CN1492528A - Lithium-cobalt composite oxide and its producing method and non-aqueous electrolyte cell - Google Patents
Lithium-cobalt composite oxide and its producing method and non-aqueous electrolyte cell Download PDFInfo
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- CN1492528A CN1492528A CNA031574270A CN03157427A CN1492528A CN 1492528 A CN1492528 A CN 1492528A CN A031574270 A CNA031574270 A CN A031574270A CN 03157427 A CN03157427 A CN 03157427A CN 1492528 A CN1492528 A CN 1492528A
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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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/40—Cobaltates
- C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
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- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
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- C01P2002/54—Solid solutions containing elements as dopants one element only
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- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- H—ELECTRICITY
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- 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
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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
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
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Abstract
Provided is a lithium secondary battery having improved discharging characteristic by anode activating material containing specified lithium-cobalt composite oxides. The secondary battery comprises: an anode(3) containing lithium-cobalt composite oxide as anode activating material, a cathode(2), and a separator(1) equipped between the anode and the cathode. The lithium-cobalt composite oxide comprises 100ppm or less of Ni and is represented by formula of LixCo(1-y)MyO2N2 (wherein M means at least one element selected from transition metal elements, elements of groups II, XIII, XIV and XV among periodic table of elements except for Co and Ni; N is halogen element; x is 0.10<=x<=1.25, y is 0<=y<=0.05, and z is 0<=z<=0.05).
Description
Technical field
The present invention relates to a kind of lithium cobalt composite oxide and manufacture method, non-aqueous electrolyte battery and portable electronic machine.
Background technology
As everyone knows, for the transition metal oxide of layered crystal structure, suitably big or small metal ion can be directed between the lattice-site and/or lattice of crystallization with hexagonal crystal system.Especially the lithium intercalation compound under specific potential difference, can be directed into lithium ion between crystal lattice point and/or lattice, can be once more with its taking-up.And, with lithium cobalt composite oxide, LiCoO
2Be the lithium storage battery of positive active material, because of having very high volume energy density, make portable electronic machine can miniaturization, lightweight, come so lithium storage battery is popularized rapidly as the power supply of pocket pc, portable phone.
On the other hand, attempt with other inexpensive transition metal for example the research of replacement such as nickel, manganese cobalt at high price also carrying out (for example with reference to patent documentation 1, patent documentation 2) always.In patent documentation 2, put down in writing by using LiCo
xNi
(1-x)O
2The lithium composite xoide that the raw material that the composition formula of (0.05≤x＜1) is represented obtains, this lithium composite xoide are with lithium cobalt composite oxide (LiCoO
2) in the Co composition, partly be replaced into the material of the crystal structure that still can keep stable behind the Ni.In such prior art, replace the cobalt of high price with nickel etc.
[patent documentation 1]
Te Kaiping 11-71114
[patent documentation 2]
Te Kaiping 11-292550
Summary of the invention
But the result of inventor's further investigation is, if partly replace the lithium cobalt composite oxide (LiCoO that works as positive active material with Ni
2) in the Co composition, the flash-over characteristic of lithium storage battery is worsened.Therefore, the object of the present invention is to provide a kind of lithium storage battery that improves flash-over characteristic.
More particularly, the invention provides as follows:
(1) be to be the lithium cobalt composite oxide of feature below the 100ppm with Ni content.
(2) as the above-mentioned described lithium cobalt composite oxide of non-aqueous electrolyte battery with lithium and cobalt oxides.
(3) with 700～1100 ℃ down heating Ni content be that the alkali formula cobalt hydroxide below the 100ppm and the mixture of lithium compound are the manufacture method of the lithium cobalt composite oxide of feature.
(4) with the lithium cobalt composite oxide described in (1) as positive active material and to be contained in the positive pole be the non-aqueous electrolyte battery of feature.
(5) to possess the portable electronic machine that the non-aqueous electrolyte battery described in (4) is a feature.
Description of drawings
Fig. 1 is the profile of the non-aqueous electrolyte battery of one embodiment of the present invention.
Fig. 2 is the figure of the relation of expression voltage of non-aqueous electrolyte battery of the present invention and discharge capacity.
Symbol description: 1 dividing plate, 2 negative poles, 3 positive poles, 4 collector plates, 5 install part, 6 outside terminals, 7 electrolyte.
Embodiment
Below further specify positive active material of the present invention and non-aqueous electrolyte battery.
