228 |
실시예2 | 220.1 | 94.5 | 97.1 | 97.0 | 25.3 | 37.2 | 0.17 | 230 |
실시예3 | 219.6 | 94.4 | 97.6 | 97.3 | 25.4 | 36.4 | 0.17 | 231 |
실시예4 | 219.8 | 94.3 | 97.4 | 97.2 | 25.7 | 36.2 | 0.16 | 231 |
참고예1 | 215.3 | 91.2 | 98.1 | 97.8 | 31.2 | 79.8 | 0.12 | 232 |
방전용량 (mAh/g) |
초기효율 (%) |
상온수명 (%) |
고온수명 (%) |
상온초기저항 (Ω) |
저항증가율 (%) |
평균 누설전류 (mA) |
DSC peak 온도 (oC) |
|
실시예5 | 219.6 | 94.3 | 93.9 | 94.4 | 29.8 | 61.4 | 0.31 | 228.0 |
실시예3 | 219.6 | 94.4 | 97.6 | 97.3 | 25.4 | 36.4 | 0.17 | 231.0 |
실시예6 | 216.5 | 92.9 | 97.6 | 97.2 | 33.7 | 38.5 | 0.18 | 232.0 |
참고예2 | 206.9 | 86.9 | 98.5 | 98.2 | 39.1 | 58.3 | 0.20 | 232.0 |
방전용량 (mAh/g) |
초기효율 (%) |
상온수명 (%) |
고온수명 (%) |
상온초기저항 (Ω) |
저항증가율 (%) |
평균 누설전류 (mA) |
DSC peak 온도 (oC) |
|
실시예7 | 222.3 | 94.8 | 91.0 | 90.9 | 37.0 | 73.9 | 0.45 | 223.0 |
실시예8 | 221.3 | 94.6 | 94.5 | 94.9 | 27.2 | 49.5 | 0.27 | 228.0 |
실시예9 | 219.3 | 94.4 | 98.6 | 95.7 | 28.5 | 45.1 | 0.23 | 230.0 |
실시예3 | 219.6 | 94.4 | 97.6 | 97.3 | 25.4 | 36.4 | 0.18 | 231.0 |
실시예10 | 217.6 | 93.5 | 99.2 | 98.8 | 23.9 | 33.1 | 0.17 | 234.4 |
참고예 3 | 209.6 | 86.1 | 99.0 | 99.7 | 22.9 | 32.1 | 0.15 | 236.1 |
방전용량 (mAh/g) |
초기효율 (%) |
상온수명 (%) |
고온수명 (%) |
상온초기저항 (Ω) |
저항증가율 (%) |
평균 누설전류 (mA) |
DSC peak 온도 (oC) |
|
실시예11 | 218.1 | 93.7 | 96.5 | 96.4 | 27.8 | 42.5 | 0.23 | 229.0 |
실시예12 | 218.8 | 94.1 | 97.0 | 96.1 | 27.3 | 40.3 | 0.20 | 231.0 |
실시예3 | 219.6 | 94.4 | 97.6 | 97.3 | 25.4 | 36.4 | 0.17 | 231.0 |
참고예 4 | 214.7 | 91.7 | 96.7 | 96.6 | 30.0 | 65.5 | 0.17 | 231.0 |
방전용량 (mAh/g) |
초기효율 (%) |
상온수명 (%) |
고온수명 (%) |
상온초기저항 (Ω) |
저항증가율 (%) |
평균 누설전류 (mA) |
DSC peak 온도 | |
비교예2(Ni78%) | 198.43 | 86.80 | 96.9 | 95.3 | 16.2 | 42.8 | 0.21 | 233 |
참고예 5 | 198.32 | 86.75 | 97.3 | 97.1 | 17.1 | 35.7 | 0.17 | 236 |
