CN102637865B - Cathode material of secondary battery and preparation method thereof - Google Patents
Cathode material of secondary battery and preparation method thereof Download PDFInfo
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- CN102637865B CN102637865B CN201110035546.7A CN201110035546A CN102637865B CN 102637865 B CN102637865 B CN 102637865B CN 201110035546 A CN201110035546 A CN 201110035546A CN 102637865 B CN102637865 B CN 102637865B
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Abstract
The embodiment of the invention discloses a compound with a general formula of Li2+2xMn0.6+xNi0.6-3xCr0.8O4, and also discloses a cathode material of secondary batteries, wherein the cathode material comprises the compound with the general formula of Li2+2xMn0.6+xNi0.6-3xCr0.8O4, and 0<x<=0.2. The invention also provides a preparation method of the cathode material of secondary batteries, which adopts lithium source compounds, manganese source compounds, nickel source compounds, and chromium source compounds as raw materials. Compared with the prior art, the cathode material prepared in the invention has a spinel structure, and also contains Ni ions and Cr ions. In the octahedral crystal field of the spinel structure of the cathode material, the electron distribution of the Ni ions and the Cr ions is changed, and thus energy splitting occurs; therefore, the cathode material prepared in the invention has a high working voltage.
Description
Technical field
The present invention relates to secondary battery technology, more particularly, relate to positive electrode of a kind of secondary cell and preparation method thereof.
Background technology
In recent years, along with highlighting of the problems such as the day by day exhausted and global warming of resource, the life style of green low-carbon has been subject to advocating.The research and development of electric motor car and hybrid electric vehicle can partly replace the internal-combustion engines vehicle of consumption of fossil fuels, is one of main method solving energy crisis and ecological deterioration.Driving power is to affect the critical component that electric motor car is promoted the use of, and nowadays widely used driving power comprises lead-acid battery, the secondary cells such as ni-mh/NI-G, lithium ion battery.Secondary cell refers to, after battery discharge, can make active material activate the battery that continues use by the mode of charging.In various secondary cells, lithium ion battery is high owing to having energy density, and cyclicity is good, and self-discharge rate is low, long service life and the advantage such as environmental pressure is little, has obtained research widely.
The positive electrode using in lithium ion battery comprises lithium cobaltate cathode material, lithium nickel cobalt dioxide positive electrode, phosphate system positive electrode, manganate cathode material for lithium and LiN
0.5mn
1.5o
4deng.For lithium cobaltate cathode material, because the abundance of cobalt element in the earth's crust is low, thereby price is higher, in addition, cobalt element also has certain toxicity, larger to environmental hazard after discarded, and therefore lithium cobaltate cathode material exists the problems such as high, the discarded after stain environment of cost, security performance be poor; Lithium nickel cobalt dioxide Capacity Ratio cobalt acid lithium increases, but synthetic cost is high, has safety problem while overcharging; Phosphate system can reduce costs, and have charge stability and security advantages, but energy density is low, and electron conduction is poor, and complicated process of preparation.
As a kind of important positive electrode, the LiMn2O4 LiMn of spinel structure
2o
4, have that fail safe is good, price is low, the advantages such as environmental protection.But the reversible capacity of LiMn2O4 is lower, and its operating voltage is lower, be 4.1V left and right, thereby the power density of the lithium ion battery taking this LiMn2O4 as positive electrode is lower.The present invention considers, develops a kind of positive electrode of novel secondary battery, and this positive electrode has higher operating voltage, contributes to improve the power density of lithium ion battery.
Summary of the invention
In view of this, positive electrode providing by a kind of secondary cell and preparation method thereof is provided the technical problem to be solved in the present invention, and the positive electrode of secondary cell prepared by the method has higher operating voltage.
The invention provides a kind of general formula is Li
2+2xmn
0.6+xni
0.6-3xcr
0.8o
4compound, wherein, 0 < x≤0.2.
The present invention also provides a kind of positive electrode of secondary cell, comprises that general formula is Li
2+2xmn
0.6+xni
0.6-3xcr
0.8o
4compound, wherein 0 < x≤0.2.
Preferably, 0.1≤x≤0.2.