＜lithium cobalt composite oxide 〉
Lithium cobalt composite oxide of the present invention is to use Li
xCo
1-yM
yO
2-zThe represented lithium composite xoide of composition of (M is one or more the element in the 2nd family, the 13rd family, the 14th family and the 15th family's element that is selected from the transition metal inequality with Co, periodic table, 0.2≤x≤1.2,0≤y≤0.5,0≤z≤1).Be preferably 0.4≤x≤1.0,0≤y≤0.1,0≤z≤0.1.Such lithium cobalt composite oxide is suitable for lithium ion non-aqueous electrolyte battery positive active material.
In the lithium cobalt composite oxide of the present invention, also can contain other element, for example be selected from least a element among B, Mg, Si, Cu, Ce, Y, Ti, V, Mn, Fe, Sn, Zr, Sb, Nb, Ru, Pb, Hf, Ta, La, Pr and the Nd.
In lithium cobalt composite oxide of the present invention, Ni content is below the 100ppm.Preferred Ni content is below 70ppm, and more preferably Ni content is below 60ppm.The lithium cobalt composite oxide that contains in the positive pole for lithium storage battery, along with the minimizing of the Ni content in the lithium cobalt composite oxide, the discharge capacity of lithium storage battery increases, and keeping of voltage also becomes easy thereupon.Therefore, the volume energy density of lithium storage battery increases, and can make portable electronic machine miniaturization, lightweight.
＜alkali formula cobalt hydroxide 〉
In manufacture method of the present invention, use Ni content to be the alkali formula cobalt hydroxide below the 100ppm.Preferably use Ni content to be the alkali formula cobalt hydroxide (CoOOH) below the 70ppm, more preferably use Ni content to be the alkali formula cobalt hydroxide (CoOOH) below the 60ppm.This is because along with the minimizing of nickel content in the reactant, the just minimizing of Ni content in the lithium cobalt composite oxide that obtains with manufacture method of the present invention.With regard to alkali formula cobalt hydroxide, can think CoOOH as main component, also think and contain Co
3O
4, CoCO
3Wait other composition.
Adopt which type of manufacture method to obtain about the used alkali formula cobalt hydroxide of manufacture method of the present invention, not special the qualification.For example, can make with the following method: method that cobalt nitrate, cobalt chloride, cobaltous sulfate etc. is contained neutralize with alkali again behind cobaltous compound oxidation with oxidant etc.
As above-mentioned oxidant, there is no particular limitation.For example, can enumerate air, oxygen, ozone, permanganic acid (HMnO
4) and use M
3MnO
4Its salt Deng expression; Chromic acid (CrO
3) and use M
3 2Cr
2O
7, M
3 2CrO
4, M
3CrO
3X, CrO
2X
2Its relationship compound Deng expression; F
2, Cl
2, Br
2, I
2Deng halogen; H
2O
2, Na
2O
2, BaO
2Deng peroxide; Peroxy acid and use M
3 2S
2O
8, M
3 2SO
5, H
2CO
3, CH
3CO
3The compound or its salt of expression such as H; Oxyacid and use M
3MClO, M
3BrO, M
3IO, M
3ClO
3, M
3BrO
3, M
3IO
3, M
3ClO
4, M
3IO
4, Na
3H
2IO
6, KIO
4Compound or its salt etc. Deng expression.M in the formula
3The expression alkali metal.As above-mentioned alkali metal, there is no particular limitation, for example, can enumerate lithium, sodium, potassium, rubidium etc.In addition, X represents halogen element.
As the alkali of neutralization usefulness, also there is no particular limitation, and the aqueous solution of the inorganic hydroxide of use lithium hydroxide, NaOH, potassium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, ammonium hydroxide etc. etc. are more suitable.
Above-mentioned alkali formula cobalt hydroxide for example is to be dissolved in and to make the aqueous solution in the water by cobalt nitrate, cobalt chloride, cobaltous sulfate etc. being contained cobaltous compound, add above-mentioned oxidant and above-mentioned alkali again, and neutralizes simultaneously and oxidation obtains.In addition, also can behind the cobalt hydroxide of synthetic divalence, add oxidant again and carry out oxidation and obtain above-mentioned alkali formula cobalt hydroxide by adding above-mentioned alkali in containing with the aqueous solution of cobaltous compound above-mentioned.And, can also by above-mentioned add above-mentioned oxidant in containing with the aqueous solution of cobaltous compound after, add above-mentioned alkali again and neutralize and obtain above-mentioned alkali formula cobalt hydroxide.
