Source: http://www.google.com/patents/US7309546?dq=6,183,366
Timestamp: 2015-01-28 18:56:30
Document Index: 52376633

Matched Legal Cases: ['application No. 2002', 'Application No. 98', 'Application No. 98', 'Application No. 98', 'Application No. 98', 'Application No. 98', 'Application No. 98', 'Application No. 98']

Patent US7309546 - Positive active material for rechargeable lithium battery - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inAdvanced Patent SearchPatentsDisclosed is a positive active material for a rechargeable lithium battery, including a lithiated intercalation compound and an additive compound. The additive compound comprises one or more intercalation element-included oxides which have a charging voltage of 4.0 to 4.6V when 5-50% of total intercalation...http://www.google.com/patents/US7309546?utm_source=gb-gplus-sharePatent US7309546 - Positive active material for rechargeable lithium batteryAdvanced Patent SearchPublication numberUS7309546 B2Publication typeGrantApplication numberUS 10/264,043Publication dateDec 18, 2007Filing dateOct 3, 2002Priority dateJan 24, 2002Fee statusPaidAlso published asCN1434527A, CN100426570C, US20030138699Publication number10264043, 264043, US 7309546 B2, US 7309546B2, US-B2-7309546, US7309546 B2, US7309546B2InventorsHo-jin Kweon, Jun-Won Suh, Kyung-Ho Kim, Hee-young SunOriginal AssigneeSamsung Sdi Co., Ltd.Export CitationBiBTeX, EndNote, RefManPatent Citations (14), Non-Patent Citations (7), Referenced by (7), Classifications (29), Legal Events (3) External Links: USPTO, USPTO Assignment, EspacenetPositive active material for rechargeable lithium batteryUS 7309546 B2Abstract Disclosed is a positive active material for a rechargeable lithium battery, including a lithiated intercalation compound and an additive compound. The additive compound comprises one or more intercalation element-included oxides which have a charging voltage of 4.0 to 4.6V when 5-50% of total intercalation elements of the one or more intercalation element-included oxides are released during charging.
a lithiated intercalation compound comprising at least one bare compound represented by the following formulas (1) to (12):
where 0.9≦�1.1; 0≦y≦0.5; 0≦z≦0.5; 0≦α≦2; M is selected from the group consisting of Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, and rare earth elements; A is selected from the group consisting of O, F, S, and P; and X is F, S, or P; and
an additive compound comprising one or more compounds represented by the formula M′Mn2-xNixO4, where M′ is Li or Na, and x ranges from 0.1 to 0.9,
wherein the bare compound is coated with a metal oxide shell and the additive compound has a charging voltage of 4.0 to 4.6V when 5-50% of the M′ is released during charging, and wherein the mixing weight ratio of the lithiated intercalation compound and the additive compound ranges from 99.99 to 70: 0.01 to 30.
2. The positive active material of claim 1 wherein the metal oxide shell includes a metal selected from the group consisting of Mg, Al, Co, K, Na, Ca, Si, Ti, V, Sn, Ge, Ga, B, As, Zr, and mixtures thereof.
3. A positive active material for a rechargeable lithium battery comprising:
where 0.9≦x ≦1.1; 0≦y≦0.5; 0≦z≦0.5; 0≦α≦2; M is selected from the group consisting of Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, and rare earth elements; A is selected from the group consisting of O, F, S, and P; and X is F, S, or P; and
an additive compound comprising one or more compounds represented by the formula M′Mn2-xNxO4, where M is Li or Na, and x ranges from 0.1 to 0.9,
wherein the bare compound is coated with a metal oxide shell, the additive compound has a discharging voltage of 4.0 to 5.0V when 5-50% of the M′ is released during discharging, and wherein the mixing weight ratio of the lithiated intercalation compound and the additive compound ranges from 99.99 to 70:0.01 to 30, and the mixing weight ratio of the lithiated intercalation compound and the additive compound ranges from 99.9 to 90:0.1 to 10.
