WO2022119156A1 - 양극 활물질 및 이를 포함하는 리튬 이차전지 - Google Patents
양극 활물질 및 이를 포함하는 리튬 이차전지 Download PDFInfo
- Publication number
- WO2022119156A1 WO2022119156A1 PCT/KR2021/016129 KR2021016129W WO2022119156A1 WO 2022119156 A1 WO2022119156 A1 WO 2022119156A1 KR 2021016129 W KR2021016129 W KR 2021016129W WO 2022119156 A1 WO2022119156 A1 WO 2022119156A1
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- WO
- WIPO (PCT)
- Prior art keywords
- space group
- lithium
- active material
- lithium manganese
- manganese oxide
- Prior art date
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 92
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 239000006182 cathode active material Substances 0.000 title abstract description 16
- 239000011572 manganese Substances 0.000 claims abstract description 35
- 229910002102 lithium manganese oxide Inorganic materials 0.000 claims description 126
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 claims description 119
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 116
- 239000007774 positive electrode material Substances 0.000 claims description 78
- 229910052751 metal Inorganic materials 0.000 claims description 49
- 229910052759 nickel Inorganic materials 0.000 claims description 48
- 239000002245 particle Substances 0.000 claims description 48
- 239000002184 metal Substances 0.000 claims description 25
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- 239000011258 core-shell material Substances 0.000 claims description 11
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 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 description 5
- 229910052738 indium Inorganic materials 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 3
- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
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- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 abstract description 27
- 239000006104 solid solution Substances 0.000 abstract description 17
- 229910052748 manganese Inorganic materials 0.000 abstract description 12
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 11
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- 239000010941 cobalt Substances 0.000 description 9
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- 238000004519 manufacturing process Methods 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
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- 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
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- C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
- C01G45/1228—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [MnO2]n-, e.g. LiMnO2, Li[MxMn1-x]O2
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Definitions
- the present invention relates to a positive electrode active material and a lithium secondary battery including the same, and more specifically, to a lithium-manganese-based oxide in excess of lithium, which is a solid solution of a phase belonging to the C2/m space group and a phase belonging to the R3-m space group, Stability caused by excess lithium and manganese in the lithium manganese oxide by the existence of a region in which an abundance ratio of a phase belonging to the C2/m space group and a phase belonging to the R3-m space group is different in the lithium manganese oxide It relates to a positive electrode active material in which deterioration is alleviated and/or prevented, and a lithium secondary battery including the same.
- a battery stores electric power by using a material capable of electrochemical reaction between the anode and the cathode.
- a representative example of such a battery is a lithium secondary battery that stores electrical energy by a difference in chemical potential when lithium ions are intercalated/deintercalated in a positive electrode and a negative electrode.
- the lithium secondary battery is manufactured by using a material capable of reversible intercalation/deintercalation of lithium ions as a positive electrode and a negative electrode active material, and filling an organic electrolyte solution or a polymer electrolyte solution between the positive electrode and the negative electrode.
- a lithium composite oxide is used as a cathode active material for a lithium secondary battery, for example, LiCoO 2 , LiMn 2 O 4 , LiNiO 2 , LiMnO 2 or Korean Patent Application Laid-Open No. 10-2015-0069334 (published on June 23, 2015) ), complex oxides in which Ni, Co, Mn, or Al are complexed are being studied.
- LiCoO 2 is used the most because of its excellent lifespan characteristics and charge/discharge efficiency, but it is expensive due to the resource limitation of cobalt used as a raw material, so it has a limitation in price competitiveness.
- LiMnO 2 , LiMn 2 O 4 Lithium manganese oxide has advantages of excellent thermal stability and low price, but has problems in that it has a small capacity and poor high temperature characteristics.
- the LiNiO 2 -based positive electrode active material exhibits high discharge capacity battery characteristics, it is difficult to synthesize due to a cation mixing problem between Li and a transition metal, and thus has a large problem in rate characteristics.
- Li by-products are generated according to the degree of intensification of the cation mixing, and most of these Li by-products are composed of LiOH and Li 2 CO 3 compounds. It causes gas generation due to charging and discharging after manufacturing. Residual Li 2 CO 3 increases cell swelling, which not only reduces the cycle, but also causes the battery to swell.
- lithium manganese-based oxide in excess of lithium in excess of the sum of the transition metal content and Mn content in the transition metal as a positive electrode active material for a lithium secondary battery.
- This lithium-rich lithium manganese-based oxide is also referred to as a lithium-overlithiated layered oxide (OLO).
- the OLO has the advantage that it can theoretically exhibit a high capacity under a high voltage operating environment, in fact, it has relatively low electrical conductivity due to the excessive amount of Mn in the oxide. It has the disadvantage of low capability rate). As such, when the rate characteristic is low, there is a problem in that the charge/discharge capacity and lifespan efficiency (cycle capacity retention rate; capacity retentio) of the lithium secondary battery are deteriorated during cycling.
- reduction in charge/discharge capacity or voltage decay during cycling of a lithium secondary battery using OLO may be induced by a phase transition according to movement of a transition metal among lithium manganese oxides.
- a transition metal among lithium manganese oxides having a layered crystal structure moves in an unintended direction to induce a phase transition
- a spinel or similar crystal structure may occur entirely and/or partially in the lithium manganese oxide.
- lithium secondary battery market While the growth of lithium secondary batteries for electric vehicles is playing a leading role in the market, the demand for positive electrode active materials used in lithium secondary batteries is also constantly changing.
- lithium secondary batteries using LFP have been mainly used from the viewpoint of securing safety, etc., but recently, the use of nickel-based lithium composite oxides having a large energy capacity per weight compared to LFP has been expanding.
- nickel-based lithium composite oxides recently used as positive electrode active materials for high-capacity lithium secondary batteries include ternary metal elements such as nickel, cobalt and manganese or nickel, cobalt, and aluminum.
- ternary metal elements such as nickel, cobalt and manganese or nickel, cobalt, and aluminum.
- cobalt Due to the unstable supply and demand and excessively expensive compared to other raw materials, there is a need for a cathode active material with a new composition capable of reducing the cobalt content or excluding cobalt.
- lithium manganese oxide in excess of lithium can meet the market expectations described above, but the electrochemical properties or stability of lithium manganese oxide are insufficient to replace the commercially available NCM or NCA type positive electrode active material. can do
- lithium manganese oxide in excess of lithium has disadvantages in terms of electrochemical properties and/or stability. If possible, it was confirmed by the present inventors that lithium manganese-based oxide in excess of lithium can also exhibit electrochemical properties and stability at a level that can be commercialized.
- the present invention provides a positive electrode active material comprising an excess lithium-manganese oxide as a solid solution of a phase belonging to the C2/m space group and a phase belonging to the R3-m space group, and among the lithium manganese oxides, the C2/m space group
- the present invention is a positive electrode active material comprising an excess lithium manganese oxide, which is a solid solution of a phase belonging to the C2/m space group and a phase belonging to the R3-m space group, in the region where the phase belonging to the R3-m space group exists.
- An object of the present invention is to provide a positive electrode active material capable of improving the low discharge capacity and rate characteristics of the existing lithium-manganese oxide in excess of lithium by allowing the concentration of Ni to exist within a predetermined range.
- an object of the present invention is to provide a lithium secondary battery having improved low rate characteristics of the existing OLO by using a positive electrode including a positive electrode active material as defined herein.