The present invention also provides a kind of preparation method of positive electrode of secondary cell, comprising:
Step a) is mixed Li source compound, manganese source compound, nickel source compound and chromium source compound in solvent, and 150～300 DEG C of reactions, the mol ratio of described lithium, manganese, nickel and chromium is 2～2.4: 0.6～0.8: 0～0.6: 0.8;
The product that step b) a) obtains step is dried, grinds, and then annealing at 300～400 DEG C, obtains intermediate;
Step c) is calcined described intermediate at 700～1000 DEG C, obtains the positive electrode of secondary cell.
Preferably, the mol ratio of described lithium, manganese, nickel and chromium is 2.2～2.4: 0.7～0.8: 0～0.3: 0.8.
Preferably, described step reaction temperature a) is 180～250 DEG C.
Preferably, described step reaction time a) is 8～20 hours.
Preferably, described step baking temperature b) is 100～150 DEG C.
Preferably, described step annealing time b) is 3～10 hours.
Preferably, described step calcination time c) is 10～15 hours.
Can find out from above-mentioned technical scheme, the invention provides a kind of positive electrode of secondary cell, comprise that general formula is Li
2+2xmn
0.6+xni
0.6-3xcr
0.8o
4compound, wherein 0 < x≤0.2.The present invention also provides a kind of preparation method of positive electrode of secondary cell, and this preparation method, taking Li source compound, manganese source compound, nickel source compound and chromium source compound as raw material, prepares the positive electrode of secondary cell.Compared with positive-material lithium manganate of the prior art, positive electrode prepared by the present invention, in having spinel structure, contains Ni ion and Cr ion.In the octahedral crystal field of the spinel structure of this positive electrode, the electron distributions of Ni ion and Cr ion changes, and then produces engery level cracking, therefore, positive electrode prepared by the present invention there is higher operating voltage.Experimental result shows, the operating voltage of positive electrode prepared by the present invention is 4.8V.
Brief description of the drawings
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, to the accompanying drawing of required use in embodiment or description of the Prior Art be briefly described below, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, do not paying under the prerequisite of creative work, can also obtain according to these accompanying drawings other accompanying drawing.
Fig. 1 is the X ray diffracting spectrum of the secondary battery positive electrode material prepared of the embodiment of the present invention 1;
Fig. 2 is the scanning electron microscopy sheet of the secondary battery positive electrode material prepared of the embodiment of the present invention 1;
Fig. 3 is the X ray diffracting spectrum of the secondary battery positive electrode material prepared of the embodiment of the present invention 2;
Fig. 4 is the scanning electron microscopy sheet of the secondary battery positive electrode material prepared of the embodiment of the present invention 2;
Fig. 5 is the X ray diffracting spectrum of the secondary battery positive electrode material prepared of the embodiment of the present invention 3;
Fig. 6 is the scanning electron microscopy sheet of the secondary battery positive electrode material prepared of the embodiment of the present invention 3;
Fig. 7 is the X ray diffracting spectrum of the secondary battery positive electrode material prepared of the embodiment of the present invention 4;
Fig. 8 is the scanning electron microscopy sheet of the secondary battery positive electrode material prepared of the embodiment of the present invention 4;
Fig. 9 is the X ray diffracting spectrum of the secondary battery positive electrode material prepared of the embodiment of the present invention 5;
Figure 10 is the scanning electron microscopy sheet of the secondary battery positive electrode material prepared of the embodiment of the present invention 5;
Figure 11 is the first charge-discharge curve of the lithium ion battery prepared of the embodiment of the present invention 6;
Figure 12 is the first charge-discharge curve of the lithium ion battery prepared of the embodiment of the present invention 7;
Figure 13 is the first charge-discharge curve of the lithium ion battery prepared of the embodiment of the present invention 8;
Figure 14 is the first charge-discharge curve of the lithium ion battery prepared of the embodiment of the present invention 9;
Figure 15 is the first charge-discharge curve of the lithium ion battery prepared of the embodiment of the present invention 10;
Figure 16 is the cycle characteristics figure of the lithium ion battery that makes of the embodiment of the present invention 6～10.
Embodiment
Below the technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiment.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtaining under creative work prerequisite, belong to the scope of protection of the invention.
The invention discloses a kind of general formula is Li
2+2xmn
0.6+xni
0.6-3xcr
0.8o
4compound, wherein, 0 < x≤0.2, preferred, 0.1≤x≤0.2.
The present invention also provides a kind of positive electrode of secondary cell, comprises that general formula is Li
2+2xmn
0.6+xni
0.6-3xcr
0.8o
4compound, wherein 0 < x≤0.2, preferred, 0.1≤x≤0.2.