비교예3(Ni81%) | 203.84 | 87.60 | 94.5 | 94.3 | 19.9 | 48.7 | 0.24 | 224 |
참고예 6 | 202.74 | 88.69 | 97.1 | 96.0 | 21.4 | 41.3 | 0.19 | 228 |
비교예4(Ni83%) | 210.5 | 89.50 | 95.5 | 95.4 | 21.9 | 44.9 | 0.21 | 222 |
실시예13 | 209.8 | 91.77 | 98.3 | 98.1 | 23.2 | 37.8 | 0.16 | 227 |
비교예5(Ni84%) | 211.7 | 91.80 | 95.3 | 95.1 | 22.2 | 47.9 | 0.23 | 223 |
실시예14 | 210.7 | 92.17 | 98.0 | 97.8 | 23.7 | 40.1 | 0.17 | 229 |
비교예6(Ni86%) | 218.8 | 92.60 | 95.5 | 95.3 | 24.3 | 45.3 | 0.21 | 218 |
실시예15 | 217.5 | 95.14 | 97.2 | 97.1 | 25.1 | 41.0 | 0.13 | 224 |
비교예1(Ni90%) | 213.7 | 90.9 | 92.4 | 92.1 | 29.3 | 79.8 | 0.37 | 228 |
실시예3 | 219.6 | 94.40 | 97.6 | 97.3 | 25.4 | 36.4 | 0.17 | 230 |
초기 확산계수 (*10-9m2/sec) | 초기 Rsei (Ω) |
초기 Rct (Ω) |
사이클 후 확산계수 (*10-9m2/sec) |
사이클 후 Rsei (Ω) |
사이클 후 Rct (Ω) |
확산계수 증가율 (%) |
Rsei 증가율 (%) |
Rct 증가율 (5) |
|
비교예1 | 7.24 | 3.22 | 5.62 | 5.96 | 11.90 | 8.88 | 21.47 | 269.5 | 58.0 |
실시예1 | 8.06 | 2.23 | 4.79 | 7.07 | 9.17 | 5.12 | 12.3 | 75.7 | 6.4 |
실시예2 | 8.04 | 2.31 | 4.84 | 7.06 | 8.76 | 5.03 | 12.2 | 73.6 | 3.8 |
실시예3 | 8.03 | 2.39 | 4.91 | 7.14 | 8.71 | 5.07 | 11.1 | 72.6 | 3.2 |
실시예4 | 8.01 | 2.51 | 4.93 | 7.21 | 8.64 | 5.11 | 10.0 | 70.9 | 3.5 |
참고예 1 | 6.24 | 3.48 | 6.17 | 6.18 | 9.64 | 7.03 | 1.0 | 63.9 | 12.2 |
Claims (15)
- 니켈, 코발트, 망간 및 알루미늄을 포함하는 금속 산화물 입자; 그리고상기 금속 산화물 입자에 도핑된 3종의 도핑 원소를 포함하는 리튬 이차 전지용 양극 활물질.
- 제1항에 있어서,상기 3종의 도핑 원소는 Nb, B 및 Zr인 리튬 이차 전지용 양극 활물질.
- 제2항에 있어서,상기 Nb의 도핑량은 니켈, 코발트, 망간, 알루미늄 및 도핑 원소의 총합 1몰에 대하여, 0.00001몰 내지 0.03몰 범위인 리튬 이차 전지용 양극 활물질.
- 제2항에 있어서,상기 B의 도핑량은 니켈, 코발트, 망간, 알루미늄 및 도핑 원소의 총합 1몰에 대하여, 0.001몰 내지 0.02몰인 리튬 이차 전지용 양극 활물질.
- 제2항에 있어서,상기 Zr의 도핑량은 니켈, 코발트, 망간, 알루미늄 및 도핑 원소의 총합 1몰에 대하여, 0.001몰 내지 0.007몰인 리튬 이차 전지용 양극 활물질.