- a positive active material comprising an excess lithium lithium manganese oxide containing at least lithium, nickel and manganese, C2 / m space group of the lithium manganese oxide
- the concentration of the metal element in the lithium manganese oxide may satisfy Equation 1 below.
- M 1 is the number of moles of all metal elements (excluding lithium) in the lithium manganese oxide
- M 2 is the number of moles of nickel based on all metal elements (excluding lithium) in the lithium manganese oxide.
- the lithium manganese oxide may be a core-shell particle including a core and a shell covering at least a portion of a surface of the core.
- the core and the shell are distinguished only to refer to regions in which the abundance ratio of the phase belonging to the C2/m space group and the phase belonging to the R3-m space group of the lithium manganese oxide is different. That is, even when the lithium manganese oxide is a core-shell particle, it should be understood that the core and the shell form a single solid solution.
- the phase belonging to the C2/m space group and the phase belonging to the R3-m space group coexist in the core, and the phase belonging to the C2/m space group in the shell
- the ratio of the phases belonging to the R3-m space group to the phases may be greater than the ratio of the phases belonging to the R3-m space group to the phases belonging to the C2/m space group in the core.
- the concentration of the metal element in the shell may satisfy Equation 3 below.
- M 3 is the number of moles of all metal elements (excluding lithium) in the shell
- M 4 is the number of moles of nickel based on all metallic elements (excluding lithium) in the shell.
- the ratio of the phase belonging to the R3-m space group to the phase belonging to the C2/m space group among the lithium manganese oxide has a gradient that increases from the core to the shell, so that in the lithium manganese oxide It is possible to prevent damage to particles during charging and discharging by reducing abrupt changes in the crystal structure.
- the lithium manganese oxide may be represented by Formula 1 below.
- M1 is Mo, Nb, Fe, Cr, V, Cu, Zn, Sn, Mg, Ru, Al, Ti, Zr, B, Na, K, Y, P, Ba, Sr, La, Ga, Gd, Sm, W, Ca, Ce, Ta, Sc, In, S, Ge, Si and at least one selected from Bi,
- the lithium manganese oxide as defined herein is a solid solution in which a phase belonging to the C2/m space group and a phase belonging to the R3-m space group coexist in a single particle.
- a single particle means "a particle of a non-agglomerated form including a single primary particle", “a particle formed by agglomeration of a relatively small number of primary particles” or “a plurality of (tens to hundreds or more) It may mean “particles formed by agglomeration of primary particles”.
- the phase belonging to the C2/m space group is caused by Li 2 MnO 3
- the phase belonging to the R3-m space group is Li a Ni x Co y Mn z M1 1-(x+y+z ) is caused by O 2 .
- a positive electrode including the above-described positive electrode active material is provided.
- a lithium secondary battery using the above-described positive electrode is provided.
- the present invention it is possible to improve the limitations of the existing lithium-excess lithium manganese-based oxide, which has several disadvantages in terms of electrochemical properties and/or stability when compared with other commercially available positive electrode active materials.
- the lithium manganese oxide contained in the positive electrode active material according to the present invention is a lithium manganese oxide in excess of lithium, which is a solid solution of a phase belonging to the C2/m space group and a phase belonging to the R3-m space group.
- the lithium manganese-based oxide containing lithium and manganese in excess may exhibit a high capacity under a high voltage operating environment.
- such lithium manganese oxide has a disadvantage in that the discharge capacity and rate characteristics are low due to excess lithium and manganese among oxides, but, like the positive electrode active material according to the present invention, it belongs to the C2/m space group.
- the proportion of the phase belonging to the R3-m space group is varied for each region, the effect of improving the discharge capacity and rate characteristics is exhibited.
- the ratio of the phase belonging to the R3-m space group to the phase belonging to the C2/m space group in the surface portion (which may be referred to as a core) of the lithium manganese oxide is large, (mainly the C2/m space group)
- the low electrical conductivity of lithium manganese oxide is improved by alleviating the charge-transfer and/or diffusion of Li ions on the particle surface (which is highly likely to be caused by a phase belonging to the It is possible to improve with
- FIG. 1 shows the TEM analysis result of the lithium manganese-based oxide contained in the positive electrode active material according to Example 4.
- FIG. 1 shows a 50 nm scale TEM image and a 5 nm scale TEM image of an enlarged area indicated in the 50 nm scale TEM image, and a crystal structure confirmed through FFT conversion for the A and B regions of the 5 nm scale TEM image. was shown.
- FIG. 2 is a line scanning the EDX mapping result of the cross-sectional TEM image of the lithium manganese oxide included in the positive active material according to Example 4 to confirm the change in the concentration (at%) of nickel from the core to the shell of the lithium manganese oxide. It is a sum spectrum. Region A indicated in the line sum spectrum of FIG. 2 corresponds to region A of FIG. 1 .
- the positive electrode active material including at least lithium, nickel, manganese, and an excess lithium manganese-based oxide containing at least lithium, nickel, manganese, and a doping metal and a lithium secondary battery including the positive electrode active material according to the present invention will be described in more detail.
- a positive electrode active material including at least lithium, nickel, manganese, and a lithium manganese-based oxide in excess of lithium including a doping metal.
- the lithium manganese oxide is a composite metal oxide capable of intercalation and deintercalation of lithium ions.
- the lithium manganese-based oxide included in the positive active material as defined herein may be a secondary particle including at least one primary particle.
- second particles including at least one primary particle is intended to include both “particles formed by agglomeration of a plurality of primary particles” or “non-agglomerated particles including a single primary particle”. will have to be interpreted.
- the primary particle and the secondary particle may each independently have a rod shape, an oval shape, and/or an irregular shape.
- the average long axis length of the primary particles constituting the lithium manganese oxide may be 0.1 ⁇ m to 5 ⁇ m, and the secondary The average long axis length of the particles may be 1 ⁇ m to 30 ⁇ m.
- the average long axis length of the secondary particles may vary depending on the number of the primary particles constituting the secondary particles, and particles having various average long axis lengths may be included in the positive active material.
- lithium manganese oxide is "a particle in a non-agglomerated form including a single primary particle” or "a particle formed by agglomeration of a relatively small number of primary particles," "Ratio including a single primary particle”
- the size (average particle diameter) of primary particles included in “aggregated particles” or “particles formed by agglomeration of a relatively small number of primary particles” is “secondary particles formed by agglomeration of dozens to hundreds or more primary particles” It may be larger than the primary particles (average particle diameter) included in “particles”.
- lithium manganese oxide which is “a particle in a non-agglomerated form including a single primary particle” or “a particle formed by agglomeration of a relatively small number of primary particles,” is generally “tens to hundreds or more. It requires stronger heat treatment conditions (high heat treatment temperature/long time heat treatment) compared to the case of manufacturing "secondary particles formed by agglomeration of primary particles.” For example, it is known that, when heat treatment is performed at a relatively high temperature (800° C. or higher) for a long time, particle growth (crystal growth) is promoted to obtain a cathode active material having a single particle size and a low aggregation degree at the same time.
- the lithium manganese oxide when the lithium manganese oxide is "particles in a non-agglomerated form including a single primary particle" or “particles formed by agglomeration of a relatively small number of primary particles," the average of the primary particles The major axis length may be in the range of 0.5 ⁇ m to 20 ⁇ m.
