CN1665052B - Lithium cobalt dioxide, preparing method thereof and non-aqueous electrolyte secondary battery - Google Patents
Lithium cobalt dioxide, preparing method thereof and non-aqueous electrolyte secondary battery Download PDFInfo
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- CN1665052B CN1665052B CN2004100077315A CN200410007731A CN1665052B CN 1665052 B CN1665052 B CN 1665052B CN 2004100077315 A CN2004100077315 A CN 2004100077315A CN 200410007731 A CN200410007731 A CN 200410007731A CN 1665052 B CN1665052 B CN 1665052B
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- acid lithium
- cobalt acid
- lithium
- cobalt
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- 238000000034 method Methods 0.000 title abstract description 6
- 239000011255 nonaqueous electrolyte Substances 0.000 title description 4
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 title 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 296
- 229910052744 lithium Inorganic materials 0.000 claims description 258
- 229910017052 cobalt Inorganic materials 0.000 claims description 248
- 239000010941 cobalt Substances 0.000 claims description 248
- 239000002253 acid Substances 0.000 claims description 243
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 237
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- 239000002245 particle Substances 0.000 claims description 59
- 238000007596 consolidation process Methods 0.000 claims description 53
- 239000007774 positive electrode material Substances 0.000 claims description 30
- 150000001875 compounds Chemical class 0.000 claims description 13
- 229910018871 CoO 2 Inorganic materials 0.000 claims description 8
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 abstract description 11
- 238000002156 mixing Methods 0.000 abstract description 3
- 229910032387 LiCoO2 Inorganic materials 0.000 abstract 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 1
- 235000013495 cobalt Nutrition 0.000 description 181
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- 230000000052 comparative effect Effects 0.000 description 27
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Classifications
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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
-
- 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
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- 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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a LiCoO2 with excellent initial capacity and capacity retaining ratio for non-water electrolyte secondary battery, and a preparing method thereof. The stacking density of LiCoO2 is above 1.8g/cu cm and the pressed density is 3.5-4.0g/cu cm. The mixing the LiCoO2 with a stacking density of 1.7-3.0g/cu cm with the one with a stacking density of 1.0-2.0g/cu cm to make the difference of stacking densities between them is above 0.20g/cu cm.
Description
Technical field
The present invention relates to cobalt acid lithium, its preparation method and be equipped with the rechargeable nonaqueous electrolytic battery of described cobalt acid lithium as the positive plate of positive active material.
Background technology
In recent years, be accompanied by the lighting of household electrical appliance, the fast development of battery, the rechargeable nonaqueous electrolytic batteries such as lithium rechargeable battery are employed as the power supply of the compact electric apparatus such as portable minisize personal computer, mobile phone, video tape recorder.
About described lithium rechargeable battery, because cobalt acid lithium can be as the positive active material of lithium rechargeable battery, so, the research that relates to the lithium based composite oxide obtains meeting the Bohai Sea development, before this, as positive active material, about compounds such as cobalt acid lithium, lithium nickelate, LiMn2O4s multiple motion is arranged.
For these positive active materials, the various motions of its performance have been improved, as its important condition, to apparent density and add percent consolidation etc. and disclose multiple technologies.
For example, the scheme that has proposes, and is calcined the granular composition that consists of containing the different initiation material more than 2 kinds of average grain diameter, makes Li
PMO
2Bulk density be 2.65g/cm
3Above positive active material (for example, with reference to Patent Document 1).
In addition, adopting with LiCoO
2In the positive electrode active material for nonaqueous electrolyte secondary battery of the cobalt acid lithium of expression, described cobalt acid lithium is that 0.1～4 μ m, average grain diameter are the one-level particle of the little crystallization below the 2 μ m with Off エ レ one footpath of the projecting figure that SEM observes, be to be gathered into spherical or oval spherical secondary particle and to be consisted of by a plurality of, the bulk density of described cobalt acid lithium is 2.2g/cm
3The existing people of above nonaqueous electrolytic secondary battery anode active compound proposes (for example, with reference to Patent Document 2).
In addition, existing people proposes to adopt following cobalt acid lithium as the nonaqueous electrolytic secondary battery anode active compound: it is in fact by with LiCoO
2The secondary particle that a plurality of small one-level particle of the cobalt acid lithium of expression is gathered into consists of, and a plurality of slight gap that can soak into electrolyte are arranged in this secondary particle, and bulk density is 2.2g/cm
3More than (for example, with reference to Patent Document 3).
[Patent Document 1] JP 2001-85009 communique (the 1st page)
[Patent Document 2] JP 2001-135313 communique (the 1st page)
[Patent Document 3] JP 2001-155729 communique (the 1st page)
Summary of the invention
Yet positive active material adopts the rechargeable nonaqueous electrolytic battery of above-mentioned cobalt acid lithium also not satisfy simultaneously discharge capacity and fast charging and discharging performance now, therefore, carries out various tests.For example, to particle diameter and shape of particle by change cobalt acid lithium, the raising electrode density improves battery capacity thus or fast charging and discharging performance is tested, but not yet obtains sufficient result.
Problem in view of above-mentioned prior art the objective of the invention is: provide a kind of have good powder property, electrode density high, can obtain good cobalt acid lithium, its preparation method of large discharge capacity and fast charging and discharging performance when in battery, using and adopt its rechargeable nonaqueous electrolytic battery.
The inventor finds, when adopting the lithium composite xoide particle as positive active material, be not only the particle properties of lithium composite xoide, and have the lithium composite xoide particle of different-grain diameter by cooperation, can bring into play to greatest extent the characteristic that this particle has, thereby finish the present invention.
That is, the present invention relates to following cobalt acid lithium, it is characterized in that bulk density is 1.8g/cm
3Or more than, and to add percent consolidation be 3.5～4.0g/cm
3
In addition, the mixture formation of the cobalt acid lithium (B) that cobalt of the present invention acid lithium is preferably assembled by the monodispersed cobalt acid lithium (A) of one-level particle and one-level particle, the bulk density of this mixture is 1.8g/cm
3Or more than, and to add percent consolidation be 3.5～4.0g/cm
3
In addition, the present invention relates to following cobalt acid lithium preparation method, it is characterized in that, is bulk density 1.7～3.0g/cm
3Cobalt acid lithium (A) and bulk density be 1.0～2.0g/cm
3Cobalt acid lithium (B) mixed, making the difference of the bulk density of above-mentioned cobalt acid lithium (A) and the sour lithium of above-mentioned cobalt (B) is 0.20g/cm
3Or more than.
Preferred above-mentioned cobalt acid lithium (A) and the sour lithium of cobalt (B) are with weight ratio (A): (B)=and 95: 5～60: 40 ratio mixed.
