U.S. patent application number 10/801655 was filed with the patent office on 2004-09-30 for non-aqueous electrolyte secondary battery, positive electrode active material and method of manufacturing the same.
This patent application is currently assigned to SANYO ELECTRIC CO., LTD.. Invention is credited to Fujimoto, Masahisa, Inoue, Takao, Itaya, Masaharu.
Application Number | 20040191628 10/801655 |
Document ID | / |
Family ID | 32985002 |
Filed Date | 2004-09-30 |
United States Patent
Application |
20040191628 |
Kind Code |
A1 |
Inoue, Takao ; et
al. |
September 30, 2004 |
Non-aqueous electrolyte secondary battery, positive electrode
active material and method of manufacturing the same
Abstract
As a positive electrode active material, a lithium transition
metal complex oxide having a layered rock-salt structure containing
lithium (Li) and containing magnesium atoms (Mg) substituted for
part of lithium atoms (Li) is used. The lithium transition metal
complex oxide is formed by chemical or electrochemical substitution
of Mg atoms for part of Li atoms in LiCoO.sub.2, LiMnO.sub.2,
LiFeO.sub.2, LiNiO.sub.2, or the like. A cell is prepared in which
a negative electrode 2 and a positive electrode 1 including the
lithium transition metal complex oxide (positive electrode active
material) are disposed in a non-aqueous electrolyte 5 including a
lithium salt, and part of Li in the lithium transition metal
complex oxide is extracted by discharging the cell. Then, the
electrolyte including Li is replaced with an electrolyte including
Mg; and the cell is discharged, so that Mg atoms are substituted
for the part of Li atoms in the lithium transition metal complex
oxide.
Inventors: |
Inoue, Takao; (Kobe-shi,
JP) ; Fujimoto, Masahisa; (Osaka, JP) ; Itaya,
Masaharu; (Kobe-shi, JP) |
Correspondence
Address: |
McDERMOTT, WILL & EMERY
600 13th Street, N.W.
Washington
DC
20005-3096
US
|
Assignee: |
SANYO ELECTRIC CO., LTD.
|
Family ID: |
32985002 |
Appl. No.: |
10/801655 |
Filed: |
March 17, 2004 |
Current U.S.
Class: |
429/231.1 ;
423/594.2; 423/594.4; 423/594.6; 423/599; 429/221; 429/223;
429/224; 429/231.3; 429/231.6 |
Current CPC
Class: |
H01M 4/485 20130101;
H01M 4/525 20130101; C01G 45/1228 20130101; H01M 10/0525 20130101;
C01P 2002/72 20130101; C01P 2002/77 20130101; C01G 49/009 20130101;
C01P 2002/54 20130101; H01M 4/0438 20130101; H01M 4/505 20130101;
C01G 51/42 20130101; Y02E 60/10 20130101; C01G 53/66 20130101; C01G
51/66 20130101; C01G 53/42 20130101; H01M 4/1391 20130101; C01P
2006/40 20130101 |
Class at
Publication: |
429/231.1 ;
429/231.6; 429/224; 429/223; 429/231.3; 429/221; 423/594.2;
423/594.4; 423/594.6; 423/599 |
International
Class: |
H01M 004/48; H01M
004/52; H01M 004/50; C01G 045/12; C01G 049/04; C01G 051/04; C01G
053/04 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 25, 2003 |
JP |
2003-082305 |
Claims
What is claimed is:
1. A non-aqueous electrolyte secondary battery comprising: a
negative electrode; a positive electrode including a positive
electrode active material capable of storage and release of
lithium; and a non-aqueous electrolyte, wherein said positive
electrode active material has a rock-salt structure containing
lithium and is composed of an oxide containing magnesium
substituted for part of lithium.
2. The non-aqueous electrolyte secondary battery according to claim
1, wherein said oxide is a lithium transition metal complex oxide
expressed by a composition formula of Li.sub.aMg.sub.bM1O.sub.2,
where a+2b=1, 0<a<1, and 0<b <0.5, and where M1 is a
metal of at least one type selected from the group consisting of
cobalt, manganese, iron and nickel.
3. The non-aqueous electrolyte secondary battery according to claim
1, wherein said oxide is a lithium transition metal complex oxide
expressed by a composition formula of Li.sub.aMg.sub.bCoO.sub.2,
where a+2b=1, 0<a<1, and 0<b<0.5.