- the lithium manganese oxide when the lithium manganese oxide is "particles formed by aggregation of a plurality of (tens to hundreds or more) primary particles," the average long axis length of the primary particles may be in the range of 0.1 ⁇ m to 5 ⁇ m. have.
- the primary particles may include at least one crystallite (crystallite). That is, the primary particle may be formed as a single crystallite or may exist as a particle including a plurality of crystallites.
- the lithium manganese oxide as defined herein is a composite metal oxide containing lithium and manganese in excess, and a phase belonging to the C2/m space group and a phase belonging to the R3-m space group coexist in the lithium manganese oxide. That is, the lithium manganese oxide is a solid solution of a phase belonging to the C2/m space group and a phase belonging to the R3-m space group.
- the solid solution means that the phase belonging to the C2/m space group and the phase belonging to the R3-m space group exist as single particles in the lithium manganese oxide.
- a single particle means "a particle of a non-agglomerated form including a single primary particle", “a particle formed by agglomeration of a relatively small number of primary particles” or “a plurality of (tens to hundreds or more) It may mean “particles formed by agglomeration of primary particles”.
- the solid solution does not mean a state in which the phase belonging to the C2/m space group and the phase belonging to the R3-m space group present in the lithium manganese oxide are physically and/or chemically bonded or attached to each other.
- a phase belonging to the C2/m space group and a phase belonging to the R3-m space group coexist, but in the lithium manganese oxide, a phase belonging to the C2/m space group and the R3-m space group Regions with different proportions of the phases to which they belong may exist.
- the concentration of the metal element in the lithium manganese oxide may satisfy Equation 1 below.
- M 1 is the number of moles of all metal elements (excluding lithium) in the lithium manganese oxide
- M 2 is the number of moles of nickel based on all metal elements (excluding lithium) in the lithium manganese oxide.
- the lithium manganese oxide according to the present application contains an excess of lithium, when the content of Ni in the lithium manganese oxide increases, cation mixing becomes severe and LiOH and Li 2 CO in the lithium manganese oxide
- the amount of lithium impurities such as 3 and the like may be increased.
- the lithium impurity is a major cause of gelation of the paste when manufacturing the positive electrode paste using the positive electrode active material or the swelling of the cell during charging and discharging after the positive electrode is manufactured.
- nickel in the lithium manganese oxide is present in the phase belonging to the R3-m space group and does not exist in the phase belonging to the C2/m space group, the content of nickel in the lithium manganese oxide is as the following formula 2 can be expressed
- M 1' is the number of moles of all metal elements (excluding lithium) in the phase belonging to the R3-m space group
- M 2' is the number of moles of nickel based on all metal elements (excluding lithium) in the phase belonging to the R3-m space group.
- Equation 2 when M 2' /M 1' exceeds 0.70, the content of Ni in the phase belonging to the R3-m space group is excessively increased, and cation mixing with Li may occur.
- M 2′ /M 1′ when M 2′ /M 1′ is less than 0.40, the content of Ni in the phase belonging to the R3-m space group becomes insufficient, and as manganese is excessively present, charge-transfer and/or diffusion of Li ions becomes difficult. can be lowered
- the lithium manganese oxide may be a core-shell particle including a core and a shell covering at least a portion of a surface of the core.
- the core and the shell are distinguished only to refer to regions in which the abundance ratio of the phase belonging to the C2/m space group and the phase belonging to the R3-m space group of the lithium manganese oxide is different. That is, even when the lithium manganese oxide is a core-shell particle, it should be understood that the core and the shell form a single solid solution.
- the shell (or surface part) and the core (or central part) of the particle are distinguished by the concentration of any metal element present in the corresponding region, or the ratio of the phase (crystal structure) present in the corresponding region as will be described later. can be distinguished as
- the shell may occupy at least a portion of the surface of the core. That is, the shell may exist partially on the surface of the core, or may occupy the entire surface of the core.
- the thickness of the shell may be 0.001r to 0.9r, but is not limited thereto, and as described above, the core and the shell are any metal element. It will be distinguished by the concentration of , or as the proportion of phases (crystal structures) present in the region, as will be described later.
- a region in which a phase belonging to the R3-m space group among the lithium manganese oxide is predominantly present may exist. That is, the abundance ratio of the phase belonging to the R3-m space group in the region where the phase belonging to the C2/m space group and the phase belonging to the R3-m space group coexist in the lithium manganese oxide is C2/m in the lithium manganese oxide When it is greater than the proportion of the phase belonging to the space group, the region may be defined as a region in which the phase belonging to the R3-m space group predominantly exists.
- the lithium manganese oxide is a core-shell particle
- a phase belonging to the C2/m space group and a phase belonging to the R3-m space group coexist in the core and the shell, but the shell in the core
- the ratio of the phase belonging to the R3-m space group to the phase belonging to the C2/m space group within the shell may be different from the ratio of the phase belonging to the R3-m space group to the phase belonging to the C2/m space group in the shell. have.
- a phase belonging to the R3-m space group may predominantly exist in any one region of the core and the shell.
- the ratio of the phases belonging to the R3-m space group is greater than the ratio of the phases belonging to the R3-m space group to the phases belonging to the C2/m space group in the core.
- the ratio of the phase belonging to the R3-m space group to the phase belonging to the C2/m space group in the core and the shell may be confirmed through the content of Ni in the core and the shell.
- the lithium manganese oxide when the lithium manganese oxide is a core-shell particle, a phase belonging to the C2/m space group and a phase belonging to the R3-m space group coexist in the core, but in the shell, the Only phases belonging to the R3-m space group can exist.
- the concentration of the metal element in the shell may satisfy Equation 3 below.
- M 3 is the number of moles of all metal elements (excluding lithium) in the shell
- M 4 is the number of moles of nickel based on all metallic elements (excluding lithium) in the shell.
- nickel in the lithium manganese oxide exists in a phase belonging to the R3-m space group and does not exist in a phase belonging to the C2/m space group
- the content of nickel in the shell can be expressed as Equation 4 below have.
- M 3' is the number of moles of all metal elements (excluding lithium) in the phase belonging to the R3-m space group in the shell
- M 4' is the number of moles of nickel based on all metallic elements (excluding lithium) in the phase belonging to the R3-m space group in the shell.
- Equation 3 when M 4 /M 3 or M 4' /M 3' exceeds 0.75, the content of Ni in the phase belonging to the R3-m space group is excessively increased, resulting in cation mixing with Li may occur, and when M 4 /M 3 in Equation 3 is less than 0.24 or M 4 ' /M 3' in Equation 4 is less than 0.40, the content of Ni in the phase belonging to the R3-m space group is insufficient, and as manganese is excessively present, charge-transfer and/or diffusion of Li ions may be reduced.
- the C2/m space group A phase belonging to the R3-m space group may partially offset the instability of the phase belonging to
- the phase belonging to the R3-m space group is predominantly present in the shell of the lithium manganese oxide, the particle surface with a high possibility of being mainly caused by a phase belonging to the C2/m space group unlike the conventional lithium manganese oxide It is possible to relax the charge-transfer and/or diffusion of Li ions in
- a ratio of the phase belonging to the R3-m space group to the phase belonging to the C2/m space group among the lithium manganese oxide may have a gradient that increases from the core toward the shell.