4. The positive active material of claim 3 wherein the metal oxide shell includes a metal selected from the group consisting of Mg, Al, Co, K, Na, Ca, Si, Ti, V, Sn, Ge, Ga, B, As, Zr, and mixtures thereof.
CROSS REFERENCE TO RELATED APPLICATION This application claims priority to application No. 2002-4292, filed in the Korean Intellectual Property Office on Jan. 24, 2002, the disclosure of which is incorporated hereinto by reference.
SUMMARY OF THE INVENTION The present invention is directed to a positive active material for a rechargeable lithium battery. According to an embodiment of the present invention, the positive active material includes a lithiated intercalation compound and an additive compound, wherein the additive compound comprises one or more intercalation element-included oxides having a charge voltage of 4.0 to 4.6V when 5-50% of total intercalation elements of the one or more intercalation element-included oxide are released during charging.
FIG. 1 is a graph showing charge and discharge characteristics of LiMn1 5Ni0 5O4 (B) prepared by a solid phase reaction according to the present invention, and LiMn1 5Ni0 5O4 (A) prepared by the conventional co-precipitation process;
FIG. 2 is a graph showing charge and discharge characteristics of LiMn1 7Ni0 3O4 (a), LiMn1 2Ni0 8O4 (b), and LiMn1 5Ni0 5O4 (c) prepared by a solid phase reaction according to the present invention and LiCoO2 (d);
FIG. 3 is a graph showing discharge voltage curves for standard capacities of prismatic cells according to Example 1 of the present invention and Comparative Example 2; and
FIG. 4 is a graph showing discharge voltage curves for standard capacities of prismatic cells according to Example 4 of the present invention and Comparative Example 5.
DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a positive active material for a rechargeable lithium battery exhibiting high capacity. The conventional research to accomplish a high-capacity positive active material has been focused on the synthesis of new active materials other than LiCoO2, which is widely used for positive active materials. The present invention improves the utilization of the conventional active material rather than synthesizing new active material.
The mixing ratio of the intercalation element source, the manganese source, and the nickel source may be controlled according to the desired composition. The heat-treating step is preferably performed at 600 to 1000� C. If the heat-treating temperature is less than 600� C., a crystalline material is not likely be formed. If the heat-treating temperature is more than 1000� C., Li is easily lost by evaporation due to to obtain unwanted material.
LixMn1-yMyA2 (1)LixMn1-yMyO2-zXz (2)LixMn2O4-zXz (3)LixCo1-yMyA2 (4)LixCo1-yMyO2-zXz (5)LixNi1-yMyA2 (6)LixNi1-yMyO2-zXz (7)LixNi1-yCoyO2-zXz (8)LixNi1-y-zCoyMzAα (9)LixNi1-y-zCoyMzO2-αXα (10)LixNi1-y-zMnyMzAα (11)LixNi1-y-zMnyMzO2-αXα (12)
0.90≦x≦1.1; 0≦y≦0.5; 0≦z≦0.5; 0≦α≦2;
COMPARATIVE EXAMPLE 1 A prismatic cell with a capacity of 950 mAh was fabricated using a surface-treated LiCoO2 positive active material. The surface-treated LiCoO2 was prepared by coating LiCoO2 with an Al-isopropoxide suspension and heat-treating it at 600� C. according to the procedure described in Korean Patent Application No. 98-42956. The negative active material used was an artificial graphite material, PHS, available from Japan Carbon Ltd., and the electrolyte used was a 1M LiPF6 solution in a mixture of ethylene carbonate, dimethyl carbonate, diethyl carbonate and fluorobenzene (3:5:1:1 volume ratio).
COMPARATIVE EXAMPLE 2 A prismatic cell was fabricated by the same procedure as in Comparative Example 1 except that the positive active material was a mixture of 99 wt % of the surface-treated LiCoO2 and 1 wt % of LiMn1 5Ni0 5O4 which was obtained from a co-precipitation process.