The preparation method who the invention also discloses a kind of above-mentioned positive electrode, comprising:
Step a) is mixed Li source compound, manganese source compound, nickel source compound and chromium source compound in solvent, reaction, and the mol ratio of described lithium, manganese, nickel and chromium is 2～2.4: 0.6～0.8: 0～0.6: 0.8;
The product that step b) a) obtains step is dried, grinds, and then annealing at 300～400 DEG C, obtains intermediate;
Step c) is calcined described intermediate at 700～1000 DEG C, obtains the positive electrode of secondary cell.
Described step a) in, described Li source compound is preferably lithium hydroxide, lithium acetate, lithium nitrate, lithium carbonate or lithium chloride, described manganese source compound is preferably manganese acetate, manganese nitrate, manganese sulfate or manganese chloride, described nickel source compound is preferably nickel acetate, nickel chloride, nickel nitrate or nickelous sulfate, and described chromium source compound is preferably chromic nitrate.The mol ratio of described lithium, manganese, nickel and chromium is preferably 2.2～2.4: 0.7～0.8: 0～0.3: 0.8, and more preferably 2.3: 0.75: 0.15: 0.8.Described solvent is preferably deionized water, and described Li source compound, manganese source compound, nickel source compound and chromium source compound mix in solvent, is preferably formulated as the solution that molar concentration is 0.5～0.8mol/L, more preferably 0.6～0.7mol/L.Described step reaction temperature a) is preferably 180～250 DEG C, more preferably 190～220 DEG C.Described step reaction time a) is preferably 8～20 hours, more preferably 10～15 hours, most preferably is 10～12 hours.
The present invention utilizes hydrothermal synthesis method to prepare the product that step a) obtains, and reaction temperature is 150～300 DEG C, is the essential condition that the present invention prepares the positive electrode with spinel structure.The methods such as the precipitation method of the prior art, collosol and gel or spray drying process, can only prepare the positive electrode of layer structure.
Step b) in, described baking temperature is preferably 100～150 DEG C, more preferably 100～130 DEG C, most preferably is 110 DEG C.The annealing temperature that invention adopts is the essential condition that obtains the positive electrode with good granularity and degree of crystallinity.Described annealing temperature is preferably 320～380 DEG C, most preferably is 330～360 DEG C.Described annealing time is preferably 3～10 hours, more preferably 3～8 hours, most preferably is 4～6 hours.
Described step c) in, the calcining of intermediate that step b) is obtained, described calcining heat is preferably 700～900 DEG C, more preferably 800 DEG C.Described calcination time is preferably 10～15 hours, more preferably 11～14 hours, most preferably is 12～13 hours.
Positive electrode prepared by the present invention has higher operating voltage and mainly contains two reasons: the one, and this positive electrode has the structure of spinelle, and the 2nd, in this positive electrode, contain Ni ion and Cr ion.In prior art, there is the average voltage of positive-material lithium manganate of spinel structure at about 4 volts.And in positive electrode prepared by the present invention owing to thering is Ni ion, Cr ion, this positive electrode reduces at the capacity of 4V platform, occurs new platform in the high voltage region that is greater than 4.5 volts simultaneously.
In the octahedral crystal field of the spinel structure of the positive electrode of preparing in the present invention, the electron distributions of Ni ion and Cr ion changes, and then produces engery level cracking, therefore, positive electrode prepared by the present invention there is higher operating voltage.
The positive electrode of preparing due to the present invention has higher operating voltage, and in 4.8V left and right, therefore, the battery that the positive electrode that should prepare with the present invention prepares has higher power density.
General formula prepared by the present invention is Li
2+2xmn
0.6+xni
0.6-3xcr
0.8o
4positive electrode can be used as the positive electrode of column lithium ion battery, rectangular lithium ion battery and button-shaped lithium ion battery, and can be used as the positive electrode of lithium-ion-power cell and lithium-ion energy storage battery.
In order to further illustrate technical scheme of the present invention, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these are described is for further illustrating the features and advantages of the present invention, instead of limiting to the claimed invention.