- a sharp change in the crystal structure between the core and the shell can be reduced. and a phase belonging to the C2/m space group and a phase belonging to the R3-m space group among the lithium manganese oxide may stably form a solid solution.
- the surface kinetics of the lithium manganese oxide can be improved by ensuring that the region in which the phase belonging to the R3-m space group exists in the core and the concentration of the metal element in the shell satisfy Equations 1 to 4 described above.
- the lithium manganese-based oxide as defined herein may be represented by Formula 1 below.
- M1 is Mo, Nb, Fe, Cr, V, Cu, Zn, Sn, Mg, Ru, Al, Ti, Zr, B, Na, K, Y, P, Ba, Sr, La, Ga, Gd, Sm, W, Ca, Ce, Ta, Sc, In, S, Ge, Si and at least one selected from Bi,
- the lithium manganese-based oxide represented by Formula 1 may optionally include cobalt.
- a ratio of the number of moles of cobalt to the number of moles of all metal elements in the lithium manganese-based oxide may be 10% or less.
- the lithium manganese-based oxide represented by Formula 1 is an oxide of C2/m phase represented as Li 2 MnO 3 and R3-m represented as Li a Ni x Co y Mn z M1 1-(x+y+z) O 2 It is a complex oxide in which the oxides of the phase coexist. At this time, the oxide of the C2/m phase and the oxide of the R3-m phase exist in a solid solution state.
- the lithium manganese oxide represented by Formula 1 when r exceeds 0.8, the ratio of Li 2 MnO 3 , which is an oxide of the C2/m phase among the lithium manganese oxides, is excessively increased, so that the cathode active material is discharged. There is a possibility that the capacity may decrease.
- a positive electrode including a positive electrode current collector and a positive electrode active material layer formed on the positive electrode current collector may be provided.
- the positive electrode active material layer may include the lithium manganese oxide according to various embodiments of the present invention described above as a positive electrode active material.
- lithium manganese oxide will be referred to as a positive electrode active material.
- the positive electrode current collector is not particularly limited as long as it has conductivity without causing chemical change in the battery, and for example, stainless steel, aluminum, nickel, titanium, fired carbon, or carbon, nickel, titanium on the surface of aluminum or stainless steel. , silver or the like surface-treated may be used.
- the positive electrode current collector may typically have a thickness of 3 to 500 ⁇ m, and may increase the adhesion of the positive electrode active material by forming fine irregularities on the surface of the current collector.
- it may be used in various forms, such as a film, a sheet, a foil, a net, a porous body, a foam, a non-woven body.
- the positive electrode active material layer may be prepared by applying a positive electrode slurry composition including a conductive material and optionally a binder along with the positive electrode active material to the positive electrode current collector.
- the positive active material may be included in an amount of 80 to 99 wt%, more specifically 85 to 98.5 wt%, based on the total weight of the positive active material layer. It may exhibit excellent capacity characteristics when included in the above content range, but is not necessarily limited thereto.
- the conductive material is used to impart conductivity to the electrode, and in the configured battery, it can be used without any particular limitation as long as it has electronic conductivity without causing chemical change.
- Specific examples include graphite such as natural graphite and artificial graphite; carbon-based materials such as carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, summer black, and carbon fiber; metal powders or metal fibers, such as copper, nickel, aluminum, and silver; conductive whiskeys such as zinc oxide and potassium titanate; conductive metal oxides such as titanium oxide; or conductive polymers such as polyphenylene derivatives, and the like, and one or a mixture of two or more thereof may be used.
- the conductive material may be included in an amount of 0.1 to 15 wt% based on the total weight of the positive electrode active material layer.
- the binder serves to improve adhesion between the positive active material particles and the adhesion between the positive active material and the current collector.
- Specific examples include polyvinylidene fluoride (PVDF), vinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinyl alcohol, polyacrylonitrile, carboxymethyl cellulose (CMC) ), starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene polymer (EPDM), sulfonated-EPDM, styrene butadiene rubber (SBR), fluororubber, or various copolymers thereof, and any one of them or a mixture of two or more thereof may be used.
- the binder may be included in an amount of 0.1 to 15 wt% based on the total weight of the positive active material layer.
- the positive electrode may be manufactured according to a conventional positive electrode manufacturing method except for using the above positive electrode active material. Specifically, the positive electrode active material and, optionally, the positive electrode slurry composition prepared by dissolving or dispersing the binder and the conductive material in a solvent may be coated on the positive electrode current collector, and then dried and rolled.
- the solvent may be a solvent generally used in the art, dimethyl sulfoxide (DMSO), isopropyl alcohol (isopropyl alcohol), N-methylpyrrolidone (NMP), acetone (acetone) or water, and the like, and any one of them or a mixture of two or more thereof may be used.
- the amount of the solvent used is enough to dissolve or disperse the positive electrode active material, the conductive material and the binder in consideration of the application thickness of the slurry and the production yield, and to have a viscosity capable of exhibiting excellent thickness uniformity when applied for the production of the positive electrode thereafter. do.
- the positive electrode may be prepared by casting the positive electrode slurry composition on a separate support and then laminating a film obtained by peeling it from the support on the positive electrode current collector.
- an electrochemical device including the above-described positive electrode may be provided.
- the electrochemical device may specifically be a battery, a capacitor, or the like, and more specifically, may be a lithium secondary battery.
- the lithium secondary battery may include a positive electrode, a negative electrode positioned opposite to the positive electrode, and a separator and an electrolyte interposed between the positive electrode and the negative electrode.
- a positive electrode a negative electrode positioned opposite to the positive electrode
- a separator and an electrolyte interposed between the positive electrode and the negative electrode.
- the lithium secondary battery may optionally further include a battery container accommodating the electrode assembly of the positive electrode, the negative electrode, and the separator, and a sealing member sealing the battery container.
- the negative electrode may include a negative electrode current collector and an anode active material layer positioned on the negative electrode current collector.
- the negative electrode current collector is not particularly limited as long as it has high conductivity without causing chemical change in the battery, and for example, copper, stainless steel, aluminum, nickel, titanium, fired carbon, copper or stainless steel surface. Carbon, nickel, titanium, silver, etc. surface-treated, aluminum-cadmium alloy, etc. may be used.
- the negative electrode current collector may have a thickness of typically 3 ⁇ m to 500 ⁇ m, and similarly to the positive electrode current collector, fine irregularities may be formed on the surface of the current collector to strengthen the bonding force of the negative electrode active material.
- it may be used in various forms, such as a film, a sheet, a foil, a net, a porous body, a foam, a nonwoven body.
- the negative electrode active material layer may be prepared by applying a negative electrode slurry composition including a conductive material and optionally a binder along with the negative electrode active material to the negative electrode current collector.
- a compound capable of reversible intercalation and deintercalation of lithium may be used.
- Specific examples include carbonaceous materials such as artificial graphite, natural graphite, graphitized carbon fiber, and amorphous carbon; metal compounds capable of alloying with lithium, such as Si, Al, Sn, Pb, Zn, Bi, In, Mg, Ga, Cd, Si alloy, Sn alloy, or Al alloy; metal oxides capable of doping and dedoping lithium, such as SiO ⁇ (0 ⁇ ⁇ ⁇ 2), SnO 2 , vanadium oxide, and lithium vanadium oxide;
- a composite including the metallic compound and a carbonaceous material such as a Si-C composite or a Sn-C composite may be used, and any one or a mixture of two or more thereof may be used.
