CN104009230A - Lithium ion battery anode material and lithium ion battery - Google Patents
Lithium ion battery anode material and lithium ion battery Download PDFInfo
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- CN104009230A CN104009230A CN201410241172.8A CN201410241172A CN104009230A CN 104009230 A CN104009230 A CN 104009230A CN 201410241172 A CN201410241172 A CN 201410241172A CN 104009230 A CN104009230 A CN 104009230A
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- lithium ion
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/626—Metals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a lithium ion battery and a lithium ion battery anode material. The anode material comprises a lithium cobalt oxide material in the shape of powdery granules, wherein an element niobium is doped in the lithium cobalt oxide material; the median size D50 of the lithium cobalt oxide material is 16-20 microns; the volume compaction density of the lithium cobalt oxide material is 4.0-4.2g/cm3; the gram volume is 162-175mAh/g. By adoption of the anode material, according to the reasonable particle ratio and transition element niobium doping, the capacity and charge and discharge voltage of the battery are improved, so that a high-capacity high-voltage lithium ion battery is obtained.
Description
Technical field
The present invention relates to battery technology field, the lithium ion battery that is specifically related to a kind of anode material for lithium-ion batteries and contains this positive electrode.
Background technology
Along with electronic product is constantly developed, lithium ion battery is used widely, and present electronic product is in continuous update, simultaneously also more and more higher to the requirement of lithium ion battery product.At present in whole battery industry, the product quality of each battery producer differs, 90% producer is all in low and middle-end level, on to the electronic product of some high requests, battery performance can not meet the demands, for example: be mainly to take bluetooth as main in early days, to the performance requirement of battery, not very high, as long as there is the enterprise of certain fund can put into lithium ion battery industry, and from current market, main electronic product is digital, panel computer, ultra thin handset, electronic product is all that touch-screen shows, this series products is because being subject to the restriction of volume, require lithium ion battery to exceed much than conventional lithium ion battery at volume and capacity ratio, if Samsung part type trumpeter machine is under same volume, the Capacity Ratio routine of its requirement exceed approximately 12% left and right, technical merit with present each producer, be difficult to reach this requirement, therefore, the polymer Li-ion battery that capacity is higher, become the first-selection of digital communication series products.
Along with the arriving in 3G/4G epoch, present most of communication product has possessed online, has played games, seen the several functions such as e-book, MP3, MP4, so more and more higher to the capacity requirement of lithium ion battery.Common polymer Li-ion battery is subject to the impact of its material behavior, can not meet the demand of some special population on capacity, therefore must develop a kind of digital communication polymer Li-ion battery of high capacity type.
The lithium ion cell positive gram volume performance that we use at present only has 142 MAhs/g, and to current smart mobile phone, the screen of panel computer maximizes, and has been difficult to meet the demands, and we must provide the lithium ion battery that volume ratio is higher the demand for development of science and technology.
Summary of the invention
In view of this, provide a kind of can raising to charge and discharge voltage, the anode material for lithium-ion batteries that promotes positive electrode capacity and the lithium ion battery that contains this positive electrode.
An anode material for lithium-ion batteries, it comprises the cobalt acid lithium material that is powdered granule, doped chemical niobium in described cobalt acid lithium material, the median particle diameter D of described cobalt acid lithium material
50for 16-20 micron, the volume compacted density of described cobalt acid lithium material is 4.0-4.2g/m
3, gram volume is 162 mAh/g-175mAh/g.
And, a kind of lithium ion battery, it comprises positive pole, negative pole, electrolyte and the barrier film between both positive and negative polarity, and the active material of described positive pole is above-mentioned anode material for lithium-ion batteries, and described battery operated voltage is 4.35-4.5V.
Above-mentioned anode material for lithium-ion batteries adopts the cobalt acid lithium material of powdered granule, and by particle size is carried out to rational proportion mixing, making material volume compacted density is 4.0-4.2g/m
3, material capacity reaches 162-175mAh/g, and doped with transition elements niobium.According to test result, adopt the lithium ion battery of this positive electrode can normally work completely in the operating voltage range of 4.45V, for example, under the operating voltage of 4.45V or 4.49V, lithium ion battery outward appearance changes without inflatable.Therefore, by adopting above-mentioned positive electrode, adopt particle rational proportion and doped with transition elements niobium, improve battery capacity and charging/discharging voltage, can obtain high power capacity high-voltage lithium ion batteries.