The co-precipitation process for preparing LiMn1 5Ni0 5O4 was performed as follows: MnSO4 and NiSO4 were dissolved in water to prepare an aqueous solution containing Mn and Ni ions in the ratio of 3:1. NH4(OH)2 was added to the solution to co-precipitate Mn and Ni ions to obtain Mn0 75Ni0 25(OH)2. The subsequently dried Mn0 75Ni0 25(OH)2 was mixed with LiOH followed by heat-treating at 450� C. to prepare LiMn1 5Ni0.5O4. The resultant material, LiMn1 5Ni0 5O4, will be referred to as �co-precipitated LiMn1 5Ni0 5O4�.
COMPARATIVE EXAMPLE 3 A prismatic cell was fabricated by the same procedure as in Comparative Example 1, except that the positive active material was a mixture of 97 wt % of the surface-treated LiCoO2 and 3 wt % of co-precipitated LiMn1 5Ni0 5O4.
COMPARATIVE EXAMPLE 4 A prismatic cell was fabricated by the same procedure as in Comparative Example 1, except that the positive active material was a mixture of 95 wt % of the surface-treated LiCoO2 and 5 wt % of co-precipitated LiMn1 5Ni0 5O4.
COMPARATIVE EXAMPLE 5 A prismatic cell was fabricated by the same procedure as in Comparative Example 1, except that the positive active material was a mixture of 90 wt % of the surface-treated LiCoO2 and 10 wt % of co-precipitated LiMn1 5Ni0 5O4.
COMPARATIVE EXAMPLE 6 A prismatic cell was fabricated by the same procedure as in Comparative Example 1, except that the positive active material was a mixture of 85 wt % of the surface-treated LiCoO2 and 15 wt % of co-precipitated LiMn1 5Ni0 5O4.
COMPARATIVE EXAMPLE 7 A prismatic cell was fabricated by the same procedure as in Comparative Example 1, except that the positive active material was a mixture of 80 wt % of the surface-treated LiCoO2 and 20 wt % of co-precipitated LiMn1 5Ni0 5O4.
COMPARATIVE EXAMPLE 8 A prismatic cell was fabricated by the same procedure as in Comparative Example 1, except that the positive active material was a mixture of 99 wt % of a surface-treated LiMn2O4 and 1 wt % of co-precipitated LiMn1 5Ni0 5O4. The surface-treated LiMn2O4 was prepared by coating LiMn2O4 with an Al-isopropoxide suspension and heat-treating them at 300� C. according to the procedure as shown in Korean Patent Application No. 98-42956.
COMPARATIVE EXAMPLE 9 A prismatic cell was fabricated by the same procedure as in Comparative Example 8, except that the positive active material was a mixture of 90 wt % of the 10 surface-treated LiMn2O4 and 10 wt % of co-precipitated LiMn1 5Ni0 5O4.
COMPARATIVE EXAMPLE 10 A prismatic cell was fabricated by the same procedure as in Comparative Example 1, except that the positive active material was a mixture of 99 wt % of a surface-treated LiNi0 9Co0 1Sr0 002O2 and 1 wt % of co-precipitated LiMn1 5Ni0.5O4. The surface-treated LiNi0 9Co0 1Sr0.002O2 was prepared by coating LiNi0 9Co0 1Sr0 002O2 with an Al-isopropoxide suspension and heat-treating them at 500� C. according to the procedure described in Korean Patent Application No. 98-42956.
COMPARATIVE EXAMPLE 11 A prismatic cell was fabricated by the same procedure as in Comparative Example 10, except that the positive active material was a mixture of 90 wt % of the surface-treated LiNi0 9Co0 1Sr0 002O2 and 10 wt % of co-precipitated LiMn1 5Ni0 5O4.
COMPARATIVE EXAMPLE 12 A prismatic cell was fabricated by the same procedure as in Comparative Example 10, except that the positive active material was a mixture of 99 wt % of LiNi0 68Mn0 2Co0 1Mg0.01Al0 01O2 and 1 wt % of co-precipitated LiMn1 5Ni0 5O4.
COMPARATIVE EXAMPLE 13 A prismatic cell was fabricated by the same procedure as in Comparative Example 10, except that the positive active material was a mixture of 90 wt % of LiNi0 68Mn0 2Co0 1Mg0 01Al0 01O2 and 10 wt % of co-precipitated LiMn1 5Ni0 5O4.