Embodiment 1
Step is a) by Li: the mol ratio of Mn: Ni: Cr is 2.07: 0.63: 0.5: 0.8 lithium hydroxide, nickel acetate, manganese acetate and chromic nitrate mix, add deionized water to be made into the solution that molar concentration is 0.6mol/L, obtain mixed solution, then described mixed solution is placed in to hydrothermal synthesis reaction still, regulate pH value to neutral, then in 200 DEG C of reactions 12 hours, centrifugation;
The product that step b) a) obtains step dries and grinds to form powder at 110 DEG C, and described powder is placed in to Muffle furnace, 350 DEG C of annealing 4 hours, naturally cooling, obtains intermediate;
Step c) by described intermediate in Muffle furnace with 800 DEG C of calcining at constant temperature 12 hours, naturally cooling, obtain the positive electrode of secondary cell.
Positive electrode prepared by the present embodiment carries out X-ray diffraction analysis, and taking copper target as diffraction target, as shown in Figure 1, as can be seen from Figure 1, positive electrode prepared by the present embodiment has spinel structure to result.In Fig. 1, asterisk represents the diffraction maximum of impurity, therefore, has the existence of a small amount of impurity in the positive electrode of secondary cell prepared by the present embodiment.
Fig. 2 is the scanning electron microscopy sheet of the positive electrode prepared of the present embodiment, as can be seen from the figure, positive electrode particle size prepared by the present embodiment is even, and size is greatly between 0.5～3 micron, there is good crystal shape, there is higher degree of crystallinity.
Embodiment 2
Step is a) by Li: the mol ratio of Mn: Ni: Cr is 2.13: 0.0.67: the lithium hydroxide of 0.40: 0.80, nickel acetate, manganese acetate and chromic nitrate mix, add deionized water to be made into the solution that molar concentration is 0.6mol/L, obtain mixed solution, then described mixed solution is placed in to hydrothermal synthesis reaction still, regulate pH value to neutral, then in 200 DEG C of reactions 12 hours, centrifugation;
The product that step b) a) obtains step dries and grinds to form powder at 110 DEG C, and described powder is placed in to Muffle furnace, 350 DEG C of annealing 4 hours, naturally cooling, obtains intermediate;
Step c) by described intermediate in Muffle furnace with 800 DEG C of calcining at constant temperature 12 hours, naturally cooling, obtain the positive electrode of secondary cell.
Positive electrode prepared by the present embodiment carries out X-ray diffraction analysis, and taking copper target as diffraction target, as shown in Figure 3, as can be seen from Figure 3, positive electrode prepared by the present embodiment has spinel structure to result.In Fig. 3, asterisk represents the diffraction maximum of impurity, therefore, has the existence of a small amount of impurity in the positive electrode of secondary cell prepared by the present embodiment.
Fig. 4 is the scanning electron microscopy sheet of the positive electrode prepared of the present embodiment, as can be seen from the figure, positive electrode particle size prepared by the present embodiment is even, and size is greatly between 0.5～3 micron, there is good crystal shape, there is higher degree of crystallinity.
Embodiment 3
Step is a) by Li: the mol ratio of Mn: Ni: Cr is 2.20: 0.0.70: the lithium hydroxide of 0.30: 0.80, nickel acetate, manganese acetate and chromic nitrate mix, add deionized water to be made into the solution that molar concentration is 0.6mol/L, obtain mixed solution, then described mixed solution is placed in to hydrothermal synthesis reaction still, regulate pH value to neutral, then in 200 DEG C of reactions 12 hours, centrifugation;
The product that step b) a) obtains step dries and grinds to form powder at 110 DEG C, and described powder is placed in to Muffle furnace, 350 DEG C of annealing 4 hours, naturally cooling, obtains intermediate;
Step c) by described intermediate in Muffle furnace with 800 DEG C of calcining at constant temperature 12 hours, naturally cooling, obtain the positive electrode of secondary cell.
Positive electrode prepared by the present embodiment carries out X-ray diffraction analysis, and taking copper target as diffraction target, as shown in Figure 5, as can be seen from Figure 5, positive electrode prepared by the present embodiment has spinel structure to result.
Fig. 6 is the scanning electron microscopy sheet of the positive electrode prepared of the present embodiment, as can be seen from the figure, positive electrode particle size prepared by the present embodiment is even, and size is greatly between 0.5～3 micron, there is good crystal shape, there is higher degree of crystallinity.