Accompanying drawing explanation
Fig. 1 is that the performance of lithium ion battery of the embodiment of the present invention detects data and curves figure.
Embodiment
Below with reference to specific embodiments and the drawings, the present invention is described in detail.
The anode material for lithium-ion batteries of the embodiment of the present invention comprises the cobalt acid lithium material that is powdered granule, doped chemical niobium in this material, the median particle diameter D of described cobalt acid lithium material
50for 16-20 micron, the volume compacted density of described cobalt acid lithium material is 4.0-4.2g/m
3, gram volume is 162 mAh/g-175mAh/g.
Cobalt acid lithium (LiCoO
2) be layer structure, space group is R3m, and oxygen atom forms cube close heap sequence, and cobalt and lithium occupy respectively octahedral 3 (a) and 3 (b) position in cubic closest packing; In charge and discharge process, it is stable that the structure of material keeps, and has reasonable cycle performance, and LiCoO
2all best in various aspects of performance such as invertibity, discharge capacity, charge efficiency, voltage stabilities.Cobalt acid lithium theoretical capacity is 272 mAh/g, and conventional batteries while using actual performance capacity be only about 145mAh/g.In order to maximize performance positive electrode capacity, the present embodiment is mainly by improving the aspects such as material composition, physicochemical characteristics, pattern, and coordinate further negative material, barrier film and electrolyte etc., expand the operating voltage range of lithium ion battery, make as far as possible capacity discharge, thereby reach to promote volume and capacity ratio, improve battery operated voltage range.
Particularly, the content of niobium is 1-20%, is preferably 2-15%.The cobalt acid lithium material volume compacted density of powdered granule is 4.0-4.2g/m
3, make material capacity performance for 162-175mAh/g, be preferably 162-175mAh/g, more preferably 165-175mAh/g.Correspondingly, adopting the accessible battery operated voltage of this material is 4.35V-4.45V, preferably brings up to 4.45V, and material capacity is about 175mAh/g, and corresponding capacity is brought up to 4.50V.Conventional lithium ion battery voltage is 4.2V, and actual capacity is 145mAh/g, and with respect to conventional voltage and capacity, the volume and capacity ratio of the present embodiment promotes 20% left and right.Compacted density computing formula is: compacted density=surface density/(thickness-collector thickness after pole piece rolls), specifically can adopt conventional method to record.
The positive electrode of take is applied to lithium ion battery as example, and lithium ion battery comprises positive pole, negative pole, electrolyte and the barrier film between both positive and negative polarity, and anodal active material is anode material for lithium-ion batteries as above.Negative pole comprises the carbon coated graphite material that is powdered granule, and median particle diameter is D
50for 8-15 micron, material volume compacted density is 1.6-1.8g/m
3.
The electrolytic salt of electrolyte is LiPF
6the solvent of electrolyte comprises the EMC (methyl ethyl carbonate) of DEC (diethyl carbonate), 30-35% of EC (ethylene carbonate), the 30-35% of the composition of following mass percent: 30-35%, the FEC of 5-8% (fluorinated ethylene carbonate), the density of solvent at 25 ℃ is 1.00～1.30g/cm
3, the conductivity of solvent at 25 ℃ is 8-12s/cm.In whole lithium-ion battery system on operating voltage range impact larger be electrolyte because electrolyte very easily decomposes and produces gas under high-voltage state, make lithium ion battery complete failure.Therefore, the present embodiment adopts above-mentioned formula electrolyte and solvent, is difficult for decomposition gas, and solvent is larger in normal temperature density, also not volatile.Like this, according to test result, charging voltage just can produce inflatable during to 4.6V-4.8V, and under the operating voltage state of the lithium ion battery of the present embodiment below 4.5V, can not cause inflatable to cause lithium ion battery to be scrapped.
Further, also contain coating material in positive electrode, described coating material is preferably Ni
xmn
yo
zcomposite oxides, 0.1≤x≤0.75 wherein, 0.3≤y≤1.5, z is 2 or 4, more preferably, 0.2≤x≤0.5,0.5≤y≤1.While having coating material, cobalt acid lithium material structural formula is expressed as: [Ni
xnb
kmn
yo
z]
n(LiCoO
2)
1-n, wherein, 0.1≤x≤0.75,0.3≤y≤1.5,0<n≤0.35, z is 2 or 4,0.1≤k≤0.6.