Above-mentioned cobalt acid lithium (A) preferably adopts the one-level particle monodispersed, and above-mentioned cobalt acid lithium (B) preferably adopts the one-level particle to assemble.
The average grain diameter of preferred above-mentioned cobalt acid lithium (A) is 5～30 μ m, and the average grain diameter of above-mentioned cobalt acid lithium (B) is 0.1～10 μ m.
In addition, the present invention relates to following rechargeable nonaqueous electrolytic battery, it is characterized in that, have the positive plate that consists of as positive active material with above-mentioned cobalt acid lithium.
The accompanying drawing summary
Fig. 1 represents the SEM photo (multiplication factor * 3000) of neat monodispersed cobalt acid lithium (A) particle structure of the one-level particle of preparation example 1.
Fig. 2 represents the SEM photo (multiplication factor * 3000) of cobalt acid lithium (B) particle structure that the one-level particle of preparation example 7 is assembled.
Fig. 3 adopts the cobalt acid lithium of embodiment 2 and comparative example 1 as the secondary cell safety evaluatio figure of positive active material.
Fig. 4 adopts the cobalt acid lithium of embodiment 2 and comparative example 1 as the fast charging and discharging result of the test figure of the secondary cell of positive active material.
The working of an invention scheme
The below is described more specifically the present invention.
Cobalt acid lithium of the present invention is characterised in that bulk density is 1.8g/cm
3Or more than, and to add percent consolidation be 3.5～4.0g/cm
3
Described cobalt acid lithium is by from the Li with general formula (1)
aCoO
2At least 2 kinds the mixture of selecting in the compound of (a represents the number in 0.2≤a≤1.2 scopes in the formula) expression consists of, perhaps, and by the Li with general formula (1)
aCoO
2The compound of expression and with the Li of general formula (2)
aCo
1-yM
yO
2-z(to represent to be selected from transition metal except Co or atomic number be at least a kind of element in the element more than 9 or 9 to M to the compound of expression in the formula, a represents the number in 0.2≤a≤1.2 scopes, y represents the number in 0＜y≤0.4 scope, z represents the number in 0≤z≤1.0 scopes) mixture consist of.
Particularly, Li
aCoO
2Or Li
aCoO
2In a part of Co also available other metallic elements (M) replace.The metallic element (M) that replaces can be that to be selected from transition metal except Co or atomic number be at least a kind of element in the element more than 9 or 9, for example is selected from least a kind among Na, Mg, Al, Ca, Ti, V, Cr, Mn, Fe, Ni, Zn, Si, Ga, Zr, Nb, W, the Mo.
In addition, at Li
aCoO
2Or Li
aCoO
2But in also coating sulfate of the cobalt acid lithium surface that replaces with other metallic elements of a part of Co.
Usually, the powder filling characteristic that bulk density represents not pressurize especially, coarse grain and particulate mix naturally.The pressurization density characteristic how lower coarse grain and particulate fill that represents to pressurize.The present invention finds, with cobalt acid lithium during as the positive active material of rechargeable nonaqueous electrolytic battery, and bulk density and to add the cobalt acid lithium of percent consolidation in particular range be important.
That is, the bulk density of cobalt acid lithium of the present invention is 1.8g/cm
3More than, be preferably 2.0g/cm
3More than, 2.5～3.5g/cm more preferably
3
In addition, the percent consolidation that adds of cobalt acid lithium of the present invention is 3.5～4.0g/cm
3, preferred 3.6～4.0g/cm
3, more preferably 3.7～4.0g/cm
3
Cobalt of the present invention acid lithium is in value in the above-mentioned particular range by making bulk density and adding percent consolidation, has the good characteristic as positive active material.
Below, the preparation method of cobalt of the present invention acid lithium is illustrated.
The preparation method of cobalt of the present invention acid lithium is that 2 kinds or multiple cobalt acid lithiums that bulk density is different mix by dry type and make.
Specifically, cobalt acid lithium preparation method of the present invention is characterised in that, is bulk density 1.7～3.0g/cm
3Cobalt acid lithium (A) and bulk density be 1.0～2.0g/cm
3Cobalt acid lithium (B) is selected to mix, make the difference of the bulk density of above-mentioned cobalt acid lithium (A) and the sour lithium of above-mentioned cobalt (B) reach 0.20g/cm
3More than.
The mixing ratio of above-mentioned cobalt acid lithium (A) and cobalt acid lithium (B) is (A) by weight: (B)=95: 5～60: 40, preferred 90: 10～80: 20.
The bulk density of cobalt acid lithium (A) is 1.7～3.0g/cm
3, preferred 2.0～3.0g/cm
3
The bulk density of cobalt acid lithium (B) is 1.2～2.0g/cm
3, preferred 1.0～1.7g/cm
3
These cobalt acid lithiums (A) preferably use the different material of bulk density with cobalt acid lithium (B), and the bulk density of these cobalt acid lithiums (A) and cobalt acid lithium (B) is poor to be more than 0.20, preferred more than 0.30.
In addition, the preferred one-level particle of cobalt acid lithium (A) is monodispersed.So-called one-level particle list disperses to refer to respectively zero scattered loose existence of smallest particles, and concrete available SEM (scanning electron microscope) takes a picture to observe and confirmed.At the single dispersion powders more than 80% in the SEM visual field as single dispersion powders.Fig. 1 illustrates the SEM photo (multiplication factor * 3000) of neat monodispersed cobalt acid lithium (A) particle structure of one-level particle of preparation example 1.
The average grain diameter of described cobalt acid lithium (A) is 5～30 μ m, the scope of preferred 10～20 μ m.Compare with cobalt acid lithium (B), cobalt acid lithium (A) is corase particles.
In addition, cobalt acid lithium (B) is preferably formed the cobalt acid lithium of secondary particle by the gathering of one-level particle.So-called one-level particle is assembled and is formed secondary particle, means that smallest particles assembles by the attraction of Van der Waals for and surface charge power, forms the state of shape of particle, and concrete available SEM takes a picture to observe and confirmed.The powder of being assembled more than 80% in the SEM visual field is also referred to as the powder of gathering.Fig. 2 illustrates the SEM photo (multiplication factor * 3000) of cobalt acid lithium (B) particle structure that the one-level particle of preparation example 5 assembles.
The average grain diameter of described cobalt acid lithium (B) is 0.1～10 μ m, the scope of preferred 2.0～8.0 μ m.
Average grain diameter among the present invention represents the accumulation 50% (D of the particle size distribution that obtains with the laser light scattering particle size distribution device
50) value.