- a metal lithium thin film may be used as the negative electrode active material.
- both low crystalline carbon and high crystalline carbon may be used.
- low crystalline carbon soft carbon and hard carbon are representative, and as high crystalline carbon, amorphous, plate-like, flaky, spherical or fibrous natural or artificial graphite, Kish graphite (Kish) graphite), pyrolytic carbon, mesophase pitch based carbon fiber, meso-carbon microbeads, liquid crystal pitches (Mesophase pitches), and petroleum and coal tar pitch (petroleum or coal tar pitch) High-temperature calcined carbon such as derived cokes) is a representative example.
- the negative active material may be included in an amount of 80 to 99 wt% based on the total weight of the negative electrode and the active material layer.
- the binder is a component that assists in bonding between the conductive material, the active material, and the current collector, and may be typically added in an amount of 0.1 to 10 wt% based on the total weight of the negative electrode and the active material layer.
- binders include polyvinylidene fluoride (PVDF), polyvinyl alcohol, carboxymethylcellulose (CMC), starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoro and roethylene, polyethylene, polypropylene, ethylene-propylene-diene polymer (EPDM), sulfonated-EPDM, styrene-butadiene rubber, nitrile-butadiene rubber, fluororubber, and various copolymers thereof.
- PVDF polyvinylidene fluoride
- CMC carboxymethylcellulose
- EPDM ethylene-propylene-diene polymer
- sulfonated-EPDM st
- the conductive material is a component for further improving the conductivity of the negative electrode active material, and may be added in an amount of 10 wt% or less, preferably 5 wt% or less, based on the total weight of the negative electrode active material layer.
- a conductive material is not particularly limited as long as it has conductivity without causing a chemical change in the battery.
- graphite such as natural graphite or artificial graphite
- carbon black such as acetylene black, Ketjen black, channel black, furnace black, lamp black, and thermal black
- conductive fibers such as carbon fibers and metal fibers
- metal powders such as carbon fluoride, aluminum, 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 may be used.
- the negative electrode active material layer is prepared by applying and drying a negative electrode slurry composition prepared by dissolving or dispersing the negative electrode active material, and optionally a binder and a conductive material in a solvent on the negative electrode current collector and drying, or the negative electrode slurry It can be prepared by casting the composition on a separate support and then laminating a film obtained by peeling it from the support onto a negative electrode current collector.
- the negative electrode active material layer is coated with a negative electrode slurry composition prepared by dissolving or dispersing the negative electrode active material, and optionally a binder and a conductive material in a solvent on the negative electrode current collector and drying, or the negative electrode slurry It can also be prepared by casting the composition on a separate support and then laminating the film obtained by peeling it off from the support on the negative electrode current collector.
- a negative electrode slurry composition prepared by dissolving or dispersing the negative electrode active material, and optionally a binder and a conductive material in a solvent on the negative electrode current collector and drying, or the negative electrode slurry It can also be prepared by casting the composition on a separate support and then laminating the film obtained by peeling it off from the support on the negative electrode current collector.
- the separator separates the anode and the anode and provides a passage for lithium ions to move, and as long as it is used as a separator in a lithium secondary battery, it can be used without any particular limitation, especially for the movement of ions in the electrolyte It is preferable to have a low resistance to respect and an excellent electrolyte moisture content.
- a porous polymer film for example, a porous polymer film made of a polyolefin-based polymer such as ethylene homopolymer, propylene homopolymer, ethylene/butene copolymer, ethylene/hexene copolymer and ethylene/methacrylate copolymer, or these
- a laminate structure of two or more layers of may be used.
- a conventional porous nonwoven fabric for example, a nonwoven fabric made of high melting point glass fiber, polyethylene terephthalate fiber, etc. may be used.
- a coated separator including a ceramic component or a polymer material may be used to secure heat resistance or mechanical strength, and may optionally be used in a single-layer or multi-layer structure.
- examples of the electrolyte used in the present invention include organic liquid electrolytes, inorganic liquid electrolytes, solid polymer electrolytes, gel polymer electrolytes, solid inorganic electrolytes, and molten inorganic electrolytes that can be used in the manufacture of lithium secondary batteries, and are limited to these. it is not going to be
- the electrolyte may include an organic solvent and a lithium salt.
- the organic solvent may be used without any particular limitation as long as it can serve as a medium through which ions involved in the electrochemical reaction of the battery can move.
- ester solvents such as methyl acetate, ethyl acetate, ⁇ -butyrolactone, ⁇ -caprolactone
- ether solvents such as dibutyl ether or tetrahydrofuran
- ketone solvents such as cyclohexanone
- aromatic hydrocarbon-based solvents such as benzene and fluorobenzene
- alcohol solvents such as ethyl alcohol and isopropyl alcohol
- nitriles such as R-CN (R is a linear, branched, or cyclic hydrocarbon group having 2
- a carbonate-based solvent is preferable, and a cyclic carbonate (eg, ethylene carbonate or propylene carbonate, etc.) having high ionic conductivity and high dielectric constant capable of increasing the charge/discharge performance of the battery, and a low-viscosity linear carbonate-based compound (for example, a mixture of ethyl methyl carbonate, dimethyl carbonate or diethyl carbonate) is more preferable.
- a cyclic carbonate and the chain carbonate are mixed in a volume ratio of about 1:1 to about 1:9, the performance of the electrolyte may be excellent.
- the lithium salt may be used without particular limitation as long as it is a compound capable of providing lithium ions used in a lithium secondary battery.
- the lithium salt is LiPF 6 , LiClO 4 , LiAsF 6 , LiBF 4 , LiSbF 6 , LiAl0 4 , LiAlCl 4 , LiCF 3 SO 3 , LiC 4 F 9 SO 3 , LiN(C 2 F 5 SO 3 ) 2 , LiN(C 2 F 5 SO 2 ) 2 , LiN(CF 3 SO 2 ) 2.
- LiCl, LiI, or LiB(C 2 O 4 ) 2 , etc. may be used.
- the concentration of the lithium salt is preferably used within the range of 0.1 to 2.0 M. When the concentration of the lithium salt is included in the above range, the electrolyte may exhibit excellent electrolyte performance because it has appropriate conductivity and viscosity, and lithium ions may move effectively.
- haloalkylene carbonate-based compounds such as difluoroethylene carbonate, pyridine, tri Ethyl phosphite, triethanolamine, cyclic ether, ethylene diamine, n-glyme, hexaphosphoric acid triamide, nitrobenzene derivative, sulfur, quinone imine dye, N-substituted oxazolidinone, N,N-substituted imida
- One or more additives such as taxdine, ethylene glycol dialkyl ether, ammonium salt, pyrrole, 2-methoxyethanol or aluminum trichloride may be further included. In this case, the additive may be included in an amount of 0.1 to 5 wt% based on the total weight of the electrolyte.
- the lithium secondary battery containing the positive electrode active material according to the present invention stably exhibits excellent discharge capacity, output characteristics and lifespan characteristics, portable devices such as mobile phones, notebook computers, digital cameras, and hybrid electric vehicles ( It is useful in the field of electric vehicles such as hybrid electric vehicle and HEV).
- the external shape of the lithium secondary battery according to the present invention is not particularly limited, but may be a cylindrical shape using a can, a prismatic shape, a pouch type, or a coin type.