It is the ceramic diaphragm of 9-16 micron that barrier film adopts particle diameter, and barrier film is two-sided respectively applies the SiO that a layer thickness is 2-4 micron
2, hole gas rate is 42 ± 4%, under 120 ℃ and normality atmospheric pressure, and longitudinal contraction < 2%, cross-direction shrinkage < 1%.By at barrier film dual coating porous silica, to overflow while having γ-ray emission also unobstructedly.
In addition, lithium ion battery has shell, and shell adopts aluminum plastic film, comprises two layers of polypropylene (PP) layer and the aluminium foil between two polypropylene layers.Adopt this PP sandwich packing, even if gas appears in inside battery, when air pressure reaches aluminum plastic film bonding strength, aluminum plastic film can AUTOMATIC ZONING carry out pressure release, thereby there will not be blast, improves security performance.
As shown in Figure 1, the lithium ion battery of the present embodiment discharges and recharges respectively under 4.2V, 4.35V, the different voltage condition of 4.45V, from test result, find out, the lithium ion battery of the present embodiment can normally be worked completely in the operating voltage range of 4.45V, during observation, lithium ion battery outward appearance changes without inflatable.
The lithium ion battery that table 1 is the present embodiment discharges and recharges data, by test, show, lithium ion battery discharges and recharges respectively under 4.2V, 4.35V, the different voltage condition of 4.45V, from test result, find out, the lithium ion battery of the present embodiment can normally be worked in the operating voltage range of 4.45V, lithium ion battery outward appearance changes without inflatable, and, all can steady operation at 4.449V and 4.452V.Conventionally known, lithium ion battery carries out under discharging condition with conventional voltage 4.2V, capacity is 2113mAh, with 4.35V, carry out under discharging condition, capacity is 2393mAh, the capacity discharging under voltage conditions when 4.35V is 1.13% of conventional 4.2V voltage, volume capacity is than upper increase by 13% left and right, anodal actual gram volume performance is 162mAh/g, and carry out under discharging condition with 4.45V, capacity is 2606mAh, the capacity discharging under voltage conditions when 4.35V is 123% of conventional 4.2V voltage, at volume capacity, than on increase by 23% left and right, the actual gram volume of positive electrode of the present embodiment can be brought into play with 175mAh/g, can greatly improve battery volume Capacity Ratio.When the electronic products such as mobile phone, flat board adopt the lithium ion battery of the present embodiment, battery capacity improves more than 20%, thereby greatly improves the service time of electronic product.
The lithium ion battery of table 1 the present embodiment discharges and recharges data
Above-mentioned method for preparing anode material of lithium-ion battery can adopt several different methods, below by preferred embodiment, illustrates that the anode material for lithium-ion batteries of the embodiment of the present invention forms and preparation method thereof.
Embodiment 1
According to the element molar ratio in predetermined product structural formula below, choosing cobaltosic oxide, nickel nitrate and manganese sulfate is raw material, after being dissolved in water, mix, the sodium hydroxide solution that adds appropriate 1mol/L, limit edged stirs, fully reaction, get product dry, in the coated layer of Ni in the surface of cobaltosic oxide
xmn
y(OH)
z, obtain functionally gradient material (FGM) [Ni
xmn
y(OH)
z]
n(Co
3o
4)
1-npresoma, then add Nb
2o
5as additive, mix, and burn next time knot 8～12 hours the temperature of 1000～1200 ℃, form [Ni
xnb
kmn
yo
z]
n(Co
3o
4)
1-nthe oxide of gradient-structure, adds after lithium compound (as lithium carbonate) at 1050～1100 ℃ sintering 10～15 hours, carries out double sintering, obtains having that high compacting is high-tension mixes niobium lithium cobaltate cathode material, and has coating material.Above in each structural formula: x=0.5, y=0.5, z=2, n=0.1, k=0.4, the mol ratio of niobium element and elemental lithium is about 0.4:9, finally obtains positive electrode structural formula and is expressed as (LiCoO
2)
0.9[Ni
0.5nb
0.4mn
0.5o
2]
0.1.
Through measuring, this anode material for lithium-ion batteries compacted density reaches 4.15g/cm
3, electrochemical discharge capacity reaches 168mAh/g, and operating voltage is more than 4.4V.
