U.S. patent application number 17/478869 was filed with the patent office on 2022-06-09 for materials and methods of producing lithium cobalt oxide materials of a battery cell.
The applicant listed for this patent is eJoule, Inc.. Invention is credited to Liang-Yuh CHEN, Haixia DENG, Mengchen LIU, Min-Duan LIU, Shengfeng LIU.
Application Number | 20220181616 17/478869 |
Document ID | / |
Family ID | 1000006225135 |
Filed Date | 2022-06-09 |
United States Patent
Application |
20220181616 |
Kind Code |
A1 |
DENG; Haixia ; et
al. |
June 9, 2022 |
Materials and Methods of Producing Lithium Cobalt Oxide Materials
of A Battery Cell
Abstract
Various lithium cobalt oxides materials doped with one or more
metal dopants having a chemical formula of Li.sub.x Co.sub.y
O.sub.z (doped Me1.sub.a Me2.sub.b Me3.sub.c . . . MeN.sub.n), and
method and apparatus of producing the various lithium cobalt oxides
materials are provided. The method includes adjusting a molar ratio
M.sub.LiSalt:M.sub.CoSalt:M.sub.Me1Salt:M.sub.Me2Salt:M.sub.Me3Salt:
. . . M.sub.MeNSalt of a lithium-containing salt, a
cobalt-containing salt and one or more metal-dopant-containing
salts within a liquid mixture to be equivalent to a ratio of
x:y:a:b:c: . . . n, drying a mist of the liquid mixture in the
presence of a gas to form a gas-solid mixture, separating the
gas-solid mixture into one or more solid particles of an oxide
material, and annealing the solid particles of the oxide material
in the presence of another gas flow to obtain crystalized particles
of the lithium cobalt oxide material. The process system has a mist
generator, a drying chamber, one or more gas-solid separator, and
one or more reactors.
Inventors: |
DENG; Haixia; (Fremont,
CA) ; LIU; Shengfeng; (Newark, CA) ; LIU;
Min-Duan; (Bethany, CT) ; LIU; Mengchen;
(Union City, CA) ; CHEN; Liang-Yuh; (Saratoga,
CA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
eJoule, Inc. |
Fremont |
CA |
US |
|
|
Family ID: |
1000006225135 |
Appl. No.: |
17/478869 |
Filed: |
September 17, 2021 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
63080023 |
Sep 18, 2020 |
|
|
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C01G 51/42 20130101;
H01M 4/0471 20130101; C01P 2002/72 20130101; H01M 4/525 20130101;
C01P 2006/40 20130101; H01M 2004/028 20130101; C01P 2004/03
20130101 |
International
Class: |
H01M 4/525 20060101
H01M004/525; H01M 4/04 20060101 H01M004/04; C01G 51/00 20060101
C01G051/00 |
Claims
1. An oxide material, comprising: a lithium cobalt oxide material
doped with at least one metal dopant (Li.sub.x Co.sub.y O.sub.z.
doped Me.sub.a), wherein x is from 0.9 to 1.1
(0.9.ltoreq.x.ltoreq.1.1), y is from 0.9 to 1.1
(0.9.ltoreq.y.ltoreq.1.1), z is from 1.8 to 2.2
(1.8.ltoreq.z.ltoreq.2.2), and wherein 0<a.ltoreq.0.05, being
obtained from a process comprising: forming a mist of a liquid
mixture, where the liquid mixture comprises: a lithium-containing
salt; a cobalt-containing salt; and at least one
metal-dopant-containing salt; mixing the mist of the liquid mixture
with a first gas flow to form a gas-liquid mixture; drying the
gas-liquid mixture to form a gas-solid mixture; separating the
gas-solid mixture into one or more solid particles of an oxide
material; and annealing the one or more solid particles of the
oxide material at an annealing temperature of 400.degree. C. or
higher to obtain crystalized particles of the lithium cobalt oxide
material doped with at least one metal dopant (Li.sub.x Co.sub.y
O.sub.z.doped Me.sub.a).
2. The oxide material of claim 1, wherein the lithium-containing
salt is selected from a group consisting of lithium sulfate
(Li.sub.2SO.sub.4), lithium nitrate (LiNO.sub.3), lithium carbonate
(Li.sub.2CO.sub.3), lithium acetate (LiCH.sub.2COO), lithium
hydroxide (LiOH), lithium formate (LiCHO.sub.2), lithium chloride
(LiCl), and combinations thereof.
3. The oxide material of claim 1, wherein the cobalt-containing
salt is selected from a group consisting of cobalt sulfate
(COSO.sub.4), cobalt nitrate (Co(NO.sub.3).sub.2), cobalt acetate
(Co(CH.sub.2COO).sub.2), cobalt formate (Co(CHO.sub.2).sub.2),
cobalt chloride (CoCl.sub.2), and combinations thereof.
4. The oxide material of claim 1, wherein the at least one metal
dopant is selected from a group consisting of Al, Mg, Mn, Zr, Zn,
Nb, La, Ce, Sn, Ga, Ba, Ac, Ca, Sc, Ti, V, Cr, Fe, Cu, B, Ge, As,
Hf, Mo, W, Re, Ru, Rh, Pt, Ag, Os, Ir, Au, and combinations
thereof.
5. The oxide material of claim 1, wherein the at least one
metal-dopant-containing salt is selected from a group consisting of
magnesium nitrate Mg(NO.sub.3).sub.2, magnesium acetate (MgAc,
Mg(CH.sub.3COO).sub.2), magnesium chloride (MgCl.sub.2), magnesium
sulfate (MgSO.sub.4), magnesium formate (C.sub.2H.sub.2MgO.sub.4),
aluminum nitrate (Al(NO.sub.3).sub.3), aluminum acetate (AlAc,
C.sub.6H.sub.9AlO.sub.6), aluminum chloride (AlCl.sub.3), aluminum
sulfate (Al.sub.2(SO.sub.4).sub.3), aluminum formate
(Al(HCOO).sub.3), manganese sulfate (MnSO.sub.4), manganese nitrate
(Mn(NO.sub.3).sub.2), manganese acetate (Mn(CH.sub.2COO).sub.2),
manganese formate (Mn(CHO.sub.2).sub.2), manganese chloride
(MnCl.sub.2), zirconium nitrate (Zr(NO.sub.3).sub.4), zirconium
acetate (C.sub.8H.sub.12O.sub.8Zr), zirconium chloride
(ZrCl.sub.4), zirconium sulfate (Zr(SO.sub.4).sub.2), zirconium
formate (C.sub.4H.sub.4O.sub.8Zr), nickel sulfate (NiSO.sub.4),
nickel nitrate (Ni(NO.sub.3).sub.2), nickel acetate
(Ni(CH.sub.2COO).sub.2), nickel formate (Ni(CHO.sub.2).sub.2),
nickel chloride (NiCl.sub.2), titanyl nitrate
((TiO(NO.sub.3).sub.2)), magnesium (Mg)-containing compound,
aluminum (Al)-containing compound, titanium (Ti)-containing
compound, sodium (Na)-containing compound, potassium (K)-containing
compound, scandium (Sc)-containing compound, niobium
(Nb)-containing compound, neodymium (Nd)-containing compound,
lanthanum (La)-containing compound, cerium (Ce)-containing
compound, silicon (Si)-containing compound, rubidium
(Rb)-containing compound, vanadium (V)-containing compound, cesium
(Cs)-containing compound, chromium (Cr)-containing compound, copper
(Cu)-containing compound, magnesium (Mg)-containing compound,
manganese (Mn)-containing compound, zirconium (Zr)-containing
compound, zinc (Zn)-containing compound, tin (Sn)-containing
compound, gallium (Ga)-containing compound, barium (Ba)-containing
compound, actinium (Ac)-containing compound, calcium
(Ca)-containing compound, iron (Fe)-containing compound, boron
(B)-containing compound, germanium (Ge)-containing compound,
arsenic (As)-containing compound, hafnium (Hf)-containing compound,
Molybdenum (Mo)-containing compound, tungsten (W)-containing
compound, rhenium (Re)-containing compound, ruthenium
(Ru)-containing compound, rhodium (Rh)-containing compound,
platinum (Pt)-containing compound, silver (Ag)-containing compound,
osmium (Os)-containing compound, iridium (Ir)-containing compound,
gold (Au)-containing compound.
6. The oxide material of claim 1, wherein the lithium cobalt oxide
material doped with the at least one metal dopant
(LixCo.sub.yO.sub.z.doped Me.sub.a), is obtained from adjusting a
molar ratio M.sub.LiSalt:M.sub.CoSalt:M.sub.MeSalt of the
lithium-containing salt, the cobalt-containing salt, and the at
least one metal-dopant-containing salts in the liquid mixture to be
a ratio of about x:y:a for making the lithium cobalt oxide material
doped with at least one metal dopant (Me) at desirable atomic ratio
of Li:Co:Me equaling to x:y:a.
7. The oxide material of claim 6, wherein the adjusting of the
molar ratio M.sub.LiSalt:M.sub.CoSalt:M.sub.MeSalt of the
lithium-containing salt, the cobalt-containing salt, and the at
least one metal-dopant-containing salt is performed prior to
forming the mist of the liquid mixture.
8. The oxide material of claim 6, wherein the adjusting of the
molar ratio M.sub.LiSalt:M.sub.CoSalt:M.sub.MeSalt of the
lithium-containing salt, the cobalt-containing salt, and the at
least one metal-dopant-containing salt is performed simultaneously
with the forming the mist of the liquid mixture.
9. The oxide material of claim 1, wherein the liquid mixture is
soluble in a suitable solvent and the suitable solvent is selected
from a group consisting of water, alcohol, methanol, isopropyl
alcohol, organic solvents, inorganic solvents, organic acids,
sulfuric acid (H.sub.2SO.sub.4), citric acid
(C.sub.6H.sub.8O.sub.7), acetic acids (CH.sub.3COOH), butyric acid
(C.sub.4HO.sub.2), lactic acid (C.sub.3H.sub.6O.sub.3), nitric acid
(HNO.sub.3), hydrochloric acid (HCl), ethanol, pyridine, ammonia,
acetone, and combinations thereof.
10. The oxide material of claim 1, wherein the one or more solid
particles of the oxide material are annealed in the presence of a
second gas flow that is heated to 550.degree. C. or higher and the
second gas flow is delivered into a reaction chamber to maintain
the annealing temperature inside the reaction chamber.
11. The oxide material of claim 1, wherein the one or more solid
particles of the oxide material are annealed in the presence of the
second gas flow inside a reaction chamber and the annealing
temperature inside the reaction chamber is maintained via a heating
element coupled to the reaction chamber.
12. The oxide material of claim 1, wherein the liquid mixture is
dried in the presence of the first gas that is heated to
200.degree. C. or higher inside a drying chamber and the first gas
is delivered into the drying chamber to maintain a drying
temperature inside the drying chamber.
13. The oxide material of claim 1, wherein the liquid mixture is
dried inside a drying chamber and a drying temperature inside the
drying chamber is maintained via a heating element coupled to the
drying chamber.
14. An oxide material, comprising: a lithium cobalt oxide material
doped with one or more metal dopants (Li.sub.x Co.sub.y O.sub.z.
doped Me1.sub.a, Me2.sub.b, Me3.sub.c, . . . MeN.sub.n), wherein x
is from 0.9 to 1.1 (0.9.ltoreq.x.ltoreq.1.1), y is from 0.9 to 1.1
(0.9.ltoreq.y.ltoreq.1.1), z is from 1.8 to 2.2
(1.8.ltoreq.z.ltoreq.2.2), and wherein N.gtoreq.1, and each a, b,
c, . . . , n is more than 0 and no more than 0.05, being obtained
from a process comprising: adjusting a molar ratio
M.sub.LiSalt:M.sub.CoSalt:M.sub.Me1Salt:M.sub.Me2Salt:M.sub.Me3Salt:
. . . M.sub.MeNSalt of a lithium-containing salt, a
cobalt-containing salt, and one or more metal-dopant-containing
salts which are soluble in a suitable solvent into a liquid
mixture, wherein each of the one or more metal-dopant-containing
salts is selected from a group consisting of a first
metal-containing salt, a second metal-containing salt, a third
metal-containing salt, . . . an N metal-containing salt and
combinations thereof, and forming a mist of the liquid mixture;
mixing the mist of the liquid mixture with a gas flow to form a
gas-liquid mixture; drying the gas-liquid mixture to form a
gas-solid mixture; separating the gas-solid mixture into one or
more solid particles of an oxide material; and annealing the one or
more solid particles of the oxide material at an annealing
temperature of 400.degree. C. or higher to obtain crystalized
particles of the lithium cobalt oxide material doped with one or
more metal dopants.
15. The oxide material of claim 14, wherein the lithium-containing
salt is selected from a group consisting of lithium sulfate
(Li.sub.2SO.sub.4), lithium nitrate (LiNO.sub.3), lithium carbonate
(Li.sub.2CO.sub.3), lithium acetate (LiCH.sub.2COO), lithium
hydroxide (LiOH), lithium formate (LiCHO.sub.2), lithium chloride
(LiCl), and combinations thereof.
16. The oxide material of claim 14, wherein the cobalt-containing
salt is selected from a group consisting of cobalt sulfate
(COSO.sub.4), cobalt nitrate (Co(NO.sub.3).sub.2), cobalt acetate
(Co(CH.sub.2COO).sub.2), cobalt formate (Co(CHO.sub.2).sub.2),
cobalt chloride (CoCl.sub.2), and combinations thereof.
17. The oxide material of claim 14, wherein each of the one or more
metal dopants is selected from a group consisting of Al, Mg, Mn,
Zr, Zn, Nb, La, Ce, Sn, Ga, Ba, Ac, Ca, Sc, Ti, V, Cr, Fe, Cu, B,
Ge, As, Hf, Mo, W, Re, Ru, Rh, Pt, Ag, Os, Ir, Au, and combinations
thereof.
18. The oxide material of claim 14, wherein each of the one or more
metal-dopant-containing salts is selected from a group consisting
of magnesium nitrate Mg(NO.sub.3).sub.2, magnesium acetate (MgAc,
Mg(CH.sub.3COO).sub.2), magnesium chloride (MgCl.sub.2), magnesium
sulfate (MgSO.sub.4), magnesium formate (C.sub.2H.sub.2MgO.sub.4),
aluminum nitrate (Al(NO.sub.3).sub.3), aluminum acetate (AlAc,
C.sub.6H.sub.9AlO.sub.6), aluminum chloride (AlCl.sub.3), aluminum
sulfate (Al.sub.2(SO.sub.4).sub.3), aluminum formate
(Al(HCOO).sub.3), manganese sulfate (MnSO.sub.4), manganese nitrate
(Mn(NO.sub.3).sub.2), manganese acetate (Mn(CH.sub.2COO).sub.2),
manganese formate (Mn(CHO.sub.2).sub.2), manganese chloride
(MnCl.sub.2), zirconium nitrate (Zr(NO.sub.3).sub.4), zirconium
acetate (C.sub.8H.sub.12O.sub.8Zr), zirconium chloride
(ZrCl.sub.4), zirconium sulfate (Zr(SO.sub.4).sub.2), zirconium
formate (C.sub.4H.sub.4O.sub.8Zr), nickel sulfate (NiSO.sub.4),
nickel nitrate (Ni(NO.sub.3).sub.2), nickel acetate
(Ni(CH.sub.2COO).sub.2), nickel formate (Ni(CHO.sub.2).sub.2),
nickel chloride (NiCl.sub.2), titanyl nitrate
((TiO(NO.sub.3).sub.2)), magnesium (Mg)-containing compound,
aluminum (Al)-containing compound, titanium (Ti)-containing
compound, sodium (Na)-containing compound, potassium (K)-containing
compound, scandium (Sc)-containing compound, niobium
(Nb)-containing compound, neodymium (Nd)-containing compound,
lanthanum (La)-containing compound, cerium (Ce)-containing
compound, silicon (Si)-containing compound, rubidium
(Rb)-containing compound, vanadium (V)-containing compound, cesium
(Cs)-containing compound, chromium (Cr)-containing compound, copper
(Cu)-containing compound, magnesium (Mg)-containing compound,
manganese (Mn)-containing compound, zirconium (Zr)-containing
compound, zinc (Zn)-containing compound, tin (Sn)-containing
compound, gallium (Ga)-containing compound, barium (Ba)-containing
compound, actinium (Ac)-containing compound, calcium
(Ca)-containing compound, iron (Fe)-containing compound, boron
(B)-containing compound, germanium (Ge)-containing compound,
arsenic (As)-containing compound, hafnium (Hf)-containing compound,
Molybdenum (Mo)-containing compound, tungsten (W)-containing
compound, rhenium (Re)-containing compound, ruthenium
(Ru)-containing compound, rhodium (Rh)-containing compound,
platinum (Pt)-containing compound, silver (Ag)-containing compound,
osmium (Os)-containing compound, iridium (Ir)-containing compound,
gold (Au)-containing compound.
19. The oxide material of claim 14, wherein the adjusting of the
molar ratio
M.sub.LiSalt:M.sub.CoSalt:M.sub.Me1Salt:M.sub.Me2Salt:M.sub.Me3Salt-
: . . . M.sub.MeNSalt of the lithium-containing salt, the
cobalt-containing salt, and the one or more metal-dopant-containing
salts is performed prior to forming the mist of the liquid
mixture.
20. The oxide material of claim 14, wherein the adjusting of the
molar ratio
M.sub.LiSalt:M.sub.CoSalt:M.sub.Me1Salt:M.sub.Me2Salt:M.sub.Me3Salt-
:M.sub.MeNSalt of the lithium-containing salt, the
cobalt-containing salt, and the one or more metal-dopant-containing
salts is performed simultaneously in forming the mist of the liquid
mixture.
21. The oxide material of claim 14, wherein the suitable solvent is
selected from a group consisting of water, alcohol, methanol,
isopropyl alcohol, organic solvents, inorganic solvents, organic
acids, sulfuric acid (H.sub.2SO.sub.4), citric acid
(C.sub.6H.sub.8O.sub.7), acetic acids (CH.sub.3COOH), butyric acid
(C.sub.4H.sub.8O.sub.2), lactic acid (C.sub.3H.sub.6O.sub.3),
Nitric acid (HNO.sub.3), hydrochloric acid (HCl), ethanol,
pyridine, ammonia, acetone, and combinations thereof.
22. An oxide material, comprising: a lithium cobalt oxide material
doped with at least one metal dopant (Li.sub.x Co.sub.y
O.sub.z.doped Me.sub.a), wherein x is from 0.9 to 1.1
(0.9.ltoreq.x.ltoreq.1.1), y is from 0.9 to 1.1
(0.9.ltoreq.y.ltoreq.1.1), z is from 1.8 to 2.2
(1.8.ltoreq.z.ltoreq.2.2), and wherein 0<a.ltoreq.0.05, being
obtained from a process comprising: adjusting a molar ratio
M.sub.LiSalt:M.sub.CoSalt:M.sub.Me Salt of a lithium-containing
salt, a cobalt-containing salt, and at least one
metal-dopant-containing salt into a liquid mixture and forming a
mist of the liquid mixture, where the liquid mixture comprises: the
lithium-containing salt; the cobalt-containing salt; the at least
one metal-dopant-containing salt; and a suitable solvent; mixing
the mist of the liquid mixture with a gas flow to form a gas-liquid
mixture; drying the gas-liquid mixture to form one or more solid
particles of an oxide material; and annealing the one or more solid
particles of the oxide material at an annealing temperature of
400.degree. C. or higher to obtain crystalized particles of the
lithium cobalt oxide material doped with at least one metal dopant
(Li.sub.x Co.sub.y O.sub.z.doped Me.sub.a).
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claim benefit of U.S. provisional patent
application Ser. No. 63/080,023, filed on Sep. 18, 2020, which is a
Continuation-in-Part application of U.S. patent application Ser.
No. 16/747,450 filed on Jan. 20, 2020, which is a continuation of
U.S. patent application Ser. No. 16/114,114 filed on Aug. 27, 2018,
which is a continuation of U.S. patent application Ser. No.
13/900,915, filed on May 23, 2013, which claims benefit of U.S.
provisional patent application Ser. No. 61/855,063, filed on May 6,
2013. All of the above-referenced applications are herein
incorporated by reference.
BACKGROUND OF THE INVENTION
[0002] Great efforts have been devoted to the development of
advanced electrochemical battery cells to meet the growing demand
of various consumer electronics, electrical vehicles and grid
energy storage applications in terms of high energy density, high
power performance, high capacity, long cycle life, low cost and
excellent safety. Thus, a need for more efficient utilization of
the available energy resources as well as air-quality-control has
generated an enormous interest in the development of advanced high
energy density batteries for electric powered vehicles.
Furthermore, cost effectiveness, great cycling life, stability,
rechargeability, and better safety characteristics have been other
factors driving the battery market.
[0003] In an electrochemically active battery cell, a cathode and
an anode are immersed in an electrolyte and electronically
separated by a separator. The separator is typically made of porous
polymer membrane materials such that metal ions released from the
electrodes into the electrolyte can diffuse through the pores of
the separator and migrate between the cathode and the anode during
battery charge and discharge. The type of a battery cell is usually
named from the metal ions that are transported between its cathode
and anode electrodes. Lithium ion battery is a secondary battery
which was developed in the early 1990s and it represent a new
generation of lightweight, compact, and yet high-energy power
sources. However, the cost for commercially manufacturing various
lithium battery materials is considerably higher than other types
of secondary batteries.
[0004] Cathode active materials are the most expensive component in
a lithium ion battery and, to a relatively large extent, determines
the energy density, cycle life, manufacturing cost and safety of a
lithium battery cell. Examples of good cathode active materials
include nanometer- or micron-sized lithium transition metal oxide
materials and lithium ion phosphate, etc. When lithium battery was
first commercialized, lithium cobalt oxide (LiCoO.sub.2) material
is used as the cathode material. While the theoretical capacity of
LiCoO.sub.2 is about 274-275 mAh/g, and a capacity of the
LiCoO.sub.2 when using 4.2 V as an upper limit voltage is about 150
mAh/g.
[0005] To further increase the battery performance of LiCoO.sub.2,
one can increase charging cut-off voltage to extract more Li.sup.+.
However, conventional material manufacturing processes such as
solid-state reaction (e.g., mixing solid precursors and then
calcination) and wet-chemistry processes (e.g., treating precursors
in solution through co-precipitation, sol-gel, or hydrothermal
reaction, etc., and then mixing and calcination) have notable
challenges in promoting cycle stability of LiCoO.sub.2 at high
voltage. Since a high voltage is applied to LiCoO.sub.2 materials,
it is difficult to consistently produce LiCoO.sub.2 having the
characteristics of high stability and long battery life cycle at a
level of industrial size.
[0006] In addition, solid-state diffusion rates affect the
performance of resulting batteries made from these lithium oxide
materials in applications requiring high-powered batteries.