Embodiment 4
Step is a) by Li: the mol ratio of Mn: Ni: Cr is 2.27: 0.0.73: the lithium hydroxide of 0.20: 0.80, nickel acetate, manganese acetate and chromic nitrate mix, add deionized water to be made into the solution that molar concentration is 0.6mol/L, obtain mixed solution, then described mixed solution is placed in to hydrothermal synthesis reaction still, regulate pH value to neutral, then in 200 DEG C of reactions 12 hours, centrifugation;
The product that step b) a) obtains step dries and grinds to form powder at 110 DEG C, and described powder is placed in to Muffle furnace, 350 DEG C of annealing 4 hours, naturally cooling, obtains intermediate;
Step c) by described intermediate in Muffle furnace with 800 DEG C of calcining at constant temperature 12 hours, naturally cooling, obtain the positive electrode of secondary cell.
Positive electrode prepared by the present embodiment carries out X-ray diffraction analysis, and taking copper target as diffraction target, as shown in Figure 7, as can be seen from Figure 7, positive electrode prepared by the present embodiment has spinel structure to result.
Fig. 8 is the scanning electron microscopy sheet of the positive electrode prepared of the present embodiment, as can be seen from the figure, positive electrode particle size prepared by the present embodiment is even, and size is greatly between 0.5～3 micron, there is good crystal shape, there is higher degree of crystallinity.
Embodiment 5
Step is a) by Li: the mol ratio of Mn: Ni: Cr is 2.33: 0.0.77: the lithium hydroxide of 0.10: 0.80, nickel acetate, manganese acetate and chromic nitrate mix, add deionized water to be made into the solution that molar concentration is 0.6mol/L, obtain mixed solution, then described mixed solution is placed in to hydrothermal synthesis reaction still, regulate pH value to neutral, then in 200 DEG C of reactions 12 hours, centrifugation;
The product that step b) a) obtains step dries and grinds to form powder at 110 DEG C, and described powder is placed in to Muffle furnace, 350 DEG C of annealing 4 hours, naturally cooling, obtains intermediate;
Step c) by described intermediate in Muffle furnace with 800 DEG C of calcining at constant temperature 12 hours, naturally cooling, obtain the positive electrode of secondary cell.
Positive electrode prepared by the present embodiment carries out X-ray diffraction analysis, and taking copper target as diffraction target, as shown in Figure 9, as can be seen from Figure 9, positive electrode prepared by the present embodiment has spinel structure to result.
Figure 10 is the scanning electron microscopy sheet of the positive electrode prepared of the present embodiment, as can be seen from the figure, positive electrode particle size prepared by the present embodiment is even, and size is greatly between 0.5～3 micron, there is good crystal shape, there is higher degree of crystallinity.
Embodiment 6～10
By positive electrode and the conductive black super P of the secondary cell of embodiment 1～5 preparation, binding agent PVDF mixes in 8: 1: 1 ratios, adds 1-METHYLPYRROLIDONE (NMP) stir post-drying, pulverizing, is pressed in aluminium and makes positive plate on the net;
Described positive plate is moved in the glove box that is full of high-purity argon gas in vacuum drying oven after 130 DEG C are dried 5 hours, and taking metal lithium sheet as negative pole, using the polypropylene of Celgard company of the U.S. as barrier film, supporting electrolyte taking LiPF6 in electrolyte, solvent is that volume ratio is EC and the DEC of 1: 1, makes CR2016 type button lithium ion battery.
Respectively the lithium ion battery of embodiment 6～10 preparations is carried out to charge-discharge test, charging and discharging currents is 20 milliamperes/gram, and charging/discharging voltage interval is between 2～5V, and probe temperature is room temperature.
Figure 11～Figure 15 is respectively the first charge-discharge curve of the lithium ion battery of embodiment 6～10 preparations.As can be seen from the figure, have two obvious voltage platforms in Figure 11～Figure 15, one at about 4.8 volts, and one at about 2.6 volts.Electric discharge specific capacity all exceeded 100 Milliampere Hours/gram, the specific discharge capacity of the lithium ion battery that the positive electrode of especially being prepared by embodiment 4 and embodiment 5 makes be respectively 169 Milliampere Hours/gram and 182 Milliampere Hours/gram.
Figure 16 is the cycle characteristics figure of the lithium ion battery that makes of embodiment 6～10, and as can be seen from the figure, the positive electrode of the embodiment of the present invention 1～5 preparation all has good cycle characteristics.For the positive electrode of preparing from embodiment 4 and embodiment 5, after 50 circulations, still can keep specific discharge capacity 120 Milliampere Hours/gram more than.
