CN1790780A - Lithium-cobalt composite oxides powder, its preparation method, lithium secondary cell and lithium secondary cell - Google Patents
Lithium-cobalt composite oxides powder, its preparation method, lithium secondary cell and lithium secondary cell Download PDFInfo
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- CN1790780A CN1790780A CNA2005101320101A CN200510132010A CN1790780A CN 1790780 A CN1790780 A CN 1790780A CN A2005101320101 A CNA2005101320101 A CN A2005101320101A CN 200510132010 A CN200510132010 A CN 200510132010A CN 1790780 A CN1790780 A CN 1790780A
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- 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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- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
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- C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
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- 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
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- 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
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Abstract
To produce such a lithium cobalt multiple oxide powder that, when the oxide is used as the positive pole active substance of a lithium secondary cell, the lithium secondary cell can be improved particularly in cycle characteristics, an industrially advantageous method for producing the same, and a positive pole active substance of the lithium secondary cell containing the same, and a lithium secondary cell having the excellent cycle characteristics. The lithium cobalt multiple oxide powder contains 0.025 to 1.0 wt% metal atoms of at least one kind selected among Mg, Al, Zr, Ca, and Ti and is produced by mixing a lithium compound, a cobalt compound, and a compound including the metal atoms selected from the phosphate or hydrogen phosphate, and firing the mixture.
Description
Technical field
The present invention relates to as the positive active material of lithium secondary battery and useful lithium-cobalt composite oxides powder and manufacture method thereof, contain the cathode active material for lithium secondary battery of this powder and the particularly lithium secondary battery of cycle characteristics excellence.
Background technology
In recent years, along with developing rapidly of portable, wireless type in the household electrical appliance, as the power supply of miniature electric machines such as portable personal computer, portable phone, video tape recorder, lithium secondary battery is by extensively practical.About this lithium rechargeable battery, 1980, be useful (" マ テ リ ア Le リ サ one チ Block レ テ Off イ Application " vol15 by report cobalts such as water island acid lithium as the positive active material of lithium rechargeable battery, P783-789 (1980)), from then on since, research and development about the lithium based composite oxide are carried out actively, propose many schemes so far.
But, exist to use in the lithium secondary battery of cobalt acid lithium the problem of the cycle characteristics variation that causes because of cobalt atom stripping etc.
In addition, as positive active material, the scheme (for example with reference to patent documentation 1～3) of the lithium-cobalt composite oxides of the Co atom of proposition usefulness Mg atomic component replacement cobalt acid lithium.
In the lithium-cobalt composite oxides that contains above-mentioned patent documentation 1～3, the Mg source that makes it to contain the Mg atom is magnesium oxide or magnesium carbonate, in addition, even as be limited to known to the applicant to Al, Zr, Ca and Ti source and in the compound that uses, the oxide of these metals or carbonate do not use the phosphate or the hydrophosphate of this metal, in addition in the reality, as for the method for these prior aries, yet there is the problem of cycle characteristics variation.
In addition, the applicant had before also proposed the scheme (patent documentation 4～5) with the lithium-cobalt composite oxides that contains these metallic atoms on the oxide of these metals or the sour lithium particle of sulfate surface treatment cobalt surface.
Patent documentation 1: the spy opens flat 5-54889 communique, the 1st page, the 8th page
Patent documentation 2: the spy opens 2000-11993 communique, the 2nd page, the 3rd page
Patent documentation 3: the spy opens 2004-79386 communique, the 2nd page, the 7th page
Patent documentation 4: the spy opens the 2003-20229 communique
Patent documentation 5: the spy opens the 2003-221234 communique
Summary of the invention
According to the said method that the applicant proposes, cycle characteristics is improved, but after making cobalt acid lithium, other operations of this cobalt acid lithium of surface treatment must be set, from the producer's that makes positive active material position, industrial be disadvantageous.
Therefore, the lithium-cobalt composite oxides powder that the object of the present invention is to provide the cycle characteristics that can make lithium secondary battery when using, especially to improve as the positive active material of lithium secondary battery, it is in industrial favourable manufacture method, the lithium secondary battery that contains the cathode active material for lithium secondary battery of this powder and use the cycle characteristics excellence of this positive active material.