＜lithium compound 〉
In manufacture method of the present invention, used lithium compound.With regard to lithium compound, there is no particular limitation, for example can suitably use the inorganic lithium salt of lithium hydroxide, lithium carbonate, lithium nitrate etc.As lithium compound, lithium carbonate is because obtain easily and cheaply industrial, so preferred.With regard to the concentration of lithium compound, what purity was high is preferred.
＜manufacture method 〉
In manufacture method of the present invention, for example, at first, above-mentioned alkali formula cobalt hydroxide and lithium compound are preferably lithium carbonate mix, obtain mixture.Just mix, any that uses dry type or wet mixed method all can, but consider preferred dry from angle easy to manufacture.When adopting dry type to mix, the mixer that preferred use can make raw material mix equably.In mixed processes, as the cooperation ratio of the lithium compound and the cobalt compound of raw material,, be 0.99～1.06 by the mol ratio (Li/Co) of Co atom and Li atom, be preferably 0.99～1.02.If (mix with dry type, recommendation is also put down in writing the scope of the particle diameter of alkali formula cobalt hydroxide and lithium compound get off.)
Then mixture is calcined.Calcining heat is preferably 700～1100 ℃, more preferably 850～1050 ℃.Calcination time is 1～24 hour, is preferably 2～10 hours.When if calcining heat is lower than 700 ℃, then can not fully synthesize lithium cobalt system composite oxides, as the alkali formula cobalt hydroxide of raw material and lithium compound is remaining gets off, inadvisable.On the other hand, when if calcining heat is higher than 1100 ℃, lithium cobalt composite oxide as purpose will begin to decompose, use the lithium cobalt composite oxide as the battery behavior of the lithium storage battery of positive active material, particularly because the voltage in discharge latter stage makes capacity deterioration and cycle characteristics deterioration, so also inadvisable.
With regard to calcining, all can carry out under any situation in atmosphere or in the aerobic environment, have no particular limits.The cooling that suits after the calcining is pulverized as required and is obtained the lithium cobalt composite oxide.In addition, the pulverizing of carrying out as required is suitably to carry out under the lithium cobalt composite oxide that obtains after the calcining becomes the state of bulk of crisp combination, and the particle of lithium cobalt composite oxide itself should have above-mentioned specific average grain diameter, BET specific area.That is, resulting lithium cobalt composite oxide, the average grain diameter of obtaining by laser method is 1～30 μ m, is preferably 3～20 μ m, be preferably 5～15 μ m especially, and the BET specific area is 0.1～2.0m
2/ g is preferably 0.2～1.5m
2/ g is preferably 0.3～1.0m especially
2/ g.
With respect to the nickel content of above-mentioned lithium cobalt composite oxide and alkali formula cobalt hydroxide, % represents with weight, greater than 0 and below 100ppm, is preferably 0～50ppm especially.Its reason is, the nickle atom in the lithium cobalt composite oxide is replaced in the position identical with cobalt atom, and the cobalt atom number of charge/discharge capacity being done contribution will tail off.Can think in addition,,, discharge and recharge needed trivalent cobalt and just tailed off for guaranteeing electric charge because nickle atom is to be replaced by cobalt with different valence mumbers.There is no particular limitation for the lower limit of nickel content.
＜Ni Determination on content method 〉
After lithium cobalt composite oxide (0.5g) being dissolved fully while boiling with perchloric acid, add distilled water and make it to reach 100ml, utilize ICP apparatus for analyzing luminosity (of science motor society system) that the amount of the Ni in this solution is carried out quantitative assay.
＜battery production method 〉
In the positive active material of lithium storage battery, used above-mentioned lithium cobalt composite oxide.Positive active material is the anode mixture of lithium storage battery described later, that is, and and the raw material of the mixture that a kind of filler that is reached interpolation as required by positive active material, conductive agent, binding agent etc. is formed.Because lithium storage battery positive active material of the present invention is made of above-mentioned lithium cobalt composite oxide, so it is mixing easily when being mixed together the modulation anode mixture with other raw material, and the smearing property the when anode mixture that obtains is coated with on positive electrode collector is also easy.
Lithium storage battery of the present invention is used for positive active material with above-mentioned lithium cobalt composite oxide.Constitute by positive pole, negative pole, dividing plate and the nonaqueous electrolyte that contains lithium salts.Positive pole for example is a coating anode mixture and to carry out drying etc. formed on positive electrode collector, and anode mixture then is to be made of positive active material, conductive agent, binding agent and the filler that adds as required etc.