Overall, the processing time for such a solid-state multi-step
batch manufacturing process will take up to a week so it is very
labor intensive and energy consuming. Batch process also increases
the chance of introducing impurity with poor run-to-run quality
consistency and low overall yield. Specifically, co-precipitation
is not suitable for the preparation of highly pure, accurate
stoichiometric phases of these lithium-containing transition metal
oxide battery materials.
[0007] Thus, there is a need for an improved method and system to
manufacture high power performance, high capacity, long cycle life,
excellent stability, properly crystalized, structured lithium metal
oxide active materials for a lithium-ion battery (LIB) cell at high
voltage and high temperature.
SUMMARY OF THE INVENTION
[0008] Embodiments of the invention generally provide lithium ion
battery materials and methods for producing lithium ion battery
materials thereof. One embodiment of the invention provides an
oxide material, such as a lithium cobalt oxide material doped with
at least one metal dopant (Li.sub.x Co.sub.y O.sub.z.doped
Me.sub.a), wherein x is from 0.9 to 1.1 (0.9.ltoreq.x.ltoreq.1.1),
y is from 0.9 to 1.1 (0.9.ltoreq.y.ltoreq.1.1), z is from 1.8 to
2.2 (1.8.ltoreq.z.ltoreq.2.2), and 0<a.ltoreq.0.05. The material
can be obtained from a process, which includes forming a mist of a
liquid mixture comprising a lithium-containing salt, a
cobalt-containing salt, and at least one metal-dopant-containing
salt, mixing the mist of the liquid mixture with a gas flow to form
a gas-liquid mixture, wherein the liquid mixture is soluble in a
suitable solvent, drying the gas-liquid mixture to form a gas-solid
mixture, separating the gas-solid mixture into one or more solid
particles of an oxide material; and annealing the one or more solid
particles of the oxide material at an annealing temperature of
400.degree. C. or higher to obtain crystalized particles of the
lithium cobalt oxide material doped with at least one metal dopant
(Li.sub.x Co.sub.y O.sub.z.doped Me.sub.a).
[0009] In one example, the lithium cobalt oxide material doped with
the at least one metal dopant (Li.sub.xCo.sub.yO.sub.z.doped
Me.sub.a), is obtained from adjusting a molar ratio
M.sub.LiSalt:M.sub.CoSalt:M.sub.MeSalt of the lithium-containing
salt, the cobalt-containing salt, and the at least one
metal-dopant-containing salts in the liquid mixture to be a ratio
of about x:y:a for making the lithium cobalt oxide material doped
with at least one metal dopant (Me) at desirable atomic ratio of
Li:Co:Me equaling to x:y:a. For example, the molar ratio
M.sub.LiSalt:M.sub.CoSalt:M.sub.MeSalt of the lithium-containing
salt, the cobalt-containing salt, and the at least one
metal-dopant-containing salt is performed prior to forming the mist
of the liquid mixture. As another example, molar ratio
M.sub.LiSalt:M.sub.CoSalt:M.sub.MeSalt of the lithium-containing
salt, the cobalt-containing salt, and the at least one
metal-dopant-containing salts can be adjusted at the same time of
forming the mist of the liquid mixture.
[0010] Another embodiment of the invention provides a lithium
cobalt oxide material doped with one or more metal dopants
(Li.sub.x Co.sub.y O.sub.z.doped Me1.sub.a, Me2.sub.b, Me3.sub.c, .
. . MeN.sub.n), wherein x is from 0.9 to 1.1
(0.9.ltoreq.x.ltoreq.1.1), y is from 0.9 to 1.1
(0.9.ltoreq.y.ltoreq.1.1), z is from 1.8 to 2.2
(1.8.ltoreq.z.ltoreq.2.2), and wherein N.gtoreq.1, and each a, b,
c, . . . , n is more than 0 and no more than 0.05. The lithium
cobalt oxide material doped with one or more metal dopants is
obtained from a process, which includes adjusting a molar ratio
M.sub.LiSalt:M.sub.CoSalt:M.sub.Me1Salt:M.sub.Me2Salt:M.sub.Me3Salt:
. . . M.sub.MeNSalt of a lithium-containing salt, a
cobalt-containing salt, and one or more metal-dopant-containing
salts which are soluble in a suitable solvent into a liquid
mixture, wherein each of the one or more metal-dopant-containing
salts is selected from a group consisting of a first
metal-containing salt, a second metal-containing salt, a third
metal-containing salt, . . . an N metal-containing salt and
combinations thereof, and forming a mist of the liquid mixture. The
process further includes mixing the mist of the liquid mixture with
a gas flow to form a gas-liquid mixture, drying the gas-liquid
mixture to form a gas-solid mixture, separating the gas-solid
mixture into one or more solid particles of an oxide material; and
annealing the one or more solid particles of the oxide material at
an annealing temperature of 400.degree. C. or higher to obtain
crystalized particles of the lithium cobalt oxide material doped
with one or more metal dopants.
[0011] Another embodiment of the invention provides a lithium
cobalt oxide material doped with at least one metal dopant
(Li.sub.x Co.sub.y O.sub.z.doped Me.sub.a), wherein x is from 0.9
to 1.1 (0.9.ltoreq.x.ltoreq.1.1), y is from 0.9 to 1.1
(0.9.ltoreq.y.ltoreq.1.1), z is from 1.8 to 2.2
(1.8.ltoreq.z.ltoreq.2.2), and wherein 0<a.ltoreq.0.05. The
lithium cobalt oxide material doped with one or more metal dopants
is obtained from a process, which includes adjusting a molar ratio
M.sub.LiSalt:M.sub.CoSalt:M.sub.Me Salt of a lithium-containing
salt, a cobalt-containing salt, and at least one
metal-dopant-containing salt into a liquid mixture and forming a
mist of the liquid mixture, where the liquid mixture comprises the
lithium-containing salt, the cobalt-containing salt; the at least
one metal-dopant-containing salt; and a suitable solvent. The
process further includes mixing the mist of the liquid mixture with
a gas flow to form a gas-liquid mixture, drying the gas-liquid
mixture to form one or more solid particles of an oxide material;
and annealing the one or more solid particles of the oxide material
at an annealing temperature of 400.degree. C. or higher to obtain
crystalized particles of the lithium cobalt oxide material doped
with at least one metal dopant (Li.sub.x Co.sub.y O.sub.z.doped
Me.sub.a).
[0012] In yet another embodiment, a method of producing a lithium
cobalt oxide material with one or more metal dopants having a
chemical formula of Li.sub.x Co.sub.y O.sub.z (doped Me1.sub.a
Me2.sub.b Me3.sub.c . . . MeN.sub.n) is provided. The method
includes forming a mist of a liquid mixture, where the liquid
mixture is obtained from adjusting a molar ratio
M.sub.LiSalt:M.sub.CoSalt:M.sub.MeSalt of a lithium-containing salt
(LiSalt), a cobalt-containing salt (CoSalt), and at least one
metal-dopant-containing salt (MeSalt) in the liquid mixture to be a
ratio of about x:y: a for making the lithium cobalt oxide material
doped with at least one metal dopant (Me) at desirable atomic ratio
of Li:Co:Me equaling to x:y:a. The method further includes mixing
the mist of the liquid mixture with a gas flow to form a gas-liquid
mixture, drying the gas-liquid mixture to form a gas-solid mixture,
separating the gas-solid mixture into one or more solid particles
of an oxide material, and annealing the one or more solid particles
of the oxide material at an annealing temperature of 400.degree. C.
or higher to obtain crystalized particles of the lithium cobalt
oxide material doped with at least one metal dopant (Me) (Li.sub.x
Co.sub.y O.sub.z.doped Me.sub.a), where x is from 0.9 to 1.1
(0.9.ltoreq.x.ltoreq.1.1), y is from 0.9 to 1.1
(0.9.ltoreq.y.ltoreq.1.1), z is from 1.8 to 2.2
(1.8.ltoreq.z.ltoreq.2.2), and 0<a.ltoreq.0.05.
BRIEF DESCRIPTION OF THE DRAWING
[0013] So that the manner in which the above recited features of
the present invention can be understood in detail, a more
particular description of the invention, briefly summarized above,
may be had by reference to embodiments, some of which are
illustrated in the appended drawings. It is to be noted, however,
that the appended drawings illustrate only typical embodiments of
this invention and are therefore not to be considered limiting of
its scope, for the invention may admit to other equally effective
embodiments.
[0014] FIG. 1A illustrates one embodiment of a flow chart of a
method of producing cathode materials for lithium ion
batteries.
[0015] FIG. 1B illustrates another embodiment of another flow chart
of a method of producing cathode materials for lithium ion
batteries.
[0016] FIG. 2 is a schematic of an exemplary processing system
useful in preparing a material for a battery electrochemical cell
according one embodiment of the invention.
[0017] FIG. 3 is a schematic of another exemplary processing system
useful in preparing a material for a battery electrochemical cell
according one embodiment of the invention.
[0018] FIG. 4 is a line graph illustrating the discharge profile of
electric capacity of lithium ion batteries prepared from various
cathode materials of the invention.
[0019] FIG. 5A is a column graph illustrating the discharge profile
of electric capacity of lithium ion batteries at a specified
voltage where the lithium ion batteries are prepared from various
exemplary cathode materials of the invention.
[0020] FIG. 5B is a column graph illustrating the discharge profile
of electric capacity of lithium ion batteries at a specified
voltage where the lithium ion batteries are prepared from exemplary
cathode materials of the invention.
[0021] FIG. 5C is a column graph illustrating the discharge profile
of electric capacity of lithium ion batteries at a specified
voltage where the lithium ion batteries are prepared from yet
several examples of a cathode material of the invention.
[0022] FIG. 6 is a graph illustrating electric charge and discharge
cycling performance of battery cells prepared by using various
examples of cathode materials of the invention.
[0023] FIG. 7A is a scanning electron microscopy (SEM) image of
another example of crystalized lithium cobalt oxide materials of
the invention.
[0024] FIG. 7B is a scanning electron microscopy (SEM) image of the
example of FIG. 7A in larger magnitude.
[0025] FIG. 7C is a scanning electron microscopy (SEM) image of
another embodiment of another example of solid particles of an
oxide material after a drying process.
[0026] FIG. 7D is a scanning electron microscopy (SEM) image of the
example of FIG. 7C in larger magnitude.
[0027] FIG. 8A is a scanning electron microscopy (SEM) image of
another example of crystalized lithium cobalt oxide materials.
[0028] FIG. 8B is a scanning electron microscopy (SEM) image of the
example of FIG. 8A in larger magnitude.
[0029] FIG. 8C is a scanning electron microscopy (SEM) image of
another embodiment of another example of solid particles of an
oxide material after a drying process.
[0030] FIG. 8D is a scanning electron microscopy (SEM) image of the
example of FIG. 8C in larger magnitude.
[0031] FIG. 9A is a scanning electron microscopy (SEM) image of
another example of crystalized lithium cobalt oxide materials of
the invention.
[0032] FIG. 9B is a scanning electron microscopy (SEM) image of the
example of FIG. 9A in larger magnitude.
[0033] FIG. 9C is a scanning electron microscopy (SEM) image of
another embodiment of another example of solid particles of an
oxide material after a drying process.
[0034] FIG. 9D is a scanning electron microscopy (SEM) image of the
example of FIG. 9C in larger magnitude.
[0035] FIG. 10A is a scanning electron microscopy (SEM) image of
another example of crystalized lithium cobalt oxide materials of
the invention.
[0036] FIG. 10B is a scanning electron microscopy (SEM) image of
the example of FIG. 10A in larger magnitude.
[0037] FIG. 10C is a scanning electron microscopy (SEM) image of
another embodiment of another example of solid particles of an
oxide material after a drying process.
[0038] FIG. 10D is a scanning electron microscopy (SEM) image of
the example of FIG. 10C in larger magnitude.
[0039] FIG. 11A is a scanning electron microscopy (SEM) image of
another example of crystalized lithium cobalt oxide materials of
the invention.
[0040] FIG. 11B is a scanning electron microscopy (SEM) image of
the example of FIG. 11A in larger magnitude.
[0041] FIG. 12A is a scanning electron microscopy (SEM) image of
another example of crystalized lithium cobalt oxide materials of
the invention.
[0042] FIG. 12B is a scanning electron microscopy (SEM) image of
the example of FIG. 12A in larger magnitude.
[0043] FIG. 13A is a scanning electron microscopy (SEM) image of
another embodiment of another example of solid particles of an
oxide material after a drying process.
[0044] FIG. 13B is a scanning electron microscopy (SEM) image of
the example of FIG. 13A in larger magnitude.
[0045] FIG. 14A is a scanning electron microscopy (SEM) image of
another example of crystalized lithium cobalt oxide materials of
the invention.
[0046] FIG. 14B is a scanning electron microscopy (SEM) image of
the example of FIG. 14A in larger magnitude.
[0047] FIG. 14C is a scanning electron microscopy (SEM) image of
the example of FIG. 14A in larger magnitude.
[0048] FIG. 15A is a scanning electron microscopy (SEM) image of
another example of crystalized lithium cobalt oxide materials of
the invention.
[0049] FIG. 15B is a scanning electron microscopy (SEM) image of
the example of FIG. 15A in larger magnitude.
[0050] FIG. 15C is a scanning electron microscopy (SEM) image of
the example of FIG. 15A in larger magnitude.
[0051] FIG. 16A is a scanning electron microscopy (SEM) image of
another example of crystalized lithium cobalt oxide materials of
the invention.
[0052] FIG. 16B is a scanning electron microscopy (SEM) image of
the example of FIG. 16A in larger magnitude.
[0053] FIG. 16C is a scanning electron microscopy (SEM) image of
the example of FIG. 16A in larger magnitude.
[0054] FIG. 17A is a scanning electron microscopy (SEM) image of
another example of crystalized lithium cobalt oxide materials of
the invention.
[0055] FIG. 17B is a scanning electron microscopy (SEM) image of
the example of FIG. 17A in larger magnitude.
[0056] FIG. 17C is a scanning electron microscopy (SEM) image of
the example of FIG. 17A in larger magnitude.
[0057] FIG. 18 is an X-ray diffraction (XRD) pattern of two
examples of crystalized lithium cobalt oxide materials of the
invention.
DETAILED DESCRIPTION
[0058] This invention generally relates to compositions, oxide
materials, battery materials, apparatuses, and methods thereof in
soluble solutions in proper molar ratio to precisely control and
obtain proper atomic-level ratios and make-up of a battery active
material to be used for a lithium-ion battery. The battery
materials and methods and apparatus provided here results in highly
pure, accurate stoichiometric phases battery cathode materials and
can be used, in turn, to make lithium-ion batteries with, with
characteristics associated with high battery cycling performance,
including high electric capacity.
[0059] FIG. 1A is a flow chart showing a method 100 of producing
lithium cobalt oxide material doped with one or more metal dopants
having a chemical formula of Li.sub.x Co.sub.y O.sub.z.doped
Me1.sub.a Me2.sub.b Me3.sub.c . . . . MeN.sub.n for lithium-ion
batteries. The method 100 includes a step 110 or series of steps of
adjusting a molar ratio
M.sub.LiSalt:M.sub.CoSalt:M.sub.Me1Salt:M.sub.Me2Salt:M.sub.Me3Salt:
. . . :M.sub.MeNSalt of a lithium-containing salt (LiSalt), a
cobalt-containing salt (CoSalt), and one or more
metal-dopant-containing salts which are soluble in a suitable
solvent into a liquid mixture, where each of the one or more
metal-dopant-containing salts is selected from a group consisting
of a first metal-containing salt, a second metal-containing salt, a
third metal-containing salt, . . . an N metal-containing salt and
combinations thereof. The molar ratio
M.sub.LiSalt:M.sub.CoSalt:M.sub.Me1Salt:M.sub.Me2Salt:M.sub.Me3Salt:
. . . : M.sub.MeNSalt of the lithium-containing salt (LiSalt), the
cobalt-containing salt (CoSalt), and the one or more
metal-dopant-containing salts is adjusted to be a ratio of about
x:y:a:b:c: . . . :n for making the lithium cobalt oxide doped with
one or more metal dopants (Li.sub.x Co.sub.y O.sub.z.doped
Me1.sub.a Me2.sub.b Me3e . . . . MeN.sub.n) at desirable atomic
ratio of Li:Co:Me1:Me2:Me3 . . . :MeN equaling to x:y:a:b:c: . . .
:n, where x is from 0.9 to 1.1 (0.9.ltoreq.x.ltoreq.1.1), y is from
0.9 to 1.1 (0.9.ltoreq.y.ltoreq.1.1), z is from 1.8 to 2.2
(1.8.ltoreq.z.ltoreq.2.2), and where N.gtoreq.1, a is from 0 to
0.05 (0.ltoreq.x.ltoreq.0.05), b is from 0 to 0.05
(0.ltoreq.b.ltoreq.0.05), c is from 0 to 0.05
(0.ltoreq.x.ltoreq.0.05), . . . , and n is from 0 to 0.05
(0.ltoreq.x.ltoreq.0.05).
[0060] In one embodiment, the desired molar ratio of
M.sub.LiSalt:M.sub.CoSalt:M.sub.Me1Salt:M.sub.Me2Salt:M.sub.Me3Salt:
. . . :M.sub.MeNSalt can be achieved by measuring and preparing
appropriate amounts a lithium-containing salt (LiSalt), a
cobalt-containing salt (CoSalt), a first metal dopant-containing
salt (Me1Salt), a second metal dopant-containing salt (Me2Salt), a
third metal dopant-containing salt (Me3Salt), . . . , and a N metal
dopant-containing salt (MeNSalt). For example, the molar ratio
M.sub.LiSalt:M.sub.CoSalt:M.sub.Me1Salt:M.sub.Me2Salt:M.sub.Me3Salt:
. . . : M.sub.MeNSalt of the lithium-containing salt, the
cobalt-containing salt, the first metal-containing salt, the second
metal-containing salt, the third metal-containing salt, . . . the N
metal-containing salt can be adjusted (e.g., manually or digitally
using a processing system of the invention) and prepared directly
into a liquid mixture in a desired concentration prior to forming
the mist of the liquid mixture. As another example, the adjusting
the molar ratio
M.sub.LiSalt:M.sub.LiSalt:M.sub.Me3Salt:M.sub.Me2Salt:M.sub.Me3Salt:
. . . :M.sub.MeNSalt of the lithium-containing salt, the
cobalt-containing salt, the first metal-containing salt, the second
metal-containing salt, the third metal-containing salt, . . . and
the N-containing salt can be performed simultaneously with forming
the mist of the liquid mixture.
[0061] The method 100 includes further includes a step 120 of
forming a liquid mixture having the lithium-containing salt at the
molarity of M.sub.LiSalt, the cobalt-containing salt at the
molarity of M.sub.CoSalt, and the one or more metal
dopant-containing salts (e.g., a. First Metal-Containing Salt at a
Molarity of M.sub.Me1Salt, a Second Metal-Containing Salt at a
Molarity of M.sub.Me2Salt, an N Metal-Containing Salt at a Molarity
of . . . . M.sub.MeNSalt, etc.) for producing lithium cobalt oxide
materials doped with one or more metal dopants with a targeting
formula of Li.sub.x Co.sub.y O.sub.z.doped Me1.sub.a Me2.sub.b
Me3.sub.c . . . . MeN.sub.n, where the one or more
metal-dopant-containing salts comprising the first-containing metal
salt, the second-containing metal salt, the third-containing metal
salt, . . . , the N-containing salt are generated, and where the
liquid mixture achieves the molar ratio of
M.sub.LiSalt:M.sub.CoSalt:M.sub.Me1Salt:M.sub.Me2Salt: . . .
M.sub.MeNSalt at about of x:y:a:b: . . . :n.
[0062] The mist of the liquid mixture may include droplets of
various reactant solution, precursor solutions, etc., in homogenous
forms, sizes, shape, etc. For example, the molar ratio
M.sub.LiSalt:M.sub.CoSalt:M.sub.Me1Salt:M.sub.Me2Salt:M.sub.Me3Salt:
. . . :M.sub.MeNSalt of the lithium-containing salt, the
cobalt-containing salt, and the first metal-containing salt, the
second metal-containing salt, the third metal-containing salt, . .
. the N-containing salt can be digitally adjusted, depending on the
desired composition of final solid product particles.
[0063] In one embodiment, the one or more metal dopants (Me1, Me2,
Me3, . . . MeN) are incorporated into the lithium cobalt oxide
materials, wherein Me1, Me2, Me3, . . . MeN are different metal
dopants. For example, each of the one or more metal dopants (i.e.
Me1, Me2, Me3 . . . . MeN) can be selected from a group consisting
of Al, Mg, Mn, Zr, Zn, Nb, La, Ce, Sn, Ga, Ba, Ac, Ca, Sc, Ti, V,
Cr, Fe, Cu, B, Ge, As, Hf, Mo, W, Re, Ru, Rh, Pt, Ag, Os, Ir, Au,
and combinations thereof.
[0064] Another embodiment of the present invention is that the
liquid form of the lithium-containing salt, the cobalt-containing
salt and the first metal-containing salt, the second
metal-containing salt, the third metal-containing salt, . . . the
N-containing salt can be dissolved or dispersed in a suitable
solvent (e.g., water, alcohol, methanol, isopropyl alcohol, organic
solvents, inorganic solvents, organic acids, sulfuric acid
(H.sub.2SO.sub.4), citric acid (C.sub.6H.sub.8O.sub.7), acetic
acids (CH.sub.3CO.sub.0H), butyric acid (C.sub.4H.sub.8O.sub.2),
lactic acid (C.sub.3H.sub.6O.sub.3), nitric acid (HNO.sub.3),
hydrochloric acid (HCl), ethanol, pyridine, ammonia, acetone, and
their combinations) to form into a liquid mixture of an aqueous
solution, slurry, gel, aerosol or any other suitable liquid forms.
For example, one or more solid particles of an oxide material can
be adjusted manually or digitally and prepared in desirable molar
ratio and mixed into a liquid mixture, such as by adjusting,
measuring and preparing appropriate amounts of the
lithium-containing salt compound, the cobalt-containing salt
compound and the one or more metal-dopant-containing salts into one
solution with suitable amounts of a solvent. Depending on the
solubility of the lithium-containing salt, the cobalt-containing
salt and the one or more metal-containing salts in a chosen
solvent, pH, temperature, and mechanical stirring and mixing can be
adjusted to obtain a liquid mixture where the one or more
metal-dopant-containing salts at the desirable molar concentrations
are fully dissolved and/or evenly dispersed.