4. The non-aqueous electrolyte secondary battery according to claim
1, wherein said magnesium is electrochemically substituted for said
part of lithium in said oxide.
5. The non-aqueous electrolyte secondary battery according to claim
1, wherein said magnesium is electrochemically substituted for said
part of lithium in said oxide using a non-aqueous electrolyte
including an imide salt or a sulfonate in which a cation is
magnesium.
6. The non-aqueous electrolyte secondary battery according to claim
1, wherein said magnesium is electrochemically substituted for said
part of lithium in said oxide using a non-aqueous electrolyte
including a sulfonyl imide salt in which a cation is magnesium.
7. A positive electrode active material capable of storage and
release of lithium, having a layered rock-salt structure containing
lithium, and being composed of an oxide containing magnesium
substituted for part of lithium.
8. The positive electrode active material according to claim 7,
wherein said oxide is a lithium transition metal complex oxide
expressed by a composition formula of Li.sub.aMg.sub.bM1O.sub.2,
where a+2b=1, 0<a<1, and 0<b<0.5, and where M1 is a
metal of at least one type selected from the group consisting of
cobalt, manganese, iron and nickel.
9. The positive electrode active material according to claim 7,
wherein said oxide is a lithium transition metal complex oxide
expressed by a composition formula of Li.sub.aMg.sub.bCoO.sub.2,
where a+2b=1, 0<a<1, and 0<b<0.5.
10. The positive electrode active material according to claim 7,
wherein said magnesium is electrochemically substituted for said
part of lithium in said oxide.
11. The positive electrode active material according to claim 7,
wherein said magnesium is electrochemically substituted for said
part of lithium in said oxide using a non-aqueous electrolyte
including an imide salt or a sulfonate in which a cation is
magnesium.
12. The positive electrode active material according to claim 7,
wherein said magnesium is substituted for said part of lithium in
said oxide using a non-aqueous electrolyte including a sulfonyl
imide salt in which a cation is magnesium.
13. A method of manufacturing a positive electrode active material
comprising the step of electrochemically substituting magnesium for
part of lithium in an oxide having a layered rock-salt structure
containing lithium.
14. The method of manufacturing a positive electrode active
material according to claim 13, wherein said step of substituting
includes the steps of: preparing a cell in which a negative
electrode and a positive electrode including said oxide are
disposed in a non-aqueous electrolyte including a lithium salt;
extracting said part of lithium in said oxide by discharging said
cell; after extracting said part of lithium in said oxide,
replacing the non-aqueous electrolyte including a lithium salt with
a non-aqueous electrolyte including a magnesium salt; and after
said replacement of non-aqueous electrolyte, inserting magnesium
into said oxide by discharging said cell.
15. The method of manufacturing a positive electrode active
material according to claim 13, wherein said oxide includes a
lithium transition metal complex oxide, and said transition metal
includes at least one type of metal selected from the group
consisting of cobalt, manganese, iron, and nickel.
16. The method of manufacturing a positive electrode active
material according to claim 13, wherein said oxide includes lithium
cobaltate.
17. The method of manufacturing a positive electrode active
material according to claim 13, wherein said step of substituting
includes the step of electrochemically substituting magnesium for
said part of lithium in said oxide using a non-aqueous electrolyte
including an imide salt or a sulfonate in which a cation is
magnesium.
18. The method of manufacturing a positive electrode active
material according to claim 13, wherein said step of substituting
includes the step of electrochemically substituting magnesium for
said part of lithium in said oxide using a non-aqueous electrolyte
including a sulfonyl imide salt in which a cation is magnesium.
Description
TITLE OF THE INVENTION
[0001] Non-aqueous electrolyte secondary battery, positive
electrode active material and method of manufacturing the same
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates to a non-aqueous electrolyte
secondary battery, positive electrode active material, and method
of manufacturing the same.
[0004] 2.Description of the Background Art
[0005] Metal oxides having a layered rock-salt structure, such as
lithium cobaltate, are currently used as high-voltage positive
electrode active materials for lithium-ion batteries. However,
since metal oxides have a capacity as low as 124 to 150 mAh/g,
techniques for higher-capacity are under development, and intensive
research on substitution materials is being carried out (refer to,
for example, JP-2001-243951-A and JP-2001-155729-A).