Present inventors further investigate the result that solve these problems repeatedly, find that a kind of containing at particular range is selected from Mg, Al, Zr, the lithium-cobalt composite oxides of the metallic atom more than at least a kind of Ca and Ti, and, as the compound that contains above-mentioned metallic atom, the phosphate that uses this metal is or/and hydrophosphate, can make the lithium secondary battery of positive active material with the lithium-cobalt composite oxides powder that contains these metallic atoms that industrial advantageous method obtains, become the particularly battery of cycle characteristics excellence, so far finished the present invention.
Promptly, the first aspect that the present invention will provide is a kind of lithium-cobalt composite oxides powder, it is characterized in that, the lithium-cobalt composite oxides that contains the metallic atom more than at least a kind that is selected from Mg, Al, Zr, Ca and Ti of 0.025～1.0 weight %, and by mixed lithiated compound, cobalt compound and the compound that contains the metallic atom of the phosphate that is selected from above-mentioned metal or hydrophosphate, this mixture of sintering and generating.
In addition, the second aspect that the present invention will provide is the manufacture method of lithium-cobalt composite oxides powder, it is characterized in that, the mixed lithiated compound, cobalt compound and contain and be selected from Mg, Al, Zr, the compound of the metallic atom more than at least a kind of Ca and Ti, and carry out sintering, wherein, as the compound that contains above-mentioned metallic atom, use the phosphate or the hydrophosphate of this metal, make lithium compound, cobalt compound and the compound that contains above-mentioned metallic atom, mol ratio with relative Co atom is a Li atom 0.90～1.20, the ratio of metallic atom 0.001～0.04 is mixed, and the mixture that obtains of sintering.
In addition, the third aspect that the present invention will provide is a cathode active material for lithium secondary battery, it is characterized in that, contains the lithium-cobalt composite oxides powder of above-mentioned first aspect.
In addition, the fourth aspect that the present invention will provide is a lithium secondary battery, it is characterized in that, uses the cathode active material for lithium secondary battery of the above-mentioned third aspect.
Lithium-cobalt composite oxides powder of the present invention is useful as the positive active material of lithium secondary battery, and in addition, the lithium secondary battery that this lithium-cobalt composite oxides is used as positive active material is the battery of cycle characteristics excellence particularly.
Description of drawings
The flash-over characteristic figure of Fig. 1 lithium secondary battery that to be the lithium-cobalt composite oxides powder that obtains with embodiment 1 use as positive active material.
The flash-over characteristic figure of Fig. 2 lithium secondary battery that to be the lithium-cobalt composite oxides powder that obtains with embodiment 2 use as positive active material.
The flash-over characteristic figure of Fig. 3 lithium secondary battery that to be the lithium-cobalt composite oxides powder that obtains with embodiment 3 use as positive active material.
The flash-over characteristic figure of Fig. 4 lithium secondary battery that to be the lithium-cobalt composite oxides powder that obtains with reference examples 1 use as positive active material.
The flash-over characteristic figure of Fig. 5 lithium secondary battery that to be the lithium-cobalt composite oxides powder that obtains with reference examples 2 use as positive active material.
The flash-over characteristic figure of Fig. 6 lithium secondary battery that to be the lithium-cobalt composite oxides powder that obtains with reference examples 3 use as positive active material.
The flash-over characteristic figure of Fig. 7 lithium secondary battery that to be the lithium-cobalt composite oxides powder that obtains with reference examples 4 use as positive active material.
Embodiment
Below, based on it the present invention is described preferred embodiment.