[0065] In another embodiment, the lithium containing salts are
mixed into the liquid mixture. Exemplary lithium containing salts
include, but not limited to, lithium sulfate (Li.sub.2SO.sub.4),
lithium nitrate (LiNO.sub.3), lithium carbonate (Li.sub.2CO.sub.3),
lithium acetate (LiCH.sub.2COO), lithium hydroxide (LiOH), lithium
formate (LiCHO.sub.2), lithium chloride (LiCl), and combinations
thereof. The cobalt containing salts are mixed into the liquid
mixture. Exemplary cobalt containing salts include, but not limited
to, cobalt sulfate (CoSO.sub.4), cobalt nitrate
(Co(NO.sub.3).sub.2), cobalt acetate (Co(CH.sub.2COO).sub.2),
cobalt formate (Co(CHO.sub.2).sub.2), cobalt chloride (CoCl.sub.2),
and combinations thereof.
[0066] In still another embodiment, the first metal-containing
salt, the second metal-containing salt, the third metal containing
salt, . . . the N-containing salts are mixed into the liquid
mixture. Exemplary metal-dopant-containing salts include, but not
limited to, of magnesium nitrate Mg(NO.sub.3).sub.2, magnesium
acetate (MgAc, Mg(CH.sub.3COO).sub.2), magnesium chloride
(MgCl.sub.2), magnesium sulfate (MgSO.sub.4), magnesium formate
(C.sub.2H.sub.2MgO.sub.4), aluminum nitrate (Al(NO.sub.3).sub.3),
aluminum acetate (AlAc, C.sub.6H.sub.9AlO.sub.6), aluminum chloride
(AlCl.sub.3), aluminum sulfate (Al.sub.2(SO.sub.4).sub.3), aluminum
formate (Al(HCOO).sub.3), manganese sulfate (MnSO.sub.4), manganese
nitrate (Mn(NO.sub.3).sub.2), manganese acetate
(Mn(CH.sub.2COO).sub.2), manganese formate (Mn(CHO.sub.2).sub.2),
manganese chloride (MnC.sub.12), zirconium nitrate
(Zr(NO.sub.3).sub.4), zirconium acetate (C.sub.8H.sub.12O.sub.8Zr),
zirconium chloride (ZrCl.sub.4), zirconium sulfate
(Zr(SO.sub.4).sub.2), zirconium formate (C.sub.4H.sub.4O.sub.8Zr),
nickel sulfate (NiSO.sub.4), nickel nitrate (Ni(NO.sub.3).sub.2),
nickel acetate (Ni(CH.sub.2COO).sub.2), nickel formate
(Ni(CHO.sub.2).sub.2), nickel chloride (NiCl.sub.2), titanyl
nitrate (TiO(NO.sub.3).sub.2), aluminum (Al)-containing compound,
magnesium (Mg)-containing compound, titanium (Ti)-containing
compound, sodium (Na)-containing compound, potassium (K)-containing
compound, scandium (Sc)-containing compound, niobium
(Nb)-containing compound, neodymium (Nd)-containing compound,
lanthanum (La)-containing compound, cerium (Ce)-containing
compound, silicon (Si)-containing compound, rubidium
(Rb)-containing compound, vanadium (V)-containing compound, cesium
(Cs)-containing compound, chromium (Cr)-containing compound, copper
(Cu)-containing compound, magnesium (Mg)-containing compound,
manganese (Mn)-containing compound, zirconium (Zr)-containing
compound, zinc (Zn)-containing compound, tin (Sn)-containing
compound, gallium (Ga)-containing compound, barium (Ba)-containing
compound, actinium (Ac)-containing compound, calcium
(Ca)-containing compound, iron (Fe)-containing compound, boron
(B)-containing compound, germanium (Ge)-containing compound,
arsenic (As)-containing compound, hafnium (Hf)-containing compound,
Molybdenum (Mo)-containing compound, tungsten (W)-containing
compound, rhenium (Re)-containing compound, ruthenium
(Ru)-containing compound, rhodium (Rh)-containing compound,
platinum (Pt)-containing compound, silver (Ag)-containing compound,
osmium (Os)-containing compound, iridium (Ir)-containing compound,
gold (Au)-containing compound, and combinations thereof, among
others.
[0067] Not wishing to be bound by theory, it is contemplated that,
all the required metal-containing salts are first prepared in
liquid phase (e.g., into a solution, slurry, or gel-like mixtures)
using the lithium-containing salt, the cobalt-containing salt, the
first metal-containing salt, the second metal-containing salt, the
third metal-containing salt, . . . the N-containing salt as the
sources of each metal element such that the different metals can be
mixed uniformly at desired ratio. As an example, to prepare a
liquid mixture of an aqueous solution, slurry or gel, one or more
metal dopants with high water solubility can be used. For example,
metal nitrate, metal sulfate, metal chloride, metal acetate, and
metal format, etc., can be used. Organic solvents, such as
alcohols, isopropanol, etc., can be used to dissolve and/or
disperse metal-containing salt compounds with low water solubility.
In some cases, the pH value of the liquid mixture can be adjusted
to increase the solubility of the one or more precursor compounds.
Optionally, chemical additives, gelation agents, and surfactants,
such as ammonia, EDTA, etc., can be added into the liquid mixture
to help dissolve or disperse the compounds in a chosen solvent.
[0068] At step 130, the mist of the liquid mixture is mixed with a
gas flow of a gas inside a mist generator to form a gas-liquid
mixture. In addition, the liquid mixture is mixed with a gas flow
of another gas inside a drying chamber. It is contemplated that
these gas flows are provided to thoroughly mix the liquid mixture
to uniformly form into the gas-liquid mixture and assist in
carrying the gas-liquid mixture inside the drying chamber. The
method 100 further includes a step 140 of drying the gas-liquid
mixture at a drying temperature in the presence of the gas flows
for a time period to obtain gas-solid mixtures.
[0069] The gases within the gas flows may be, for example, air,
oxygen, carbon dioxide, nitrogen gas, hydrogen gas, inert gas,
noble gas, and combinations thereof, among others. The gas flows
may be pumped through an air filter to remove any particles,
droplets, or contaminants, and the flow rate of the gases can be
adjusted by a valve or other means. Accordingly, one embodiment of
the invention provides that the gases are used as the gas source
for carrying out drying reaction, evaporation, dehydration, and/or
other reactions. In another embodiment, the gases are heated to a
drying temperature to mix with the mist and remove moisture from
the mist.
[0070] The drying temperature can be, for example, about
200.degree. C. or higher, such as from 200.degree. C. to
300.degree. C., or at 250.degree. C. The time period is around 1
second to 1 hour. Optionally, additional gas flow may be used to
perform the drying reaction. The additional gas may be, for
example, air, oxygen, carbon dioxide, nitrogen gas, hydrogen gas,
inert gas, noble gas, and combinations thereof, among others. The
additional gas flow may be pumped through an air filter to remove
any particles, droplets, or contaminants, and the flow rate of the
additional gas can be adjusted by a valve or other means.
[0071] Next, at step 150, step 150 includes separating the
gas-solid mixture into one or more solid particles of an oxide
material and waste products. The gas-solid mixture comprising of
the gas and the compounds mixed together are separated into one or
more solid particles of oxide materials and waste products. The one
or more solid particles of the oxide material may include
thoroughly mixed solid particles of the compounds. Accordingly, the
step 150 of the method 100 of preparing a battery material includes
obtaining one or more solid particles of the oxide material from a
gas-solid mixture comprised of a gas and one or more compounds.
[0072] The method 100 further includes a step 160 of annealing the
one or more solid particles of an oxide material at an annealing
temperature for a time period to obtain crystalized lithium cobalt
oxide materials doped with one or more metal dopants of desired
size, morphology and crystal structure with a formula of Li.sub.x
Co.sub.y O.sub.z.doped Me1.sub.a Me2.sub.b Me3.sub.c . . . .
MeN.sub.n, wherein the atomic ratio of Li:Co:Me1:Me2:Me3 . . . :MeN
equaling to x:y:a:b:c: . . . :n. The annealing temperature is from
400.degree. C. to 1200.degree. C., for example, more than
900.degree. C., such as 1050.degree. C. The time period is about 1
second to 10 hours.
[0073] FIG. 1B illustrates another embodiment of a flow chart of a
method 200 of producing a lithium cobalt oxide material doped with
one or more metal dopants for lithium ion batteries. The method 200
comprises a first step 210 of forming a mist of a liquid mixture
having a lithium-containing salt compound, a cobalt-containing salt
compound, and one or more metal-dopant-containing salts compounds
at a molar ratio of
M.sub.LiSalt:M.sub.CoSalt:M.sub.Me1Salt:M.sub.Me2Salt:M.sub.Me3Salt:
. . . :M.sub.MeNSalt, where each of the one or more
metal-dopant-containing salts compounds is selected from a group
consisting of a first metal-containing salt compound, a second
metal-containing salt compound, a third metal-containing salt
compound, . . . an N metal-containing salt compound and
combinations thereof. The molar ratio
M.sub.LiSalt:M.sub.CoSalt:M.sub.Me1Salt:M.sub.Me2Salt:M.sub.Me3Salt:
. . . M.sub.MeNSalt is adjusted to be a ratio of about x:y:a:b:c: .
. . :n for making the lithium cobalt oxide doped with one or more
metal dopants (Li.sub.x Co.sub.y O.sub.z.doped Me1.sub.a Me2.sub.b
Me3.sub.c . . . . MeN.sub.n) at desirable atomic ratio of
Li:Co:Me1:Me2:Me3 . . . :MeN equaling to x:y:a:b:c: . . . :n, where
x is from 0.9 to 1.1 (0.9.ltoreq.x.ltoreq.1.1), y is from 0.9 to
1.1 (0.9.ltoreq.y.ltoreq.1.1), z is from 1.8 to 2.2
(1.8.ltoreq.z.ltoreq.2.2), and where N.gtoreq.1, a is from 0 to
0.05 (0.ltoreq.x.ltoreq.0.05), b is from 0 to 0.05
(0.ltoreq.b.ltoreq.0.05), c is from 0 to 0.05
(0.ltoreq.x.ltoreq.0.05), . . . , and n is from 0 to 0.05
(0.ltoreq.x.ltoreq.0.05).
[0074] In one embodiment, the desired molar ratio of
M.sub.LiSalt:M.sub.CoSalt:M.sub.Me1Salt
M.sub.Me2Salt:M.sub.Me3Salt: . . . :M.sub.MeNSalt can be achieved
by measuring and preparing appropriate amounts a lithium-containing
salt (LiSalt), a cobalt-containing salt (CoSalt), a first metal
dopant-containing salt (Me1Salt), a second metal dopant-containing
salt (Me2Salt), a third metal dopant-containing salt (Me3Salt), . .
. , and a N metal dopant-containing salt (MeNSalt). For example,
the molar ratio
M.sub.LiSalt:M.sub.CoSalt:M.sub.Me1Salt:M.sub.Me2Salt:M.sub.Me3Salt:
. . . :M.sub.MeNSalt of the lithium-containing salt, the
cobalt-containing salt, the first metal-containing salt, the second
metal-containing salt, the third metal-containing salt, . . . the N
metal-containing salt can be adjusted (e.g., manually or digitally
using a processing system of the invention) and prepared directly
into a liquid mixture in a desired concentration prior to forming
the mist of the liquid mixture. As another example, the adjusting
the molar ratio
M.sub.LiSalt:M.sub.CoSalt:M.sub.Me1Salt:M.sub.Me2Salt:M.sub.Me3Salt:
. . . :M.sub.MeNSalt of the lithium-containing salt, the
cobalt-containing salt, the first metal-containing salt, the second
metal-containing salt, the third metal-containing salt, . . . and
the N-containing salt can be performed simultaneously with forming
the mist of the liquid mixture.
[0075] In one embodiment, liquid form of lithium-containing salt
compound, cobalt-containing salt compound and one or more
metal-dopant-containing salts can be adjusted and prepared directly
into a liquid mixture in a desired concentration. The liquid form
of the lithium-containing salt compound, the cobalt-containing salt
compound and the one or more metal-dopant-containing salts can be
dissolved or dispersed in a suitable solvent (e.g., water, alcohol,
methanol, isopropyl alcohol, organic solvents, inorganic solvents,
organic acids, sulfuric acid (H.sub.2SO.sub.4), citric acid
(C.sub.6H.sub.8O.sub.7), acetic acids (CH.sub.3COOH), butyric acid
(C.sub.4H.sub.8O.sub.2), lactic acid (C.sub.3HO.sub.3), Nitric acid
(HNO.sub.3), hydrochloric acid (HCl), ethanol, pyridine, ammonia,
acetone, and their combinations) to form into a liquid mixture of
an aqueous solution, slurry, gel, aerosol or any other suitable
liquid forms.
[0076] In another embodiment, the lithium-containing salt, the
cobalt-containing salt and the one or more metal-dopant-containing
salts can be used, depending on the desired composition of final
solid product particles. For example, one or more solid particles
of an oxide material can be digitally adjusted and prepared in
desirable molar ratio and mixed into a liquid mixture, such as by
digitally adjusting, measuring and preparing appropriate amounts of
the lithium-containing salt, the cobalt-containing salt and the one
or more metal-dopant-containing salts into a container with
suitable amounts of a solvent. Depending on the solubility of the
lithium-containing salt, the cobalt-containing salt and the one or
more metal-dopant-containing salts in a chosen solvent, pH,
temperature, and mechanical stirring and mixing can be adjusted to
obtain a liquid mixture where the one or more
metal-dopant-containing salts at the desirable molar concentrations
are fully dissolved and/or evenly dispersed.
[0077] In yet another embodiment, the lithium-containing salt, the
cobalt-containing salt and the one or more metal-dopant-containing
salts are mixed into a liquid mixture for obtaining final solid
product particles of a mixed metal oxide material.
[0078] For example, the lithium containing salts and the cobalt
containing salts are mixed into the liquid mixture. Exemplary
lithium containing salts include, but not limited to, lithium
sulfate (Li.sub.2SO.sub.4), lithium nitrate (LiNO.sub.3), lithium
carbonate (Li.sub.2CO.sub.3), lithium acetate (LiCH.sub.2COO),
lithium hydroxide (LiOH), lithium formate (LiCHO.sub.2), lithium
chloride (LiCl), and combinations thereof. Exemplary cobalt
containing salts include, but not limited to, cobalt sulfate
(COSO.sub.4), cobalt nitrate (Co(NO.sub.3).sub.2), cobalt acetate
(Co(CH.sub.2COO).sub.2), cobalt formate (Co(CHO.sub.2).sub.2),
cobalt chloride (CoCl.sub.2), and combinations thereof.
[0079] As another example, the one or more metal-dopant-containing
salts are mixed into the liquid mixture. Exemplary other
metal-containing salts include, but not limited to, of magnesium
nitrate Mg(NO.sub.3).sub.2, magnesium acetate (MgAc,
Mg(CH.sub.3COO).sub.2), magnesium chloride (MgCl.sub.2), magnesium
sulfate (MgSO.sub.4), magnesium formate (C.sub.2H.sub.2MgO.sub.4),
aluminum nitrate (Al(NO.sub.3).sub.3), aluminum acetate (AlAc,
C.sub.6H.sub.9AlO.sub.6), aluminum chloride (AlCl.sub.3), aluminum
sulfate (Al.sub.2(SO.sub.4).sub.3), aluminum formate
(Al(HCOO).sub.3), manganese sulfate (MnSO.sub.4), manganese nitrate
(Mn(NO.sub.3).sub.2), manganese acetate (Mn(CH.sub.2COO).sub.2),
manganese formate (Mn(CHO.sub.2).sub.2), manganese chloride
(MnCl.sub.2), zirconium nitrate (Zr(NO.sub.3).sub.4), zirconium
acetate (C.sub.8H.sub.12O.sub.8Zr), zirconium chloride
(ZrCl.sub.4), zirconium sulfate (Zr(SO.sub.4).sub.2), zirconium
formate (C.sub.4H.sub.4O.sub.8Zr), nickel sulfate (NiSO.sub.4),
nickel nitrate (Ni(NO.sub.3).sub.2), nickel acetate
(Ni(CH.sub.2COO).sub.2), nickel formate (Ni(CHO.sub.2).sub.2),
nickel chloride (NiCl.sub.2), titanyl nitrate
((TiO(NO.sub.3).sub.2)), aluminum (Al)-containing compound,
magnesium (Mg)-containing compound, titanium (Ti)-containing
compound, sodium (Na)-containing compound, potassium (K)-containing
compound, scandium (Sc)-containing compound, niobium
(Nb)-containing compound, neodymium (Nd)-containing compound,
lanthanum (La)-containing compound, cerium (Ce)-containing
compound, silicon (Si)-containing compound, rubidium
(Rb)-containing compound, vanadium (V)-containing compound, cesium
(Cs)-containing compound, chromium (Cr)-containing compound, copper
(Cu)-containing compound, magnesium (Mg)-containing compound,
manganese (Mn)-containing compound, zirconium (Zr)-containing
compound, zinc (Zn)-containing compound, tin (Sn)-containing
compound, gallium (Ga)-containing compound, barium (Ba)-containing
compound, actinium (Ac)-containing compound, calcium
(Ca)-containing compound, iron (Fe)-containing compound, boron
(B)-containing compound, germanium (Ge)-containing compound,
arsenic (As)-containing compound, hafnium (Hf)-containing compound,
Molybdenum (Mo)-containing compound, tungsten (W)-containing
compound, rhenium (Re)-containing compound, ruthenium
(Ru)-containing compound, rhodium (Rh)-containing compound,
platinum (Pt)-containing compound, silver (Ag)-containing compound,
osmium (Os)-containing compound, iridium (Ir)-containing compound,
gold (Au)-containing compound, and combinations thereof, among
others.
[0080] Not wishing to be bound by theory, it is contemplated that,
all of the required metal elements are first mixed in liquid phase
(e.g., into a solution, slurry, or gel) using metal-containing
salts as the sources of each metal element such that the different
metals can be mixed uniformly at desired ratio. As an example, to
prepare a liquid mixture of an aqueous solution, slurry or gel, one
or more metal dopants with high water solubility can be used. For
example, metal nitrate, metal sulfate, metal chloride, metal
acetate, and metal format, etc., can be used. Organic solvents,
such as alcohols, isopropanol, etc., can be used to dissolve and/or
disperse metal-containing salt with low water solubility. In some
cases, the pH value of the liquid mixture can be adjusted to
increase the solubility of the one or more precursor compounds.
Optionally, chemical additives, gelation agents, and surfactants,
such as ammonia, EDTA, etc., can be added into the liquid mixture
to help dissolve or disperse the compounds in a chosen solvent.
[0081] Secondly, at step 220 of the method 200, the method includes
flowing a flow of a gas into a drying chamber. The flow of the gas
may be pumped through an air filter to remove any particles,
droplets, or contaminants, and the flow rate of the gas can be
adjusted by a valve or other means. In one embodiment, the gas is
heated to a drying temperature to mix with the mist and remove
moisture from the mist.
[0082] The mist of the liquid mixture may be generated by a mist
generator, such as a nozzle, a sprayer, an atomizer, or any other
mist generators. Most mist generators employ air pressure or other
means to covert a liquid mixture into liquid droplets. The mist
generator can be coupled to a portion of the drying chamber to
generate a mist (e.g., a large collection of small size droplets)
of the liquid mixture directly within the drying chamber. As an
example, an atomizer can be attached to a portion of the drying
chamber to spray or inject the liquid mixture into a mist
containing small sized droplets directly inside the drying chamber.
In general, a mist generator that generates a mist of mono-sized
droplets are desirable. Alternatively, a mist can be generated
outside the drying chamber and delivered into the drying
chamber.
[0083] Desired liquid droplet sizes can be adjusted by adjusting
the sizes of liquid delivery/injection channels within the mist
generator. Droplet size ranging from a few nanometers to a few
hundreds of micrometers can be generated. Suitable droplet sizes
can be adjusted according to the choice of the mist generator used,
the precursor compounds, the temperature of the drying chamber, the
flow rate of the gas, and the residence time inside the drying
chamber. As an example, a mist with liquid droplet sizes between
one tenth of a micron and one millimeter is generated inside the
drying chamber.
[0084] Then, at step 230 of the method 200, a mist of the liquid
mixture is mixed with the flow of a gas to form a gas-liquid
mixture prior to and/or after the liquid mixture is inside the
drying chamber. The mist is formed from a liquid mixture dissolved
and/or dispersed in a suitable liquid solvent. The flow of one or
more gases and the flow of the mist are mixed together to form a
gas-liquid mixture. The gases may be, for example, air, oxygen,
carbon dioxide, nitrogen gas, hydrogen gas, inert gas, noble gas,
and combinations thereof, among others. The gases may be pumped
through an air filter to remove any particles, droplets, or
contaminants, and the flow rate of the gases can be adjusted by a
valve or other means.
[0085] In one example, the mist of the liquid mixture is mixed with
a flow of a carrying gas inside the mist generator prior to
delivering into the drying chamber. In another example, the mist of
the liquid mixture is mixed with a flow of a drying gas inside the
drying chamber and carrying through the drying chamber to be dried.
Accordingly, one embodiment of the invention provides that one or
more gases flown within the drying chamber are used as the gas
source for carrying out drying reaction, evaporation, dehydration,
and/or other reactions inside the drying chamber such that
gas-liquid mixtures are dried into gas-solid mixtures. In another
embodiment, the gases is heated to a drying temperature to mix with
the mist and remove moisture from the mist.
[0086] At step 240, drying the gas-liquid mixture at a drying
temperature in the presence of the gas and forming a gas-solid
mixture is performed. The mist of the liquid mixture is dried
(e.g., removing its moisture, liquid, etc.) at a drying temperature
for a desired residence time and form into a gas-solid mixture with
the flow of the gases within the drying chamber. As the removal of
the moisture from the mist of the liquid mixture is performed
within the drying chamber filled with the gases, a gas-solid
mixture comprising of the gases and the compounds is formed.
Accordingly, one embodiment of the invention provides that the
gases flown within the drying chamber are used as the gas source
for forming a gas-solid mixture within the drying chamber. To
illustrate, the liquid mixture is dried inside the drying chamber
and the drying temperature inside the drying chamber is maintained
via a heating element coupled to the drying chamber, where the
heating element can be a suitable heating mechanism, such as
wall-heated furnace, electricity powered heater, fuel-burning
heater, etc.
[0087] In another embodiment, the gases flown within the drying
chamber is heated and the thermal energy of the heated gas is
served as the energy source for carrying out drying reaction,
evaporation, dehydration, and/or other reactions inside the drying
chamber. The gas can be heated to a drying temperature by passing
through a suitable heating mechanism, such as electricity powered
heater, fuel-burning heater, etc. The drying temperature is about
200.degree. C. or higher, for example, from 200.degree. C. to
300.degree. C., such as 250.degree. C. For instance, the liquid
mixture is dried in the presence of the gas that is heated to
200.degree. C. or higher inside the drying chamber and the gas is
delivered into the drying chamber to maintain the drying
temperature inside the drying chamber.