As positive electrode collector, so long as do not cause that the electronic conductor of chemical change gets final product in the battery that constitutes, there is no particular limitation.For example can enumerate stainless steel, nickel, aluminium, titanium, calcining carbon, aluminium or stainless surface and carry out surface-treated material etc. through carbon, nickel, titanium, silver.
As conductive agent, for example can enumerate graphite, carbon black, acetylene black, carbon fiber, carbon nanotube or the conductive materials such as metal, nickel powder of native graphite and Delanium etc.As native graphite, for example can enumerate flaky graphite, flaky graphite and amorphous graphite etc.These materials can be used in combination with one or two or more kinds.The cooperation ratio of conductive agent is 1～50 weight % in anode mixture, is preferably 2～30 weight %.
As binding agent, for example can enumerate Kynoar, polyvinyl alcohol, carboxymethyl cellulose, hydroxy propyl cellulose, regenerated cellulose, diacetyl cellulose, polyvinylpyrrolidone, ethylene-propylene-diene polymer (EPDM), sulfonated epdm, styrene butadiene ribber, fluorubber, polyethylene glycol oxide etc. polysaccharide, thermoplastic resin, have the polymer of caoutchouc elasticity etc., can or will be used in combination more than two kinds with a kind of in them.The cooperation ratio of binding agent in anode mixture, is 2～30 weight %, is preferably 5～15 weight %.
In anode mixture, filler has been the material that suppresses the effects such as volumetric expansion of positive pole, adds as required.As filler, in the battery that is constituted, so long as do not cause the fibrous material of chemical change, use any material all can.For example, can use the fiber of the olefin polymer, glass, carbon etc. of polypropylene, polyethylene etc.There is no particular limitation for the addition of filler, in anode mixture, is preferably 0～30 weight %.
Negative pole is coated with negative material and carries out drying etc. and forms on negative electrode collector.As negative electrode collector, so long as do not cause that the electronic conductor of chemical change gets final product in the battery that constitutes, there is no particular limitation.For example can enumerate stainless steel, nickel, copper, titanium, aluminium, calcining carbon, copper or stainless surface and carry out surface-treated material and aluminium-cadmium alloy etc. through carbon, nickel, titanium, silver.
As negative material, there is no particular limitation, for example can enumerate carbonaceous material or composite oxide of metal, lithium metal, lithium alloy etc.As carbonaceous material, for example can enumerate difficult graphitized carbon material, graphite-like raw material of wood-charcoal material etc.As composite oxide of metal, for example can enumerate Sn
pM
1-pM
2 qO
r(in the formula, M
1Expression is selected from one or more the element among Mn, Fe, Pb and the Ge, M
2Expression is selected from one or more the element in Al, B, P, Si, periodic table the 1st family, the 2nd family, the 3rd family and the halogen, 0＜p≤1,1≤q≤3,1≤r≤8) etc. compound.
As dividing plate, used the insulating properties film that has big ion permeability and have the mechanical strength of regulation.Because need have organic solvent resistance and hydrophobicity, so adopted sheet material, the nonwoven fabrics of making by olefin polymers such as polypropylene or glass fibre or polyethylene etc.As the aperture of dividing plate, generally in useful scope, get final product as the battery time spent, for example be 0.01～10 μ m.As the thickness of dividing plate,, for example be 5～300 μ m so long as the scope that general battery is used gets final product.In addition, as electrolyte described later, when using the solid electrolyte of polymer etc., also can be with solid electrolyte double as dividing plate.In addition, for reaching the purpose of improving discharge, charge characteristic, also can in electrolyte, add the compound of pyridine, triethyl group phosphatization thing, triethanolamine etc.
The nonaqueous electrolyte that contains lithium salts is made of nonaqueous electrolyte and lithium salts.As nonaqueous electrolyte, nonaqueous electrolytic solution or organic solid electrolyte based have been used.As nonaqueous electrolytic solution, can enumerate for example N-N-methyl-2-2-pyrrolidone N-, propene carbonate, ethylene carbonate, butylene, dimethyl carbonate, diethyl carbonate, γ-furanidine ketone, 1, the 2-dimethoxy-ethane, the tetrahydroxy furans, 2-methyl tetrahydroxy furans, dimethyl sulfoxide (DMSO), 1,3-two oxa-s penta ring, formamide, dimethyl formamide, two oxa-s, penta ring, acetonitrile, nitromethane, methyl formate, methyl acetate, phosphotriester, trimethoxy-methane, two oxa-s, penta ring derivatives, sulfolane, 3-methyl-2-oxazolone, the propylene carbonate ester derivant, tetrahydrofuran derivatives, diethyl ether, 1, the 3-N-morpholinopropanesulfonic acid lactone (1,3-propanesaltone) one or two or more kinds mixed solvent of non-proton organic solvent such as grade.