In the present invention, the cobalt acid lithium that the cobalt acid lithium (B) that the one-level particle is gathered into and monodispersed cobalt acid lithium (A) are mixed into shows good battery behavior during as positive grade of active material of rechargeable nonaqueous electrolytic battery.Its reason is indefinite, but this particles mixture not only improves the packed density on the positive plate, and aggregate particles is given good fast charging and discharging, and monodisperse particle is given safe characteristic.
In addition, among the preparation method of the present invention, described cobalt acid lithium (A) adopts the Li with general formula (1)
aCoO
2(a represents the number in 0.2≤a≤1.2 scopes in the formula) compound of expression is preferred.In addition, described cobalt acid lithium (B) adopts with the compound of above-mentioned general formula (1) expression or with the Li of general formula (2)
aCo
1-yM
yO
2-z(to represent to be selected from transition metal except Co or atomic number be at least a kind of element in the element more than 9 to M in the formula, a represents the number in 0.2≤a≤1.2 scopes, y represents the number in 0＜y≤0.4 scope, and z represents the number in 0≤z≤1.0 scopes) compound of expression is preferred.
Cobalt of the present invention acid lithium can be by evenly being mixed to get the cobalt acid lithium that has different stacking densities and average grain diameter more than 2 kinds or 2 kinds, mixed uniformly method so long as the industrial method that can implement can and not be particularly limited.For example, can enumerate container rotary mixers such as adopting horizontal circle tubular, V-arrangement, dual cone shape, with shape, flat spin shape, oar shape, perpendicular with shape, mill shape, wandering star sports, static mixer, single shaft roll forming, enjoy the She Er mixer, the fixing method of shape mixer etc. of the containers such as the jet mixer that flows.
Rechargeable nonaqueous electrolytic battery of the present invention is by formations such as positive pole, negative pole, dividing plate, nonaqueous electrolytes (electrolyte that for example, contains lithium salts).
Positive pole contains the anode mixture that positive active material, conductive agent and adhesive consist of in positive plate (positive electrode collector: for example aluminium sheet) coating to be made.Rechargeable nonaqueous electrolytic battery of the present invention uses the positive active material that is made of above-mentioned cobalt acid lithium as the positive active material that consists of positive plate.Also have, do not prepare in advance positive active material, can when the preparation anode mixture, the cobalt acid lithium of the present invention of the formation that satisfies the positive active material condition be cooperated, evenly mix.
In the anode mixture, except positive active material, also can add conductive agent, adhesive and filler etc.
As conductive agent, such as adopting one kind or two or more in the metal powder conductive materials such as being selected from native graphite (flaky graphite, flaky graphite, amorphous graphite etc.), Delanium, carbon black, alkynes are black, carbon fiber, nickel powder.Wherein, graphite and alkynes are black and to be used as conductive agent be preferred.Also have, the use level of conductive agent in anode mixture is 1～50 % by weight, preferably in the scope of 2～30 % by weight.
In addition; as adhesive; for example, can use polysaccharide, the thermoplastic resins such as polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, regenerated cellulose, diacetyl cellulose, PVP, ethylene-propylene-diene terpolymer (EPDM), sulfonated epdm, styrene butadiene ribber, fluorubber, poly(ethylene oxide), have a kind in the polymer etc. of caoutchouc elasticity or more than 2 clocks.The use level of adhesive in anode mixture is preferred in the scope of 2～30 % by weight.
In addition, filler is not so long as cause any of fibrous material of chemical change and all can adopt in rechargeable nonaqueous electrolytic battery, but usually adopt polypropylene, the fibers such as olefin polymer, glass fibre, carbon fiber such as polyethylene.The use level of filler in anode mixture is not particularly limited, but the scope of preferred 0～30 % by weight.
Also have, the use level of positive active material in anode mixture that cobalt acid lithium of the present invention consists of is not particularly limited, but preferred 60～95 % by weight, in the scope particularly preferably in 70～94 % by weight.
The negative material used to non-aqueous electrolyte secondary cell negative electrode of the present invention is not particularly limited, and for example, can enumerate carbonaceous material, composite oxide of metal, lithium metal or lithium alloy etc.Carbonaceous material can be enumerated and be difficult to graphited carbonaceous material, graphite-like carbonaceous material etc.Composite oxide of metal can be enumerated SnM
1 1-xM
2 yO
z(in the formula, M
1Expression is selected from the element more than a kind or a kind among Mn, Fe, Pb or the Ge, M
2Expression is selected from element more than 2 kinds or 2 kinds in Al, B, P, Si, periodic table the 1st family, the 2nd family, the 3rd family or the halogen element, and x represents the number in 0＜x≤1 scope, and y represents the number in 1≤y≤3 scopes, and z represents the number in 1≤z≤8 scopes) etc. compound.
In addition, used nonaqueous electrolytic solution in the rechargeable nonaqueous electrolytic battery, for example, by propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, gamma-butyrolacton, 1, the 2-dimethoxy-ethane, oxolane, the 2-methyltetrahydrofuran, methyl-sulfoxide, 1,3-dioxa penta ring, formamide, dimethyl formamide, dioxa penta ring, acetonitrile, nitromethane, methyl formate, methyl acetate, phosphotriester, trimethoxy-methane, dioxa penta ring derivatives, sulfolane, 3-methyl-2-oxazolidone (オ キ サ ゾ ジ ノ Application), the polypropylene carbonate ester derivant, tetrahydrofuran derivatives, ether, 1, the mixed solvent more than at least a kind of the non-proton organic solvents such as 3-プ ロ パ Application サ Le ト Application and, be dissolved in the lithium salts in this solvent, for example LiClO
4, LiBF
4, LiPF
6, LiCF
3SO
3, LiCF
3CO
2, LiAsF
6, LiSbF
6, LiB
10Cl
10, LiAlCl
4, the lithium salts more than a kind or a kind such as chloroborane lithium, lower aliphatic carboxylic acid lithium, tetraphenyl lithium borate consists of.
In addition, except non-aqueous solution electrolysis liquid, can also adopt organic solid electrolyte based.For example, can enumerate polythene derivative or contain its polymer, poly propylene oxide derivative or contain its polymer, phosphate ester polymer etc.
The collector body of electrode is not so long as cause the electric conductor of chemical change and can and not be particularly limited that stainless steel, nickel, aluminium, titanium, burnt carbon, aluminium or stainless steel surfaces carried out the surface-treated product through carbon, nickel, copper, titanium or silver but positive pole for example can adopt in the rechargeable nonaqueous electrolytic battery that consists of.Negative pole can also adopt copper or stainless steel surfaces to carry out surface-treated product, Al-Cd alloy etc. through carbon, nickel, titanium or silver etc. except adopting such as stainless steel, nickel, copper, titanium, aluminium, the burnt carbon etc.