- the lithium secondary battery may be used not only in a battery cell used as a power source for a small device, but may also be preferably used as a unit cell in a medium or large battery module including a plurality of battery cells.
- a battery module including the lithium secondary battery as a unit cell and/or a battery pack including the same may be provided.
- the battery module or the battery pack is a power tool (Power Tool); electric vehicles, including electric vehicles (EVs), hybrid electric vehicles, and plug-in hybrid electric vehicles (PHEVs); Alternatively, it may be used as a power source for any one or more medium-to-large devices in a system for power storage.
- Power Tool Power Tool
- electric vehicles including electric vehicles (EVs), hybrid electric vehicles, and plug-in hybrid electric vehicles (PHEVs);
- PHEVs plug-in hybrid electric vehicles
- NiSO 4 ⁇ 6H 2 O and MnSO 4 ⁇ H 2 O were mixed aqueous solution in a molar ratio of 25:75, and stirred while adding NaOH and NH 4 OH.
- the temperature in the reactor was maintained at 45° C., and the precursor synthesis reaction was performed while N 2 gas was introduced into the reactor. After completion of the reaction, washing and dehydration were performed to obtain a Ni 0.25 Mn 0.75 (OH) 2 precursor.
- step (a) The temperature of the kiln in the atmosphere was raised at a rate of 2°C/min, and then the precursor obtained in step (a) was heat-treated for 5 hours while maintaining 550°C, followed by furnace cooling.
- the temperature of the kiln in the O 2 atmosphere is raised at a rate of 2° C./min and then maintained at 900° C., and the mixture is heat-treated for 8 hours and then furnace cooled to a positive electrode containing excess lithium manganese oxide. An active material was obtained.
- the positive active material according to Example 1 had a composition of 0.54Li 2 MnO 3 ⁇ 0.46 LiNi 0.538 Mn 0.462 O 2 .
- the positive active material according to Example 2 had a composition of 0.23Li 2 MnO 3 ⁇ 0.77 LiNi 0.523 Mn 0.477 O 2 .
- the positive active material according to Example 3 had a composition of 0.19Li 2 MnO 3 ⁇ 0.81 LiNi 0.557 Mn 0.443 O 2 .
- NiSO 4 ⁇ 6H 2 O and MnSO 4 ⁇ H 2 O were mixed aqueous solution in a molar ratio of 40:60, and stirred while adding NaOH and NH 4 OH.
- the temperature in the reactor was maintained at 45° C., and the precursor synthesis reaction was performed while N 2 gas was introduced into the reactor. After completion of the reaction, washing and dehydration were performed to obtain a Ni 0.40 Mn 0.60 (OH) 2 precursor.
- CoSO 4 ⁇ 7H 2 O aqueous solution NaOH and NH 4 OH were added to the reactor in which the precursor obtained in step (a) was stirred. At this time, CoSO 4 ⁇ 7H 2 O was added after weighing so as to be 10 mol%. After completion of the reaction, washed and dehydrated, and then dried at 150° C. for 14 hours to obtain a coated precursor.
- step (b) The temperature of the kiln in the atmosphere was raised at a rate of 2°C/min, and then the precursor obtained in step (b) was heat-treated for 5 hours while maintaining 550°C, followed by furnace cooling.
- the temperature of the kiln in an O 2 atmosphere is raised at a rate of 2° C./min, and then maintained at 850° C., and the mixture is heat-treated for 8 hours and then furnace cooled to a positive electrode containing excess lithium manganese oxide. An active material was obtained.
- the positive active material according to Example 3 had a composition of 0.23Li 2 MnO 3 ⁇ 0.77 LiNi 0.467 Co 0.127 Mn 0.405 O 2 .
- the positive active material according to Comparative Example 3 had a composition of 0.36Li 2 MnO 3 ⁇ 0.64LiNi 0.389 Mn 0.611 O 2 .
- the positive active material according to Comparative Example 3 had a composition of 0.49Li 2 MnO 3 ⁇ 0.51LiNi 0.793 Mn 0.207 O 2 .
- a positive electrode slurry was prepared by dispersing 90 wt% of each of the positive active material prepared according to Preparation Example 1, 5.5 wt% of carbon black, and 4.5 wt% of PVDF binder in 30 g of N-methyl-2 pyrrolidone (NMP). The positive electrode slurry was uniformly applied to an aluminum thin film having a thickness of 15 ⁇ m and vacuum dried at 135° C. to prepare a positive electrode for a lithium secondary battery.
- NMP N-methyl-2 pyrrolidone
- lithium foil as a counter electrode
- a porous polyethylene membrane (Celgard 2300, thickness: 25 ⁇ m) as a separator
- LiPF in a solvent in which ethylene carbonate and ethylmethyl carbonate were mixed in a volume ratio of 3:7
- a coin battery was prepared using an electrolyte in which 6 was present at a concentration of 1.15M.
- FIG. 1 shows the TEM analysis result of the lithium manganese-based oxide contained in the positive electrode active material according to Example 4.
- FIG. 1 shows a 50 nm scale TEM image and a 5 nm scale TEM image of an enlarged area indicated in the 50 nm scale TEM image, and a crystal structure confirmed through FFT conversion for the A and B regions of the 5 nm scale TEM image. was shown.
- the crystal structure in the shell region was confirmed in a region where the distance from the outermost of the lithium manganese oxide was 0 to 0.03 ⁇ m, and the crystal structure in the core region was 0.12 from the outermost of the lithium manganese oxide. to 0.15 ⁇ m.
- EDX mapping was performed on the cross-sectional TEM image of the lithium manganese oxide contained in each positive active material prepared according to Preparation Example 1, and the EDX mapping result was line-scanning the nickel from the shell to the core of the lithium manganese oxide. Concentration (at%) change was confirmed.
- the concentration of nickel in the shell region is the average concentration (at%) of nickel based on the lithium manganese oxide (bulk) measured from a region where the distance from the outermost of the lithium manganese oxide is 0 to 0.03 ⁇ m. ) and the average concentration (at%) of nickel converted based on the R3-m phase in the lithium manganese oxide.
- the concentration of nickel in the core region is the average concentration of nickel based on the lithium manganese oxide (bulk) measured from a region where the distance from the outermost of the lithium manganese oxide is 0.12 to 0.15 ⁇ m (at%) and the average concentration (at%) of nickel converted based on the R3-m phase among the lithium manganese oxides.
- the concentration of nickel in the intermediate region is the average concentration of nickel based on the lithium manganese oxide (bulk) measured from the region where the distance from the outermost of the lithium manganese oxide is 0.075 to 0.1 ⁇ m (at%) and the average concentration (at%) of nickel converted based on the R3-m phase among the lithium manganese oxides.
- FIG. 2 is a line scanning the EDX mapping result of the cross-sectional TEM image of the lithium manganese oxide included in the positive active material according to Example 4 to confirm the change in the concentration (at%) of nickel from the core to the shell of the lithium manganese oxide. It is a sum spectrum. Region A indicated in the line sum spectrum of FIG. 2 corresponds to region A of FIG. 1 .