Lithium-cobalt composite oxides powder of the present invention, be to contain 0.025～1.0 weight %, the Mg that is selected from that preferably contains 0.025～0.5 weight %, Al, Zr, the metallic atom more than at least a kind of Ca and Ti (below, slightly be designated as " metallic atom ") lithium-cobalt composite oxides, it is characterized in that, by the mixed lithiated compound, cobalt compound and be selected from the phosphate of above-mentioned metal or the compound that contains metallic atom more than a kind of hydrophosphate, and this mixture of sintering and generating, lithium-cobalt composite oxides powder of the present invention with such formation, than as the existing compound that contains metallic atom, use the oxide of these metals or the powder of carbonate, in with the lithium secondary battery of this lithium-cobalt composite oxides powder, can give excellent cycle characteristics as positive active material.
In addition, in the present invention, the reason that the content of above-mentioned metallic atom is made as this scope is because metallic atom content during less than 0.025 weight %, can't see the raising of lithium secondary battery cycle characteristics, on the other hand, when greater than 1.0 weight %, the electric capacity of lithium secondary battery just has the tendency of decline.
Among the present invention, the above-mentioned metallic atom that makes it to contain is the Mg atomic time, the cycle characteristics of lithium secondary battery is improved more, and preferred especially above-mentioned metallic atom is the Mg atom.
Other rerum natura as lithium-cobalt composite oxides powder of the present invention, the average grain diameter that can be obtained by laser particle size measure of spread method is 0.5～30 μ m, be preferably 10～25 μ m, because average grain diameter is in this scope the time, just can form filming of uniform thickness, so it is preferred, during preferred especially 10～20 μ m, just can make the fail safe of this lithium-cobalt composite oxides powder as the lithium secondary battery of positive active material improved more.
In addition, lithium-cobalt composite oxides powder of the present invention, the BET specific area is 0.05～1m
2/ g, be preferably 0.15～0.6m
2/ g.The BET specific area is in this scope the time, and is preferred because fail safe is good.
In the lithium-cobalt composite oxides powder of the present invention, can think that the phosphate of above-mentioned metal is or/and hydrophosphate, sintering by lithium compound and cobalt compound, its metal ingredient is by effect of phosphate composition etc., particle surface at this lithium-cobalt composite oxides preferentially exists as oxide, on the other hand, phosphate composition and lithium reaction, be immobilized with chemical bond and exist at particle surface as lithium phosphate, but this lithium phosphate is had an effect as impurity, impedance increase along with lithium secondary battery becomes the main cause that makes the charge variation.Therefore, in lithium-cobalt composite oxides powder of the present invention, come from the PO of stripping in the water of this lithium phosphate
4 2-Amount be 1 weight % following, be preferably 0.2 weight % when following, the performance of these batteries is variation not just, can give the lithium secondary battery excellence characteristic and preferably.
In addition, among the present invention, the PO of stripping in this water
4 2-Amount, be utilize that the chromatography of ions obtains make the 30g lithium-cobalt composite oxides powder under 5 minutes, 25 ℃, be distributed to the 100ml pure water time dispersion liquid in PO
4 2-Amount.
The manufacture method of lithium-cobalt composite oxides powder of the present invention then, is described.
The manufacture method of lithium-cobalt composite oxides powder of the present invention, it is characterized in that, by the mixed lithiated compound, cobalt compound and contain and be selected from Mg, Al, Zr, the compound of at least a kind the metallic atom of Ca and Ti, and carry out sintering, and the manufacturing lithium-cobalt composite oxides, wherein, as the compound that contains above-mentioned metallic atom, use the phosphate or the hydrophosphate of this metal, make lithium compound, cobalt compound and the compound that contains metallic atom, with the mol ratio with respect to the Co atom is Li atom 0.90～1.20, the mixed of metallic atom 0.001～0.04, and the mixture that obtains of sintering.
As the operable first raw material lithium compound, can enumerate for example oxide, hydroxide, carbonate, nitrate and the acylate etc. of lithium, the wherein lithium carbonate of preferred industrial cheapness.In addition, reactive good because the average grain diameter that this lithium compound can be obtained by laser particle size measure of spread method is when being 0.1～200 μ m, preferred 2～50 μ m, so preferred especially.