[0006] Lithium cobaltate has a theoretical capacity approximately
as high as 274 mAh/g. However, 55% of the theoretical capacity,
which is approximately 150 mAh/g, is said to be the limitation of
its use as positive electrode active material at present. For this
reason, it is desired that the capacity of lithium cobaltate be
increased.
SUMMARY OF THE INVENTION
[0007] An object of the present invention is to provide a
non-aqueous electrolyte secondary battery having improved capacity,
a positive electrode active material capable of improving the
capacity, and method of manufacturing the same.
[0008] Another object of the present invention is to provide a
positive electrode active material capable of improving the
capacity of a non-aqueous electrolyte secondary battery.
[0009] Still another object of the present invention is to provide
a method of manufacturing a positive electrode active material
capable of improving the capacity of a non-aqueous electrolyte
secondary battery.
[0010] In the case where lithium cobaltate is expressed by
Li.sub.1-xCoO.sub.2, and belongs to a hexagonal system, the length
of the a-axis tends to shrink when x is less than approximately
0.5, and tends to extend when x is not less than that value. On the
other hand, the length of the c-axis tends to extend when x is less
than approximately 0.6, and tends to shrink when x is not less than
that value, to be shorter than that of the starting material when x
is 0. In other words, the lattice volume of lithium cobaltate
expands along with charge when x is less than 0.6, and shrinks when
x is not less than 0.6. The phase transition, as expressed in the
following formula, occurs in a region almost intermediate (x=0.45
to 0.55) in a region of 0.25.ltoreq.x<0.75. The substantial
capacity of lithium cobaltate is determined on the basis of this
region as a boundary.
R{overscore (3)}m<=>C2/m<=>R{overscore (3)}m
[0011] Such a structural change in lithium colbaltate is probably
attributed to increased structural instability caused by release of
excessive lithium positioned in a 3b site of the layered rock-salt
structure.
[0012] The present inventors focused on this structural change in
lithium cobaltate, and as a result of experiment and examination
wholeheartedly performed by the inventors, it was found out that a
stabilized structure can be realized by substitution of magnesium
for part of a 3b site (lithium) in the layered rock-salt structure,
leading to the following invention.
[0013] A non-aqueous electrolyte secondary battery according to one
aspect of the present invention comprises a negative electrode; a
positive electrode including a positive electrode active material
capable of storage and release of lithium; and a non-aqueous
electrolyte, wherein the positive electrode active material has a
rock-salt structure containing lithium and is composed of an oxide
containing magnesium substituted for part of lithium.
[0014] When magnesium is positioned in an octahedral 3b site in the
layered rock-salt structure, the ion has a radius of 0.86 .ANG.,
which is similar to the radius of an ion of 0.90 .ANG. when lithium
is positioned in an octahedral 3b site. Therefore, the layered
rock-salt structure is stabilized by substitution of magnesium in
an octahedral 3b site. In this manner, an oxide in which a phase
change hardly occurs on insertion and release of excessive lithium
can be realized. As a result, the capacity of an oxide can be
increased, leading to improved capacity of a non-aqueous secondary
battery.
[0015] The oxide may a lithium transition metal complex oxide
expressed by a composition formula of Li.sub.aMg.sub.bM1O.sub.2,
where a+2b=1, 0<a<1, and 0<b<0.5, and where M1 is a
metal of at least one type selected from the group consisting of
cobalt, manganese, iron and nickel. In particular,
0.5.ltoreq.a<1 and 0<b.ltoreq.0.25 are preferable. This
allows sufficiently increased capacity of a lithium transition
metal complex oxide.
[0016] The oxide may be a lithium transition metal complex oxide
expressed by a composition formula of Li.sub.aMg.sub.bCoO.sub.2,
where a+2b=1, 0<a<1, and 0<b<0.5. In particular,
0.5.ltoreq.a<1 and 0<b .ltoreq.0.25 are preferable. This
allows sufficiently increased capacity of lithium cobaltate.
[0017] The magnesium may be electrochemically substituted for the
part of lithium in the oxide. Alternatively, the magnesium may be
chemically substituted for the part of lithium in the oxide.