As organic solid electrolyte based, for example can enumerate polythene derivative or contain its polymer, polypropylene oxide derivatives or contain its polymer, phosphate ester polymer etc.As lithium salts, can use the lithium salts that is dissolved in above-mentioned nonaqueous electrolyte, for example can enumerate LiClO
4, LiBF
4, LiPF
6, LiCF
3SO
3, LiCF
3CO
2, LiAsF
6, LiSbF
6, LiB
10Cl
10, LiAlCl
4, chloroborane lithium, lower aliphatic carboxylic acid lithium, tetraphenyl lithium borate etc. one or two or more kinds mixed salt.
The shape of lithium storage battery of the present invention, button, chip, column, square shape etc. are any all to be suitable for.The purposes of lithium storage battery of the present invention, there is no particular limitation, for example can enumerate the civil electronic machine etc. of the e-machine, motor vehicle, motor vehicle, game machine etc. of notebook PC, laptop personal computer, packed word processor, portable phone, cordless telephone handset, portable CD player, broadcast receiver etc.In addition, lithium storage battery is included in the non-aqueous electrolyte battery.
＜portable electronic machine 〉
In the present invention, provide the portable electronic machine that contains above-mentioned non-aqueous electrolyte battery.As portable electronic machine, for example can enumerate notebook PC, packed word processor, portable phone, cordless telephone handset, portable CD player, broadcast receiver, game machine etc.
[embodiment]
Below lithium cobalt composite oxide of the present invention and non-aqueous electrolyte battery are further specified.
In embodiment described later and comparative example, (average grain diameter is preferably 10～15 μ m, for example is 11.0 μ m at this with lithium carbonate.) and nickel content be 25,49,98,205 or the alkali formula cobalt hydroxide (QNI society chemical grade) of 502ppm (average grain diameter is preferably 10～15 μ m, for example is 12.0 μ m at this.), be that 0.99～1.060 ratio is carried out weighing in the atomic ratio of Li/Co, in mortar, mix then, be modulated into uniform mixture.Then, this mixture is packed in the alumina crucible, put into again in the electrons heat stove, under atmospheric environment, heat up, and under 700～1100 ℃ temperature, kept 10 hours, carry out calcination processing, after resulting calcined material is cooled off in air, synthesize by pulverizing, classification.
[embodiment 1]
Carry out 10 hours calcination processing under 950 ℃, obtaining Ni content is the lithium cobalt composite oxide (LiCoO of 28ppm
2).Average grain diameter is 10.2 μ m.
[embodiment 2]
Carry out 10 hours calcination processing under 800 ℃, obtaining Ni content is the lithium cobalt composite oxide (LiCoO of 45ppm
2).Average grain diameter is 12.0 μ m.
[embodiment 3]
Carry out 10 hours calcination processing under 1050 ℃, obtaining Ni content is the lithium cobalt composite oxide (LiCoO of 100ppm
2).Average grain diameter is 10.5 μ m.
[comparative example 1]
Carry out 10 hours calcination processing under 1060 ℃, obtaining Ni content is the lithium cobalt composite oxide (LiCoO of 201ppm
2).Average grain diameter is 10.7 μ m.
[comparative example 2]
Carry out 10 hours calcination processing under 820 ℃, obtaining Ni content is the lithium cobalt composite oxide (LiCoO of 490ppm
2).Average grain diameter is 11.2 μ m.
＜particle size distribution method 〉
At this, the average grain diameter of putting down in writing in this specification is the value that records by laser particle size distribution device at random.There is no particular limitation for determinator, and what use in the present invention is day laser type particle size distribution device (Microtrac) of machine dress society manufacturing.
＜battery performance test 〉
(I) making of lithium storage battery;
With mixing as anode mixture of 91 weight %, it is dispersed in is modulated into mixing cream in the N-N-methyl-2-2-pyrrolidone N-again as the embodiment 1～3 of above-mentioned making and the lithium cobalt composite oxide of comparative example 1～2, the powdered graphite of 6 weight %, the Kynoar of 3 weight %.Should mixing cream be coated on the aluminium foil and after carrying out drying, suppress, strike out the disk that diameter is 15mm, obtain positive plate.