The operable second raw material cobalt compound, can enumerate for example oxide, hydroxide, carbonate, nitrate and the acylate etc. of cobalt, wherein, from industrial cheapness, reactivity, consider preferred especially cobaltosic oxide (Co aspect the fail safe of the accessory substance that in sintering, generates
3O
4) or hydroxy cobalt oxide (CoOOH).In addition, because the average grain diameter that this cobalt compound can be obtained by laser particle size measure of spread method when being 0.1～20 μ m, preferred 1～15 μ m, just can obtain uniform raw mix, so preferred especially.
The compound that contains the metallic atom more than at least a kind that is selected from Mg, Al, Zr, Ca and Ti of operable the 3rd raw material be the phosphate of these metals or/and hydrophosphate, this hydrophosphate can be dibasic alkaliine or dihydric phosphate.Especially in the present invention, the lithium-cobalt composite oxides powder that uses magnesium phosphate and obtain is shown the raising of high cycle characteristics as the lithium secondary battery of positive active material, can especially preferably use magnesium phosphate in this.In addition, containing the compound of operable above-mentioned metallic atom, can be that moisture thing also can be an anhydride.In addition, reactive good when the average grain diameter that can be obtained by laser particle size measure of spread method is 0.1～20 μ m, preferred 2～15 μ m because contain the compound of this metallic atom, so preferred especially.
In addition, the lithium compound of above-mentioned first～the 3rd raw material, cobalt compound and the compound that contains metallic atom, its manufacture process is self-evident, but in order to make the high-purity lithium-cobalt composite oxides powder, preferably makes the poor material of impurity as far as possible.
Operation at first, mixes lithium compound, the cobalt compound of above-mentioned first～the 3rd raw material and the compound that contains metallic atom to determine amount.Mixing can utilize wantonly a kind of method of dry type or wet type, but for easy to manufacture and preferred dry.When dry type is mixed, preferably make the mixed uniformly blender of raw material.
The cooperation ratio that contains lithium compound, the cobalt compound of above-mentioned first～the 3rd raw material and contain the compound of metallic atom, molar ratio computing with relative Co atom, the Li atom is 0.90～1.20, is preferably 0.98～1.10, metallic atom is 0.001～0.04, is preferably 0.01～0.02, by carrying out sintering described later with this cooperation ratio, the lithium-cobalt composite oxides that can be obtained relatively and contain the lithium-cobalt composite oxides powder that above-mentioned metallic atom is 0.025～1.0 weight %, preferred 0.025～0.5 weight %.
Then, sintering evenly mixes the mixture of above-mentioned first～the 3rd raw material.Among the present invention, sintering temperature is 800～1150 ℃, is preferably 900～1100 ℃, the reason that sintering temperature is defined as this scope is because during less than 800 ℃, the raw material cobalt compound is residual, cause that electric capacity reduces, on the other hand, during greater than 1150 ℃, lithium-cobalt composite oxides decomposes, and the tendency that electric capacity is reduced is arranged.
Sintering time is 1～30 hour, is preferably 1～5 hour.Sintering can carry out in atmosphere or in the oxygen atmosphere gas, has no particular limits.In addition, these sintering can carry out repeatedly as required.
Behind the sintering, suitably cooling is pulverized as required, obtains lithium-cobalt composite oxides powder.
In addition, as required and the pulverizing of carrying out, the lithium-cobalt composite oxides powder that obtains at sintering suitably carries out during for the block of more crisp ground combination etc., but the lithium-cobalt composite oxides particle itself has specific average grain diameter, BET specific area.That is, the lithium-cobalt composite oxides powder that obtains, its average grain diameter is 0.5～30 μ m, is preferably 10～25 μ m that the BET specific area is 0.05～1m
2/ g, be preferably 0.15～0.6m
2/ g.
The lithium-cobalt composite oxides powder that obtains like this, it is the lithium-cobalt composite oxides that contains the metallic atom more than at least a kind that is selected from Mg, Al, Zr, Ca and Ti of 0.025～1 weight %, preferred 0.025～0.5 weight %, in addition, has beyond the above-mentioned particle property PO of stripping in water
4 2-Amount be 1 weight % following, be preferably below the 0.5 weight %.Lithium-cobalt composite oxides powder of the present invention like this can suitably use by positive pole, negative pole, spacer and the positive active material that contains the lithium secondary battery that the nonaqueous electrolyte of lithium salts forms.