[0018] The magnesium may be electrochemically substituted for the
part of lithium in the oxide using a non-aqueous electrolyte
including an imide salt or a sulfonate in which a cation is
magnesium. In particular, the magnesium may be electrochemically
substituted for the part of lithium in the oxide using a
non-aqueous electrolyte including a sulfonyl imide salt in which a
cation is magnesium.
[0019] A positive electrode active material capable of storage and
release of lithium according to another aspect of the present
invention has a layered rock-salt structure containing lithium and
is composed of an oxide containing magnesium substituted for part
of lithium.
[0020] In the positive electrode active material according to the
present invention, the magnesium is substituted for part of an
octahedral 3b site in the layered rock-salt structure, so that the
layered rock-salt structure is stabilized. In this manner, an oxide
in which a phase change hardly occurs on insertion and release of
excessive lithium can be realized. As a result, the capacity of a
positive electrode active material can be increased.
[0021] The oxide may a lithium transition metal complex oxide
expressed by a composition formula of Li.sub.aMg.sub.bM1O.sub.2,
where a+2b=1, 0<a <1, and 0<b <0.5, and where M1 is a
metal of at least one type selected from the group consisting of
cobalt, manganese, iron and nickel. In particular, 0.5.ltoreq.a
<1 and 0<b.ltoreq.0.25 are preferable. This allows
sufficiently increased capacity of a lithium transition metal
complex oxide.
[0022] The oxide may be a lithium transition metal complex oxide
expressed by a composition formula of Li.sub.aMg.sub.bCoO.sub.2,
where a+2b=1, 0<a<1, and 0<b <0.5. In particular,
0.5.ltoreq.a<1 and 0<b .ltoreq.0.25 are preferable. This
allows sufficiently increased capacity of lithium cobaltate.
[0023] The magnesium may be electrochemically substituted for the
part of lithium in the oxide. Alternatively, the magnesium may be
chemically substituted for the part of lithium in the oxide.
[0024] The magnesium may be electrochemically substituted for the
part of lithium in the oxide using a non-aqueous electrolyte
including an imide salt or a sulfonate in which a cation is
magnesium. In particular, the magnesium may be electrochemically
substituted for the part of lithium in the oxide using a
non-aqueous electrolyte including a sulfonyl imide salt in which a
cation is magnesium.
[0025] A method of manufacturing a positive electrode active
material according to still another aspect of the present invention
comprises the step of electrochemically substituting magnesium for
part of lithium in an oxide having a layered rock-salt structure
containing lithium.
[0026] In the method of manufacturing the positive electrode active
material according to the present invention, magnesium is
substituted for the part of lithium in an octahedral 3b site in the
layered rock-salt structure, so that the layered rock-salt
structure is stabilized. In this manner, an oxide in which a phase
change hardly occurs on insertion and release of excessive lithium
can be realized. As a result, the capacity of an oxidecan be
increased.
[0027] The step of substituting may include the steps of preparing
a cell in which a negative electrode and a positive electrode
including the oxide are disposed in a non-aqueous electrolyte
including a lithium salt (electrolyte salt); extracting the part of
lithium in the oxide by charging the cell; after extracting the
part of lithium in the oxide, replacing the non-aqueous electrolyte
including a lithium salt (electrolyte salt) with a non-aqueous
electrolyte including a lithium salt (electrolyte salt); and after
the replacement of non-aqueous electrolyte, inserting magnesium
into the oxide by discharging the cell.
[0028] In this case, the replacement of non-aqueous electrolyte can
facilitate the substitution of magnesium for the part of lithium in
the oxide.
[0029] The oxide may include a lithium transition metal complex
oxide, and the transition metal may include at least one type of
metal selected from the group consisting of cobalt, manganese,
iron, and nickel. The oxide may include lithium cobaltate.
[0030] The step of substituting may comprise the step of
electrochemically substituting magnesium for the part of lithium in
the oxide using a non-aqueous electrolyte including an imide salt
or a sulfonate in which a cation is magnesium. In particular, the
step of substituting may comprise the step of electrochemically
substituting magnesium for the part of lithium in the oxide using a
non-aqueous electrolyte including a sulfonyl imide salt in which a
cation is magnesium. In this case, the substitution of magnesium
for the part of lithium in the oxide can be facilitated.