Embodiment 2
According to the element molar ratio in predetermined product structural formula below, choose cobaltosic oxide, nickelous sulfate, manganese nitrate and Nb
2o
5for raw material, mix after being dissolved in water, add the potassium hydroxide solution of appropriate 0.5mol/L, limit edged stirs, and fully reaction, gets product dry, in the coated layer of Ni in the surface of cobaltosic oxide
xmn
y(OH)
z, obtain functionally gradient material (FGM) [Ni
xmn
y(OH)
z]
n(Co
3o
4)
1-npresoma, then the temperature of 1100～1200 ℃, burn next time knot 10～12 hours, form [Ni
xnb
kmn
yo
z]
n(Co
3o
4)
1-nthe oxide of gradient-structure, adds after lithium carbonate at 1000～1100 ℃ sintering 12～15 hours, carries out double sintering, obtains having that high compacting is high-tension mixes niobium lithium cobaltate cathode material, and has coating material.In formula: x=0.5, y=1, z=2, n=0.2, k=0.2, the mol ratio of niobium element and elemental lithium is about 1:20, finally obtains positive electrode structural formula and is expressed as (LiCoO
2)
0.8[Ni
0.5nb
0.2mnO
2]
0.2.
Through measuring, this anode material for lithium-ion batteries compacted density reaches 4.2g/cm
3, electrochemical discharge capacity reaches 171mAh/g, and operating voltage is more than 4.45V.
Embodiment 3
According to the element molar ratio in predetermined product structural formula below, selecting the lithium carbonate of LITHIUM BATTERY and the cobaltosic oxide of LITHIUM BATTERY is raw material, and adds Nb
2o
5mix, by the above-mentioned material mixing sintering 10～12 hours at 1000～1100 ℃ of temperature, and through surface treatment, obtain highdensity compound lithium cobaltate one defective material, in above-mentioned compound lithium cobaltate one defective material, add coating material raw material, the present embodiment adds nickelous carbonate and manganese carbonate, mixes, further sintering 10～15 hours at 1000～1200 ℃, and through surface treatment, just can obtain compound lithium cobaltate cathode material, its structural formula is expressed as (LiCoO
2)
0.85(Ni
0.25nb
0.1mn
0.75o
2)
0.15.Lithium cobaltate cathode material particle crystal surface prepared by the present embodiment is Paint Gloss, even, and particle is monocrystalline, records compacted density and reaches 4.2g/cm
3, more than electrochemical discharge capacity reaches 172mAh/g, operating voltage is more than 4.45V.
Embodiment 4
According to the element molar ratio in predetermined product structural formula below, selecting the lithium carbonate of LITHIUM BATTERY and the cobaltosic oxide of LITHIUM BATTERY is raw material, and adds Nb
2o
5mix, by the above-mentioned material mixing sintering 8～10 hours at 1050～1100 ℃ of temperature, and through surface treatment, obtain highdensity compound lithium cobaltate one defective material, in above-mentioned compound lithium cobaltate one defective material, add coating material raw material, the present embodiment adds nickelous carbonate and manganese carbonate, mixes, further sintering 10～15 hours at 1000～1200 ℃, and through surface treatment, just can obtain compound lithium cobaltate cathode material, its structural formula is expressed as (LiCoO
2)
0.75(Ni
0.2nb
0.2mn
0.8o
2)
0.25.Lithium cobaltate cathode material particle crystal surface prepared by the present embodiment is Paint Gloss, even, and particle is monocrystalline, records compacted density and reaches 4.1g/cm
3, more than electrochemical discharge capacity reaches 166mAh/g, operating voltage is more than 4.4V.
Hence one can see that, and above-mentioned anode material for lithium-ion batteries adopts the cobalt acid lithium material of powdered granule, and by particle size is carried out to rational proportion mixing, making material volume compacted density is 4.0-4.2g/m
3, material capacity reaches 162-175mAh/g, and doped with transition elements niobium.According to test result, adopt the lithium ion battery of this positive electrode can normally work completely in the operating voltage range of 4.45V, for example, under the operating voltage of 4.45V or 4.49V, lithium ion battery outward appearance changes without inflatable.Therefore, by adopting above-mentioned positive electrode, adopt particle rational proportion and doped with transition elements niobium, improve battery capacity and charging/discharging voltage, can obtain high power capacity high-voltage lithium ion batteries.