Cathode active material for lithium secondary battery of the present invention can use above-mentioned lithium-cobalt composite oxides powder.Positive active material is the anode mixture of lithium secondary battery described later, that is, and and one of raw material of the mixture of forming by positive active material, conductive agent, adhesive and filler as required etc.Cathode active material for lithium secondary battery of the present invention, it is above-mentioned lithium-cobalt composite oxides powder, the powder that has preferred size characteristic as described above by use, be mixed together with other raw material, mixing easy when the preparation anode mixture, coating when in addition, being coated with the anode mixture that obtains on positive electrode collector becomes easy.
Lithium secondary battery of the present invention is to use the battery of above-mentioned cathode active material for lithium secondary battery, is made up of positive pole, negative pole, spacer and the nonaqueous electrolyte that contains lithium salts.Positive pole be for example by on positive electrode collector to anode mixture be coated with, drying etc. and forming, anode mixture is made up of positive active material, conductive agent, adhesive and the filler that adds as required etc.Lithium secondary battery of the present invention is coated with the above-mentioned lithium-cobalt composite oxides as positive active material equably on positive pole.
Therefore, lithium secondary battery of the present invention is difficult to produce the decline of part throttle characteristics and cycle characteristics especially.
As positive electrode collector, if in the battery that constitutes, do not cause the electrical conductivity body of chemical change, just have no particular limits, for example can enumerate stainless steel, nickel, aluminium, titanium, sintered carbon, make carbon, nickel, titanium, silver carry out surface-treated object etc. at aluminium or stainless steel surfaces.On also can the surface of these materials of oxidation and use, also can produce concavo-convex on the collector body surface and use by surface treatment.In addition, as the form of collector body, can enumerate formed body of for example paillon foil, film, sheet, net, punching press thing, lath body, porous plastid, foaming body, groups of fibers, nonwoven fabrics etc.The thickness of collector body has no particular limits, and preferably becomes 1～500 μ m.
As conductive agent, just there is no particular limitation if do not cause the electrically conductive material of chemical change in the battery that constitutes.Can enumerate the graphite, carbon black, acetylene carbon black, section's qin carbon black, channel carbon black, oven process carbon black of for example native graphite and Delanium etc., dim, heat is black etc. carbon black class, the conducting fibre class of carbon fiber and metallic fiber etc., the metal dust class of fluorocarbons, aluminium, nickel powder etc., the conductive metal palpus class of zinc oxide, potassium titanate etc., the conductive material of the conductive metal oxide of titanium oxide etc. or polyphenylene derivative etc., as native graphite, can enumerate for example flaky graphite, flaky graphite and amorphous graphite etc.These materials can 1 kinds or are made up more than 2 kinds and use.The cooperation ratio of conductive agent is 1～50 weight %, 2～30 weight % preferably in anode mixture.
As adhesive, can enumerate for example starch; Kynoar; polyvinyl alcohol; carboxymethyl cellulose; hydroxypropyl cellulose; regenerated cellulose; diacetyl cellulose; polyvinylpyrrolidone; tetrafluoroethene; polyethylene; polypropylene; ethylene-propylene-diene polymer (EPDM); sulfonated epdm; styrene butadiene ribber; fluorubber; tetrafluoroethene-hexafluoroethylene copolymer; tetrafluoraoethylene-hexafluoropropylene copolymer; tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer; vinylidene fluoride-hexafluoropropylene copolymer; vinylidene-chlorotrifluoroethylene; ethylene-tetrafluoroethylene copolymer; polychlorotrifluoroethylene; vinylidene fluoride pentafluor propylene copolymer; propylene-TFE copolymer; ethylene-chlorotrifluoro-ethylene copolymer; biasfluoroethylene-hexafluoropropylene-TFE copolymer; vinylidene-perfluoro methyl vinyl ether-TFE copolymer; ethylene-acrylic acid copolymer or its (Na
+) ionomer body, ethylene-methacrylic acid copolymer or its (Na
+) ionomer body, ethylene-methyl acrylate copolymer or its (Na
+) ionomer body, ethylene-methyl methacrylate methyl terpolymer or its (Na
+) ionomer body, poly(ethylene oxide) etc. polysaccharide, thermoplastic resin, have the polymer of caoutchouc elasticity etc., these adhesives can 1 kinds or are made up more than 2 kinds and use.In addition, when use contained the compound of the functional group of reacting with lithium as polysaccharide, for example, the preferred compound that adds as isocyanate group made its functional group's inactivation.The cooperation ratio of adhesive is 1～50 weight %, 5～15 weight % preferably in anode mixture.