[0031] The foregoing and other objects, features, aspects and
advantages of the present invention will become more apparent from
the following detailed description of the present invention when
taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0032] FIG. 1 is a diagram showing the layered rock-salt structure
of LiCoO.sub.2;
[0033] FIG. 2 is a diagram showing a test cell using lithium
cobaltate containing magnesium atoms substituted for part of
lithium atoms as a positive electrode active material;
[0034] FIG. 3 is a diagram showing the measurement results of
discharge curves of lithium cobaltate before and after substitution
of magnesium atoms for lithium atoms;
[0035] FIG. 4 is a diagram showing the measurement results of XRD
patterns of a positive electrode before and after substitution of
magnesium atoms for lithium atoms.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0036] Description will, hereinafter, be made of a non-aqueous
electrolyte secondary battery according to a first embodiment of
the present invention and method of manufacturing the same.
[0037] The non-aqueous electrolyte secondary battery according to
the present embodiment comprises a negative electrode, a positive
electrode, and a non-aqueous electrolyte.
[0038] As the negative electrode, carbon materials, such as
graphite, lithium metal, lithium alloy, or the like capable of
storage and release of lithium atoms (Li) may be used.
[0039] As the positive electrode active material, a lithium
transition metal complex oxide having a layered rock-salt structure
containing lithium and in which magnesium atoms (Mg) are
substituted for part of lithium atoms is used. As the lithium
transition metal complex oxide, Li.sub.aMg.sub.bCoO.sub.2,
Li.sub.aMg.sub.bMnO.sub.2, Li.sub.aMg.sub.bFeO.sub.2,
Li.sub.aMg.sub.bNiO.sub.2, and or like may be used. In these
composition formulas, a+2b=1, 0<a<1, and 0 <b <0.5. In
particular, 0.5.ltoreq.a<1 and 0<b .ltoreq.0.25 are
preferable, where approximately a=0.8 and b=0.1, for example. This
allows sufficiently increased capacity of the lithium transition
metal complex oxide.
[0040] The above-mentioned lithium transition metal complex oxide
is formed by chemical or electrochemical substitution of magnesium
atoms (Mg) for part of lithium atoms (Li) in LiCoO.sub.2,
LiMnO.sub.2, LiFeO.sub.2, LiNiO.sub.2, or the like, as described
later.
[0041] As a non-aqueous solvent (organic solvent) for the
non-aqueous electrolyte, non-aqueous solvents (organic solvents)
generally used in non-aqueous electrolyte secondary batteries may
be used. At least one type selected from, for example, ethylene
carbonate, diethyl carbonate, dimethyl carbonate, propylene
carbonate, cyclic ether, chain ether, or carbonate fluoride may be
used. As a lithium salt (electrolyte salt) to be added into the
organic solvent, lithium salts (electrolyte salts) generally used
for non-aqueous electrolyte secondary batteries may-be used, and at
least one selected from, for example, LiBF.sub.4, LiPF.sub.6,
LiCF.sub.3SO.sub.3, LiC.sub.4FgSO.sub.3, LiN
(CF.sub.3SO.sub.2).sub.2, LiN (C.sub.2F.sub.5SO.sub.2).sub.2, LiN
(CF.sub.3SO.sub.2) (COCF.sub.3), and LiAsF.sub.6 may be used. It is
noted that the types of non-aqueous electrolytes are not limited to
those described herein, and various types of non-aqueous
electrolytes for non-aqueous secondary batteries may be used.
[0042] FIG. 1 is a diagram showing the layered rock-salt structure
of LiCoO.sub.2: (a) in a cubic representation, and (b) in a
hexagonal representation.
[0043] In FIG. 1, white circles represent oxygen atoms(O),
half-tone circles represent cobalt atoms(Co), and hatched circles
represent lithium atoms (Li).
[0044] The layered rock-salt structure of LiCoO.sub.2 has a basic
skeleton in which oxygen atoms form a cubic closest packed
arrangement having -A-B-C-stacked layers, where the numbers of
anions and cations are equal, and where all spaces in octahedral
oxygen are occupied with cations. Moreover, cobalt and lithium
atoms individually form single layers in octahedral 3a sites and
octahedral 3b sites between (111) oxygen layers, respectively,
forming alternate stacked layers.