The shape of rechargeable nonaqueous electrolytic battery can adopt coin-shaped, button-type, sheet shape, cylindrical shape, square etc. any.
The purposes of rechargeable nonaqueous electrolytic battery of the present invention is not particularly limited, for example, can enumerate the electrical equipment such as notebook computer, portable minisize personal computer, pocket word processor, mobile phone, radio telephone, portable CD, radio receiver, the civil electric appliances such as automobile, electric car, game machine etc.
Embodiment
The below provides embodiment, is described more specifically the present invention.
By embodiment positive active material of the present invention and rechargeable nonaqueous electrolytic battery are described.
(1) assay method of bulk density
The graduated cylinder bone dry, measure the weight of empty graduated cylinder.Taking by weighing the about 70g of sample is placed on the charta.With funnel sample is moved in the graduated cylinder.Graduated cylinder is fixed on (ュ ァ サ ァ ィ ォ ニ Network ス (strain) preparation on the automatic TD determinator, デ ュ ァ Le ォ one ト タ ッ プ), be adjusted to 500 rapping (タ ッ ピ Application ダ) number of times, rap, read the scale of sample face, mensuration has been put into the graduated cylinder weight of sample, calculates bulk density.Rap height 3.2mm, rap speed 200 times/minute (according to ASTM:B527-93,85).
(2) add the assay method of percent consolidation
In the metal die of diameter 15mm, put into sample, with 1.96 * 10
8(2 tons/cm of Pa
2) (shape number: WPN-10) pressurization is 1 minute, makes bead for Ha Application De プ レ ス, Japan merchant worker society preparation for forcing press.Then, measure weight and the volume of bead, calculate bead density as adding percent consolidation.
Preparation example 1
Weighing lithium carbonate and cobalt oxide make the Li/Co atomic ratio reach 1.02, fully mix in mortar, make uniform mixture.Then, this mixture is put into alumina crucible, place electric furnace to heat up at atmosphere, keep carrying out in 10 hours calcination processing 700 ℃～1000 ℃ temperature, the calcined material that obtains is pulverized after cooling off in atmosphere, classification, and obtaining average grain diameter is that 15.5 μ m, bulk density are 2.80g/cm
3, to add percent consolidation be 3.45g/cm
3Cobalt acid lithium (LiCoO
2).
This cobalt acid lithium is the neat monodispersed cobalt acid lithium (A-1) of one-level particle.
Preparation example 2
Same with preparation example 1, lithium carbonate and cobalt oxide are mixed, make the Li/Co atomic ratio reach 1.04, make uniform mixture, carried out calcination processing 10 hours 1000 ℃～1050 ℃ temperature, obtaining average grain diameter is that 12.3 μ m, bulk density are 2.50g/cm
3, to add percent consolidation be 3.48g/cm
3Cobalt acid lithium (LiCoO
2).
The SEM image of this cobalt acid lithium is the neat monodispersed cobalt acid lithium (A-2) of one-level particle.
Preparation example 3
Same with preparation example 1, lithium carbonate and cobalt oxide are mixed, make the Li/Co atomic ratio reach 1.02, make uniform mixture, carried out calcination processing 10 hours 1000 ℃～1050 ℃ temperature, obtaining average grain diameter is that 7.8 μ m, bulk density are 1.90g/cm
3, to add percent consolidation be 3.41g/cm
3Cobalt acid lithium.
This cobalt acid lithium is the neat monodispersed cobalt acid lithium (A-3) of one-level particle.
Preparation example 4
Same with preparation example 1, lithium carbonate and cobalt oxide are mixed, make the Li/Co atomic ratio reach 1.00, make uniform mixture, carried out calcination processing 10 hours 900 ℃～1000 ℃ temperature, obtaining average grain diameter is that 7.4 μ m, bulk density are 1.80g/cm3
,Adding percent consolidation is 3.20g/cm
3Cobalt acid lithium (LiCoO
2).
This cobalt acid lithium is the cobalt acid lithium (B-1) that the one-level particle is assembled.
Preparation example 5
Same with preparation example 1, lithium carbonate and cobalt oxide are mixed, make the Li/Co atomic ratio reach 1.00, make uniform mixture, carried out calcination processing 10 hours 900 ℃～1000 ℃ temperature, obtaining average grain diameter is that 5.2 μ m, bulk density are 1.50g/cm
3, to add percent consolidation be 3.15g/cm
3Cobalt acid lithium (LiCoO
2).
This cobalt acid lithium is the cobalt acid lithium (B-2) that the one-level particle is assembled.
Preparation example 6
Same with preparation example 1, lithium carbonate and cobalt oxide are mixed, make the Li/Co atomic ratio reach 1.00, make uniform mixture, carried out calcination processing 10 hours 800 ℃～900 ℃ temperature, obtaining average grain diameter is that 3.2 μ m, bulk density are 1.20g/cm
3, to add percent consolidation be 3.21g/cm
3Cobalt acid lithium (LiCoO
2).
The SEM image of this cobalt acid lithium is the cobalt acid lithium (B-3) that the one-level particle is assembled.
Preparation example 7
Adopt the method same with preparation example 1, Co is added 2 % by mole Al, synthetic LiCo
0.98Al
0.02O
2Method for calcinating and preparation example 1 are same, when mortar mixes, mix making Al (OH)
3Co reaches 2 % by mole relatively, calcines 800 ℃～900 ℃ temperature, obtains cobalt acid lithium (LiCo
0.98Al
0.02O
2).
The average grain diameter of this cobalt acid lithium is that 2.8 μ m, bulk density are 1.18g/cm
3, to add percent consolidation be 3.19g/cm
3
The SEM image of this cobalt acid lithium is the cobalt acid lithium (B-4) that the one-level particle is assembled.
Fig. 1 is the SEM photo (multiplication factor * 3000) of neat monodispersed cobalt acid lithium (A) particle structure of the one-level particle of expression preparation example 1.
Fig. 2 is the SEM photo (multiplication factor * 3000) of gathering cobalt acid lithium (B) particle structure of expression preparation example 7.
The cobalt that obtains in the above-mentioned preparation example 1～7 acid lithium (A) and cobalt acid lithium (B) gather and are shown in table 1.
Table 1
(A) expression cobalt acid lithium (A) in (notes) table, (B) expression cobalt acid lithium (B).