Filler suppresses the volumetric expansion of positive pole etc. in anode mixture, can add as required.As filler,, for example can use the fiber of the alkenes polymer, glass, carbon etc. of polypropylene, polyethylene etc. if in the battery that constitutes, do not cause that the fibrous material of chemical change just can use arbitrarily.The addition of filler has no particular limits, preferred 0～30 weight % in anode mixture.
Negative pole by anticathode material on negative electrode collector be coated with, drying etc. and forming.As negative electrode collector, just there is no particular limitation if do not cause the electrical conductivity body of chemical change in the battery that constitutes, and for example can enumerate stainless steel, nickel, copper, titanium, aluminium, sintered carbon, make carbon, nickel, titanium, silver carry out surface-treated object and aluminium-cadmium alloy etc. on the surface of copper and stainless steel etc.In addition, use on surface that also can these materials of oxidation, also can be produced concavo-convex on the collector body surface and used by surface treatment.In addition, as the form of collector body, can enumerate formed body of for example paillon foil, film, sheet, net, punching press thing, lath body, porous plastid, foaming body, groups of fibers, nonwoven fabrics etc.The thickness of collector body has no particular limits, and is preferably 1～500 μ m.
As negative material, have no particular limits, can enumerate for example carbonaceous material, composite oxide of metal, lithium metal, lithium alloy, silicon class alloy, tin class alloy, metal oxide, electroconductive polymer, chalcogen compound, Li-Co-Ni class material etc.As carbonaceous material, can enumerate for example difficult graphited material with carbon element, graphite-like material with carbon element etc.As composite oxide of metal, can enumerate for example Sn
pM
1 1-pM
2 qO
r(in the formula, M
1Expression is selected from the element more than a kind, the M of Mn, Fe, Pb and Ge
2Expression is selected from the element more than a kind, 0＜p≤1,1≤q≤3,1≤r≤8 of Al, B, P, Si, periodic table first family, second family, three races and halogen), Li
xFe
2O
3(0≤x≤1), Li
xWO
2The compound of (0≤x≤1) etc.As metal oxide, can enumerate GeO, GeO
2, SnO, SnO
2, PbO, PbO
2, Pb
2O
3, Pb
3O
4, Sb
2O
3, Sb
2O
4, Sb
2O
5, Bi
2O
3, Bi
2O
4, Bi
2O
5Deng.As electroconductive polymer, can enumerate polyacetylene, polyparaphenylene etc.
As spacer, can use the insulating properties film that has big ion permeability, has definite mechanical strength.Consider from organic solvent resistance and hydrophobicity, can use sheet or the nonwoven fabrics made by alkenes polymer such as polypropylene or glass fibre or polyethylene etc.The aperture of spacer generally as battery usefulness, if useful scope is just passable, for example is 0.01～10 μ m.The thickness of spacer generally as battery usefulness, if useful scope is just passable, for example is 5～300 μ m.In addition, as electrolyte described later, in the time of can using the solid electrolyte of polymer etc., solid electrolyte can double as be a spacer also.