[0045] In the present embodiment, magnesium atoms are substituted
for part of lithium atoms in octahedral 3b sites, so that the
layered rock-salt structure is stabilized. In this manner, a
lithium transition metal complex oxide in which a phase change
hardly occurs on insertion and release of excessive lithium atoms
can be realized.
[0046] Description will, hereinafter, be made of a method in which
a positive electrode active material is formed by electrochemical
substitution of magnesium atoms for part of lithium atoms in a
lithium transition metal complex oxide.
[0047] First, a cell is prepared in which a negative electrode and
a positive electrode including a lithium transition metal complex
oxide (positive electrode active material) are disposed in a
non-aqueous electrolyte including a lithium salt (electrolyte
salt). Part of lithium atoms in the lithium transition metal
complex oxide are then extracted by charging the cell. After that,
the non-aqueous electrolyte including a lithium salt (electrolyte
salt) is replaced with a non-aqueous electrolyte including a
magnesium salt (electrolyte salt), and the cell is discharged.
Consequently, magnesium atoms are substituted for the part of
lithium atoms in the lithium transition metal complex oxide.
[0048] In this case, by using an imide salt or a sulfonate as a
magnesium salt (electrolyte salt), electrochemical substitution of
magnesium atoms for the part of lithium atoms in 3b sites is
allowed.
[0049] As imide salts, ((CF.sub.3SO.sub.2).sub.2N).sub.2Mg,
((C.sub.2F.sub.5SO.sub.2).sub.2N).sub.2Mg,
((C.sub.4F.sub.9SO.sub.2) (CF.sub.3SO.sub.2)N).sub.2Mg,
((C.sub.6F.sub.5SO.sub.2) (CF.sub.3SO.sub.2)N).sub.2Mg,
((C.sub.8F.sub.17SO.sub.2) (CF.sub.3SO.sub.2)N).sub.2Mg,
((CF.sub.3CH.sub.2OSO.sub.2).sub.2N).sub.2M- g,
((CF.sub.3CF.sub.2CH.sub.2OSO.sub.2).sub.2N).sub.2Mg,
((HCF.sub.2CF.sub.2CH.sub.2OSO.sub.2 ).sub.2N).sub.2Mg,
(((CF.sub.3).sub.2CHOSO.sub.2).sub.2N).sub.2Mg, or the like may be
used.
[0050] As sulfonate, (CF.sub.3SO.sub.3).sub.2Mg,
(CH.sub.3SO.sub.3).sub.2M- g, (C.sub.4F.sub.9SO.sub.3).sub.2Mg,
(C.sub.6F.sub.5SO.sub.3).sub.2Mg, (C.sub.6H.sub.5SO.sub.3).sub.2Mg,
(C.sub.8F.sub.17SO.sub.3).sub.2Mg, or the like may be used.
[0051] One of the above-mentioned imide salts and sulfonates may be
used, or at least two of them may be combined for use.
[0052] It is noted that the electrolyte salt is dissolved for use
in a non-aqueous solvent (organic solvent) at a concentration of
0.1 to 1.5 M, preferably at a concentration of 0.5 to 1.5 M.
[0053] In addition, as a non-aqueous electrolyte solvent (organic
solvent) used at the time of electrochemical substitution of
magnesium atoms (Mg) for lithium atoms (Li), non-aqueous solvents
generally used for batteries may be used. For example, cyclic ester
carbonate, chain ester carbonate, esters, cyclic ethers, chain
ethers, nitriles, amides, or the like may be used.
[0054] Cyclic ester carbonates may be illustrated by ethylene
carbonate, propylene carbonate, butylene carbonate, and the like.
Substances obtained by fluorinating part of or all of hydrogen
atoms in the above-mentioned substances can also be used, such as
trifluoropropylene carbonate and fluoroethyl carbonate.
[0055] Chain ester carbonates may be illustrated by dimethyl
carbonate, ethylmethyl carbonate, diethyl carbonate, methyl propyl
carbonate, ethyl propyl carbonate, methyl isopropyl carbonate, and
the like, and substances obtained by fluorinating part of or all of
hydrogen atoms in the above-mentioned substances can also be
used.