[0088] In one configuration, the gas is pre-heated to a drying
temperature of about 200.degree. C. or higher prior to flowing into
the drying chamber. In another configuration, drying the mist can
be carried out by heating the drying chamber directly, such as
heating the chamber body of the drying chamber. For example, the
drying chamber can be a wall-heated furnace to maintain the drying
temperature within internal plenum of the drying chamber. The
advantages of using heated gas are fast heat transfer, high
temperature uniformity, and easy to scale up, among others. The
drying chambers may be any chambers, furnaces with enclosed chamber
body, such as a dome type ceramic drying chamber, a quartz chamber,
a tube chamber, etc. Optionally, the chamber body is made of
thermal insulation materials (e.g., ceramics, etc.) to prevent heat
loss during drying.
[0089] The gases may be, for example, air, oxygen, carbon dioxide,
nitrogen gas, hydrogen gas, inert gas, noble gas, and combinations
thereof, among others. For example, heated air can be used as an
inexpensive gas source and energy source for drying the mist. The
choice of the gases may be a gas that mix well with the mist of the
liquid mixture and dry the mist without reacting to the compounds.
In some cases, the chemicals in the droplets/mist may react to the
gases and/or to each other to certain extent during drying,
depending on the drying temperature and the chemical composition of
the compounds. In addition, the residence time of the mist of
thoroughly mixed compounds within the drying chamber is adjustable
and may be, for example, between one second and one hour, depending
on the flow rate of the gases, and the length and volume of the
path that the mist has to flow through within the drying
chamber.
[0090] The gas-liquid mixture is being dried within the drying
chamber using the heated gases flow continuously and/or at
adjustable, variable flow rates. At the same time, dried solid
particles of compounds are carried by the gases, as a
thoroughly-mixed gas-solid mixture, through a path within the
drying chamber, and as more gases is flown in, the gas-solid
mixture is delivered out of the drying chamber and continuously
delivered to a gas-solid separator connected to the drying
chamber.
[0091] Not wishing to be bound by theory, in the method 200 of
manufacturing a battery material using the lithium-containing salt,
the cobalt-containing salt and the one or more
metal-dopant-containing salts, it is contemplated that the
lithium-containing salt, the cobalt-containing salt and the one or
more metal-dopant-containing salts are prepared into a liquid
mixture and then converted into droplets, each droplet will have
the one or more liquid mixture uniformly distributed. Then, the
moisture of the liquid mixture is removed by passing the droplets
through the drying chamber and the flow of the gas is used to carry
the mist within the drying chamber for a suitable residence time.
It is further contemplated that the concentrations of the compounds
in a liquid mixture and the droplet sizes of the mist of the liquid
mixture can be adjusted to control the chemical composition,
particle sizes, and size distribution of final solid product
particles of the battery material. It is designed to obtain
spherical solid particles from a thoroughly mixed liquid mixture of
two or more precursors after drying the mist of the liquid mixture.
In contrast, conventional solid-state manufacturing processes
involve mixing or milling a solid mixture of precursor compounds,
resulting in uneven mixing of precursors.
[0092] Next, at step 250, step 250 includes separating the
gas-solid mixture into one or more solid particles of an oxide
material and waste products by a gas-solid separator. The gas-solid
mixture comprising of the gas and the compounds mixed together are
separated into one or more solid particles of an oxide material and
a waste product. The one or more solid particles of an oxide
material may include thoroughly mixed solid particles of the
compounds. Accordingly, the step 250 of the method 200 of preparing
a battery material includes obtaining one or more solid particles
of an oxide material from a gas-solid mixture comprised of a gas
and one or more compounds.
[0093] In the method 200 of preparing final solid product particles
of the battery material in multiple stages, it is contemplated to
perform one or more reactions of the compounds in a drying stage,
two or more reaction stages, one or more cooling stages, etc., in
order to obtain final solid product particles of the crystalized
lithium cobalt oxide materials at desired size, morphology and
crystal structure, which are ready for further battery
applications. Not wishing to be bound by theory, it is designed to
perform the reaction of the compounds in two or more reaction
stages to allow sufficient time and contact of the compounds to
each other, encourage nucleation of proper crystal structure and
proper folding of particle morphology, incur lower-thermodynamic
energy partial reaction pathways, ensure thorough reactions of all
compounds, and finalize complete reactions, among others.
[0094] The one or more solid particles of a lithium cobalt oxide
material comprising the compounds are then processed in two or more
processing stages using at least a reaction module designed for
initiating reactions, and one or more reaction modules designed for
completing reactions and obtaining final solid product particles of
the crystalized lithium cobalt oxide materials. Additional reaction
modules can also be used. In one embodiment, the reaction module
includes one anneal reaction to react and oxidize the one or more
solid particles of a lithium cobalt oxide material into an oxidized
reaction product, where a portion of them are partially reacted
(some complete reactions may occur). The another reaction module
includes annealing the oxidized reaction product into final solid
product particles of the crystalized lithium cobalt oxide materials
to ensure complete reactions of all the reaction products.
[0095] Accordingly, the method 200 may include a processing stage
of drying a mist of a liquid mixture and obtaining one or more
solid particles of an oxide material using a processing module
comprised of a drying chamber and a gas-solid separator. The method
200 may further include another processing stage of reacting,
oxidizing and annealing the f one or more solid particles of an
oxide material using a reaction module comprised of an annealing
chamber.
[0096] At step 260, step 260 includes delivering the solid
particles of the oxide material into an annealing chamber to react
and anneal the solid particles of the oxide material in the
presence of a flow of a gas at an annealing temperature to obtain
crystalized lithium cobalt oxide materials doped with one or more
metal dopants.
[0097] The one or more solid particles of an oxide material is
delivered into an annealing chamber once the one or more solid
particles of an oxide material are separated from the waste
product. The one or more solid particles of the oxide material is
reacted and oxidized in the presence of a gas within the annealing
chamber to form an oxidized reaction product. Reactions of the one
or more solid particles of the oxide material within the annealing
chamber may include any of oxidation, reduction, decomposition,
combination reaction, phase-transformation, re-crystallization,
single displacement reaction, double displacement reaction,
combustion, isomerization, and combinations thereof. For example,
the one or more solid particles of the oxide material may be
oxidized, such as oxidizing the precursor compounds into an oxide
material.
[0098] Exemplary gases include, but not limited to air, oxygen,
carbon dioxide, an oxidizing gas, nitrogen gas, inert gas, noble
gas, and combinations thereof. For an oxidation reaction inside the
annealing chamber, such as forming an oxide material from one or
more precursors, an oxidizing gas can be used as the gas for
annealing. Accordingly, one embodiment of the invention provides
that the gas flows within the annealing chamber is used to oxidize
the one or more solid particles of the oxide material. The gases,
for example, can be air or oxygen and combination thereof. If
desired, the gases can be oxygen with high purity; the purity of
the oxygen is more than 50%, for example more than 80%, such as
95%. Accordingly, the gas flows within the annealing chamber is
served as the energy source for carrying out reaction, oxidation,
and/or other reactions inside the annealing chamber.
[0099] At this stage of the process, the step 260 further includes
delivering the solid particles of the oxide material into an
annealing chamber to react and annealing the solid particles of the
lithium cobalt oxide material in the presence of a flow of a gas at
an annealing temperature of 400.degree. C. or higher for a
residence time to obtain crystalized lithium cobalt oxide materials
doped with one or more metal dopants. For example, the annealing
temperature can be more than 900.degree. C., such as 1050.degree.
C., such as 1000.degree. C. The residence time is about 1 second to
10 hours.
[0100] In one embodiment, the gas flown within the annealing
chamber is heated and the thermal energy of the heated gas is
served as the energy source for carrying out annealing reaction,
and/or other reactions inside the annealing chamber. The gas can be
heated to a temperature of 550.degree. C. or higher by passing
through a suitable heating mechanism, such as electricity powered
heater, fuel-burning heater, etc. For instance, the one or more
solid particles of the oxide materials are annealed in the presence
of the gas that is heated to 550.degree. C. or higher inside the
annealing chamber and the gas is delivered into the annealing
chamber to maintain the annealing temperature inside the annealing
chamber.
[0101] Another embodiment of the present invention is that the one
or more solid particles of the oxide materials are annealed inside
the annealing chamber and the annealing temperature inside the
annealing chamber is maintained via a heating element coupled to
the annealing chamber, where the heating element can be a suitable
heating mechanism, such as wall-heated furnace, electricity powered
heater, fuel-burning heater, etc.
[0102] In one configuration, the gas is pre-heated to a temperature
of about 550.degree. C. or higher prior to flowing into the
annealing chamber. In another configuration, annealing the one or
more solid particles of the oxide materials can be carried out by
heating the annealing chamber directly, such as heating the chamber
body of the annealing chamber. For example, the annealing chamber
can be a wall-heated furnace to maintain the annealing temperature
within internal plenum of the annealing chamber. The advantages of
using heated gas are fast heat transfer, high temperature
uniformity, and easy to scale up, among others. The annealing
chambers may be any chambers, furnaces with enclosed chamber body,
such as a dome type ceramic annealing chamber, a quartz chamber, a
tube chamber, etc. Optionally, the chamber body of the annealing
chamber is made of thermal insulation materials (e.g., ceramics,
etc.) to prevent heat loss during annealing process.
[0103] The gas may be, for example, air, oxygen, carbon dioxide,
nitrogen gas, hydrogen gas, inert gas, noble gas, and combinations
thereof, among others. For example, heated air can be used as an
inexpensive gas source and energy source for drying the mist. In
addition, the residence time within the annealing chamber is
adjustable and may be, for example, between one second and one
hour, depending on the flow rate of the gas, and the length and
volume of the path that the solid particles have to pass through
within the annealing chamber.
[0104] The method 200 may include a processing stage of cooling the
crystalized lithium cobalt oxide materials doped with one or more
metal dopants and obtaining final solid product particles of the
crystalized lithium cobalt oxide materials doped with one or more
metal dopants at desired size, morphology and crystal structure at
step 270. For example, the temperature of the final solid product
particles of the crystalized lithium cobalt oxide materials doped
with one or more metal dopants may be slowly cooled down to room
temperature to avoid interfering or destroying a process of forming
into its stable energy state with uniform morphology and desired
crystal structure. In another example, the cooling stage may be
performed very quickly to quench the reaction product such the
crystal structure of the solid particles of the reaction product
can be formed at its stable energy state. As another example, a
cooling processing stage in a multi-stage continuous process may
include a cooling module comprised of one or more cooling
mechanisms. Exemplary cooling mechanisms may be, for example, a
gas-solid separator, a heat exchanger, a gas-solid feeder, a
fluidized bed cooling mechanism, and combinations thereof, among
others.
[0105] FIG. 2 illustrates a flow chart of incorporating the method
100 of preparing a material for a battery electrochemical cell
using a system 300 fully equipped with all of the required
manufacturing tools. The system 300 generally includes a mist
generator 306, a drying chamber 310, a gas-solid separator 320, and
a reactor 340. First, a liquid mixture containing two or more
precursors is prepared and delivered into the mist generator 306 of
the system 300. The mist generator 306 is coupled to the drying
chamber 310 and adapted to generate a mist from the liquid mixture.
A flow of heated gases can be flowed into the drying chamber 310 to
fill and pre-heat an internal volume of the drying chamber 310
prior to the formation of the mist or at the same time when the
mist is generated inside the drying chamber 310. The mist is mixed
with the heated gas and its moisture is removed such that a
gas-solid mixture, which contains the heated gases, two or more
precursors, and/or other gas-phase waste product or by-products,
etc., is formed.
[0106] Next, the gas-solid mixture is continuously delivered into
the gas-solid separator 320 which separates the gas-solid mixture
into solid particles and waste products. The solid particles is
then delivered into the reactor 340 to be mixed with a flow of
heated gas and form a gas-solid mixture. The reaction inside the
reactor is carried out for a reaction time until reaction products
can be obtained. Optionally, the reaction product gas-solid mixture
can be delivered into a gas-solid separator (e.g., a gas-solid
separator 328) to separate and obtain final solid product particles
and a gaseous side product. In addition, one or more flows of
cooling fluids (e.g., gases or liquids) may be used to cool the
temperature of the reaction products. The final solid product
particles can be delivered out of the system 300 for further
analysis on their properties (e.g., specific capacity, power
performance, battery charging cycle performance, etc.), particle
sizes, morphology, crystal structure, etc., to be used as a
material in a battery cell. Finally, the final particles are packed
into a component of a battery cell.
[0107] FIG. 3 is a schematic of the system 300, which is one
example of an integrated tool/apparatus that can be used to carry
out a fast, simple, continuous and low cost manufacturing process
for preparing a material for a battery electrochemical cell. The
system 300 is connected to a liquid mixer 304, which in turn is
connected to two or more reactant sources 302A, 302B. The reactant
sources 302A, 302B are provided to store various precursor
compounds and liquid solvents. Desired amounts of precursor
compounds (in solid or liquid form) and solvents are dosed and
delivered from the reactant sources 302A, 302B to the liquid mixer
304 so that the precursor compounds can be dissolved and/or
dispersed in the solvent and mix well into a liquid mixture. If
necessary, the liquid mixer 304 is heated to a temperature, such as
between 30.degree. C. and 90.degree. C. to help uniformly dissolve,
disperse, and/or mix the precursors. The liquid mixer 304 is
optionally connected to a pump 305, which pumps the liquid mixture
from the liquid mixer 304 into the mist generator 306 of the system
300 to generate a mist.
[0108] The mist generator 306 converts the liquid mixture into a
mist with desired droplet size and size distribution. In addition,
the mist generator 306 is coupled to the drying chamber 310 in
order to dry and remove moisture from the mist and obtain
thoroughly-mixed solid precursor particles. In one embodiment, the
mist generator 306 is positioned near the top of the drying chamber
310 that is positioned vertically (e.g., a dome-type drying
chamber, etc.) to inject the mist into the drying chamber 310 and
pass through the drying chamber vertically downward. Alternatively,
the mist generator can be positioned near the bottom of the drying
chamber 310 that is vertically positioned to inject the mist upward
into the drying chamber to increase the residence time of the mist
generated therein. In another embodiment, when the drying chamber
310 is positioned horizontally (e.g., a tube drying chamber, etc.)
and the mist generator 306 is positioned near one end of the drying
chamber 310 such that a flow of the mist, being delivered from the
one end through another end of the drying chamber 310, can pass
through a path within the drying chamber 310 for the length of its
residence time.
[0109] The drying chamber 310 generally includes a chamber inlet
315, a chamber body 312, and a chamber outlet 317. In one
configuration, the mist generator 306 is positioned inside the
drying chamber 310 near the chamber inlet 315 and connected to a
liquid line 303 adapted to flow the liquid mixture therein from the
liquid mixer 304. For example, the liquid mixture within the liquid
mixer 304 can be pumped by the pump 305 through the liquid line 303
connected to the chamber inlet 315 into the internal volume of the
drying chamber 310. Pumping of the liquid mixture by the pump 305
can be configured, for example, continuously at a desired delivery
rate (e.g., adjusted by a metered valve or other means) to achieve
good process throughput of system 300. In another configuration,
the mist generator 306 is positioned outside the drying chamber 310
and the mist generated therefrom is delivered to the drying chamber
310 via the chamber inlet 315.
[0110] One or more gas lines (e.g., gas lines 331A, 331B, 331C,
331D, etc.) can be coupled to various portions of the drying
chamber 310 and adapted to flow a gas from a gas source 332 into
the drying chamber 310. A flow of the gas stored in the gas source
332 can be delivered, concurrently with the formation of the mist
inside drying chamber 310, into the drying chamber 310 to carry the
mist through the drying chamber 310, remove moisture from the mist,
and form a gas-solid mixture containing the precursors. Also, the
flow of the gas can be delivered into the drying chamber 310 prior
to the formation of the mist to fill and preheat an internal volume
of the drying chamber 310 prior to generating the mist inside the
drying chamber 310.
[0111] In one example, the gas line 331A is connected to the top
portion of the drying chamber 310 to deliver the gas into the mist
generator 306 positioned near the chamber inlet 315 to be mixed
with the mist generated by the mist generator 306 inside the drying
chamber 310. In one embodiment, the gas is preheated to a
temperature of between 70.degree. C. and 600.degree. C. to mix with
and remove moisture from the mist. As another example, the gas line
331B delivering the gas therein is connected to the chamber inlet
315 of the drying chamber 310, in close proximity with the liquid
line 303 having the liquid mixture therein. Accordingly, the gas
can thoroughly mix with the mist of the liquid mixture inside the
drying chamber 310.
[0112] In another example, the gas line 331C is connected to the
chamber body 312 of the drying chamber 310 to deliver the gas
therein and mix the gas with the mist generated from the mist
generator 306. In addition, the gas line 331D connected to the
drying chamber 310 near the chamber outlet 317 may be used to
ensure the gas-solid mixture formed within the drying chamber 310
is uniformly mixed with the gas.
[0113] The flow of the gas may be pumped through an air filter to
remove any particles, droplets, or contaminants, and the flow rate
of the gas can be adjusted by a valve or other means. In one
embodiment, the gas is heated to a drying temperature to mix with
the mist and remove moisture from the mist. It is designed to
obtain spherical solid particles from a thoroughly-mixed liquid
mixture of two or more precursors after drying the mist of the
liquid mixture. In contrast, conventional solid-state manufacturing
processes involve mixing or milling a solid mixture of precursor
compounds, resulting in uneven mixing of precursors.
[0114] Once the mist of the liquid mixture is dried and formed into
a gas-solid mixture with the gas, the gas-solid mixture is
delivered out of the drying chamber 310 via the chamber outlet 317.
The drying chamber 310 is coupled to the gas-solid separator 320 of
the system 300. The gas-solid separator 320 collects chamber
products (e.g., a gas-solid mixture having the gas and the one or
more solid particles of a lithium cobalt oxide material mixed
together) from the chamber outlet 317.
[0115] The gas-solid separator 320 includes a separator inlet 321A,
two or more separator outlets 322A, 324A. The separator inlet 321A
is connected to the chamber outlet 317 and adapted to collect the
gas-solid mixture and other chamber products from the drying
chamber 310. The gas-solid separator 320 separates the gas-solid
mixture from the drying chamber 310 into one or more solid
particles of a lithium cobalt oxide material and waste products.
The separator outlet 322A is adapted to deliver the one or more
solid particles of a lithium cobalt oxide material to the reactor
340 for further processing and reactions. The separator outlet 324A
is adapted to deliver waste products out of the gas-solid separator
320.
[0116] The waste products may be delivered into a gas abatement
device 326A to be treated and released out of the system 300. The
waste product may include, for example, water (H.sub.2O) vapor,
organic solvent vapor, nitrogen-containing gas, oxygen-containing
gas, O.sub.2, O.sub.3, nitrogen gas (N.sub.2), NO, NO.sub.2,
NO.sub.2, N.sub.2O, N.sub.4O, NO.sub.3, N.sub.2O.sub.3,
N.sub.2O.sub.4, N.sub.2O.sub.5, N(NO.sub.2).sub.3,
carbon-containing gas, carbon dioxide (CO.sub.2), CO,
hydrogen-containing gas, H.sub.2, chlorine-containing gas,
Cl.sub.2, sulfur-containing gas, SO.sub.2, small particles of the
one or more solid particles of a lithium cobalt oxide material, and
combinations thereof.
[0117] The one or more solid particles of a lithium cobalt oxide
material may include at least particles of the two or more
precursors that are dried and uniformly mixed together. It is
contemplated to separate the one or more solid particles of a
lithium cobalt oxide material away from any side products, gaseous
products or waste products, prior to reacting the two or more
precursors in the reactor 340. Accordingly, the system 300 is
designed to mix the two or more precursors uniformly, dry the two
or more precursors, separate the dried two or more precursors, and
react the two or more precursors into final solid product particles
of the crystalized lithium cobalt oxide materials in a continuous
manner.
[0118] Suitable gas-solid separators include cyclones,
electrostatic separators, electrostatic precipitators, gravity
separators, inertia separators, membrane separators, fluidized
beds, classifiers, electric sieves, impactors, particles
collectors, leaching separators, elutriators, air classifiers,
leaching classifiers, and combinations thereof, among others.
[0119] Once the one or more solid particles of a lithium cobalt
oxide material are separated and obtained, it is delivered into the
reactor 340 for further reaction. The reactor 340 includes a gas
inlet 333, a reactor inlet 345, and a reactor outlet 347. The
reactor inlet 345 is connected to the separator outlet 322A and
adapted to receive the solid particles. Optionally, a vessel 325 is
adapted to store the solid particles prior to adjusting the amounts
of the solid particles delivered into the reactor 340.
[0120] The gas inlet 333 of the reactor 340 is coupled to a heating
mechanism 380 to heat a gas from a gas source 334 to an annealing
temperature of between 400.degree. C. and 1200.degree. C. The
heating mechanism 380 can be, for example, an electric heater, a
gas-fueled heater, a burner, among other heaters. Additional gas
lines can be used to deliver heated air or gas into the reactor
340, if needed. The pre-heated gas can fill the reactor 340 and
maintained the internal temperature of the reactor 340, much better
and energy efficient than conventional heating of the chamber body
of a reactor.
[0121] The gas flown inside the reactor 340 is designed to be mixed
with the one or more solid particles of a lithium cobalt oxide
material and form an oxidized reaction product inside the reactor
340. Thermal energy from the pre-heated gas is used as the energy
source for reacting the one or more solid particles of a lithium
cobalt oxide material within the reactor 340. The reaction process
includes, but not limited to, reduction, decomposition, combination
reaction, phase-transformation, re-crystallization, single
displacement reaction, double displacement reaction, combustion,
isomerization, and combinations thereof. The oxidized reaction
product is then going through annealing process for a residence
time of between 1 second and ten hours, or longer, depending on the
annealing temperature and the type of the precursors initially
delivered into the system 300. One embodiment of the invention
provides the control of the temperature of the reactor 340 by the
temperature of the heated gas. The use of the heated gas as the
energy source inside the reactor 340 provides the benefits of fast
heat transfer, precise temperature control, uniform temperature
distribution therein, and/or easy to scale up, among others.
[0122] Once the reactions inside the reactor 340 are complete, for
example, upon the formation of desired crystal structure, particle
morphology, and particle size, oxidized reaction products are
delivered out of the reactor 340 via the reactor outlet 347 and/or
a reactor outlet 348. The cooled reaction products include final
solid product particles of the crystalized lithium cobalt oxide
materials containing, for example, oxidized reaction product
particles of the precursor compounds which are suitable as a
material of a battery cell.
[0123] Optionally, the system 300 includes a gas-solid separator,
such as a gas-solid separator 328, which collects the reaction
products from the reactor outlet 347 of the reactor 340. The
gas-solid separator 328 may be a particle collector, such as
cyclone, electrostatic separator, electrostatic precipitator,
gravity separator, inertia separator, membrane separator, fluidized
beds classifiers electric sieves impactor, leaching separator,
elutriator, air classifier, leaching classifier, and combinations
thereof.