It should be noted that; the present invention is not limited to above-mentioned execution mode, and according to creative spirit of the present invention, those skilled in the art can also make other variations; the variation that these are done according to creative spirit of the present invention, within all should being included in the present invention's scope required for protection.
Claims (10)
1. an anode material for lithium-ion batteries, it comprises the cobalt acid lithium material that is powdered granule, it is characterized in that, doped chemical niobium in described cobalt acid lithium material, the median particle diameter D of described cobalt acid lithium material
50for 16-20 micron, the volume compacted density of described cobalt acid lithium material is 4.0-4.2g/m
3, gram volume is 162 mAh/g-175mAh/g.
2. anode material for lithium-ion batteries as claimed in claim 1, is characterized in that, the content of described niobium is 1-20%.
3. anode material for lithium-ion batteries as claimed in claim 1, is characterized in that, the gram volume of described cobalt acid lithium material is 170 mAh/g-175mAh/g.
4. anode material for lithium-ion batteries as claimed in claim 1, is characterized in that, described cobalt acid lithium material also contains coating material, and the structural formula of described coating material is expressed as Ni
xmn
yo
z, wherein, 0.1≤x≤0.75,0.3≤y≤1.5, z is 2 or 4.
5. anode material for lithium-ion batteries as claimed in claim 4, is characterized in that, described cobalt acid lithium material structural formula is expressed as: [Ni
xnb
kmn
yo
z]
n(LiCoO
2)
1-n, wherein, 0.1≤x≤0.75,0.3≤y≤1.5,0<n≤0.35, z is 2 or 4,0.1≤k≤0.6.
6. a lithium ion battery, it comprises positive pole, negative pole, electrolyte and the barrier film between both positive and negative polarity, it is characterized in that, the active material of described positive pole is the anode material for lithium-ion batteries described in claim 1 to 5 any one, and described battery operated voltage is 4.35-4.5V.
7. lithium ion battery as claimed in claim 6, is characterized in that, described negative pole comprises the carbon coated graphite material that is powdered granule, and the median particle diameter of described negative material is D
50for 8-15 micron, volume compacted density is 1.6-1.8g/m
3.
8. lithium ion battery as claimed in claim 6, is characterized in that, the electrolytic salt of described electrolyte is LiPF
6, the solvent of described electrolyte comprises the ethylene carbonate of the composition of following mass percent: 30-35%, the methyl ethyl carbonate of the diethyl carbonate of 30-35%, 30-35%, the fluorinated ethylene carbonate of 5-8%, and the density of solvent at 25 ℃ is 1.00～1.30g/cm
3, the conductivity of solvent at 25 ℃ is 8-12s/cm.
9. lithium ion battery as claimed in claim 6, is characterized in that, it is the ceramic diaphragm of 9-16 micron that described barrier film adopts particle diameter, and described barrier film is two-sided respectively applies the SiO that a layer thickness is 2-4 micron
2, its hole gas rate is 42 ± 4%, under 120 ℃ and normality atmospheric pressure, and longitudinal contraction < 2%, cross-direction shrinkage < 1%.
10. lithium ion battery as claimed in claim 6, is characterized in that, described lithium ion battery operating voltage is 4.45-4.5V.
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| CN113597692A (en) * | 2019-04-26 | 2021-11-02 | 松下知识产权经营株式会社 | Positive electrode active material for secondary battery and secondary battery |
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| CN103050682A (en) * | 2012-12-24 | 2013-04-17 | 北京理工大学 | Sodium ion battery electrode material and preparation method thereof |
| CN103236541A (en) * | 2013-04-12 | 2013-08-07 | 中信国安盟固利电源技术有限公司 | Method for improving storage performance of lithium cobalt oxide at high voltage and high temperature |
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| CN103682326A (en) * | 2013-12-13 | 2014-03-26 | 南通瑞翔新材料有限公司 | High-capacity lithium cobalt oxide-base lithium ion battery anode material and preparation method thereof |
| CN103647074A (en) * | 2013-12-25 | 2014-03-19 | 西安物华新能源科技有限公司 | High-rate type lithium cobaltate and preparation method thereof |
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| CN113597692A (en) * | 2019-04-26 | 2021-11-02 | 松下知识产权经营株式会社 | Positive electrode active material for secondary battery and secondary battery |
| CN113597692B (en) * | 2019-04-26 | 2024-01-05 | 松下知识产权经营株式会社 | Positive electrode active material for secondary battery and secondary battery |
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