[0056] Esters may be illustrated by methyl acetate, ethyl acetate,
propyl acetate, methyl propionate, ethyl propionate,
.gamma.-butyrolactone, and the like.
[0057] Cyclic ethers may be illustrated by 1,3-dioxolane,
4-methyl-1,3-dioxolane, tetrahydrofuran, 2-methyl tetrahydrofuran,
propylene oxide, 1,2-butylene oxide, 1,4-dioxiane, 1,3,5-trioxane,
furan, 2-methy furan, 1,8-cineole, crown ether, and the like.
[0058] Chain ethers may be illustrated by 1,2-dimethoxyethane,
diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether,
dihexyl ether, ethyl vinyl ether, butyl vinyl ether, methyl phenyl
ether, ethyl phenyl ether, butyl phenyl ether, pentylphenyl ether,
methoxytoluene, benzyl ethyl ether, diphenyl ether, dibenzyl ether,
o-dimethoxybenzene, 1,2-diethoxyethane, 1,2-dibutoxyethane,
diethylene glycol dimethyl ether, diethylene glycol diethyl ether,
diethylene glycol dibutyl ether, 1,1-dimethoxymethane,
1,1-diethoxyethane, triethylene glycol dimethyl ether,
tetraethylene glycol dimethyl, and the like.
[0059] Nitriles may be illustrated by acetonitrile and the like,
and amides may be illustrated by dimethylformamide and the
like.
[0060] The positive electrode active material formed by the method
in the present embodiment has a stable rock-salt structure.
Accordingly, a phase change hardly occurs on insertion and release
of excessive lithium atoms. As a result, the capacity of a positive
electrode active material can be increased, leading to improved
capacity of a non-aqueous secondary battery.
(EXAMPLE 1)
[0061] In Example 1, the test cell shown in FIG. 2 was prepared to
measure the discharge capacity of lithium cobaltate in which
magnesium atoms are substituted for part of lithium atoms.
[0062] As shown in FIG. 2, a positive electrode 1, a negative
electrode 2, and a reference electrode 3 are disposed in a cell
vessel 10. A separator 4 is inserted between the positive electrode
1 and negative electrode 2. A non-aqueous electrolyte 5 is poured
into the cell vessel 10.
[0063] In Example 1, lithium cobaltate (LiCoO2), a conducting agent
made of carbon, and a binder made of polyvinilidene di fluoride
(PVdF) were mixed at a weight ratio of 90:5:5, respectively, and
N-methyl-2-pyrrolidone was added to the mixture to prepare a
slurry. This slurry was applied to a current collector made of
aluminum foil, forming the positive electrode 1. Metallic lithium
was used for the negative electrode 2 and reference electrode
3.
[0064] A non-aqueous electrolyte (non-aqueous electrolyte including
a lithium salt) including lithium hexafluorophosphate (LiPF.sub.6)
as a solute dissolved at a ratio of 1 mol/l in a mixed solvent of
ethylene carbonate (EC) and diethyl carbonate (DEC) (volume ratio
of EC:DEC=50:50); and a non-aqueous electrolyte (non-aqueous
electrolyte including a magnesium salt) including magnesium bis
(trifluoromethyl sulfonyl) imide
(((CF.sub.3SO.sub.2).sub.2N).sub.2Mg) dissolved as a solute at a
ratio of 1 mol/l in a solvent of .gamma.-butyrolactone
((CH.sub.2).sub.3OCO) were used.
[0065] The test cell thus prepared was discharged at a constant
current by the following manner to evaluate the positive electrode
active material. Table 1 shows non-aqueous electrolyte and charge
and discharge conditions. Moreover, FIG. 3 shows the measurement
results of discharge curves of lithium cobaltate before and after
substitution of magnesium atoms for lithium atoms.
1TABLE 1 charge and current cycle discharge non-aqueous capacity
density number conditions electrolyte mAh/g mA/cm.sup.2 first cycle
charge LiPF.sub.6 EC/DEC 120 1 discharge LiPF.sub.6 EC/DEC 110 1
second cycle charge LiPF.sub.6 EC/DEC 150 1 discharge
Mg(TFSI).sub.2 60 0.025 .gamma.-BL discharge LiPF.sub.6 EC/DEC 124
0.025 third cycle charge LiPF.sub.6 EC/DEC 135 0.05 discharge
LiPF.sub.6 EC/DEC 136 0.05
[0066] In FIG. 1, .gamma.-BL denotes .gamma.-butyrolactone, and Mg
(TFSI).sub.2 denotes magnesium bis (trifluoromethyl sulfonyl)
imide.