[0124] The gas-solid separator 328 of the system 300 generally
includes a separator inlet 321B, a separator outlet 322B and a
separator outlet 324B and is used to separate the reaction products
into the solid particles and gaseous side products. The gaseous
side products may be delivered into a gas abatement device 326B to
be treated and released out of the system 300. The gaseous side
products separated by the gas-solid separator 328 may generally
contain water (H.sub.2O) vapor, organic solvent vapor,
nitrogen-containing gas, oxygen-containing gas, O.sub.2, O.sub.3,
nitrogen gas (N.sub.2), NO, NO.sub.2, NO.sub.2, N.sub.2O, N.sub.4O,
NO.sub.3, N.sub.2O.sub.3, N.sub.2O.sub.4, N.sub.2O.sub.5,
N(NO.sub.2).sub.3, carbon-containing gas, carbon dioxide
(CO.sub.2), CO, hydrogen-containing gas, H.sub.2,
chlorine-containing gas, Cl.sub.2, sulfur-containing gas, SO.sub.2,
small particles of the solid particles, and combinations thereof.
In addition, the system 300 may further include one or more cooling
fluid lines 353, 355 connected to the reactor outlet 347 or the
separator outlet 322A of the gas solid separator 328 and adapted to
cool the reaction products and/or the solid particles. The cooling
fluid line 353 is adapted to deliver a cooling fluid (e.g., a gas
or liquid) from a source 352 to the separator inlet 321B of the
gas-solid separator 328. The cooling fluid line 355 is adapted to
deliver a cooling fluid, which may filtered by a filter 354 to
remove particles, into a heat exchanger 350.
[0125] The heat exchanger 350 is adapted to collect and cool the
solid particles and/or reaction products from the gas-solid
separator 328 and/or the reactor 340 by flowing a cooling fluid
through them. The cooling fluid has a temperature lower than the
temperature of the reaction products and the solid particles
delivered from the gas-solid separator 328 and/or the reactor 340.
The cooling fluid may have a temperature of between 4.degree. C.
and 30.degree. C. The cooling fluid may be liquid water, liquid
nitrogen, an air, an inert gas or any other gas which would not
react to the reaction products.
[0126] Final solid products particles are collected and cooled by
one or more separators, cooling fluid lines, and/or heat
exchangers, and once cooled, the solid particles are delivered out
of the system 300 and collected in a final product collector 368.
The solid particles may include oxidized form of precursors, such
as an oxide material, suitable to be packed into a battery cell
370. Additional pumps may also be installed to achieve the desired
pressure gradient.
[0127] A process control system 390 can be coupled to the system
300 at various locations to automatically control the manufacturing
process performed by the system 300 and adjust various process
parameters (e.g., flow rate, mixture ratio, temperature, residence
time, etc.) within the system 300. For example, the flow rate of
the liquid mixture into the system 300 can be adjusted near the
reactant sources 302A, 302B, the liquid mixer 304, or the pump 305.
As another example, the droplet size and generation rate of the
mist generated by the mist generator 306 can be adjusted. In
addition, flow rate and temperature of various gases flown within
the gas lines 331A, 331B, 331C, 331D, 333, 353, 355, 515, etc., can
be controlled by the process control system 390. In addition, the
process control system 390 is adapted to control the temperature
and the residence time of various gas-solid mixture and solid
particles at desired level at various locations.
[0128] Accordingly, a continuous process for producing a material
of a battery cell using a system having a mist generator, a drying
chamber, one or more gas-solid separators and a reactor is
provided. A mist generated from a liquid mixture of one or more
metal precursor compounds in desired ratio is mixed with air and
dried inside the drying chamber, thereby forming gas-solid
mixtures. One or more gas-solid separators are used in the system
to separate the gas-solid mixtures from the drying chamber into
solid particles packed with the one or more metal precursors and
continuously deliver the solid particles into the reactor for
further reaction to obtain final solid material particles with
desired ratio of two or more intercalated metals.
[0129] In one embodiment, preparation and manufacturing of a metal
oxide material is provided. Depending on the details and ratios of
the metal precursor compounds that are delivered into the system
300, the resulting final solid material particles obtained from the
system 300 may be a metal oxide material, a doped metal oxide
material, an inorganic metal salts, among others. In addition, the
metal oxide materials can exhibit a crystal structure of metals in
the shape of layered, spinel, olivine, etc. In addition, the
morphology of the final solid product particles (such as the
oxidized reaction product prepared using the method 100 and the
system 300 as described herein) exists as desired solid powders.
The particle sizes of the solid powders range between 10 nm and 100
.mu.m.
[0130] In operation, a mist is mixed with a gas flow of a gas
inside a mist generator to form a gas-liquid mixture, where the
liquid mixture includes a lithium-containing salt compound, a
cobalt-containing salt compound, and one or more
metal-dopant-containing salts compounds. In addition, the liquid
mixture is mixed with a gas flow of another gas inside a drying
chamber. It is contemplated that these gas flows are provided to
thoroughly mix the liquid mixture to uniformly form into the
gas-liquid mixture and assist in carrying the gas-liquid mixture
inside the drying chamber. The liquid mixture can be adjusted
digitally or manually prepared in a desirable molar ratio of the
lithium-containing salt compound, the cobalt-containing salt
compound, and the one or more metal-dopant-containing salts
compounds at a ratio of around x:y:a:b: . . . :n inside reactant
sources and delivered into one or more liquid mixers.
[0131] In one embodiment, the adjusting of the molar ratio of the
lithium-containing salt compound, the cobalt-containing salt
compound, and the one or more metal-dopant-containing salt
compounds is performed prior to the forming the mist of the liquid
mixture inside a liquid mixer. Desired molar ratio of the
lithium-containing salt, the cobalt-containing salt, and the one or
more metal-dopant-containing salts are digitally or manually
measured and delivered from reactant sources to the liquid mixer so
that the lithium-containing salt compound, the cobalt-containing
salt compound, and the one or more metal-dopant-containing salts
compounds can be dissolved and/or dispersed in the solvent and mix
well into the liquid mixture inside the liquid mixer. The
lithium-containing salt compound, the cobalt-containing salt
compound, and the one or more metal-containing salts compounds are
all soluble in a suitable solvent within the liquid mixture.
[0132] In another embodiment, the adjusting of the molar ratio of
the lithium-containing salt compound, the cobalt-containing salt
compound, and the one or more metal-dopant-containing salt
compounds is performed simultaneously with the forming the mist of
the liquid mixture. The desirable molar ratio of the
lithium-containing salt compound, the cobalt-containing salt
compound, and the one or more metal-dopant-containing salt
compounds can be adjusted digitally or manually from each reactant
source and delivered into the mist generator to generate the mist
of the liquid mixture inside the mist generator.
[0133] The liquid mixture comprising the lithium-containing salt
compound, the cobalt-containing salt compound, and the one or more
metal-containing salts compounds is mixed with a gas flow to form a
gas-liquid mixture inside a drying chamber. Then, the gas-liquid
mixture is dried at a drying temperature inside the drying chamber
to form a gas-solid mixture of solid particles of an oxide
material. The gas-solid mixture is continuously delivered into the
gas-solid separator which separates the gas-solid mixture into one
or more solid particles of the oxide material and waste
products.
[0134] The one or more solid particles of the oxide material are
then delivered into an annealing chamber to be mixed with a flow of
a gas. The one or more solid particles of the oxide material are
reacted and annealed at an annealing temperature inside the
annealing chamber to obtain high quality lithium cobalt oxide
materials doped with one or more metal dopants at desired size,
morphology and crystal structure.
EXAMPLE
[0135] SUITABLE EXAMPLES: Exemplary material compositions and
formulations of the present inventions are shown in Table 1. In
group of A (Example #: A2-A8), lithium cobalt oxides materials
doped with one or more metal dopants having a chemical formula of
Li.sub.x Co.sub.y O.sub.z.doped Me1.sub.a Me2.sub.b Me3e . . . .
MeN.sub.n, is designed and prepared such that a ratio of x:y:a:b:c:
. . . n is equivalent to
M.sub.LiSalt:M.sub.CoSalt:M.sub.Me1Salt:M.sub.Me2Salt:M.sub.Me3Salt:
. . . M.sub.MeNSalt, wherein x is from 0.95-0.99
(0.95.ltoreq.x.ltoreq.0.99), y is 1.0, the a is from 0-0.05
(0.ltoreq.a.ltoreq.0.05), the b is from 0-0.05
(0.ltoreq.b.ltoreq.0.05), the c is from 0-0.05
(0.ltoreq.c.ltoreq.0.05), N.gtoreq.1, and wherein Me1, Me2, Me3 are
different metal dopants incorporated into lithium cobalt oxide
materials.
[0136] For example, each of the one or more metal dopants (i.e.
Me1, Me2, Me3 . . . MeN) can be selected from a group consisting of
Al, Mg, Mn, Zr, Zn, Nb, La, Ce, Sn, Ga, Ba, Ac, Ca, Sc, Ti, V, Cr,
Fe, Cu, B, Ge, As, Hf, Mo, W, Re, Ru, Rh, Pt, Ag, Os, Ir, Au, and
combinations thereof.
[0137] For example, in group A, exemplary lithium-containing salt
compounds include, but not limited to lithium sulfate
(Li.sub.2SO.sub.4), lithium nitrate (LiNO.sub.3), lithium carbonate
(Li.sub.2CO.sub.3), lithium acetate (LiCH.sub.2COO), lithium
hydroxide (LiOH), lithium formate (LiCHO.sub.2), lithium chloride
(LiCl), and combinations thereof. Exemplary cobalt-containing salt
compounds include, but not limited to cobalt containing salts
include, but not limited to, cobalt sulfate (CoSO.sub.4), cobalt
nitrate (Co(NO.sub.3).sub.2), cobalt acetate
(Co(CH.sub.2COO).sub.2), cobalt formate (Co(CHO.sub.2).sub.2),
cobalt chloride (CoCl.sub.2), and combinations thereof.
[0138] Exemplary metal-dopant-containing salts include, but not
limited to, of magnesium nitrate Mg(NO.sub.3).sub.2, magnesium
acetate (MgAc, Mg(CH.sub.3COO).sub.2), magnesium chloride
(MgCl.sub.2), magnesium sulfate (MgSO.sub.4), magnesium formate
(C.sub.2H.sub.2MgO.sub.4), aluminum nitrate (Al(NO.sub.3).sub.3),
aluminum acetate (AlAc, C.sub.6H.sub.9AlO.sub.6), aluminum chloride
(AlCl.sub.3), aluminum sulfate (Al.sub.2(SO.sub.4).sub.3), aluminum
formate (Al(HCOO).sub.3), manganese sulfate (MnSO.sub.4), manganese
nitrate (Mn(NO.sub.3).sub.2), manganese acetate
(Mn(CH.sub.2COO).sub.2), manganese formate (Mn(CHO.sub.2).sub.2),
manganese chloride (MnCl.sub.2), zirconium nitrate
(Zr(NO.sub.3).sub.4), zirconium acetate (C.sub.8H.sub.12O.sub.8Zr),
zirconium chloride (ZrCl.sub.4), zirconium sulfate
(Zr(SO.sub.4).sub.2), zirconium formate (C.sub.4H.sub.4O.sub.8Zr),
nickel sulfate (NiSO.sub.4), nickel nitrate (Ni(NO.sub.3).sub.2),
nickel acetate (Ni(CH.sub.2COO).sub.2), nickel formate
(Ni(CHO.sub.2).sub.2), nickel chloride (NiCl.sub.2), titanyl
nitrate (TiO(NO.sub.3).sub.2). The annealing temperature and
annealing time in group A experiments can be controlled from 900 to
949.degree. C. for 15 to 20 hours.
TABLE-US-00001 TABLE 1 Exemplary LCO materials doped with one or
more metal dopants compositions Example Anneal Temp Anneal Time #
M.sub.LiSalt M.sub.CoSalt M.sub.Me1Salt M.sub.Me2Salt M.sub.Me3Salt
(.degree. C.) (hour) A2 0.95-0.99 1.0 0-0.05 0 0 900-949 15-20 A3
0.95-0.99 1.0 0 0-0.05 0 900-949 15-20 A4 0.95-0.99 1.0 0 0 0-0.05
900-949 15-20 A5 0.95-0.99 1.0 0-0.05 0-0.05 0 900-949 15-20 A6
0.95-0.99 1.0 0-0.05 0 0-0.05 900-949 15-20 A7 0.95-0.99 1.0 0
0-0.05 0-0.05 900-949 15-20 A8 0.95-0.99 1.0 0-0.05 0-0.05 0-0.05
900-949 15-20
[0139] Additional material compositions and formulations are shown
in Table 2. In group of B (Example #: B2-B8), lithium cobalt oxides
materials doped with one or more metal dopants having a chemical
formula of Li.sub.x Co.sub.y O.sub.z.doped Me1.sub.a Me2.sub.b
Me3.sub.c . . . MeN.sub.n, is designed and prepared such that a
ratio of x:y:a:b:c: . . . n is equivalent to
M.sub.LiSalt:M.sub.CoSalt:M.sub.Me1Salt:M.sub.Me2Salt:M.sub.Me3Salt:
. . . M.sub.MeNSalt, wherein x is from 0.95-0.99
(0.95.ltoreq.x.ltoreq.0.99), y is 1.0, the a is from 0-0.05
(0.ltoreq.a.ltoreq.0.05), the b is from 0-0.05
(0.ltoreq.b.ltoreq.0.05), the c is from 0-0.05
(0.ltoreq.c.ltoreq.0.05), N.gtoreq.1, and wherein Me1, Me2, Me3 are
different metal dopants incorporated into lithium cobalt oxide
materials.
[0140] For example, each of the one or more metal dopants (i.e.
Me1, Me2, Me3, . . . MeN) can be selected from a group consisting
of Al, Mg, Mn, Zr, Zn, Nb, La, Ce, Sn, Ga, Ba, Ac, Ca, Sc, Ti, V,
Cr, Fe, Cu, B, Ge, As, Hf, Mo, W, Re, Ru, Rh, Pt, Ag, Os, Ir, Au,
and combinations thereof.
[0141] For example, in group B, exemplary lithium-containing salt
compounds include, but not limited to lithium sulfate
(Li.sub.2SO.sub.4), lithium nitrate (LiNO.sub.3), lithium carbonate
(Li.sub.2CO.sub.3), lithium acetate (LiCH.sub.2COO), lithium
hydroxide (LiOH), lithium formate (LiCHO.sub.2), lithium chloride
(LiCl), and combinations thereof. Exemplary cobalt-containing salt
compounds include, but not limited to cobalt containing salts
include, but not limited to, cobalt sulfate (CoSO.sub.4), cobalt
nitrate (Co(NO.sub.3).sub.2), cobalt acetate
(Co(CH.sub.2COO).sub.2), cobalt formate (Co(CHO.sub.2).sub.2),
cobalt chloride (CoCl.sub.2), and combinations thereof.
[0142] Exemplary metal-dopant-containing salts include, but not
limited to, of magnesium nitrate Mg(NO.sub.3).sub.2, magnesium
acetate (MgAc, Mg(CH.sub.3COO).sub.2), magnesium chloride,
(MgCl.sub.2), magnesium sulfate (MgSO.sub.4), magnesium formate
(C.sub.2H.sub.2MgO.sub.4), aluminum nitrate (Al(NO.sub.3).sub.3),
aluminum acetate (AlAc, C.sub.6H.sub.9AlO.sub.6), aluminum chloride
(AlCl.sub.3), aluminum sulfate (Al.sub.2(SO.sub.4).sub.3), aluminum
formate (Al(HCOO).sub.3), manganese sulfate (MnSO.sub.4), manganese
nitrate (Mn(NO.sub.3).sub.2), manganese acetate
(Mn(CH.sub.2COO).sub.2), manganese formate (Mn(CHO.sub.2).sub.2),
manganese chloride (MnCl.sub.2), zirconium nitrate
(Zr(NO.sub.3).sub.4), zirconium acetate (C.sub.8H.sub.12O.sub.8Zr),
zirconium chloride (ZrCl.sub.4), zirconium sulfate
(Zr(SO.sub.4).sub.2), zirconium formate (C.sub.4H.sub.4O.sub.8Zr),
nickel sulfate (NiSO.sub.4), nickel nitrate (Ni(NO.sub.3).sub.2),
nickel acetate (Ni(CH.sub.2COO).sub.2), nickel formate
(Ni(CHO.sub.2).sub.2), nickel chloride (NiCl.sub.2), titanyl
nitrate (TiO(NO.sub.3).sub.2). The annealing temperature and
annealing time in group B experiments can be controlled from 950 to
999.degree. C. for 15 to 20 hours.
TABLE-US-00002 TABLE 2 Exemplary LCO materials doped with one or
more metal dopants compositions Example Anneal Temp Anneal Time #
M.sub.LiSalt M.sub.CoSalt M.sub.Me1Salt M.sub.Me2Salt M.sub.Me3Salt
(.degree. C.) (hour) B2 0.95-0.99 1.0 0-0.05 0 0 950-999 15-20 B3
0.95-0.99 1.0 0 0-0.05 0 950-999 15-20 B4 0.95-0.99 1.0 0 0 0-0.05
950-999 15-20 B5 0.95-0.99 1.0 0-0.05 0-0.05 0 950-999 15-20 B6
0.95-0.99 1.0 0-0.05 0 0-0.05 950-999 15-20 B7 0.95-0.99 1.0 0
0-0.05 0-0.05 950-999 15-20 B8 0.95-0.99 1.0 0-0.05 0-0.05 0-0.05
950-999 15-20
[0143] Additional material compositions and formulations are shown
in Table 3. In group of C (Example #: C2-C8), lithium cobalt oxides
materials doped with one or more metal dopants having a chemical
formula of Li.sub.x Co.sub.y O.sub.z.doped Me1.sub.a Me2.sub.b Me3e
. . . MeN.sub.n, is designed and prepared such that a ratio of
x:y:a:b:c: . . . n is equivalent to
M.sub.LiSalt:M.sub.CoSalt:M.sub.Me1Salt:M.sub.Me2Salt:M.sub.Me3Salt:
. . . M.sub.MeNSalt, wherein x is 1.0, y is 1.0, the a is from
0-0.05 (0.ltoreq.a.ltoreq.0.05), the b is from 0-0.05
(0.ltoreq.b.ltoreq.0.05), the cis from 0-0.05
(0.ltoreq.c.ltoreq.0.05), N.gtoreq.1, and wherein Me1, Me2, Me3 are
different metal dopants.
[0144] For example, each of the one or more metal dopants (i.e.
Me1, Me2, Me3 . . . . MeN) can be selected from a group consisting
of Al, Mg, Mn, Zr, Zn, Nb, La, Ce, Sn, Ga, Ba, Ac, Ca, Sc, Ti, V,
Cr, Fe, Cu, B, Ge, As, Hf, Mo, W, Re, Ru, Rh, Pt, Ag, Os, Ir, Au,
and combinations thereof.
[0145] For example, in group C, exemplary lithium-containing salt
compounds include, but not limited to lithium sulfate
(Li.sub.2SO.sub.4), lithium nitrate (LiNO.sub.3), lithium carbonate
(Li.sub.2CO.sub.3), lithium acetate (LiCH.sub.2COO), lithium
hydroxide (LiOH), lithium formate (LiCHO.sub.2), lithium chloride
(LiCl), and combinations thereof. Exemplary cobalt-containing salt
compounds include, but not limited to cobalt containing salts
include, but not limited to, cobalt sulfate (CoSO.sub.4), cobalt
nitrate (Co(NO.sub.3).sub.2), cobalt acetate
(Co(CH.sub.2COO).sub.2), cobalt formate (Co(CHO.sub.2).sub.2),
cobalt chloride (CoCl.sub.2), and combinations thereof.
[0146] Exemplary metal-dopant-containing salts include, but not
limited to, of magnesium nitrate Mg(NO.sub.3).sub.2, magnesium
acetate (MgAc, Mg(CH.sub.3COO).sub.2), magnesium chloride
(MgCl.sub.2), magnesium sulfate (MgSO.sub.4), magnesium formate
(C.sub.2H.sub.2MgO.sub.4), aluminum nitrate (Al(NO.sub.3).sub.3),
aluminum acetate (AlAc, C.sub.6H.sub.9AlO.sub.6), aluminum chloride
(AlCl.sub.3), aluminum sulfate (Al.sub.2(SO.sub.4).sub.3), aluminum
formate (Al(HCOO).sub.3), manganese sulfate (MnSO.sub.4), manganese
nitrate (Mn(NO.sub.3).sub.2), manganese acetate
(Mn(CH.sub.2COO).sub.2), manganese formate (Mn(CHO.sub.2).sub.2),
manganese chloride (MnCl.sub.2), zirconium nitrate
(Zr(NO.sub.3).sub.4), zirconium acetate (C.sub.8H.sub.2O.sub.8Zr),
zirconium chloride (ZrCl.sub.4), zirconium sulfate
(Zr(SO.sub.4).sub.2), zirconium formate (C.sub.4H.sub.4O.sub.8Zr),
nickel sulfate (NiSO.sub.4), nickel nitrate (Ni(NO.sub.3).sub.2),
nickel acetate (Ni(CH.sub.2COO).sub.2), nickel formate
(Ni(CHO.sub.2).sub.2), nickel chloride (NiCl.sub.2), titanyl
nitrate (TiO(NO.sub.3).sub.2). The annealing temperature and
annealing time in group C experiments can be controlled from 900 to
999.degree. C. for 15 to 20 hours.
TABLE-US-00003 TABLE 3 Exemplary LCO materials doped with one or
more metal dopants compositions Exam- Anneal Anneal ple Temp Time #
M.sub.LiSalt M.sub.CoSalt M.sub.Me1Salt M.sub.Me2Salt M.sub.Me3Salt
(.degree. C.) (hour) C2 1.0-1.05 1.0 0-0.05 0 0 900-999 15-20 C3
1.0-1.05 1.0 0 0-0.05 0 900-999 15-20 C4 1.0-1.05 1.0 0 0 0-0.05
900-999 15-20 C5 1.0-1.05 1.0 0-0.05 0-0.05 0 900-999 15-20 C6
1.0-1.05 1.0 0-0.05 0 0-0.05 900-999 15-20 C7 1.0-1.05 1.0 0 0-0.05
0-0.05 900-999 15-20 C8 1.0-1.05 1.0 0-0.05 0-0.05 0-0.05 900-999
15-20
[0147] Additional material compositions and formulations are shown
in Table 4. In group of D (Example #: D2-D8), lithium cobalt oxides
materials doped with one or more metal dopants having a chemical
formula of Li.sub.x Co.sub.y O.sub.z.doped Me1.sub.a Me2.sub.b Me3
. . . . MeN.sub.n, is designed and prepared such that a ratio of
x:y:a:b:c: . . . n is equivalent to
M.sub.LiSalt:M.sub.CoSalt:M.sub.Me1Salt:M.sub.Me2Salt:M.sub.Me3Salt:
. . . M.sub.MeNSalt, wherein x is 1.0, y is 1.0, the a is from
0-0.05 (0.ltoreq.a.ltoreq.0.05), the b is from 0-0.05
(0.ltoreq.b.ltoreq.0.05), the cis from 0-0.05
(0.ltoreq.c.ltoreq.0.05), N.gtoreq.1, and wherein Me1, Me2, Me3 are
different metals.