- 제2항에 있어서,상기 Nb 및 Zr의 도핑량은 하기 식 1의 관계를 만족하는 것인 리튬 이차 전지용 양극 활물질.[식 1]0.5 < [Zr]/[Nb] < 10(식 1에서, [Nb] 및 [Zr]은 니켈, 코발트, 망간, 알루미늄 및 도핑 원소의 총합 1몰을 기준으로 한 각 원소의 도핑량을 의미함)
- 제2항에 있어서,상기 Nb 및 B의 도핑량은 하기 식 2의 관계를 만족하는 것인 리튬 이차 전지용 양극 활물질.[식 2]0.3 < [B]/[Nb] < 30(식 1에서, [Nb] 및 [B]은 니켈, 코발트, 망간, 알루미늄 및 도핑 원소의 총합 1몰을 기준으로 한 각 원소의 도핑량을 의미함)
- 제1항에 있어서,상기 양극 활물질은 하기 화학식 1로 표현되는 것인 리튬 이차 전지용 양극 활물질.[화학식 1]Lia[NixCoyMnzAlh]1-t(NbiZrjBk)tO2-pX2p(상기 화학식 1에서,X는, F, N, 및 P을 포함하는 군에서 선택된 하나 이상의 원소이며, Zra는 0.8 ≤ a ≤ 1.3이고,t는 0.0061 ≤ t ≤ 0.057이고,0.6 ≤ x ≤ 0.95, 0 < y ≤ 0.2, 0 < z ≤ 0.2, 0.008 ≤ h ≤ 0.029, 0.0001 ≤ i ≤ 0.03, 0.001 ≤ j ≤ 0.007, 0.005) ≤ k ≤ 0.02, 0 ≤ p ≤ 0.02이다.
- 제8항에 있어서,상기 h는 0.005 ≤ h ≤ 0.025 범위인 리튬 이차 전지용 양극 활물질.
- 제1항에 있어서,상기 양극 활물질의 초기 확산계수는 7.30*10-9m2/sec 내지 8.10*10-9m2/sec 범위인 리튬 이차 전지용 양극 활물질.
- 제1항에 있어서,상기 금속 산화물 입자의 결정립 크기는 1,000Å 내지 1,560Å 범위인 리튬 이차 전지용 양극 활물질.
- 제1항에 있어서,상기 금속 산화물 입자의 (110)면에 대한 반치폭(FWHM) 값은 0.1901 내지 0.2017 범위인 리튬 이차 전지용 양극 활물질.
- 제1항에 있어서,상기 리튬 이차 전지용 양극 활물질은 X-선 회절 패턴 측정시,(104)면의 피크 강도에 대한 (003)면의 피크 강도비인 I(003)/I(104)는 1.2350 내지 1.2410 범위인 리튬 이차 전지용 양극 활물질.
- 제1항에 있어서,상기 금속 산화물 입자에서 니켈의 함량은,상기 니켈, 코발트, 망간, 및 알루미늄의 총합 1몰을 기준으로, 0.8몰 이상인 리튬 이차 전지용 양극 활물질.
- 제1항 내지 제14항 중 어느 한 항의 양극 활물질을 포함하는 양극;음극; 및비수 전해질을 포함하는 리튬 이차 전지.
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KR20180071714A (ko) * | 2016-12-20 | 2018-06-28 | 주식회사 포스코 | 리튬 이차 전지용 양극 활물질, 이의 제조 방법, 및 이를 포함하는 리튬 이차 전지 |
KR20190078498A (ko) * | 2017-12-26 | 2019-07-04 | 주식회사 포스코 | 리튬 이차 전지용 양극 활물질, 이의 제조 방법, 및 이를 포함하는 리튬 이차 전지 |
KR20200070650A (ko) * | 2018-12-10 | 2020-06-18 | 주식회사 엘지화학 | 리튬이차전지용 양극재, 이를 포함하는 양극 및 리튬이차전지 |
CN111430700A (zh) * | 2019-10-10 | 2020-07-17 | 蜂巢能源科技有限公司 | 用于锂离子电池的四元正极材料及其制备方法和锂离子电池 |
CN111435743A (zh) * | 2019-12-19 | 2020-07-21 | 蜂巢能源科技有限公司 | 四元正极材料、正极、电池 |
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EP4266422A1 (en) | 2023-10-25 |
CN116615817A (zh) | 2023-08-18 |
KR20220089244A (ko) | 2022-06-28 |
JP2024500892A (ja) | 2024-01-10 |
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