- the lithium manganese-based oxides included in each positive electrode active material prepared according to Preparation Example 1 are all different from the phase belonging to the C2/m space group and the phase belonging to the R3-m space group within a single particle. coexistence can be observed. That is, the lithium manganese oxide contained in each positive active material prepared according to Preparation Example 1 is a solid solution represented by the following Chemical Formula 1,
- the phase belonging to the C2/m space group is caused by Li 2 MnO 3
- the phase belonging to the R3-m space group is caused by Li a Ni x Co y Mn z M1 1-(x+y+z) O 2
- the lithium manganese oxides included in the positive electrode active materials according to Examples 1 to 3 there is a region in which the abundance ratio of the phase belonging to the C2/m space group and the phase belonging to the R3-m space group are different. have.
- the result is the lithium manganese-based oxide.
- the proportion of phases belonging to the R3-m space group increases from the core to the shell of the oxide. Accordingly, the ratio of the phase belonging to the R3-m space group to the phase belonging to the C2/m space group among the lithium manganese oxide will have a gradient that increases from the core to the shell.
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Abstract
Description
구분 | 코어 영역 | 쉘 영역 |
실시예 1 | C2/m + R3-m | C2/m + R3-m |
실시예 2 | C2/m + R3-m | C2/m + R3-m |
실시예 3 | C2/m + R3-m | C2/m + R3-m |
실시예 4 | C2/m + R3-m | R3-m |
비교예 1 | C2/m + R3-m | C2/m + R3-m |
비교예 2 | C2/m + R3-m | C2/m + R3-m |
구분 | 코어 영역 | 중간 영역 | 쉘 영역 | |||
bulk | R3-m | bulk | R3-m | bulk | R3-m | |
실시예 1 | 24 | 52 | 25 | 54 | 27 | 58 |
실시예 2 | 39 | 51 | 41 | 52 | 43 | 56 |
실시예 3 | 44 | 55 | 46 | 57 | 47 | 59 |
실시예 4 | 40 | 51 | 46 | 60 | 63 | 63 |
비교예 1 | 25 | 39 | 25 | 39 | 25 | 39 |
비교예 2 | 40 | 79 | 40 | 79 | 40 | 79 |
구분 | 초기 충전용량 (0.1C-rate) |
초기 방전용량 (0.1C-rate) |
초기 가역효율 |
단위 | mAh/g | mAh/g | % |
실시예 1 | 270.3 | 218.9 | 81.0 |
실시예 2 | 254.5 | 221.1 | 86.9 |
실시예 3 | 219.7 | 193.7 | 88.1 |
실시예 4 | 254.5 | 224.8 | 88.3 |
비교예 1 | 103.5 | 96.9 | 93.7 |
비교예 2 | 235.4 | 177.6 | 75.5 |
구분 | 방전용량비율 (2C/0.1C) |
방전용량비율 (5C/0.1C) |
단위 | % | % |
실시예 1 | 65 | 54 |
실시예 2 | 73 | 62 |
실시예 3 | 66 | 49 |
실시예 4 | 82 | 72 |
비교예 1 | 34 | 12 |
비교예 2 | 64 | 49 |
Claims (11)
- 적어도 리튬, 니켈 및 망간을 포함하는 리튬 과잉의 리튬 망간계 산화물을 포함하는 양극 활물질로서,상기 리튬 망간계 산화물 중 C2/m 공간군에 속하는 상과 R3-m 공간군에 속하는 상이 공존하되,상기 리튬 망간계 산화물 중 C2/m 공간군에 속하는 상과 상기 R3-m 공간군에 속하는 상의 존재 비율이 상이한 영역이 존재하는,양극 활물질.
- 제1항에 있어서,상기 리튬 망간계 산화물 중 금속 원소의 농도는 하기의 식 1을 만족하는,양극 활물질.[식 1]0.24 ≤ M2/M1 ≤ 0.55여기서,M1은 상기 리튬 망간계 산화물 중 전체 금속 원소(리튬을 제외함)의 몰 수이며,M2는 상기 리튬 망간계 산화물 중 전체 금속 원소(리튬을 제외함)를 기준으로 한 니켈의 몰 수이다.
- 제1항에 있어서,상기 리튬 망간계 산화물 중 금속 원소의 농도는 하기의 식 2를 만족하는,양극 활물질.[식 2]0.40 ≤ M2'/M1' ≤ 0.70여기서, M1'은 상기 R3-m 공간군에 속하는 상 내의 전체 금속 원소(리튬을 제외함) 몰 수이며,M2'는 상기 R3-m 공간군에 속하는 상 내의 전체 금속 원소(리튬을 제외함)를 기준으로 한 니켈의 몰 수이다.
- 제1항에 있어서,상기 리튬 망간계 산화물은 코어 및 상기 코어의 표면 중 적어도 일부를 커버하는 쉘을 포함하는 코어-쉘 입자로서,상기 코어 내에는 상기 C2/m 공간군에 속하는 상과 상기 R3-m 공간군에 속하는 상이 공존하며,상기 쉘 내 상기 C2/m 공간군에 속하는 상 대비 상기 R3-m 공간군에 속하는 상의 비율은 상기 코어 내 상기 C2/m 공간군에 속하는 상 대비 상기 R3-m 공간군에 속하는 상의 비율보다 큰,양극 활물질.
- 제4항에 있어서,상기 쉘 내 금속 원소의 농도는 하기의 식 3을 만족하는,양극 활물질.[식 3]0.24 ≤ M4/M3 ≤ 0.75여기서,M3은 상기 쉘 내 전체 금속 원소(리튬을 제외함)의 몰 수이며,M4는 상기 쉘 내 전체 금속 원소(리튬을 제외함)를 기준으로 한 니켈의 몰 수이다.
- 제4항에 있어서,상기 쉘 내 금속 원소의 농도는 하기의 식 4를 만족하는,양극 활물질.[식 4]0.40 ≤ M4'/M3' ≤ 0.75여기서, M3'은 상기 쉘 내 R3-m 공간군에 속하는 상 내의 전체 금속 원소(리튬을 제외함) 몰 수이며,M4'는 상기 쉘 내 R3-m 공간군에 속하는 상 내의 전체 금속 원소(리튬을 제외함)를 기준으로 한 니켈의 몰 수이다.
- 제4항에 있어서,상기 리튬 망간계 산화물 중 상기 C2/m 공간군에 속하는 상 대비 상기 R3-m 공간군에 속하는 상의 비율은 상기 코어로부터 상기 쉘을 향해 증가하는 구배를 가지는,양극 활물질.
- 제4항에 있어서,상기 쉘 내에는 상기 R3-m 공간군에 속하는 상만 존재하는,양극 활물질.
- 제1항에 있어서,상기 리튬 망간계 산화물은 하기의 화학식 1로 표시되는,양극 활물질.[화학식 1]rLi2MnO3·(1-r)LiaNixCoyMnzM11-(x+y+z)O2여기서,M1은 Mo, Nb, Fe, Cr, V, Cu, Zn, Sn, Mg, Ru, Al, Ti, Zr, B, Na, K, Y, P, Ba, Sr, La, Ga, Gd, Sm, W, Ca, Ce, Ta, Sc, In, S, Ge, Si 및 Bi로부터 선택되는 적어도 하나이며,0<r≤0.8, 0<a≤1, 0<x≤1, 0≤y<1, 0<z<1 및 0<x+y+z≤1이다.
- 제1항 내지 제9항 중 어느 한 항에 따른 양극 활물질을 포함하는 양극.
- 제10항에 따른 양극을 사용하는 리튬 이차전지.