[0148] For example, each of the one or more metal dopants (i.e.
Me1, Me2, Me3 . . . . MeN) can be selected from a group consisting
of Al, Mg, Mn, Zr, Zn, Nb, La, Ce, Sn, Ga, Ba, Ac, Ca, Sc, Ti, V,
Cr, Fe, Cu, B, Ge, As, Hf, Mo, W, Re, Ru, Rh, Pt, Ag, Os, Ir, Au,
and combinations thereof.
[0149] For example, in group D, exemplary lithium-containing salt
compounds include, but not limited to lithium sulfate
(Li.sub.2SO.sub.4), lithium nitrate (LiNO.sub.3), lithium carbonate
(Li.sub.2CO.sub.3), lithium acetate (LiCH.sub.2COO), lithium
hydroxide (LiOH), lithium formate (LiCHO.sub.2), lithium chloride
(LiCl), and combinations thereof. Exemplary cobalt-containing salt
compounds include, but not limited to cobalt containing salts
include, but not limited to, cobalt sulfate (CoSO.sub.4), cobalt
nitrate (Co(NO.sub.3).sub.2), cobalt acetate
(Co(CH.sub.2COO).sub.2), cobalt formate (Co(CHO.sub.2).sub.2),
cobalt chloride (CoCl.sub.2), and combinations thereof.
[0150] Exemplary metal-dopant-containing salts include, but not
limited to, of magnesium nitrate Mg(NO.sub.3).sub.2, magnesium
acetate (MgAc, Mg(CH.sub.3COO).sub.2), magnesium chloride
(MgCl.sub.2), magnesium sulfate (MgSO.sub.4), magnesium formate
(C.sub.2H.sub.2MgO.sub.4), aluminum nitrate (Al(NO.sub.3).sub.3),
aluminum acetate (AlAc, C.sub.6H.sub.9AlO.sub.6), aluminum chloride
(AlCl.sub.3), aluminum sulfate (Al.sub.2(SO.sub.4).sub.3), aluminum
formate (Al(HCOO).sub.3), manganese sulfate (MnSO.sub.4), manganese
nitrate (Mn(NO.sub.3).sub.2), manganese acetate
(Mn(CH.sub.2COO).sub.2), manganese formate (Mn(CHO.sub.2).sub.2),
manganese chloride (MnCl.sub.2), zirconium nitrate
(Zr(NO.sub.3).sub.4), zirconium acetate (C.sub.8H.sub.12O.sub.8Zr),
zirconium chloride (ZrCl.sub.4), zirconium sulfate
(Zr(SO.sub.4).sub.2), zirconium formate (C.sub.4H.sub.4O.sub.8Zr),
nickel sulfate (NiSO.sub.4), nickel nitrate (Ni(NO.sub.3).sub.2),
nickel acetate (Ni(CH.sub.2COO).sub.2), nickel formate
(Ni(CHO.sub.2).sub.2), nickel chloride (NiCl.sub.2), titanyl
nitrate (TiO(NO.sub.3).sub.2). The annealing temperature and
annealing time in group A experiments can be controlled from 1000
to 1049.degree. C. for 15 to 20 hours.
TABLE-US-00004 TABLE 4 Exemplary LCO materials doped with one or
more metal dopants compositions Example Anneal Temp Anneal Time #
M.sub.LiSalt M.sub.CoSalt M.sub.Me1Salt M.sub.Me2Salt M.sub.Me3Salt
(.degree. C.) (hour) D2 1.0-1.05 1.0 0-0.05 0 0 1000-1049 15-20 D3
1.0-1.05 1.0 0 0-0.05 0 1000-1049 15-20 D4 1.0-1.05 1.0 0 0 0-0.05
1000-1049 15-20 D5 1.0-1.05 1.0 0-0.05 0-0.05 0 1000-1049 15-20 D6
1.0-1.05 1.0 0-0.05 0 0-0.05 1000-1049 15-20 D7 1.0-1.05 1.0 0
0-0.05 0-0.05 1000-1049 15-20 D8 1.0-1.05 1.0 0-0.05 0-0.05 0-0.05
1000-1049 15-20
[0151] Additional material compositions and formulations are shown
in Table 2. In group of E (Example #: E2-E8), lithium cobalt oxides
materials doped with one or more metal dopants having a chemical
formula of Li.sub.x Co.sub.y O.sub.z.doped Me1l.sub.a Me2.sub.b
Me3, . . . MeN.sub.n, is designed and prepared such that a ratio of
x:y:a:b:c: . . . n is equivalent to
M.sub.LiSalt:M.sub.CoSalt:M.sub.Me1Salt:M.sub.Me2Salt:M.sub.Me3Salt
. . . M.sub.MeNSalt, wherein x is 1.0, y is 1.0, the a is from
0-0.05 (0.ltoreq.a.ltoreq.0.05), the b is from 0-0.05
(0.ltoreq.b.ltoreq.0.05), the cis from 0-0.05
(0.ltoreq.c.ltoreq.0.05),N.gtoreq.1, and wherein Me1, Me2, Me3 are
different metal dopants.
[0152] For example, each of the one or more metal dopants (i.e.
Me1, Me2, Me3 . . . . MeN) can be selected from a group consisting
of Al, Mg, Mn, Zr, Zn, Nb, La, Ce, Sn, Ga, Ba, Ac, Ca, Sc, Ti, V,
Cr, Fe, Cu, B, Ge, As, Hf, Mo, W, Re, Ru, Rh, Pt, Ag, Os, Ir, Au,
and combinations thereof.
[0153] For example, in group E, exemplary lithium-containing salt
compounds include, but not limited to lithium sulfate
(Li.sub.2SO.sub.4), lithium nitrate (LiNO.sub.3), lithium carbonate
(Li.sub.2CO.sub.3), lithium acetate (LiCH.sub.2COO), lithium
hydroxide (LiOH), lithium formate (LiCHO.sub.2), lithium chloride
(LiCl), and combinations thereof. Exemplary cobalt-containing salt
compounds include, but not limited to cobalt containing salts
include, but not limited to, cobalt sulfate (CoSO.sub.4), cobalt
nitrate (Co(NO.sub.3).sub.2), cobalt acetate
(Co(CH.sub.2COO).sub.2), cobalt formate (Co(CHO.sub.2).sub.2),
cobalt chloride (CoCl.sub.2), and combinations thereof.
[0154] Exemplary metal-dopant-containing salts include, but not
limited to, of magnesium nitrate Mg(NO.sub.3).sub.2, magnesium
acetate (MgAc, Mg(CH.sub.3COO).sub.2), magnesium chloride
(MgCl.sub.2), magnesium sulfate (MgSO.sub.4), magnesium formate
(C.sub.2H.sub.2MgO.sub.4), aluminum nitrate (Al(NO.sub.3).sub.3),
aluminum acetate (AlAc, C.sub.6H.sub.9AlO.sub.6), aluminum chloride
(AlCl.sub.3), aluminum sulfate (Al.sub.2(SO.sub.4).sub.3), aluminum
formate (Al(HCOO).sub.3), manganese sulfate (MnSO.sub.4), manganese
nitrate (Mn(NO.sub.3).sub.2), manganese acetate
(Mn(CH.sub.2COO).sub.2), manganese formate (Mn(CHO.sub.2).sub.2),
manganese chloride (MnCl.sub.2), zirconium nitrate
(Zr(NO.sub.3).sub.4), zirconium acetate (C.sub.8H.sub.12O.sub.8Zr),
zirconium chloride (ZrCl.sub.4), zirconium sulfate
(Zr(SO.sub.4).sub.2), zirconium formate (C.sub.4H.sub.4O.sub.8Zr),
nickel sulfate (NiSO.sub.4), nickel nitrate (Ni(NO.sub.3).sub.2),
nickel acetate (Ni(CH.sub.2COO).sub.2), nickel formate
(Ni(CHO.sub.2).sub.2), nickel chloride (NiCl.sub.2), titanyl
nitrate (TiO(NO.sub.3).sub.2). The annealing temperature and
annealing time in group E experiments can be controlled from 1050
to 1200.degree. C. for 15 to 20 hours.
TABLE-US-00005 TABLE 5 Exemplary LCO materials doped with one or
more metal dopants compositions Example Anneal Temp Anneal Time #
M.sub.LiSalt M.sub.CoSalt M.sub.Me1Salt M.sub.Me2Salt M.sub.Me3Salt
(.degree. C.) (hour) E2 1.0-1.05 1.0 0-0.05 0 0 1050-1200 15-20 E3
1.0-1.05 1.0 0 0-0.05 0 1050-1200 15-20 E4 1.0-1.05 1.0 0 0 0-0.05
1050-1200 15-20 E5 1.0-1.05 1.0 0-0.05 0-0.05 0 1050-1200 15-20 E6
1.0-1.05 1.0 0-0.05 0 0-0.05 1050-1200 15-20 E7 1.0-1.05 1.0 0
0-0.05 0-0.05 1050-1200 15-20 E8 1.0-1.05 1.0 0-0.05 0-0.05 0-0.05
1050-1200 15-20
[0155] PREPARATION: Lithium cobalt oxide materials doped with one
or more metal dopants were prepared in the following steps: (a)
mixing 1 M solutions of forming a liquid mixture having a
lithium-containing salt at a molarity of M.sub.LiSalt, a
cobalt-containing salt at a molarity of M.sub.CoSalt, a first metal
salt at a molarity of M.sub.Me1Salt, a second metal salt at a
molarity of M.sub.Me2Salt, and a third metal salt at a molarity of
M.sub.Me3Salt wherein the liquid mixture achieves a molar ratio of
M.sub.LiSalt:M.sub.CoSalt:M.sub.Me1Salt:M.sub.Me2Salt:M.sub.Me3S-
alt; (b) generating a mist of the liquid mixture inside a mist
generator of the drying chamber. The mist of the liquid mixture is
mixed with a gas flow of a gas inside a mist generator to form a
gas-liquid mixture. In addition, the liquid mixture is mixed with a
gas flow of another gas inside a drying chamber; (c) mixing the
mist of the liquid mixture with a gas flow to form a gas-liquid
mixture inside the drying chamber; (d) dry the gas-liquid mixture
at a drying temperature for a time period and form a gas-solid
mixture inside the drying chamber; (e) separate the gas-solid
mixture into one or more solid particles of a an oxide material and
a waste product; (f) deliver the solid particles of the lithium
cobalt oxide material into an annealing chamber to react and anneal
the solid particles of the lithium cobalt oxide material in the
presence of a flow of a gas at an annealing temperature to obtain
crystalized lithium cobalt oxide materials doped with one or more
metal dopants, and anneal the crystalized lithium cobalt oxide
materials doped with one or more metal dopants inside the annealing
chamber for a time period to obtain crystalized lithium cobalt
oxide materials; (g) cool the crystalized lithium cobalt oxide
materials doped with one or more metal dopants and obtain final
solid product particles of crystalized lithium cobalt oxide
materials doped with one or more metal dopants at desired size,
morphology and crystal structure.
[0156] In some embodiments, the compositions and formulations of
the present inventions being tested are as shown in the below Table
6. The compositions of the present inventions, prepared according
to Example #12 and Example #16, have a chemical formula of Li.sub.x
Co.sub.y O.sub.z.doped Zr.sub.c, wherein a ratio of x:y:c is
equivalent to M.sub.LiSalt:M.sub.CoSalt:M.sub.ZrSalt, wherein x is
from 0.9-1.1 (0.9.ltoreq.x.ltoreq.1.1), x is 0.97, y is 1.0, c is
0.0017.
[0157] In Example 12 and Example 16, exemplary lithium-containing
salt compounds include, but not limited to, lithium nitrate
(LiNO.sub.3), exemplary cobalt-containing salt compound include,
but not limited to cobalt nitrate (Co(NO.sub.3).sub.2) and
combinations thereof, exemplary zirconium-containing salt compound
include, but not limited to, zirconium nitrate (Zr(NO.sub.3).sub.4)
and combinations thereof. The annealing temperature and annealing
time in Example 12 and Example 16 were heated to 950.degree. C. for
17 hours. The List of chemistries used for in the present invention
is displayed in Table 6.
TABLE-US-00006 TABLE 6 Exemplary compositions of measured LCO doped
with zirconium material Example M.sub.Me1Salt M.sub.Me2Salt
M.sub.ZrSalt Anneal Temp Anneal Time # M.sub.LiSalt M.sub.CoSalt
(Mg(NO.sub.3).sub.2) (Al(NO.sub.3).sub.3) (Zr(NO.sub.3).sub.4)
(.degree. C.) (hour) 12 0.97 1.0 0 0 0.0017 950 17 16 1.0 1.0 0 0
0.0017 950 17
[0158] Table 7 illustrates testing results of exemplary
compositions of measured LCO material doped with zirconium (Example
#12). One observation is that the testing results of the ratio of
the measured LCO. doped Zr material compositions of Li:Co:Zr are
within an expected range from the prepared molar ratio of
M.sub.LiSalt:M.sub.CoSalt:M.sub.ZrSalt being prepared.
TABLE-US-00007 TABLE 7 Exemplary compositions of measured LCO doped
with zirconium material Example # Li Ni Co Al Mg Zr 12 1.0312
0.0022 0.9963 0.0013 0.0001 0.0019
[0159] Table 8 illustrates testing results of electric capacity and
coulombic efficiency (CE) of battery cells made by lithium cobalt
oxide materials doped with zirconium at different cutoff voltage of
4.45 voltage and 4.5 voltage, prepared according to Example #16.
One observation can be found that the cutoff voltage affect the
initial charge and discharge capacity and CE of exemplary lithium
cobalt oxide material doped with zirconium. Further observation can
be found that with lower cutoff voltage, the exemplary lithium
cobalt oxide material doped with zirconium demonstrates slightly
higher coulombic efficiency (CE) as shown in Table 8. To be more
specific, under the upper cutoff voltage of 4.45 V, the coulombic
efficiency (CE) is 96.3%, while the coulombic efficiency (CE) is
92.9% under the upper cutoff voltage of 4.5 V.
TABLE-US-00008 TABLE 8 Measured electric performance of
lithium-ion-battery cells made from exemplary LCO doped with
Zirconium materials Example #16 Upper cut off 1st charge 1st
discharge voltage, V capacity, mAh/g capacity, mAh/g 1st CE, % 4.45
187.297 180.337 96.3 4.5 195.108 181.306 92.9
[0160] In other embodiments, the compositions and formulations of
the present inventions being tested are as shown in the below Table
8. The compositions of the present inventions, prepared according
to Example #22-#26, have a chemical formula of Li.sub.x Co.sub.y
O.sub.z.doped Mg.sub.a, Al.sub.b, Zr.sub.c, wherein a ratio of
x:y:a:b:c is equivalent to
M.sub.LiSalt:M.sub.CoSalt:M.sub.MgSalt:M.sub.AlSalt:M.sub.ZrSalt,
wherein x is 1.0, y is 1.0, the a is from 0-0.05
(0.ltoreq.a.ltoreq.0.05), the b is from 0-0.05
(0.ltoreq.b.ltoreq.0.05), the c is from 0-0.05
(0.ltoreq.c.ltoreq.0.05).
[0161] In Example #22-#26, exemplary lithium-containing salt
compound include, but not limited to, lithium nitrate (LINO.sub.3)
and combinations thereof, exemplary cobalt-containing salt compound
include, but not limited to cobalt nitrate (Co(NO.sub.3).sub.2) and
combinations thereof, exemplary first metal-containing salt Me1
include, but not limited to, magnesium nitrate (Mg(NO.sub.3).sub.2)
and combinations thereof, exemplary second metal-containing salt
Me2 compound include, but not limited to, aluminum nitrate
(Al(NO.sub.3).sub.3) and combinations thereof, exemplary third
metal-containing salt Me3 compound include, but not limited to,
zirconium nitrate (Zr(NO.sub.3).sub.4) and combinations thereof.
The annealing temperature and annealing time in the Example #22-#26
were heated to 1020.degree. C. for 17 hours. The list of
chemistries used for in the present invention is displayed in Table
9.
TABLE-US-00009 TABLE 9 Exemplary compositions of measured LCO
material doped with one or more metal dopants Example M.sub.Me1Salt
M.sub.Me2Salt M.sub.Me3Salt Anneal Temp Anneal Time # M.sub.LiSalt
M.sub.CoSalt (Mg(NO.sub.3).sub.2) (Al(NO.sub.3).sub.3)
(Zr(NO.sub.3).sub.4) (.degree. C.) (hour) 22 1.0 1.0 0.0017 0 0
1020 17 23 1.0 1.0 0.0045 0 0 1020 17 24 1.0 1.0 0 0.0045 0 1020 17
25 1.0 1.0 0.0010 0.0035 0 1020 17 26 1.0 1.0 0 0 0.0017 1020
17
[0162] Table 10 illustrates testing results of exemplary measured
LCO material doped with one or more metal dopants compositions
(Example #22-#26). One observation is that the testing results of
the ratio of the measured LCO material compositions of
Li:Co:Mg:Al:Zr are within an expected range from the prepared molar
ratio of
M.sub.LiSalt:M.sub.CoSalt:M.sub.MgSalt:M.sub.AlSalt:M.sub.ZrSalt
being prepared.
TABLE-US-00010 TABLE 10 Exemplary compositions of measured LCO
material doped with one or more metal dopants Example # Li Ni Co Al
Mg Zr 22 1.0040 0.0014 0.998 0.0003 0.0021 0.0002 23 1.0099 0 0.999
0.0007 0.0053 0 24 1.0131 0 0.9954 0.0044 0.0001 0 25 1.0165 0
0.9954 0.0044 0.0017 0 26 1.0140 0 0.9995 0.0003 0.0001 0.0009
[0163] Table 11 illustrates testing results of tap density (TD) and
contaminants of crystalized lithium cobalt oxide materials doped
with one or more metal dopants after annealing process of exemplary
LCO doped with one or more metal dopants (Example #22-26). To
obtain an ideal lithium cobalt oxide material with high discharge
capacity, excellent cycling performance and high-volume energy
density, the morphology and tap density of the material have to be
controlled precisely during the preparation process. It is found
that the tap density of the obtained precursor is around 2.38
(g/cc), which can be attributed to the homogeneous distributions of
particles with good packing properties.
TABLE-US-00011 TABLE 11 Measurement of tap density (TD) &
contaminants of exemplary LCO materials doped with one or more
metal dopants Example # TD (g/cc) Li.sub.2CO.sub.3 LiOH 22 2.17
0.024 0 23 2.38 0.036 0.005 24 2.27 0.035 0.005 25 2.18 0.027 0 26
2.10 0.031 0
[0164] Table 12 illustrates testing results of electric capacity
and coulombic efficiency (CE) of battery cells made by lithium
cobalt oxide materials doped with magnesium tested under different
upper cutoff voltages from 4.45 voltage to 4.6 voltage, prepared
according to Example #22.One observation can be found that the
battery samples made by exemplary lithium cobalt oxide materials
doped with magnesium overall show a highcoulombic efficiency (CE)
under different cutoff voltages. For example, under the upper
cutoff voltage of 4.45 V, the discharge capacity and the coulombic
efficiency (CE) is around 181.404 mAh/g and 98%, respectively. In
another example, under the upper cutoff voltage of 4.5 V, the
discharge capacity and coulombic efficiency (CE) is around 194.346
mAh/g and 99.4%, respectively. In still another example, under the
upper cutoff voltage of 4.6 V, the discharge capacity and the
coulombic efficiency (CE) is around 226.019 mAh/g and 97%,
respectively.
[0165] Referring back to Table 8, further observation can be found
that samples of batter cells made from lithium cobalt oxide
materials doped with magnesium (Li.sub.1.0 Co.sub.1.0 O.sub.2. a
doped Mg.sub.0.0017) demonstrate higher coulombic efficiency (CE)
than the CE made from lithium cobalt oxide materials doped with
zirconium (Li.sub.1.0 Co.sub.1.0 O.sub.2.doped Zr.sub.0.0017). To
be more specific, the measured CE of battery cells made from
exemplary LCO doped with zirconium materials is ranged from 92.9%
to 96.3%, while the measured CE of battery cells made from
exemplary LCO doped with magnesium materials is ranged from 96.9%
to 99.4%
TABLE-US-00012 TABLE 12 Measured electric performance of
lithium-ion-battery cells made from exemplary LCO doped with
Magnesium materials Example #22 Upper cut off 1st charge 1st
discharge voltage, V capacity, mAh/g capacity, mAh/g 1st CE, % 4.45
185.104 181.404 98 4.45 185.557 181.493 97.8 4.5 195.423 194.346
99.4 4.5 193.576 191.201 98.8 4.6 233.032 226.019 97 4.6 233.108
225.913 96.9
[0166] Table 13 illustrates testing results of electric capacity
and coulombic efficiency (CE) of battery cells made by lithium
cobalt oxide materials doped with magnesium tested under different
upper cutoff voltages from 4.3 voltage to 4.6 voltage, prepared
according to Example #23. One observation can be found that the
battery samples made by exemplary lithium cobalt oxide materials
doped with magnesium overall show a high coulombic efficiency (CE)
under different cutoff voltages. For example, under the upper
cutoff voltage of 4.3 V, the discharge capacity and the coulombic
efficiency (CE) is around 160.434 mAh/g and 97.7%, respectively. In
another example, under the upper cutoff voltage of 4.45 V, the
discharge capacity and the coulombic efficiency (CE) is around
183.173 mAh/g and 97.6%, respectively. In still another example,
under the upper cutoff voltage of 4.5 V, the discharge capacity and
the coulombic efficiency (CE) is around and 193.217 mAh/g and
97.3%, respectively. In yet another example, under the upper cutoff
voltage of 4.6 V, the discharge capacity and the coulombic
efficiency (CE) is around 228.309 mAh/g and 96.6%, respectively
[0167] Referring back to Table 12, further observation can be found
that samples of batter cells made from lithium cobalt oxide
materials doped with different percentage of magnesium demonstrate
similar coulombic efficiency (CE). To be more specific, the
measured CE of battery cells made from exemplary LCO doped with
0.0017 magnesium materials (Li.sub.1.0 Co.sub.1.0 O.sub.2.doped
Mg.sub.0.0017) is ranged from 96.9% to 99.4% under different upper
cutoff voltage ranged from 4.45 V to 4.6 V, while the measured CE
of battery cells made from exemplary LCO doped with 0.0045
(Li.sub.1.0 Co.sub.1.0 O.sub.2.doped Mg.sub.0.0045) magnesium
materials is ranged from 95.7% to 97.7% under different upper
cutoff voltage ranged from 4.3 V to 4.6 V
TABLE-US-00013 TABLE 13 Measured electric performance of
lithium-ion-battery cells made from exemplary LCO doped Magnesium
materials Example #23 Upper cut off 1st charge 1st discharge
voltage, V capacity, mAh/g capacity, mAh/g 1st CE, % 4.3 164.16
160.434 97.7 4.3 166.873 159.676 95.7 4.45 187.556 182.718 97.4
4.45 187.757 183.173 97.6 4.5 198.574 193.217 97.3 4.6 236.302
228.309 96.6
[0168] Table 14 illustrates testing results of electric capacity
and coulombic efficiency (CE) of battery cells made by lithium
cobalt oxide materials doped with aluminum tested under different
upper cutoff voltages from 4.4 voltage to 4.6 voltage, prepared
according to Example #24. One observation can be found that the
cutoff voltage the battery samples made by exemplary lithium cobalt
oxide materials doped with aluminum overall have a high coulombic
efficiency (CE). For example, under the upper cutoff voltage of 4.4
V, the discharge capacity and the coulombic efficiency (CE) is
around 173.592 mAh/g and 97%, respectively. In another example, the
discharge capacity and under the upper cutoff voltage of 4.45V, the
coulombic efficiency (CE) is around 181.861 mAh/g and 97.3%,
respectively. In still another example, under the upper cutoff
voltage of 4.5 V, the discharge capacity and the coulombic
efficiency (CE) is around 191.712 mAh/g and 97%, respectively. In
yet another example, under the upper cutoff voltage of 4.6 V, the
discharge capacity and the coulombic efficiency (CE) is around
225.187 mAh/g and 96.4%.