As shown in Figure 1, use this positive plate, and use each material of dividing plate 1, negative pole 2, positive pole 3, collector plate 4, installation part 5, outside terminal 6, electrolyte 7 etc., be made into lithium storage battery, that is, and non-aqueous electrolyte battery.Wherein, negative pole uses metallic lithium foil, and electrolyte uses is to have dissolved 1 mole of LiPF in 1 liter of ethylene carbonate and diethyl carbonate are 1: 1 mixing liquid
6Solution.
(II) performance evaluation of battery;
The lithium storage battery that is made into is at room temperature made it work, measure its initial stage discharge capacity, battery performance is estimated.
(III) evaluation method;
Discharge capacity is, charge to 4.3V with respect to positive pole with CCCV (1.0C) after, be discharged to 2.7V again, measure the discharge capacity of this moment.In addition, about the lithium storage battery of making as positive active material with the lithium cobalt composite oxide of modulation in embodiment 1,2,3 and the comparative example 1,2, the relation of its voltage and discharge capacity as shown in Figure 2.
＜experimental result 〉
After the active material that will obtain in embodiment 1,2,3 and comparative example 1,2 carries out the electrode coating, at 2.7V～4.3V (vs.Li/Li
+) under carried out deciding electric current and discharged and recharged test.The curve that it discharges and recharges is shown.Charging and discharging currents carries out with 0.2C.Test shows, the active material that obtains in the active material that obtains in embodiment 1,2 and 3 and comparative example 1 and 2 is compared, and has obtained very big discharge capacity.This can think to have formed solid solution because the Ni that is contained in the lithium cobalt composite oxide is replaced by Co, so the Co amount of using as capacity reduces, the capacity minimizing has just taken place.
The invention effect
It is a kind of by using Ni content to be the lithium cobalt composite oxygen below the 100ppm that the present invention can provide The lithium storage battery that compound has improved as positive active material, flash-over characteristic. By using like this Lithium storage battery, can make portable electronic machine realize miniaturization, lightweight.
Claims (5)
1. lithium cobalt composite oxide, it is characterized in that: Ni content is below the 100ppm.
2. lithium cobalt composite oxide as claimed in claim 1 is characterized in that: be nonaqueous electrolyte storage battery lithium cobalt composite oxide.
3. the manufacture method of a lithium cobalt composite oxide is characterized in that: with Ni content is that the alkali formula cobalt hydroxide below the 100ppm and the mixture of lithium compound heat under 700～1100 ℃.
4. non-aqueous electrolyte battery is characterized in that:, and be contained in the positive pole as positive active material with the described lithium cobalt composite oxide of claim 1.
5. a portable electronic apparatus is characterized in that: possess the described non-aqueous electrolyte battery of claim 4.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002297976 | 2002-10-10 | ||
| JP2002297976 | 2002-10-10 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1492528A true CN1492528A (en) | 2004-04-28 |
| CN1328807C CN1328807C (en) | 2007-07-25 |
Family
ID=34260187
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|---|---|---|---|
| CNB031574270A Expired - Lifetime CN1328807C (en) | 2002-10-10 | 2003-09-19 | Lithium-cobalt composite oxide and its producing method and non-aqueous electrolyte cell |
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| Country | Link |
|---|---|
| CN (1) | CN1328807C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100420086C (en) * | 2005-01-17 | 2008-09-17 | 夏普株式会社 | Lithium secondary battery |
| CN1770515B (en) * | 2005-08-22 | 2010-05-12 | 中国科学院成都有机化学有限公司 | Anode, cathode material conductive agent for lithium-ion secondary battery and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0824087B1 (en) * | 1996-08-13 | 1999-10-27 | Murata Manufacturing Co., Ltd. | Manufacturing method of lithium complex oxide comprising cobalt or nickel |
| JP2001060459A (en) * | 1999-08-23 | 2001-03-06 | Sumitomo Metal Mining Co Ltd | Lithium cobaltate for lithium secondary battery and its manufacture |
| JP2002151155A (en) * | 2000-11-13 | 2002-05-24 | Mitsubishi Cable Ind Ltd | Lithium ion secondary battery |
-
2003
- 2003-09-19 CN CNB031574270A patent/CN1328807C/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100420086C (en) * | 2005-01-17 | 2008-09-17 | 夏普株式会社 | Lithium secondary battery |
| CN1770515B (en) * | 2005-08-22 | 2010-05-12 | 中国科学院成都有机化学有限公司 | Anode, cathode material conductive agent for lithium-ion secondary battery and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1328807C (en) | 2007-07-25 |
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