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP4361102A1 (en) * | 2022-10-24 | 2024-05-01 | Ecopro Bm Co., Ltd. | Positive electrode active material and lithium secondary battery comprising the same |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011096650A (ja) * | 2009-09-30 | 2011-05-12 | Toda Kogyo Corp | 正極活物質粒子粉末及びその製造方法、並びに非水電解質二次電池 |
JP2012174642A (ja) * | 2011-02-24 | 2012-09-10 | National Institute For Materials Science | リチウム二次電池正極材化合物、その製造方法及び充放電プロセス |
KR20140008344A (ko) * | 2011-02-18 | 2014-01-21 | 미쓰이 긴조꾸 고교 가부시키가이샤 | 리튬망간계 고용체 양극 재료 |
KR20140034606A (ko) * | 2012-09-12 | 2014-03-20 | 삼성에스디아이 주식회사 | 복합양극활물질, 이를 채용한 양극과 리튬전지 및 그 제조방법 |
KR20170141130A (ko) * | 2016-06-14 | 2017-12-22 | 삼성전자주식회사 | 복합양극활물질, 이를 채용한 양극과 리튬 전지 및 그 제조방법 |
Family Cites Families (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006012426A (ja) * | 2004-06-22 | 2006-01-12 | Nichia Chem Ind Ltd | 非水電解質二次電池用正極活物質および非水電解質二次電池 |
KR100822012B1 (ko) * | 2006-03-30 | 2008-04-14 | 한양대학교 산학협력단 | 리튬 전지용 양극 활물질, 그 제조 방법 및 그를 포함하는리튬 이차 전지 |
US8492030B2 (en) * | 2006-06-19 | 2013-07-23 | Uchicago Argonne Llc | Cathode material for lithium batteries |
KR101473322B1 (ko) * | 2008-02-28 | 2014-12-24 | 삼성에스디아이 주식회사 | 양극 활물질 및 이를 채용한 양극과 리튬 전지 |
WO2012164752A1 (ja) * | 2011-05-30 | 2012-12-06 | 住友金属鉱山株式会社 | 非水系二次電池用正極活物質とその製造方法、ならびに該正極活物質を用いた非水系電解質二次電池 |
WO2013002457A1 (ko) * | 2011-06-27 | 2013-01-03 | 주식회사 에코프로 | 양극활물질, 상기 양극활물질을 포함하는 전극, 및 리튬 전기 화학 전지 |
JP2013075773A (ja) * | 2011-09-29 | 2013-04-25 | Tanaka Chemical Corp | リチウム過剰型のリチウム金属複合酸化物 |
JP5687169B2 (ja) * | 2011-10-03 | 2015-03-18 | 日本化学工業株式会社 | リチウム二次電池用正極活物質、その製造方法及びリチウム二次電池 |
KR20130138073A (ko) * | 2012-06-08 | 2013-12-18 | 한양대학교 산학협력단 | 리튬 이차 전지용 양극활물질 전구체, 이를 이용하여 제조된 양극활물질 및 이를 포함하는 리튬 이차 전지 |
KR102007411B1 (ko) * | 2013-01-07 | 2019-10-01 | 삼성에스디아이 주식회사 | 양극 활물질, 이를 포함하는 양극과 리튬 전지, 및 상기 양극 활물질의 제조방법 |
KR101794097B1 (ko) * | 2013-07-03 | 2017-11-06 | 삼성에스디아이 주식회사 | 리튬 이차 전지용 양극 활물질, 이의 제조 방법, 그리고 이를 포함하는 리튬 이차 전지용 양극 및 리튬 이차 전지 |
KR20150016129A (ko) * | 2013-07-31 | 2015-02-11 | 주식회사 포스코 | 리튬 복합 산화물, 이의 제조 방법 및 이를 포함하는 리튬 이차 전지 |
KR102210892B1 (ko) | 2013-12-13 | 2021-02-02 | 삼성에스디아이 주식회사 | 양극 활물질, 이의 제조방법 및 이를 포함하는 리튬이차전지 |
CN103943822B (zh) * | 2014-05-13 | 2017-03-29 | 南通瑞翔新材料有限公司 | 一种锂离子二次电池用镍基正极活性材料及其制备方法 |
JP6493408B2 (ja) * | 2014-09-10 | 2019-04-03 | 日立金属株式会社 | リチウムイオン二次電池用正極活物質、リチウムイオン二次電池用正極及びリチウムイオン二次電池 |
CN104347853B (zh) * | 2014-09-24 | 2017-04-12 | 秦皇岛中科远达电池材料有限公司 | 一种锰酸锂复合正极材料、其制备方法及锂离子电池 |
JP6554799B2 (ja) * | 2015-01-29 | 2019-08-07 | 住友金属鉱山株式会社 | 非水系電解質二次電池用正極活物質とその製造方法、および非水系電解質二次電池 |
KR101913906B1 (ko) * | 2015-06-17 | 2018-10-31 | 주식회사 엘지화학 | 이차전지용 양극활물질, 이의 제조방법 및 이를 포함하는 이차전지 |
KR102081858B1 (ko) * | 2016-12-02 | 2020-02-26 | 주식회사 엘지화학 | 이차전지용 양극활물질 전구체 및 이를 이용하여 제조한 이차전지용 양극활물질 |
CN110120513A (zh) * | 2019-05-24 | 2019-08-13 | 哈尔滨理工大学 | 一种利用原子气相沉积技术制备镍钴锰酸锂/氧化钼球形电极材料的方法 |
-
2021
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- 2021-11-08 EP EP21900844.8A patent/EP4231389A1/en active Pending
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- 2021-11-08 WO PCT/KR2021/016129 patent/WO2022119156A1/ko active Application Filing
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- 2021-11-08 EP EP21900845.5A patent/EP4216311A4/en active Pending
- 2021-11-08 WO PCT/KR2021/016132 patent/WO2022119158A1/ko unknown
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- 2021-11-08 JP JP2023533618A patent/JP2023551720A/ja active Pending
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-
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- 2023-03-23 US US18/189,133 patent/US20230261179A1/en active Pending
- 2023-04-28 US US18/309,018 patent/US20230268497A1/en active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011096650A (ja) * | 2009-09-30 | 2011-05-12 | Toda Kogyo Corp | 正極活物質粒子粉末及びその製造方法、並びに非水電解質二次電池 |
KR20140008344A (ko) * | 2011-02-18 | 2014-01-21 | 미쓰이 긴조꾸 고교 가부시키가이샤 | 리튬망간계 고용체 양극 재료 |
JP2012174642A (ja) * | 2011-02-24 | 2012-09-10 | National Institute For Materials Science | リチウム二次電池正極材化合物、その製造方法及び充放電プロセス |
KR20140034606A (ko) * | 2012-09-12 | 2014-03-20 | 삼성에스디아이 주식회사 | 복합양극활물질, 이를 채용한 양극과 리튬전지 및 그 제조방법 |
KR20170141130A (ko) * | 2016-06-14 | 2017-12-22 | 삼성전자주식회사 | 복합양극활물질, 이를 채용한 양극과 리튬 전지 및 그 제조방법 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP4361102A1 (en) * | 2022-10-24 | 2024-05-01 | Ecopro Bm Co., Ltd. | Positive electrode active material and lithium secondary battery comprising the same |
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US20230231128A1 (en) | 2023-07-20 |
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