[0169] Referring back to Table 13, further observation can be found
that samples of batter cells made from lithium cobalt oxide
materials doped with magnesium (Li.sub.1.0 Co.sub.1.0 O.sub.2.doped
Mg.sub.0.0045) demonstrate similar coulombic efficiency (CE) to
lithium cobalt oxide materials doped with aluminum (Li.sub.1.0
Co.sub.1.0 O.sub.2.doped Al.sub.0.0045). To be more specific, the
measured CE of battery cells made from exemplary LCO doped with
magnesium materials is ranged from 95.7% to 97.7%, while the
measured CE of battery cells made from exemplary LCO doped with
aluminum materials is ranged from 96.4% to 97.3%
TABLE-US-00014 TABLE 14 Measured electric performance of
lithium-ion-battery cells made from exemplary LCO doped Aluminum
materials Example #24 Upper cut off 1st charge 1st discharge
voltage, V capacity, mAh/g capacity, mAh/g 1st CE, % 4.4 178.991
173.592 97 4.45 186.964 181.861 97.3 4.45 186.955 181.729 97.2 4.5
197.624 191.712 97 4.6 233.659 225.187 96.4
[0170] Table 15 illustrates testing results of electric capacity
and coulombic efficiency (CE) of battery cells made by lithium
cobalt oxide materials doped with aluminum tested under different
upper cutoff voltages from 4.45 voltage to 4.6 voltage, prepared
according to Example #25. One observation can be found that the
cutoff voltage the battery samples made by exemplary lithium cobalt
oxide materials doped with magnesium and aluminum overall have a
high coulombic efficiency (CE). For example, under the upper cutoff
voltage of 4.45 V, the discharge capacity and the coulombic
efficiency (CE) is around 180.661 mAh/g and 93.2%, respectively. In
another example, under the upper cutoff voltage of 4.5V, the
discharge capacity and the coulombic efficiency (CE) is around
190.324 mAh/g and 96.5%, respectively. In still another example,
under the upper cutoff voltage of 4.6 V, the discharge capacity and
the coulombic efficiency (CE) is around 224.68 mAh/g and 95.8%,
respectively.
[0171] Referring back to Table 11, Table 12, Table 13 and Table 14,
further observation can be found that samples of battery cells made
from lithium cobalt oxide materials with one metal dopant in
average demonstrate higher coulombic efficiency (CE) to lithium
cobalt oxide materials with two metal dopants (Li.sub.1.0
Co.sub.1.0 O.sub.2.doped Mg.sub.0.0010 Al.sub.0.0035). To be more
specific, the measured CE of battery cells made from exemplary LCO
with one metal dopant is ranged from 96.4% to 99.4%, while the
measured CE of battery cells made from exemplary LCO doped with
magnesium and aluminum materials is ranged from 93.2% to 96.5%
TABLE-US-00015 TABLE 15 Measured electric performance of
lithium-ion-battery cells made from exemplary LCO.doped Mg, Al
materials Example #25 Upper cut off 1st charge 1st discharge
voltage, V capacity, mAh/g capacity, mAh/g 1st CE, % 4.45 193.756
180.661 93.2 4.5 197.212 190.324 96.5 4.6 232.562 222.25 95.6 4.6
234.493 224.638 95.8
[0172] Table 16 illustrates testing results of electric capacity
and coulombic efficiency (CE) of battery cells made by lithium
cobalt oxide materials doped with zirconium tested under different
upper cutoff voltages from 4.3 voltage to 4.6 voltage, prepared
according to Example #26. One observation can be found that the
cutoff voltage the battery samples made by exemplary lithium cobalt
oxide materials doped with zirconium overall show a high coulombic
efficiency (CE). For example, under the upper cutoff voltage of 4.3
V, the discharge capacity and the coulombic efficiency (CE) is
around 159.025 mAh/g and 98.3%, respectively. In another example,
under the upper cutoff voltage of 4.45 V, the discharge capacity
and coulombic efficiency (CE) is around 181.71 mAh/g and 98.0%,
respectively. In still another example, under the upper cutoff
voltage of 4.5 V, the discharge capacity and the coulombic
efficiency (CE) is around 194.107 mAh/g and 97.9%, respectively. In
yet another example, under the upper cutoff voltage of 4.6 V, the
discharge capacity and the coulombic efficiency (CE) is around
230.09 mAh/g and 96.9%, respectively.
[0173] Referring back to Table 8, further observation can be found
that samples of batter cells made from lithium cobalt oxide
materials doped with zirconium annealed at 950.degree. C. for 17
hours (Li.sub.1.0 Co.sub.1.0 O.sub.2.doped Zr.sub.0.0017)
demonstrate lower coulombic efficiency (CE) than the CE made from
lithium cobalt oxide materials doped with zirconium annealed at
1020.degree. C. for 17 hours (Li.sub.1.0 Co.sub.1.0 O.sub.2.doped
Zr.sub.0.0017). To be more specific, the measured CE of battery
cells made from exemplary LCO doped with zirconium materials
annealed at 1020.degree. C. is ranged from 96.9% to 98.3%, while
the measured CE of battery cells made from exemplary LCO doped with
zirconium materials annealed at 950.degree. C. is ranged from 92.9%
to 96.3%
TABLE-US-00016 TABLE 16 Measured electric performance of
lithium-ion-battery cells made from exemplary LCO.doped Zr
materials Example #26 Upper cut off 1st charge 1st discharge
voltage, V capacity, mAh/g capacity, mAh/g 1st CE, % 4.3 161.831
159.025 98.3 4.45 185.369 181.71 98.0 4.5 198.267 194.107 97.9 4.6
237.538 230.09 96.9
[0174] In still other embodiments, the compositions and
formulations of the present inventions being tested are as shown in
the below Table 17. The compositions of the present inventions for
Example 32 having a chemical formula of Li.sub.x Co.sub.y
O.sub.z.doped Mg.sub.a, wherein a ratio of x:y:a is equivalent to
M.sub.LiSalt:M.sub.CoSalt:M.sub.MgSalt, wherein x is 1.0, y is 1.0,
a is 0.0017.
[0175] In Example 32, exemplary lithium-containing salt compound
include, but not limited to, lithium nitrate (LiNO.sub.3) and
combinations thereof, exemplary cobalt-containing salt compound
include, but not limited to cobalt nitrate (Co(NO.sub.3).sub.2) and
combinations thereof, exemplary first metal-containing salt Me1
include, but not limited to, magnesium nitrate (Mg(NO.sub.3).sub.2)
and combinations thereof. The annealing temperature and annealing
time in the Example 32 were heated to 1090.degree. C. for 17 hours.
The list of chemistries used for in the present invention is
displayed in Table 17.
TABLE-US-00017 TABLE 17 Exemplary compositions of measured LCO
material doped with magnesium Example M.sub.Me1Salt M.sub.Me2Salt
M.sub.Me3Salt Anneal Temp Anneal Time # M.sub.LiSalt M.sub.CoSalt
(Mg(NO.sub.3).sub.2) (Al(NO.sub.3).sub.3) (Zr(NO.sub.3).sub.4)
(.degree. C.) (hour) 32 1.0 1.0 0.0017 0 0 1090 17
[0176] Table 18 illustrates testing results of exemplary measured
LCO material compositions (Example #32). One observation is that
the testing results of the ratio of the measured LCO material
compositions of Li:Co:Mg are within an expected range from the
prepared molar ratio of M.sub.LiSalt:M.sub.CoSalt:M.sub.MgSalt
being prepared.
TABLE-US-00018 TABLE 18 Exemplary compositions of measured LCO
material doped with magnesium Example # Li Ni Co Al Mg Zr 32 1.0072
0 0.9979 0.0018 0.0020 0
[0177] Table 19 illustrates testing results of electric capacity
and coulombic efficiency (CE) of battery cells made by lithium
cobalt oxide materials doped with magnesium annealed at
1090.degree. C. tested under different upper cutoff voltages from
4.3 voltage to 4.6 voltage, prepared according to Example #32. One
observation can be found that the battery samples made by exemplary
lithium cobalt oxide materials doped with magnesium overall show a
high coulombic efficiency (CE) under different cutoff voltages. For
example, under the upper cutoff voltage of 4.3 V, the discharge
capacity and the coulombic efficiency (CE) is around 146.55 mAh/g
and 98.2%, respectively. In another example, under the upper cutoff
voltage of 4.45 V, the discharge capacity and the coulombic
efficiency (CE) is around 175.842 mAh/g and 98.3%, respectively. In
still another example, under the upper cutoff voltage of 4.5 V, the
discharge capacity and the coulombic efficiency (CE) is around and
175.7 mAh/g and 98.2%, respectively. In yet another example, under
the upper cutoff voltage of 4.6 V, the discharge capacity and the
coulombic efficiency (CE) is around 217.2 mAh/g and 97.5%,
respectively
[0178] Referring back to Table 12, further observation can be found
that samples of batter cells made from lithium cobalt oxide
materials doped with magnesium (Li.sub.1.0 C.sub.1.0 O.sub.2.doped
Mg.sub.0.0017) annealed at different annealing temperatures
demonstrate similar coulombic efficiency (CE). To be more specific,
the measured CE of battery cells made from exemplary LCO doped with
magnesium materials annealed at 1020.degree. C. is ranged from
96.9% to 99.4%, while the measured CE of battery cells made from
exemplary LCO doped with magnesium materials annealed at
1090.degree. C. is ranged from 97.1% to 98.3%
TABLE-US-00019 TABLE 19 Measured electric performance of
lithium-ion-battery cells made from exemplary LCO.doped Mg
materials Example #32 Upper cut off 1st charge 1st discharge
voltage, V capacity, mAh/g capacity, mAh/g 1st CE, % 4.3 149.23
146.55 98.2 4.45 178.845 175.842 98.3 4.5 178.9 175.7 98.2 4.5
192.3 186.7 97.1 4.6 222.8 217.2 97.5
[0179] FIG. 4 illustrates testing results of the discharge profile
of electric capacity of lithium ion batteries prepared from lithium
cobalt oxide materials doped with one or metal dopants of the
invention. In one embodiment, line 410 represents lithium cobalt
oxide materials doped with zirconium (Li.sub.1.0 Co.sub.1.0
O.sub.2.doped Zr.sub.0.0017). In another embodiment, line 430
represents lithium cobalt oxide materials doped with Aluminum
(Li.sub.1.0 Co.sub.1.0 O.sub.2.doped Al.sub.0.0045). All dopants
affect the discharge capacity of the lithium cobalt oxide
materials. One observation can be found that the samples LCO
dependent on different dopant composition ratios has a higher
capacity at a higher voltage as shown in FIG. 4.
[0180] Other observation can be found that at the same upper
cut-off voltage, the discharge capacities drop slightly due to the
different dopants at different ratios, however no significant drop
can be observed, which confirms that substituted dopant levels do
not affect the electrochemical performance of the sample
significantly.
[0181] Further observation can be found that at the upper cut-off
voltage 4.6 V, the lithium cobalt oxide materials doped with
zirconium (Li.sub.1.0 Co.sub.1.0 O.sub.2.doped Zr.sub.0.0017) have
the optimal and the highest discharge capacity of 230.09 mAh/g and
96.7% coulombic efficiency (CE) among other composition ratios of
cathode material mixtures as shown in FIG. 4.
[0182] FIG. 5A, FIG. 5B and FIG. 5C illustrate the discharge
profile of electric capacity of lithium ion batteries at different
cut-off voltages (from 4.45 voltage to 4.6 voltage), where the
lithium ion batteries are prepared according to Example #22-#26 of
lithium cobalt oxide materials doped with one or more metal dopants
of the invention.
[0183] FIG. 5A is a column graph illustrating the discharge profile
of electric capacity of lithium ion batteries prepared according to
Example #22-#26 of the invention at 4.45 cut-off voltage. One
observation can be found that at 4.45 cut-off voltage, the
discharge capacities drop slightly due to the different dopants at
different ratios. Further observation can be found that at the
upper cut-off voltage 4.45 V, the lithium cobalt oxide materials
doped with magnesium (Li.sub.1.0 Co.sub.1.0 O.sub.2.doped
Mg.sub.0.0045), prepared according to Example #23, have the highest
discharge capacity of 183.17 mAh/g among other composition ratios
of Example #22-26 as shown in FIG. 5A.
[0184] FIG. 5B is a column graph illustrating the discharge profile
of electric capacity of lithium ion batteries prepared from Example
#22-26 of the invention at 4.5 voltage. One observation can be
found that at 4.5 cut-off voltage, the discharge capacities drop
slightly due to the different dopants at different ratios. Further
observation can be found that at the upper cut-off voltage 4.5 V,
the lithium cobalt oxide materials doped with magnesium (Li.sub.1.0
Co.sub.1.0 O.sub.2.doped Mg.sub.0.0017), prepared according to
Example #22, and lithium cobalt oxide materials doped with
zirconium (Li.sub.1.0 Co.sub.1.0 O.sub.2. doped Zr.sub.0.0017),
prepared according to Example #26, have higher discharge capacity
of 194.35 mAh/g and 194.11 mAh/g, respectively, among other
composition ratios of Example #22-26 as shown in FIG. 5B.
[0185] FIG. 5C is a column graph illustrating the discharge profile
of electric capacity of lithium ion batteries prepared from Example
#22-26 of the invention at 4.6 voltage. As shown in FIG. 5C, a
higher discharge capacity reading is observed as the cut-off
voltage increases. Further observation can be found that the
lithium cobalt oxide materials doped with zirconium (Li.sub.1.0
Co.sub.1.0 O.sub.2.doped Zr.sub.0.0017), prepared according to
Example #26, have the higher discharge capacity of 230.09 mAh/g
among other composition ratios of Example #22-26.
[0186] FIG. 6 is a graph illustrating cycling performance of
samples of battery cells made from lithium cobalt oxide materials
doped with different metal dopants and concentrations at a cutoff
voltage of 4.5 V. FIG. 6 compares the cycle and discharge
capability test results for the doped examples.
[0187] In one embodiment, line 610 illustrates the charge cycles of
battery cells made from lithium cobalt oxide doped with zirconium
(LiCO.sub.2.doped Zr.sub.0.17%). In another embodiment, line 620
illustrates the charge cycles of battery cells made from lithium
cobalt oxide doped with magnesium (LiCoO.sub.2.doped Mg.sub.0.17%).
In yet another embodiment, line 630 illustrates the charge cycles
of battery cells made from lithium cobalt oxide doped with
magnesium (LiCoO.sub.2.doped Mg.sub.0.45%). In yet another
embodiment, line 640 illustrates the charge cycles of battery cells
made from lithium cobalt oxide doped with magnesium and aluminum
(LiCO.sub.2.doped Mg.sub.0.1%, Al.sub.0.35%). In yet another
embodiment, line 650 illustrates the charge cycles of battery cells
made from lithium cobalt oxide doped with aluminum
(LiCoO.sub.2.doped Al.sub.0.45%).
[0188] Observation can be seen by FIG. 6 is that the cycling of
battery cells doped with zirconium containing compound
(LiCoO.sub.2.doped Zr.sub.0.17%) performs better than the battery
cells doped with other metals containing compound. Further
illustration can be seen from FIG. 6 is that between 0-25 battery
cycles, the battery cell made from lithium cobalt oxide materials
doped with zirconium (LiCoO.sub.2.doped Zr.sub.0.17%) has higher
capacity than the other samples made from lithium cobalt oxide
materials doped with magnesium, lithium cobalt oxide materials
doped with aluminum, and lithium cobalt oxide materials doped with
magnesium and aluminum of the battery cells. Further observation is
that the discharge capacity of these samples starts to slowly fade
by the time they reach 25.sup.th cycle.
[0189] FIG. 7A and FIG. 7B are scanning electron microscopy (SEM)
images of one example of crystalized lithium cobalt oxide materials
doped with magnesium (LiCoO.sub.2.doped Mg.sub.0.17%) of the
invention after the annealing process at 1020.degree. C. for 17
hours inside the annealing chamber. The SEM Image shows the
compositions and formulations of the present inventions having a
molar ratio of a lithium-containing salt, a cobalt-containing salt,
a magnesium-containing salt is
M.sub.LiSalt:M.sub.CoSalt:MMg.sub.Salt. The present invention
having a chemical formula of Li.sub.x Co.sub.y O.sub.z.doped
Mg.sub.a, wherein a ratio of x:y:a is equivalent to
M.sub.LiSalt:M.sub.CoSalt:M.sub.MgSalt, wherein the x is 1.0, the y
is 1.0, and a is 0.0017. In FIG. 7A and FIG. 7B, exemplary
lithium-containing salt compound include, but not limited to,
lithium nitrate (LiNO.sub.3) and combinations thereof, exemplary
cobalt-containing salt compound include, but not limited to cobalt
nitrate (Co(NO.sub.3).sub.2) and combinations thereof, exemplary
magnesium-containing salt (Mg) include, but not limited to,
magnesium nitrate (Mg(NO.sub.3).sub.2) and combinations
thereof.
[0190] FIG. 7A illustrates the morphology and particle size of one
example of lithium cobalt oxide material doped with magnesium
particles at an annealing temperature of 1020.degree. C. for 17
hours having crystalized structure. In addition, FIG. 7B shows a
closer look of FIG. 7A. In one example as shown in FIG. 7B one
lithium cobalt oxide material doped with magnesium particle 710 has
a crystal structure.
[0191] FIG. 7C and FIG. 7D are scanning electron microscopy (SEM)
images of another example of solid particles of an oxide material
doped with magnesium (LiCoO.sub.2. doped Mg.sub.0.17%) after a
drying process inside a drying chamber. The SEM Image shows the
compositions and formulations of the present inventions having a
molar ratio of a lithium-containing salt, a cobalt-containing salt,
a magnesium-containing salt is
M.sub.LiSalt:M.sub.CoSalt:M.sub.MgSalt. The present invention
having a chemical formula of Li.sub.x Co.sub.y O.sub.z. doped
Mg.sub.a, wherein a ratio of x:y:a is equivalent to
M.sub.LiSalt:M.sub.CoSalt:M.sub.MgSalt, wherein the x is 1.0, the y
is 1.0, and a is 0.0017. In FIG. 7C and FIG. 7D, exemplary
lithium-containing salt compound include, but not limited to,
lithium nitrate (LiNO.sub.3) and combinations thereof, exemplary
cobalt-containing salt compound include, but not limited to cobalt
nitrate (Co(NO.sub.3).sub.2) and combinations thereof, exemplary
magnesium-containing salt (Mg) include, but not limited to,
magnesium nitrate (Mg(NO.sub.3).sub.2) and combinations
thereof.
[0192] FIG. 7C illustrates the morphology and particle size of one
example of lithium cobalt oxide material doped with magnesium
particles after the drying process having crystalized structure. In
addition, FIG. 7D shows a closer look of FIG. 7C. In one example as
shown in FIG. 7D, one solid particle of a lithium cobalt oxide
material doped with magnesium 720 is spherical in shape.
[0193] FIG. 8A and FIG. 8B are scanning electron microscopy (SEM)
images of crystalized lithium cobalt oxide materials doped with
magnesium (LiCoO.sub.2.doped Mg.sub.0.45%) of the invention after
the annealing process at 1020.degree. C. for 17 hours inside the
annealing chamber. The SEM Image shows the compositions and
formulations of the present inventions having a molar ratio of a
lithium-containing salt, a cobalt-containing salt, a
magnesium-containing salt is
M.sub.LiSalt:M.sub.CoSalt:M.sub.MgSalt. The present invention
having a chemical formula of Li.sub.x Co.sub.y O.sub.z.doped
Mg.sub.a, wherein a ratio of x:y:a is equivalent to
M.sub.LiSalt:M.sub.CoSalt:M.sub.MgSalt, wherein the x is 1.0, the y
is 1.0, and a is 0.0045. In FIG. 8A and FIG. 8B, exemplary
lithium-containing salt compound include, but not limited to,
lithium nitrate (LiNO.sub.3) and combinations thereof, exemplary
cobalt-containing salt compound include, but not limited to cobalt
nitrate (Co(NO.sub.3).sub.2) and combinations thereof, exemplary
magnesium-containing salt (Mg) include, but not limited to,
magnesium nitrate (Mg(NO.sub.3).sub.2) and combinations
thereof.
[0194] FIG. 8A illustrates the morphology and particle size of one
example of lithium cobalt oxide material doped with magnesium
particles at an annealing temperature of 1020.degree. C. for 17
hours having crystalized structure. In addition, FIG. 8B shows a
closer look of FIG. 8A. In one example as shown in FIG. 8B one
lithium cobalt oxide material doped with magnesium particle 810 has
a crystal structure. Referring back to FIG. 7B, further observation
can be found that the morphology does not change significantly with
different percentage of magnesium dopants.