The percent consolidation that adds of the cobalt acid lithium (A) among the present invention is 3.3～3.7g/cm
3, preferred 3.5～3.7g/cm
3In addition, the percent consolidation that adds of the acid lithium of the cobalt among the present invention (B) is 3.1～3.5g/cm
3, preferred 3.1～3.3g/cm
3
Cobalt acid lithium (A) among the present invention and the pressurization density contrast of cobalt acid lithium (B) are 0.2g/cm
3More than, preferred 0.8～1.5g/cm
3
Embodiment 1
Be the average grain diameter that obtains in the preparation example 1 that 15.5 μ m, bulk density are 2.80g/cm
3Cobalt acid lithium (A-1) 95 weight portions and preparation example 6 in the average grain diameter that obtains be that 3.2 μ m, bulk density are 1.20g/cm
3Cobalt acid lithium (B-3) 5 weight portions, evenly be mixed with the sour lithium of cobalt with the miniature belt type mixer.The average grain diameter of resulting cobalt acid lithium is that 15.0 μ m, bulk density are 2.75g/cm
3, to add percent consolidation be 3.65g/cm
3
Be the average grain diameter that obtains in the preparation example 1 that 15.5 μ m, bulk density are 2.80g/cm
3Cobalt acid lithium (A-1) 70 weight portions and preparation example 6 in the average grain diameter that obtains be that 3.2 μ m, bulk density are 1.20g/cm
3Cobalt acid lithium (B-3) 30 weight portions evenly be mixed with cobalt acid lithium.The average grain diameter of resulting cobalt acid lithium is that 11.9 μ m, bulk density are 2.40g/cm
3, to add percent consolidation be 3.92g/cm
3
Be the average grain diameter that obtains in the preparation example 1 that 15.5 μ m, bulk density are 2.80g/cm
3Cobalt acid lithium (A-1) 70 weight portions and preparation example 5 in the average grain diameter that obtains be that 5.2 μ m, bulk density are 1.50g/cm
3Cobalt acid lithium (B-2) 30 weight portions evenly be mixed with cobalt acid lithium.The average grain diameter of resulting cobalt acid lithium is that 12.8 μ m, bulk density are 2.53g/cm
3, to add percent consolidation be 3.82g/cm
3
Be the average grain diameter that obtains in the preparation example 2 that 12.3 μ m, bulk density are 2.50g/cm
3Cobalt acid lithium (A-2) 80 weight portions and preparation example 5 in the average grain diameter that obtains be that 5.2 μ m, bulk density are 1.50g/cm
3Cobalt acid lithium (B-2) 20 weight portions evenly be mixed with cobalt acid lithium.The average grain diameter of resulting cobalt acid lithium is that 10.5 μ m, bulk density are 2.40g/cm
3, to add percent consolidation be 3.75g/cm
3
Embodiment 5
Be the average grain diameter that obtains in the preparation example 2 that 12.3 μ m, bulk density are 2.50g/cm
3Cobalt acid lithium (A-2) 60 weight portions and preparation example 4 in the average grain diameter that obtains be that 7.4 μ m, bulk density are 1.80g/cm
3Cobalt acid lithium (B-1) 40 weight portions evenly be mixed with cobalt acid lithium.The average grain diameter of resulting cobalt acid lithium is that 10.1 μ m, bulk density are 2.35g/cm
3, to add percent consolidation be 3.65g/cm
3
Embodiment 6
Be the average grain diameter that obtains in the preparation example 3 that 7.8 μ m, bulk density are 1.90g/cm
3Cobalt acid lithium (A-3) 85 weight portions and preparation example 6 in the average grain diameter that obtains be that 3.2 μ m, bulk density are 1.20g/cm
3Cobalt acid lithium (B-3) 15 weight portions evenly be mixed with cobalt acid lithium.The average grain diameter of resulting cobalt acid lithium is that 7.0 μ m, bulk density are 1.83g/cm
3, to add percent consolidation be 3.55g/cm
3
Embodiment 7
Be the average grain diameter that obtains in the preparation example 1 that 15.5 μ m, bulk density are 2.80g/cm
3Cobalt acid lithium (A-1) 60 weight portions and preparation example 6 in the average grain diameter that obtains be that 3.2 μ m, bulk density are 1.20g/cm
3Cobalt acid lithium (B-3) 40 weight portions evenly be mixed with cobalt acid lithium.The average grain diameter of resulting cobalt acid lithium is that 7.8 μ m, bulk density are 1.88g/cm
3, to add percent consolidation be 3.50g/cm
3
Embodiment 8
Be the average grain diameter that obtains in the preparation example 1 that 15.5 μ m, bulk density are 2.80g/cm
3Cobalt acid lithium (A-1) 70 weight portions and preparation example 7 in the average grain diameter that obtains be that 2.8 μ m, bulk density are 1.18g/cm
3Interpolation the cobalt acid lithium (LiCo of Al
0.98Al
0.02O
2) (B-4) 30 weight portions evenly be mixed with cobalt acid lithium.The average grain diameter of resulting cobalt acid lithium is that 7.7 μ m, bulk density are 2.38g/cm
3, to add percent consolidation be 3.89g/cm
3
Embodiment 9
Be the average grain diameter that obtains in the preparation example 1 that 15.5 μ m, bulk density are 2.80g/cm
3Cobalt acid lithium (A-1) 90 weight portions and preparation example 6 in the average grain diameter that obtains be that 3.2 μ m, bulk density are 1.20g/cm
3Cobalt acid lithium (B-3) 10 weight portions evenly be mixed with cobalt acid lithium.The average grain diameter of resulting cobalt acid lithium is that 13.8 μ m, bulk density are 2.65g/cm
3, to add percent consolidation be 3.72g/cm
3
Embodiment 10
Be the average grain diameter that obtains in the preparation example 1 that 15.5 μ m, bulk density are 2.80g/cm
3Cobalt acid lithium (A-1) 90 weight portions and preparation example 4 in the average grain diameter that obtains be that 7.4 μ m, bulk density are 1.80g/cm
3Cobalt acid lithium (B-1) 10 weight portions evenly be mixed with cobalt acid lithium.The average grain diameter of resulting cobalt acid lithium is that 14.8 μ m, bulk density are 2.70g/cm
3, to add percent consolidation be 3.60g/cm
3
Embodiment 11
Be the average grain diameter that obtains in the preparation example 1 that 15.5 μ m, bulk density are 2.80g/cm
3Cobalt acid lithium (A-1) 80 weight portions and preparation example 6 in the average grain diameter 3.2 μ m, the bulk density that obtain be 1.20g/cm
3Cobalt acid lithium (B-3) 20 weight portions evenly be mixed with cobalt acid lithium.The average grain diameter of resulting cobalt acid lithium is that 13.2 μ m, bulk density are 2.85g/cm
3, to add percent consolidation be 3.74g/cm
3
Embodiment 12
Be the average grain diameter that obtains in the preparation example 1 that 15.5 μ m, bulk density are 2.80g/cm
3Cobalt acid lithium (A-1) 80 weight portions and preparation example 4 in the average grain diameter that obtains be that 7.4 μ m, bulk density are 1.80g/cm
3Cobalt acid lithium (B-1) 20 weight portions evenly be mixed with cobalt acid lithium.The average grain diameter of resulting cobalt acid lithium is that 13.8 μ m, bulk density are 2.62g/cm
3, to add percent consolidation be 3.58g/cm
3
In above-described embodiment 1～12 cobalt acid lithium (A), (B) being mixed resulting cobalt acid lithium gathers and is shown in table 2 and table 3.