[0067] First, in the first cycle, the above-mentioned non-aqueous
electrolyte including a lithium salt is poured into the cell vessel
10. The test cell was charged, and then discharged. The current
density during charge and discharge was set to 1 mA/cm.sup.2. In
this case, the charge capacity was 120 mAh/g, and the discharge
capacity was 110 mAh/g.
[0068] Then, in the second cycle, the test cell was charged while
the above-mentioned non-aqueous electrolyte including a lithium
salt is held in the cell vessel 10. This caused extraction of
lithium atoms (Li) from the lithium cobaltate forming the positive
electrode active material. The current density during charge was 1
mA/cm.sup.2.
[0069] After that, the non-aqueous electrolyte in the cell vessel
10 was replaced with the above-mentioned non-aqueous electrolyte
including a magnesium salt, and the test cell was discharged. This
caused insertion of magnesium atoms (Mg) into the lithium cobaltate
forming the positive electrode active material, and the magnesium
atoms were substituted for part of lithium atoms (Li). In this
case, the current density during discharge was 0.025
mA/cm.sup.2.
[0070] Subsequently, the electrolyte in the cell vessel 10 was
replaced with the above-mentioned non-aqueous electrolyte including
a lithium salt, and the test cell was discharged. The current
density during discharge was 0.025 mA/cm.sup.2. In this case, the
discharge capacity was 124 mAh/g.
[0071] Further, in the third cycle, the test cell was charged while
the above-mentioned non-aqueous electrolyte including a lithium
salt is held in the cell vessel 10. The current density during
discharge was 0.05 mA/cm.sup.2. In this case, the charge capacity
was 135 mAh/g.
[0072] The test cell was subsequently discharged. The current
density during discharge was 0.05 mA/cm.sup.2. In this case, the
discharge capacity was 136 mAh/g.
[0073] As a result, the extraction of lithium atoms from the
lithium cobaltate and substitution of magnesium atoms for the part
of lithium atoms improved the capacity by 123%.
(EXAMPLE 2)
[0074] In Example 2, a structural change in lithium cobaltate
before and after substitution of magnesium atoms (Mg) for part of
lithium atoms (Li) was confirmed by XRD (X-ray diffraction)
measurement.
[0075] In the XRD measurement, measurements were made on a range of
2 .theta. from 10 to 80 degrees with a scanning rate set to 1
degree/min., using CU (40 kV, 40 mA) as a source.
[0076] FIG. 4 shows the measurement results of XRD patterns of the
positive electrode before and after substitution of magnesium atoms
for lithium atoms.
[0077] In FIG. 4, thin solid line below represents an XRD pattern
before substitution of magnesium atoms for lithium atoms, and thick
solid line above represents an XRD pattern after substitution of
magnesium atoms for lithium atoms.
[0078] Black rhombuses represent reflection peaks from lithium
cobaltate (LiCoO.sub.2), and white circles represent reflection
peaks from Al.sub.2O.sub.3. The reflection peaks from
Al.sub.2O.sub.3 were derived from an aluminum oxide on the surface
of the current collector.
[0079] As shown in FIG. 4, no change exists between the reflection
peaks from lithium CoO.sub.2 before substitution of magnesium atoms
for lithium atoms and the reflection peaks from lithium CoO.sub.2
after substitution of magnesium atoms for lithium atoms. This fact
shows that the substitution of magnesium atoms for lithium atoms
caused no phase change in LiCoO.sub.2.
[0080] As can be seen from this Example, substitution of magnesium
atoms (Mg) for part of lithium atoms (Li) in LiCoO.sub.2 causes no
structural change in LiCoO.sub.2.
[0081] Although the present invention has been described and
illustrated in detail, it is clearly understood that the same is by
way of illustration and example only and is not to be taken by way
of limitation, the spirit and scope of the present invention being
limited only by the terms of the appended claims.
* * * * *