[0195] FIG. 8C and FIG. 8D are scanning electron microscopy (SEM)
images of another example of solid particles of an oxide material
doped with magnesium (LiCoO.sub.2. doped Mg.sub.0.45%) after a
drying process inside a drying chamber. The SEM Image shows the
compositions and formulations of the present inventions having a
molar ratio of a lithium-containing salt, a cobalt-containing salt,
a magnesium-containing salt is
M.sub.LiSalt:M.sub.CoSalt:M.sub.MgSalt. The present invention
having a chemical formula of Li.sub.x Co.sub.y O.sub.z. doped
Mg.sub.a, wherein a ratio of x:y:a is equivalent to
M.sub.LiSalt:M.sub.CoSalt:M.sub.MgSalt, wherein the x is 1.0, the y
is 1.0, and a is 0.0045. In FIG. 8C and FIG. 8D, exemplary
lithium-containing salt compound include, but not limited to,
lithium nitrate (LiNO.sub.3) and combinations thereof, exemplary
cobalt-containing salt compound include, but not limited to cobalt
nitrate (Co(NO.sub.3).sub.2) and combinations thereof, exemplary
magnesium-containing salt (Mg) include, but not limited to,
magnesium nitrate (Mg(NO.sub.3).sub.2) and combinations
thereof.
[0196] FIG. 8C illustrates the morphology and particle size of one
example of lithium cobalt oxide material doped with magnesium
particles after the drying process having crystalized structure. In
addition, FIG. 8D shows a closer look of FIG. 8C. In one example as
shown in FIG. 8D, one solid particle of a lithium cobalt oxide
material doped with magnesium 820 is spherical in shape.
[0197] FIG. 9A and FIG. 9B are scanning electron microscopy (SEM)
images of crystalized lithium cobalt oxide materials doped with
aluminum (LiCoO.sub.2.doped Al.sub.0.45%) of the invention after
the annealing process at 1020.degree. C. for 17 hours inside the
annealing chamber. The SEM Image shows the compositions and
formulations of the present inventions having a molar ratio of a
lithium-containing salt, a cobalt-containing salt, an
aluminum-containing salt is M.sub.LiSalt:M.sub.CoSalt:M.sub.AlSalt.
The present invention having a chemical formula of Li.sub.x
Co.sub.y O.sub.z.doped Al.sub.b, wherein a ratio of x:y:b is
equivalent to M.sub.LiSalt:M.sub.CoSalt:M.sub.AlSalt, wherein the x
is 1.0, the y is 1.0, and b is 0.0045. In FIG. 9A and FIG. 9B,
exemplary lithium-containing salt compound include, but not limited
to, lithium nitrate (LiNO.sub.3) and combinations thereof,
exemplary cobalt-containing salt compound include, but not limited
to cobalt nitrate (Co(NO.sub.3).sub.2) and combinations thereof,
exemplary aluminum-containing salt (Al) include, but not limited
to, aluminum nitrate (Al(NO.sub.3).sub.3) and combinations
thereof.
[0198] FIG. 9A illustrates the morphology and particle size of one
example of lithium cobalt oxide material doped with aluminum
particles at an annealing temperature of 1020.degree. C. for 17
hours having crystalized structure. In addition, FIG. 9B shows a
closer look of FIG. 9A. In one example as shown in FIG. 9B one
lithium cobalt oxide material doped with aluminum particle 910 has
a crystal structure.
[0199] FIG. 9C and FIG. 9D are scanning electron microscopy (SEM)
images of another example of solid particles of an oxide material
doped with aluminum (LiCoO.sub.2. doped Al.sub.0.45%) after a
drying process inside a drying chamber. The SEM Image shows the
compositions and formulations of the present inventions having a
molar ratio of a lithium-containing salt, a cobalt-containing salt,
an aluminum-containing salt is
M.sub.LiSalt:M.sub.CoSalt:M.sub.AlSalt. The present invention
having a chemical formula of Li.sub.x Co.sub.y O.sub.z.doped
Al.sub.b, wherein a ratio of x:y:b is equivalent to
M.sub.LiSalt:M.sub.CoSalt:M.sub.AlSalt, wherein the x is 1.0, the y
is 1.0, and b is 0.0045. In FIG. 9C and FIG. 9D, exemplary
lithium-containing salt compound include, but not limited to,
lithium nitrate (LiNO.sub.3) and combinations thereof, exemplary
cobalt-containing salt compound include, but not limited to cobalt
nitrate (Co(NO.sub.3).sub.2) and combinations thereof, exemplary
aluminum-containing salt (Al) include, but not limited to, aluminum
nitrate (Al(NO.sub.3).sub.3) and combinations thereof.
[0200] FIG. 9C illustrates the morphology and particle size of one
example of lithium cobalt oxide material doped with aluminum
particles after the drying process having crystalized structure. In
addition, FIG. 9D shows a closer look of FIG. 9C. In one example as
shown in FIG. 9D, one solid particle of a lithium cobalt oxide
material doped with aluminum 920 is spherical in shape.
[0201] FIG. 10A and FIG. 10B are scanning electron microscopy (SEM)
images of crystalized lithium cobalt oxide materials doped with
magnesium and aluminum (LiCoO.sub.2.doped Mg.sub.0.10%,
Al.sub.0.35) of the invention after the annealing process at
1020.degree. C. for 17 hours inside the annealing chamber. The SEM
Image shows the compositions and formulations of the present
inventions having a molar ratio of a lithium-containing salt, a
cobalt-containing salt, a magnesium-containing salt, an
aluminum-containing salt is
M.sub.LiSalt:M.sub.CoSalt:M.sub.MgSalt:M.sub.AlSalt. The present
invention having a chemical formula of Li.sub.x Co.sub.y
O.sub.z.doped Mg.sub.a, Al.sub.b, wherein a ratio of x:y:a:b is
equivalent to M.sub.LiSalt:M.sub.CoSalt:M.sub.MgSalt:M.sub.AlSalt,
wherein the x is 1.0, the y is 1.0, a is 0.001 and b is 0.0035. In
FIG. 10A and FIG. 10B, exemplary lithium-containing salt compound
include, but not limited to, lithium nitrate (LiNO.sub.3) and
combinations thereof, exemplary cobalt-containing salt compound
include, but not limited to cobalt nitrate (Co(NO.sub.3).sub.2) and
combinations thereof. Exemplary magnesium-containing salt (Mg)
include, but not limited to, magnesium nitrate (Mg(NO.sub.3).sub.2)
and combinations thereof. Exemplary aluminum-containing salt (Al)
include, but not limited to, aluminum nitrate (Al(NO.sub.3).sub.3)
and combinations thereof.
[0202] FIG. 10A illustrates the morphology and particle size of one
example of lithium cobalt oxide material doped with magnesium and
aluminum particles at an annealing temperature of 1020.degree. C.
for 17 hours having crystalized structure. In addition, FIG. 10B
shows a closer look of FIG. 10A. In one example as shown in FIG.
10B one lithium cobalt oxide material doped with magnesium and
aluminum particle 1010 has a crystal structure.
[0203] FIG. 10C and FIG. 10D are scanning electron microscopy (SEM)
images of another example of solid particles of an oxide material
doped with magnesium and aluminum (LiCoO.sub.2.doped Mg.sub.0.10%,
Al.sub.0.35%) after a drying process inside a drying chamber. The
SEM Image shows the compositions and formulations of the present
inventions having a molar ratio of a lithium-containing salt, a
cobalt-containing salt, a magnesium-containing salt, an
aluminum-containing salt is
M.sub.LiSalt:M.sub.CoSalt:M.sub.MgSalt:M.sub.AlSalt. The present
invention having a chemical formula of Li.sub.x Co.sub.y
O.sub.z.doped Mg.sub.a, Al.sub.b, wherein a ratio of x:y:a:b is
equivalent to M.sub.LiSalt:M.sub.CoSalt:M.sub.MgSalt:M.sub.AlSalt,
wherein the x is 1.0, the y is 1.0, a is 0.001 and b is 0.0035. In
FIG. 10C and FIG. 10D, exemplary lithium-containing salt compound
include, but not limited to, lithium nitrate (LiNO.sub.3) and
combinations thereof, exemplary cobalt-containing salt compound
include, but not limited to cobalt nitrate (Co(NO.sub.3).sub.2) and
combinations thereof. Exemplary magnesium-containing salt (Mg)
include, but not limited to, magnesium nitrate (Mg(NO.sub.3).sub.2)
and combinations thereof. Exemplary aluminum-containing salt (Al)
include, but not limited to, aluminum nitrate (Al(NO.sub.3).sub.3)
and combinations thereof.
[0204] FIG. 10C illustrates the morphology and particle size of one
example of lithium cobalt oxide material doped with magnesium and
aluminum particles after the drying process having crystalized
structure. In addition, FIG. 10D shows a closer look of FIG. 10C.
In one example as shown in FIG. 10D, one solid particle of a
lithium cobalt oxide material doped with magnesium and aluminum
1020 is spherical in shape.
[0205] FIG. 11A and FIG. 11B are scanning electron microscopy (SEM)
images of crystalized lithium cobalt oxide materials doped with
zirconium (LiCoO.sub.2.doped Zr.sub.0.17%) of the invention after
the annealing process at 1020.degree. C. for 17 hours inside the
annealing chamber. The SEM Image shows the compositions and
formulations of the present inventions having a molar ratio of a
lithium-containing salt, a cobalt-containing salt, a
magnesium-containing salt is
M.sub.LiSalt:M.sub.CoSalt:M.sub.ZrSalt. The present invention
having a chemical formula of Li.sub.x Co.sub.y O.sub.z.doped
Zr.sub.c, wherein a ratio of x:y:c is equivalent to
M.sub.LiSalt:M.sub.CoSalt:M.sub.ZrSalt, wherein the x is 1.0, the y
is 1.0, and c is 0.0017. In FIG. 11A and FIG. 11B, exemplary
lithium-containing salt compound include, but not limited to,
lithium nitrate (LiNO.sub.3) and combinations thereof, exemplary
cobalt-containing salt compound include, but not limited to cobalt
nitrate (Co(NO.sub.3).sub.2) and combinations thereof, and
exemplary zirconium-containing salt (Zr) include, but not limited
to, zirconium nitrate (Zr(NO.sub.3).sub.4) and combinations
thereof.
[0206] FIG. 11A illustrates the morphology and particle size of one
example of lithium cobalt oxide material doped with zirconium
particles at an annealing temperature of 1020.degree. C. for 17
hours having crystalized structure. In addition, FIG. 11B shows a
closer look of FIG. 11A. In one example as shown in FIG. 11B one
lithium cobalt oxide material doped with zirconium particle 1110
has a crystal structure. Referring back to FIG. 7B-FIG. 10B,
further observation can be found that the morphology does not
change significantly with different dopants.
[0207] FIG. 12A and FIG. 12B are scanning electron microscopy (SEM)
images of one example of crystalized lithium cobalt oxide materials
doped with magnesium (Li.sub.0.97Co.sub.1.0O.sub.2.doped
Mg.sub.0.17%) of the invention after the annealing process at
1020.degree. C. for 17 hours inside the annealing chamber. The SEM
Image shows the compositions and formulations of the present
inventions having a molar ratio of a lithium-containing salt, a
cobalt-containing salt, a magnesium-containing salt is
M.sub.LiSalt:M.sub.CoSalt:M.sub.MgSalt. The present invention
having a chemical formula of Li.sub.x Co.sub.y O.sub.z.doped
Mg.sub.a, wherein a ratio of x:y:a is equivalent to
M.sub.LiSalt:M.sub.CoSalt:M.sub.MgSalt, wherein the x is 0.97, the
y is 1.0, and a is 0.0017. In FIG. 12A and FIG. 12B, exemplary
lithium-containing salt compound include, but not limited to,
lithium nitrate (LiNO.sub.3) and combinations thereof, exemplary
cobalt-containing salt compound include, but not limited to cobalt
nitrate (Co(NO.sub.3).sub.2) and combinations thereof, exemplary
magnesium-containing salt (Mg) include, but not limited to,
magnesium nitrate (Mg(NO.sub.3).sub.2) and combinations
thereof.
[0208] FIG. 12A illustrates the morphology and particle size of one
example of lithium cobalt oxide material doped with magnesium
particles at an annealing temperature of 1020.degree. C. for 17
hours having crystalized structure. In addition, FIG. 12A shows a
closer look of FIG. 12A. In one example as shown in FIG. 12B one
lithium cobalt oxide material doped with magnesium particle 1210
has a crystal structure. Referring back to FIG. 7B-FIG. 11B,
further observation can be found that the morphology does not
change significantly with different dopants.
[0209] FIG. 13A and FIG. 13B are scanning electron microscopy (SEM)
images of one example of solid particles of an oxide material doped
with magnesium and aluminum (LiCoO.sub.2.doped Mg.sub.0.10%,
Al.sub.0.35%) after a drying process inside a drying chamber. The
SEM Image shows the compositions and formulations of the present
inventions having a molar ratio of a lithium-containing salt, a
cobalt-containing salt, a magnesium-containing salt, an
aluminum-containing salt is
M.sub.LiSalt:M.sub.CoSalt:M.sub.MgSalt:M.sub.AlSalt. The present
invention having a chemical formula of Li.sub.x Co.sub.y
O.sub.z.doped Mg.sub.a, Al.sub.b, wherein a ratio of x:y:a:b is
equivalent to M.sub.LiSalt:M.sub.CoSalt:M.sub.MgSalt:M.sub.AlSalt,
wherein the x is 1.0, the y is 1.0, a is 0.001 and b is 0.0035.
[0210] In FIG. 13A and FIG. 13B, exemplary lithium-containing salt
compound include, but not limited to, lithium nitrate (LiNO.sub.3)
and combinations thereof, exemplary cobalt-containing salt compound
include, but not limited to cobalt nitrate (Co(NO.sub.3).sub.2) and
combinations thereof. Exemplary magnesium-containing salt (Mg)
include, but not limited to, magnesium nitrate (Mg(NO.sub.3).sub.2)
and combinations thereof. Exemplary aluminum-containing salt (Al)
include, but not limited to, aluminum nitrate (Al(NO.sub.3).sub.3)
and combinations thereof.
[0211] FIG. 13A illustrates the morphology and particle size of one
example of lithium cobalt oxide material doped with magnesium and
aluminum particles after the drying process having crystalized
structure. In addition, FIG. 13B shows a closer look of FIG. 13A.
In one example as shown in FIG. 13B, one solid particle of a
lithium cobalt oxide material doped with magnesium and aluminum
1310 is spherical in shape.
[0212] Referring back to FIG. 13A and FIG. 13B, the tap density
("TD") and particle size distribution (known as "PSD" or "SPAN") of
the solid particles of a lithium cobalt oxide material is shown as
Table 20.
[0213] To be precise, the "SPAN" value represents a degree of
particle size distribution ("PSD"), defined as (D90-D10)/D50.
"D10", "D50", and "D90" are defined as the particle size at 10%,
50%, and 90% of the cumulative volume % distribution. D50
represents an average particle size which is larger than 50% (by
number) of the total particles that are present (also known as the
median diameter). D90 and D10 respectively stand for particle
diameters that are larger than 90% and 10% of all the particles (by
number). Further, the particle size is expressed in .mu.m. The
tapped density of the solid particles of a lithium cobalt oxide
material is 0.86 g/cc, D10 value is 3.69 .mu.m, D50 value is 7.71
.mu.m, D90 value is 13.3 .mu.m and PSD value is 1.25.
TABLE-US-00020 TABLE 20 Measurement of tap density (TD) and
particle size of solid particles of a lithium cobalt oxide material
after a drying process Tap Density D10 D50 D90 PSD 0.86 3.69 7.71
13.3 1.25
[0214] FIG. 14A-14C, FIG. 15A-15C, FIG. 16A-16C, and FIG. 17A-17C
are scanning electron microscopy (SEM) images of crystalized
lithium cobalt oxide materials doped with magnesium and aluminum
(LiCoO.sub.2.doped Mg.sub.0.10%, Al.sub.0.35%) of the invention
after the annealing process at different annealing temperatures
(from 900.degree. C. to 1050.degree. C.) for 17 hours inside the
annealing chamber. The SEM Image shows the compositions and
formulations of the present inventions having a molar ratio of a
lithium-containing salt, a cobalt-containing salt, a
magnesium-containing salt, an aluminum-containing salt is
M.sub.LiSalt:M.sub.CoSalt:M.sub.MgSalt:M.sub.AlSalt. The present
invention having a chemical formula of Li.sub.x Co.sub.y
O.sub.z.doped Mg.sub.a, Al.sub.b, wherein a ratio of x:y:a:b is
equivalent to M.sub.LiSalt:M.sub.CoSalt:M.sub.MgSalt:M.sub.AlSalt,
wherein the x is 1.0, the y is 1.0, a is 0.001 and b is 0.0035.
[0215] In FIG. 14A-14C, FIG. 15A-15C, FIG. 16A-16C, and FIG.
17A-17C, exemplary lithium-containing salt compound include, but
not limited to, lithium nitrate (LiNO.sub.3) and combinations
thereof, exemplary cobalt-containing salt compound include, but not
limited to cobalt nitrate (Co(NO.sub.3).sub.2) and combinations
thereof. Exemplary magnesium-containing salt (Mg) include, but not
limited to, magnesium nitrate (Mg(NO.sub.3).sub.2) and combinations
thereof. Exemplary aluminum-containing salt (Al) include, but not
limited to, aluminum nitrate (Al(NO.sub.3).sub.3) and combinations
thereof.
[0216] In one example as shown in FIG. 14A, the SEM shows the
morphology and particle size of lithium cobalt oxide material
particles doped with magnesium and aluminum (LiCoO.sub.2.doped
Mg.sub.0.10%, Al.sub.0.35%) at an annealing temperature of
900.degree. C. for 17 hours having crystalized structure. FIG. 14 B
and FIG. 14C show a closer look of FIG. 14A.
[0217] In another example as shown in FIG. 15A, the SEM shows the
morphology and particle size of lithium cobalt oxide material
particles doped with magnesium and aluminum at an annealing
temperature of 950.degree. C. for 17 hours having crystalized
structure. FIG. 15B and FIG. 15C show a closer look of FIG.
15A.
[0218] Referring back to FIG. 16A, the SEM shows the morphology and
particle size of yet another example of lithium cobalt oxide
material particles doped with magnesium and aluminum
(LiCoO.sub.2.doped Mg.sub.0.10%, Al.sub.0.35%) at an annealing
temperature of 1000.degree. C. for 17 hours having crystalized
structure. FIG. 16B and FIG. 16C show a closer look of FIG.
16A.
[0219] In still another example as shown in FIG. 17A, the SEM shows
the morphology and particle size of lithium cobalt oxide material
particles doped with magnesium and aluminum (LiCoO.sub.2.doped
Mg.sub.0.10%, Al.sub.0.35%) at an annealing temperature of
1050.degree. C. for 17 hours having crystalized structure. FIG. 17B
and FIG. 17C show a closer look of FIG. 17A.
[0220] Referring back to FIG. 13-17, Table 21 illustrates testing
results of samples of exemplary measured LCO material doped with
magnesium and aluminum (LiCoO.sub.2. doped Mg.sub.0.10%,
Al.sub.0.35%). One observation is that the testing results of the
ratio of the measured LCO material compositions of Li:Co:Mg:Al are
within an expected range from the prepared molar ratio of
M.sub.LiSalt:M.sub.CoSalt:M.sub.MgSalt:M.sub.AlSalt being
prepared.
TABLE-US-00021 TABLE 21 Exemplary measured LCO material
compositions Corresponding FIG. Li Co Al Mg Condition FIG. 13A,
1.0862 0.9875 0.0125 0.0040 After Drying FIG. 13B FIG. 14A, 1.0629
0.9873 0.0127 0.0041 Anneal at FIG. 14B 900.degree. C. FIG. 15A,
1.0424 0.9862 0.0138 0.0041 Anneal at FIG. 15B 950.degree. C. FIG.
16A, 1.0313 0.9867 0.0133 0.0040 Anneal at FIG. 16B 1000.degree. C.
FIG. 17A, 1.0067 0.9856 0.0144 0.0039 Anneal at FIG. 17B
1050.degree. C.
[0221] FIG. 22 illustrates a comparison of X-ray diffraction
patterns, prepared according to Example #25 and Example #26. The
crystal structure of the lithium cobalt oxide materials doped with
one or more metal dopants (Example #25 and Example #26) have been
investigated by means of X-ray diffraction. Example #25 and Example
#26 exhibit a LiCoO.sub.2 single phases. No second phases, impurity
phases, such as Li.sub.2Co.sub.3, Co.sub.3O.sub.4 are observed.
[0222] Details of XRD results, prepared according to Example #25
and Example #26 are shown as Table 22. Comparison of the XRD
results, prepared according to Example #25 and Example #26 are
shown as Table 23. Based on the XRD results, one observation can be
found that the intensity ratio I(003)/I(104) of Example #25 is
higher than the intensity ratio I(003)/I(104) of Example #16.
Further observation can be found that FWHM (003) and (104) of
Example #25 is lower than Example #26. Another observation can be
found that c/a of Example #26 is higher than c/a of Example #25.
Still another observation can be found that
.DELTA.2.theta.[(012)-(006)], .DELTA.2.theta.[(110)-(018)] of
Example #25 is similar to the data of) Example #26.
TABLE-US-00022 TABLE 22 XRD Results Example #25 Example #26 a
[.ANG.] 2.8143 .+-. 0.002 2.8159 .+-. 0.0002 (0.07%) (0.007%) c
[.ANG.] 14.044 .+-. 0.001 14.058 .+-. 0.001 (0.007%) (0.007%) c/a
4.990 4.992 hkl 003 104 003 104 2.theta.[.degree.] 18.955 45.253
18.917 45.225 FWHM[.degree.] 0.09 0.07 0.10 0.09 I (003)/I (104)
3.96 2.27 hkl 006 012 006 012 2.theta.[.degree.] 38.427 39.090
38.395 39.062 .DELTA.2.theta.[(012)-(016)][.degree.] 0.663 0.667
hkl 018 110 018 110 2.theta.[.degree.] 65.456 66.372 65.431 66.346
.DELTA.2.theta.[(010)-(018)][.degree.] 0.916 0.915 r.sub.l 0.51
0.45 K.sub.Fm 23.53 15.37
TABLE-US-00023 TABLE 23 Comparison of the XRD Results Sample no.
Example 25 Example 26 I (003)/I (104) 3.96 2.27 hkl 003 104 003 104
FWHM[.degree.] 0.09 0.07 0.10 0.09
.DELTA.2.theta.[(012)-(006)][.degree.] 0.663 0.667
.DELTA.2.theta.[(110)-(118)][.degree.] 0.916 0.915 c/a 4.990 4.992
r.sub.l 0.51 0.45 K.sub.Fm 23.53 15.37
* * * * *