Table 2
| (A) bulk density (g/cm 3) | (B) bulk density (g/cm 3) | Bulk density (g/cm 3) | Mix proportion A: B | Hybrid density (g/cm 3) | Average grain diameter (μ m) | |
| Embodiment 1 | 2.80 (A-1) | 1.20 (B-3) | 1.60 | 95∶5 | 2.75 | 15.0 |
| Embodiment 2 | 2.80 (A-1) | 1.20 (B-3) | 1.60 | 70∶30 | 2.40 | 11.9 |
| Embodiment 3 | 2.80 (A-1) | 1.50 (B-2) | 1.30 | 70∶30 | 2.53 | 12.8 |
| Embodiment 4 | 2.50 (A-2) | 1.50 (B-2) | 1.00 | 80∶20 | 2.40 | 10.5 |
| Embodiment 5 | 2.50 (A-2) | 1.80 (B-1) | 0.70 | 60∶40 | 2.35 | 10.1 |
| Embodiment 6 | 1.90 (A-3) | 1.20 (B-3) | 0.70 | 85∶15 | 1.83 | 7.0 |
| Embodiment 7 | 2.80 (A-1) | 1.20 (B-3) | 1.60 | 60∶40 | 1.88 | 7.8 |
| Embodiment 8 | 2.80 (A-1) | 1.18 (B-4) | 1.62 | 70∶30 | 2.38 | 7.7 |
| Embodiment 9 | 2.80 (A-1) | 1.20 (B-3) | 1.60 | 90∶10 | 2.65 | 13.8 |
| Embodiment 10 | 2.80 (A-1) | 1.80 (B-1) | 1.00 | 90∶10 | 2.70 | 14.8 |
| Embodiment 11 | 2.80 (A-1) | 1.20 (B-3) | 1.60 | 80∶20 | 2.58 | 13.2 |
| Embodiment 12 | 2.80 (A-1) | 1.80 (B-1) | 1.00 | 80∶20 | 2.62 | 13.8 |
Table 3
| (A) add percent consolidation (g/cm 3) | (B) add percent consolidation (g/cm 3) | Pressurization density contrast (g/cm 3) | Mix proportion A: B | Mix and add percent consolidation (g/cm 3) | Average grain diameter (μ m) | |
| Embodiment 1 | 3.45 (A-1) | 3.21 (B-3) | 0.24 | 95∶5 | 3.65 | 15.0 |
| Embodiment 2 | 3.45 (A-1) | 3.21 (B-3) | 0.24 | 70∶30 | 3.95 | 11.9 |
| Embodiment 3 | 3.45 (A-1) | 3.15 (B-2) | 0.30 | 70∶30 | 3.82 | 12.8 |
| Embodiment 4 | 3.48 (A-2) | 3.15 (B-2) | 0.33 | 80∶20 | 3.75 | 10.5 |
| Embodiment 5 | 3.48 (A-2) | 3.20 (B-1) | 0.28 | 60∶40 | 3.65 | 10.1 |
| Embodiment 6 | 3.41 (A-3) | 3.21 (B-3) | 0.20 | 85∶15 | 3.55 | 7.0 |
| Embodiment 7 | 3.45 (A-1) | 3.21 (B-3) | 0.24 | 60∶40 | 3.50 | 7.8 |
| Embodiment 8 | 3.45 (A-1) | 3.19 (B-4) | 0.26 | 70∶30 | 3.89 | 7.7 |
| Embodiment 9 | 3.45 (A-1) | 3.21 (B-3) | 0.24 | 90∶10 | 3.72 | 13.8 |
| Embodiment 10 | 3.45 (A-1) | 3.20 (B-1) | 0.25 | 90∶10 | 3.60 | 14.8 |
| Embodiment 11 | 3.45 (A-1) | 3.21 (B-3) | 0.24 | 80∶20 | 3.74 | 13.2 |
| Embodiment 12 | 3.45 (A-1) | 3.20 (B-1) | 0.25 | 80∶20 | 3.58 | 13.8 |
(A) expression cobalt acid lithium (A) in (notes) table, (B) expression cobalt acid lithium (B).
Comparative example 1
Be the average grain diameter that obtains in the preparation example 2 that 12.3 μ m, bulk density are 2.50g/cm
3, to add percent consolidation be 3.48g/cm
3Cobalt acid lithium (LiCoO
2) as a comparative example.
The SEM image of this cobalt acid lithium is the neat single cobalt acid lithium (A) that disperses of one-level particle.
The comparative example of the cobalt acid lithium that obtains during secondly, the mixing change of cobalt acid lithium (A) of the present invention and cobalt acid lithium (B) illustrates.
Preparation example 8 (relatively preparation example)
Lithium carbonate and cobalt oxide are mixed, make the Li/Co atomic ratio reach 1.00, make uniform mixture, keep carrying out in 10 hours calcination processing 1000 ℃～1050 ℃ temperature, the calcined material that obtains is pulverized in atmosphere, classification, and obtaining average grain diameter is that 4.5 μ m, bulk density are 1.60g/cm
3, to add percent consolidation be 3.25g/cm
3Cobalt acid lithium (LiCoO
2).
This cobalt acid lithium is the monodispersed cobalt acid of one-level particle lithium (C-1).
Preparation example 9 (relatively preparation example)
Lithium carbonate and cobalt oxide are mixed, make the Li/Co atomic ratio reach 1.00, make uniform mixture, keep carrying out in 10 hours calcination processing 800 ℃～850 ℃ temperature, the calcined material that obtains is pulverized in atmosphere, classification, and obtaining average grain diameter is that 11.0 μ m, bulk density are 2.20g/cm
3, to add percent consolidation be 3.30g/cm
3Cobalt acid lithium (LiCoO
2).
This cobalt acid lithium is the cobalt acid lithium (C-2) that the one-level particle is assembled.