EXAMPLE 1 99 weight percent (wt %) of �surface-treated LiCoO2�, which was coated with an Al-isopropoxide suspension and heat-treated at 600� C. as described in Korean Patent Application No. 98-42956, was mixed with 1 weight portion of a LiMn1 5Ni0 5O4 compound, which was synthesized via a solid phase reaction to prepare a positive active material. The solid phase reaction was performed by the following method. LiOH, MnO2, and NiO2 were mixed well in the mole ratio of 1:1.5:0.5. The resulting mixture was heat-treated at 800� C. to prepare the LiMn1 5Ni0 5O4 compound, which will be referred to as �solid phase-LiMn1 5Ni0 5O4�.
EXAMPLE 2 A prismatic cell was fabricated by the same procedure as in Example 1, except that the positive active material was a mixture of 97 wt % of the surface-treated LiCoO2 and 3 wt % of solid-phase LiMn1 5Ni0 5O4.
EXAMPLE 3 A prismatic cell was fabricated by the same procedure as in Example 1, except that the positive active material was a mixture of 95 wt % of the surface-treated LiCoO2 and 5 wt % of solid-phase LiMn1 5NiO0 5O4.
EXAMPLE 4 A prismatic cell was fabricated by the same procedure as in Example 1, except that the positive active material was a mixture of 90 wt % of the surface-treated LiCoO2 and 10 wt % of solid-phase LiMn1 5Ni0 5O4.
EXAMPLE 5 A prismatic cell was fabricated by the same procedure as in Example 1, except that 80 wt % of the surface-treated LiCoO2 was mixed with 20 wt % of solid-phase LiMn1 5Ni0 5O4 to prepare a positive active material.
EXAMPLE 6 LiOH, MnO2, and NiO2 were mixed in the mole ratio of 1:1.7:0.3, and the mixture was heat-treated at 800� C. to prepare solid-phase LiMn1 7Ni0 3O4. 10 wt % of the solid-phase LiMn1 7Ni0 3O4 as an additive compound was mixed with 90 wt % of the surface-treated LiCoO2 to prepare a positive active material. Using the positive active material, a prismatic cell was fabricated by the same procedure as in Example 1.
EXAMPLE 7 LiOH, MnO2 and NiO2 were mixed in the mole ratio of 1:1.2:0.8, and the mixture was heat-treated at 800� C. to prepare solid-phase LiMn1 2Ni0 8O4. 10 wt % of the solid-phase LiMn1 2Ni0 8O4 as an additive compound was mixed with 90 wt % of the surface-treated LiCoO2 to prepare a positive active material. Using the positive active material, a prismatic cell was fabricated by the same procedure as in Example 1.
EXAMPLE 8 A prismatic cell was fabricated by the same procedure as in Example 1, except that the positive active material was a mixture of 99 wt % of the surface-treated LiCoO2 and 1 wt % of the solid-phase LiMn1.5Ni0 5O4. The solid-phase LiMn1 5Ni0 5O4 was prepared by the same procedure as in Example 1, except that the heat-treatment was performed at 900� C.
EXAMPLE 9 A prismatic cell was fabricated by the same procedure as in Example 8, except that the positive active material was a mixture of 90 wt % of the surface-treated LiCoO2 and 10 wt % of the solid-phase LiMn1 5Ni0 5O4.
EXAMPLE 10 A prismatic cell was fabricated by the same procedure as in Example 1, except that the positive active material was a mixture of 99 wt % of the surface-treated LiCoO2 and 1 wt % of the solid-phase LiMn1 5Ni0 5O4. The solid-phase LiMn1.5Ni0 5O4 was prepared by the same procedure as in Example 1, except that the heat-treatment was performed at 700� C.
EXAMPLE 11 A prismatic cell was fabricated by the same procedure as in Example 10, except that the positive active material was a mixture of 90 wt % of the surface-treated LiCoO2 and 10 wt % of the solid-phase LiMn1 5Ni0.5O4.