As can be seen here, positive electrode prepared by the present invention has high-purity, high-crystallinity and good battery behavior, with traditional spinel lithium manganate LiMn
2o
4compare, not only there is high specific discharge capacity, and because its discharge voltage plateau is 4.8V, higher than spinel lithium manganate LiMn
2o
44V, therefore also there is higher power density than spinel lithium manganate.Can find out from above-described embodiment, the operating voltage of positive electrode prepared by the present invention is 4.8V, therefore has very large competitiveness as Olivine-type Cathode Material in Li-ion Batteries.
To the above-mentioned explanation of the disclosed embodiments, make professional and technical personnel in the field can realize or use the present invention.To be apparent for those skilled in the art to the multiple amendment of these embodiment, General Principle as defined herein can, in the situation that not departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention will can not be restricted to these embodiment shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (10)
1. a general formula is Li
2+2xmn
0.6+xni
0.6-3xcr
0.8o
4compound, wherein, 0 < x≤0.2.
2. a positive electrode for secondary cell, is characterized in that, comprises that general formula is Li
2+2xmn
0.6+xni
0.6-3xcr
0.8o
4compound, wherein 0 < x≤0.2.
3. positive electrode according to claim 2, is characterized in that, 0.1≤x≤0.2.
4. a preparation method for the positive electrode of secondary cell, is characterized in that, comprising:
Step a) is mixed Li source compound, manganese source compound, nickel source compound and chromium source compound in solvent, and 150～300 DEG C of reactions, the mol ratio of described lithium, manganese, nickel and chromium is 2～2.4: 0.6～0.8: 0～0.6: 0.8;
The product that step b) a) obtains step is dried, grinds, and then annealing at 300～400 DEG C, obtains intermediate;
Step c) is calcined described intermediate at 700～1000 DEG C, obtains the positive electrode of secondary cell.
5. preparation method according to claim 4, is characterized in that, the mol ratio of described lithium, manganese, nickel and chromium is 2.2～2.4: 0.7～0.8: 0～0.3: 0.8.
6. preparation method according to claim 4, is characterized in that, described step reaction temperature a) is 180～250 DEG C.
7. preparation method according to claim 5, is characterized in that, described step reaction time a) is 8～20 hours.
8. preparation method according to claim 5, is characterized in that, described step baking temperature b) is 100～150 DEG C.
9. preparation method according to claim 5, is characterized in that, described step annealing time b) is 3～10 hours.
10. preparation method according to claim 5, is characterized in that, described step calcination time c) is 10～15 hours.
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ID=46622172
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0779669A1 (en) * | 1995-12-06 | 1997-06-18 | Kerr-Mcgee Chemical Corporation | Lithium manganese oxide compound and method of preparation |
| US6613476B2 (en) * | 2000-01-03 | 2003-09-02 | Samsung Sdi Co., Ltd. | Positive active material for rechargeable lithium battery and method of preparing same |
| CN1702043A (en) * | 2005-04-12 | 2005-11-30 | 武汉理工大学 | Preparation of spinel type Li-Mn-oxide lithium ion screening materials by hydrothermal method |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5900385A (en) * | 1997-10-15 | 1999-05-04 | Minnesota Mining And Manufacturing Company | Nickel--containing compounds useful as electrodes and method for preparing same |
| JP2001126731A (en) * | 1999-08-19 | 2001-05-11 | Mitsubishi Chemicals Corp | Positive electrode material for lithium secondary cell, positive electrode for lithium secondary cell, and the lithium secondary cell |
| AU2001253150A1 (en) * | 2000-04-05 | 2001-10-23 | Johnson Research And Development Company, Inc. | Method of producing a thin film battery |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0779669A1 (en) * | 1995-12-06 | 1997-06-18 | Kerr-Mcgee Chemical Corporation | Lithium manganese oxide compound and method of preparation |
| US6613476B2 (en) * | 2000-01-03 | 2003-09-02 | Samsung Sdi Co., Ltd. | Positive active material for rechargeable lithium battery and method of preparing same |
| CN1702043A (en) * | 2005-04-12 | 2005-11-30 | 武汉理工大学 | Preparation of spinel type Li-Mn-oxide lithium ion screening materials by hydrothermal method |
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