Preparation example 10 (relatively preparation example)
Lithium carbonate and cobalt oxide are mixed, make the Li/Co atomic ratio reach 1.00, make uniform mixture, keep carrying out in 10 hours calcination processing 1000 ℃～1050 ℃ temperature, the calcined material that obtains is pulverized in atmosphere, classification, and obtaining average grain diameter is that 5.0 μ m, bulk density are 1.32g/cm
3, to add percent consolidation be 3.12g/cm
3Cobalt acid lithium (LiCoO
2).
This cobalt acid lithium is the monodispersed cobalt acid of one-level particle lithium (C-3).
Comparative example 2
Cobalt acid lithium (B-3) 20 weight portions that obtain in cobalt acid lithium (C-1) 80 weight portions that obtain in the preparation example 8 and the preparation example 6 evenly are mixed with cobalt acid lithium with the miniature belt type mixer.
The average grain diameter of the cobalt acid lithium that obtains is that 3.5 μ m, bulk density are 1.32g/cm
3, to add percent consolidation be 3.22g/cm
3
Comparative example 3
Cobalt acid lithium (B-3) 20 weight portions that obtain in cobalt acid lithium (C-2) 80 weight portions that obtain in the preparation example 9 and the preparation example 6 evenly are mixed with cobalt acid lithium with the miniature belt type mixer.
The average grain diameter of the cobalt acid lithium that obtains is that 11.2 μ m, bulk density are 2.15g/cm
3, to add percent consolidation be 3.45g/cm
3
Comparative example 4
Cobalt acid lithium (C-2) 20 weight portions that obtain in cobalt acid lithium (A-1) 80 weight portions that obtain in the preparation example 1 and the preparation example 9 evenly are mixed with cobalt acid lithium with the miniature belt type mixer.
The average grain diameter of the cobalt acid lithium that obtains is that 11.2 μ m, bulk density are 2.56g/cm
3, to add percent consolidation be 3.37g/cm
3
Comparative example 5
Cobalt acid lithium (C-3) 20 weight portions that obtain in cobalt acid lithium (A-1) 80 weight portions that obtain in the preparation example 1 and the preparation example 10 evenly are mixed with cobalt acid lithium with the miniature belt type mixer.
The average grain diameter of the cobalt acid lithium that obtains is that 13.4 μ m, bulk density are 2.62g/cm
3, to add percent consolidation be 3.40g/cm
3
Comparative example 6
Cobalt acid lithium (B-3) 50 weight portions that obtain in cobalt acid lithium (A-1) 50 weight portions that obtain in the preparation example 1 and the preparation example 6 evenly are mixed with cobalt acid lithium with the miniature belt type mixer.
The average grain diameter of the cobalt acid lithium that obtains is that 9.5 μ m, bulk density are 1.71g/cm
3, to add percent consolidation be 3.42g/cm
3
Table 4
Table 5
| (A) bulk density (g/cm 3) | (B) bulk density (g/cm 3) | Poor (the g/cm of bulk density 3) | Mix proportion A: B | Mixed-stacking density (g/cm 3) | Average grain diameter (μ m) | |
| Comparative example 1 | 2.50 (A-2) | - | - | 100 | 2.50 | 12.3 |
| Comparative example 2 | 1.60 (C-1) | 1.20 (B-3) | 0.40 | 80∶20 | 1.32 | 3.5 |
| Comparative example 3 | 2.20 (C-2) | 1.20 (B-3) | 1.00 | 80∶20 | 2.15 | 11.2 |
| Comparative example 4 | 2.80 (A-1) | 2.20 (C-2) | 0.60 | 80∶20 | 2.56 | 11.2 |
| Comparative example 5 | 2.80 (A-1) | 1.32 (C-3) | 1.48 | 80∶20 | 2.62 | 13.4 |
| Comparative example 6 | 2.80 (A-1) | 1.20 (B-3) | 1.60 | 50∶50 | 1.71 | 9.5 |
Table 6
| (A) add percent consolidation (g/cm 3) | (B) add percent consolidation (g/cm 3) | Pressurization density contrast (g/cm 3) | Mix proportion A: B | Mix and add percent consolidation (g/cm 3) | Average grain diameter (μ m) | |
| Comparative example 1 | 3.48 (A-2) | - | - | 100 | 3.48 | 12.3 |
| Comparative example 2 | 3.25 (C-1) | 3.21 (B-3) | 0.04 | 80∶20 | 3.22 | 3.5 |
| Comparative example 3 | 3.30 (C-2) | 3.21 (B-3) | 0.09 | 80∶20 | 3.45 | 11.2 |
| Comparative example 4 | 3.45 (A-1) | 3.30 (C-2) | 0.15 | 80∶20 | 3.37 | 11.2 |
| Comparative example 5 | 3.45 (A-1) | 3.12 (C-3) | 0.33 | 80∶20 | 3.40 | 13.4 |
| Comparative example 6 | 3.45 | 3.21 | 0.24 | 50∶50 | 3.42 | 9.5 |
| (A-1) | (B-3) |
The below provides and adopts cobalt acid lithium of the present invention as secondary cell safety evaluatio and the fast charging and discharging result of the test of positive active material.
Safety evaluatio
Adopt respectively the cobalt acid lithium (A) of the cobalt acid lithium of embodiment 2 and comparative example 1 as positive active material.This positive active material is coated on the aluminium foil, uses this positive plate, the parts such as the anchor clamps of employing dividing plate, negative pole, positive pole, collector body, assembling usefulness, outside terminal, electrolyte are made the lithium ion secondary battery.Wherein, negative pole adopts lithium metal, and electrolyte adopts in 1 liter of 1: 1 mixed solution of EC (ethylene carbonate) and MEC (ethyl-methyl carbonic ester) and dissolves LiPF
61 mole solution is as electrolyte.After battery is made, use Li/Li
+4.3V after the charging, fully wash in addition dry with acetone.1: 1 mixed solution of this electrode and electrolyte EC (ethylene carbonate) and MEC (ethyl-methyl carbonic ester) is enclosed airtight container together, then, carry out heat stabilization test by DSC mensuration.The results are shown in Fig. 3.
By the result of Fig. 3 as can be known, near the 1st exothermal peak of embodiment 2 (low temperature side is 180 ℃) is low than near the 1st exothermal peak (low temperature side is 180 ℃) of comparative example 1, and caloric value is little.Also as can be known, the fail safe of the active material of embodiment 2 is high than the active material of comparative example 1.Generally speaking, large, reactive high, the poor stability of atomic specific area.Yet, can infer that the cobalt acid lithium of embodiment 2 is by (cobalt acid lithium (A) coexistence because corase particles is safe, presents and can suppress the particulate (effect that the fail safe of cobalt acid lithium (B) worsens with corase particles.