EXAMPLE 12 A prismatic cell was fabricated by the same procedure as in Example 1, except that the positive active material was a mixture of 99 wt % of a surface-treated LiMn2O4 and 1 wt % of the solid-phase LiMn1.5Ni0 5O4. The surface-treated LiMn2O4 was prepared by coating with an Al-isopropoxide suspension and heat-treating it at 800� C., according to the procedure described in Korean Patent Application No. 98-42956.
EXAMPLE 13 A prismatic cell was fabricated by the same procedure as in Example 12, except that the positive active material was a mixture of 90 wt % of the surface-treated LiMn2O4 and 10 wt % of the solid-phase LiMn1 5Ni0 5O4.
EXAMPLE 14 A prismatic cell was fabricated by the same procedure as in Example 1, except that the positive active material was a mixture of 99 wt % of a surface-treated LiNi0 9Co0 1Sr0 002O2 and 1 wt % of solid-phase LiMn1 5Ni0.5O4. The surface-treated LiNi0 9Co0 1Sr0 002O2was prepared by coating with an Al-isopropoxide suspension and heat-treating it at 800� C., according to the procedure described in Korean Patent Application No. 98-42956. The solid-phase LiMn1 5Ni0 5O4 was prepared by the same procedure as in Example 1.
EXAMPLE 15 A prismatic cell was fabricated by the same procedure as in Example 14, except that 90 wt % of the surface-treated LiNi0.9Co0 1Sr0.002O2 was mixed with 10 wt % of the solid-phase LiMn1 5Ni0 5O4 to prepare a positive active material.
EXAMPLE 16 A prismatic cell was fabricated by the same procedure as in Example 1, except that 99 wt % of a surface-treated LiNi0 68Mn0 2Co0.1Mg0 01Al0 01O2was mixed with 1 wt % of the solid-phase LiMn1 5Ni0 5O4 to prepare a positive active material. The surface-treated LiNi0 68Mn0 2Co0 1Mg0 01Al0 01O2was prepared by coating with an Al-isopropoxide suspension and heat-treating it at 800� C., according to the procedure described in Korean Patent Application No. 98-42956.
EXAMPLE 17 A prismatic cell was fabricated by the same procedure as in Example 1, except that 90 wt % of the surface treated LiNi0 68Mn0 2Co0 1Mg0 01Al0 01O2was mixed with 10 wt % of the solid-phase LiMn1.5Ni0 5O4 to prepare a positive active material.
In addition, to evaluate the effect of the additive composition, the charge and discharge characteristic of LiMn2-xNixO4 while varying the value of x, was measured, and the results are presented in FIG. 2. For a control reference, the charge and discharge characteristics of LiCoO2 is also presented in FIG. 2. In FIG. 2, �a� refers to LiMn1.7Ni0 3O4 (additive compound used in Example 6), �b� refers to LiMn1 2Ni0 8O4 (additive compound used in Example 7), �c� refers to LiMn1.5Ni0 5O4 (additive compound used in Example 1) and �d� refers to LiCoO2. As shown in FIG. 2, the charge and discharge characteristic of LiMn2-xNixO4 is significantly different from that of LiCoO2. The charge and discharge characteristics vary according to the value of x (i.e. the ratio between Mn and Ni).
FIG. 3 shows the discharge voltage curves for the standard capacity measurement of the prismatic cells according to Example 1 and Comparative Example 2. FIG. 4 shows those of the prismatic cells according to Example 4 and Comparative Example 5. It can be seen from FIGS. 3 and 4 that the cell according to Example 1 had a capacity of about 999 mAh, and the cell according to Example 4 had about 996 mAh. However, the cell according to Comparative Example 2 had a capacity of about 900 mAh, and the cell according to Comparative Example 5 had a capacity of about 910 mAh. That is, the cells according to Examples 1 and 4 had surprisingly higher capacities than those of Comparative Examples 1 and 5. From these results, it is believed that the positive active material of the present invention provides a high-capacity rechargeable lithium battery.
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