The fast charging and discharging test
Adopt respectively the cobalt acid lithium (A) of the cobalt acid lithium of embodiment 2 and comparative example 1 as positive active material.This positive active material is coated on the aluminium foil, uses this positive plate, each parts such as the anchor clamps of employing dividing plate, negative pole, positive pole, collector body, assembling usefulness, outside terminal, electrolyte are made lithium rechargeable battery.Wherein, negative pole adopts lithium metal, and electrolyte adopts in 1 liter of 1: 1 mixed solution of EC (ethylene carbonate) and MEC (ethyl-methyl carbonic ester) and dissolves LiPF
61 mole solution.
At 2.7V～4.3V (to Li/Li
+) carry out deciding electric current and discharge and recharge test, its charging and discharging curve is shown in Fig. 4.In this case, 0.2C → 0.5C → 1.0C → 2.0C (1.0C → discharge 1 hour, 2.0C → discharge 0.5 hour) rises current value, the test fast charging and discharging performance.Positive pole and negative pole: metal Li, electrolyte: 1M LiPF
6/ EC+NEC, charging modes: CCCV (0.5C, 5H), scanning current potential: 2.7V, 4.3V.
By the result of Fig. 4 as can be known, the discharge capacity of embodiment 2 is large than comparative example 1.This can think in the cobalt acid lithium of embodiment 2 that the fast charging and discharging of contained particulate (cobalt acid lithium (B)) is good and present superperformance.
Macroparticle is given high fail safe, and small-particle enters the space of macroparticle, because the conductivity between powder raises, can obtain high fast charging and discharging performance.Yet when adding percent consolidation too high (more than 4.0), when making electrode, electrode density too rises, and electrolyte is insufficient to the dipping of electrode, and fast charging and discharging performance worsens, and is inappropriate.In addition, when adding percent consolidation and bulk density and be unsuitable value, can not get sufficient electrode density.
Secondly, the percent consolidation that adds of cobalt acid lithium of the present invention is illustrated.
Cobalt of the present invention acid lithium is the mixture formation of the cobalt acid lithium (B) assembled by the monodispersed cobalt acid lithium (A) of one-level particle and one-level particle, and the bulk density of this mixture is 1.8g/cm
3Or more than, and to add percent consolidation be 3.5～4.0g/cm
3
As the preferred embodiment of the invention described above cobalt acid lithium, be 1.7～3.0g/cm by bulk density
3, to add percent consolidation be 3.4～3.7g/cm
3Cobalt acid lithium (A) and bulk density be 1.0～2.0g/cm
3, to add percent consolidation be 3.1～3.5g/cm
3The mixture of cobalt acid lithium (B) consist of, and the bulk density of cobalt acid lithium (A) and the sour lithium of cobalt (B) is poor to be 0.10g/cm
3Above cobalt acid lithium is preferred.
The effect of invention
As mentioned above, cobalt of the present invention acid lithium is by being mixed 2 kinds of different cobalts acid lithiums, can obtain high percent consolidation and the suitable bulk density of adding, and when it is used for positive plate as positive active material, can obtain the effect of electrode density rising.
In addition, adopting preparation method of the present invention easily to obtain can be as the cobalt acid lithium of positive active material.
Also have, according to the present invention, adopting above-mentioned cobalt acid lithium is effectively as positive active material, can obtain the good rechargeable nonaqueous electrolytic battery of fail safe and fast charging and discharging.
Claims (7)
1. cobalt acid lithium is characterized in that bulk density is 1.8g/cm
3Or more than, and to add percent consolidation be 3.5～4.0g/cm
3, described cobalt acid lithium comprises cobalt acid lithium (A) and cobalt acid lithium (B), and described cobalt acid lithium (A) is that one-level particle list disperses, described cobalt acid lithium (B) is that the one-level particle is assembled, and, to compare with the average grain diameter of cobalt acid lithium (B), cobalt acid lithium (A) is corase particles.
2. according to the preparation method of the cobalt of claim 1 acid lithium, it is characterized in that, is bulk density 1.7～3.0g/cm
3Cobalt acid lithium (A) and bulk density be 1.0～2.0g/cm
3Cobalt acid lithium (B) mixed, make the poor 0.20g/cm of being of bulk density of described cobalt acid lithium (A) and cobalt acid lithium (B)
3Or more than, described cobalt acid lithium (A) is that one-level particle list disperses, described cobalt acid lithium (B) is that the one-level particle is assembled, and, to compare with the average grain diameter of cobalt acid lithium (B), cobalt acid lithium (A) is corase particles.
3. according to the cobalt described in the claim 2 acid lithium preparation method, it is characterized in that above-mentioned cobalt acid lithium (A) and the sour lithium of cobalt (B) are with weight ratio (A): (B)=95: 5～60: 40 ratio mixed.
4. according to cobalt acid lithium preparation method claimed in claim 2, it is characterized in that the average grain diameter of described cobalt acid lithium (A) is 5～30 μ m, the average grain diameter of described cobalt acid lithium (B) is 0.1～10 μ m.
5. according to cobalt acid lithium preparation method claimed in claim 3, it is characterized in that the average grain diameter of described cobalt acid lithium (A) is 5～30 μ m, the average grain diameter of described cobalt acid lithium (B) is 0.1～10 μ m.
6. according to any one described cobalt acid lithium preparation method in the claim 2～5, it is characterized in that, described cobalt acid lithium (A) is the compound with general formula (1) expression, described cobalt acid lithium (B) is with the compound of general formula (1) expression or the compound that represents with general formula (2)
Li
aCoO
2General formula (1)
In general formula (1), a represents the number in 0.2≤a≤1.2 scopes,
Li
aCo
1-yM
yO
2-zGeneral formula (2)
In general formula (2), it is at least a kind of element in the element more than 9 or 9 that M represents to be selected from transition metal except Co or atomic number, a represents the number in 0.2≤a≤1.2 scopes, and y represents the number in 0＜y≤0.4 scope, and z represents the number in 0≤z≤1.0 scopes.
7. a rechargeable nonaqueous electrolytic battery is characterized in that, has with the positive plate of the acid of the cobalt described in the claim 1 lithium as positive active material.
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| CN102779976B (en) * | 2011-10-10 | 2015-05-20 | 北大先行泰安科技产业有限公司 | Preparation method of cathode material of LCO (lithium cobaltate)-based lithium ion battery |
| CN102447107A (en) * | 2011-10-17 | 2012-05-09 | 江苏科捷锂电池有限公司 | High density lithium ion battery cathode material lithium cobalt oxide and preparation method thereof |
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