The nonaqueous electrolyte that contains lithium salts is made up of nonaqueous electrolyte and lithium salts.As nonaqueous electrolyte, can use nonaqueous electrolytic solution, organic solid electrolyte based, inorganic solid electrolyte.As nonaqueous electrolytic solution, can enumerate for example N-methyl-2-pyrrolidine-diones, propene carbonate, ethylene carbonate, butylene, dimethyl carbonate, diethyl carbonate, gamma-butyrolacton, 1, the 2-dimethoxy-ethane, oxolane, the 2-methyltetrahydrofuran, 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, methyl sulfolane, 3-methyl-2-oxazoline diketone, 1,3-dimethyl-2-imidazolinedione, the propylene carbonate ester derivant, tetrahydrofuran derivatives, Anaesthetie Ether, 1,3-propane sultone, methyl propionate, 1 kind of the non-proton organic solvent of ethyl propionate etc. or mix solvent more than 2 kinds.
As organic solid electrolyte based, can enumerate for example polythene derivative, polyethylene oxide derivant contain these polymer, poly propylene oxide derivative or contain these polymer, phosphate ester polymer, polyphosphazene, polyethylene imine, polyvinyl sulfide, polyvinyl alcohol, Kynoar, polyhexafluoropropylene etc. the polymer that contains the ionic base that dissociates, contain the ionic polymer of base and the mixture of above-mentioned nonaqueous electrolytic solution etc. of dissociating.
As inorganic solid electrolyte, can use nitride, halide, oxysalt, sulfide of Li etc., can enumerate for example Li
3N, LiI, Li
5NI
2, Li
3N-LiI-LiOH, LiSiO
4, LiSiO
4-LiI-LiOH, Li
2SiS
3, Li
4SiO
4, Li
4SiO
4-LiI-LiOH, P
2S
5, Li
2S or Li
2S-P
2S
5, Li
2S-SiS
2, Li
2S-GeS
2, Li
2S-Ga
2S
3, Li
2S-B
2S
3, Li
2S-P
2S
5-X, Li
2S-SiS
2-X, Li
2S-GeS
2-X, Li
2S-Ga
2S
3-X, Li
2S-B
2S
3(in the formula, X is selected from LiI, B to-X
2S
3Or Al
2S
3More than at least a kind) etc.
In addition, when inorganic solid electrolyte is noncrystalline (glass), can in inorganic solid electrolyte, contain lithium phosphate (Li
3PO
4), lithia (Li
2O), lithium sulfate (Li
2SO
4), phosphorous oxide (P
2O
5), lithium borate (Li
3BO
3) oxygenatedchemicals that waits, Li
3PO
4-xN
2x/3(being 0＜x＜4), Li
4SiO
4-xN
2x/3(x is 0＜x＜4), Li
4GeO
4-xN
2x/3(x is 0＜x＜4), Li
3BO
3-xN
2x/3The nitrogen-containing compound of (x is 0＜x＜3) etc.By adding this oxygenatedchemicals or nitrogen-containing compound, the gap of the noncrystalline skeleton that expansion forms, alleviate the obstacle that lithium ion moves, ionic conductivity is improved more.
As lithium salts, can use the lithium salts that in above-mentioned nonaqueous electrolyte, dissolves, can enumerate for example LiCl, LiBr, LiI, LiClO
4, LiBF
4, LiB
10Cl
10, LiPF
6, LiCF
3SO
3, LiCF
3CO
2, LiAsF
6, LiSbF
6, LiB
10Cl
10, LiAlCl
4, CH
3SO
3Li, CF
3SO
3Li, (CF
3SO
2)
2NLi, chlorination monoborane lithium, lower aliphatic carboxylic acid lithium, tetraphenyl lithium borate, imido base class etc. a kind or mix salt more than 2 kinds.
In addition, in nonaqueous electrolyte, be purpose with improvement discharge, charge characteristic, anti-flammability, can add compound shown below.Pyridine for example, triethyl phosphate, triethanolamine, cyclic ethers, ethylenediamine, the n-glyme, hexamethylene alkyd triamide, nitrobenzene derivative, sulphur, quinoneimine dye, N-substituted oxazole quinoline diketone and N, N-substituted imidazoline diketone, the ethylene glycol bisthioglycolate alkyl ether, ammonium salt, polyethylene glycol, the pyrroles, 2-methyl cellosolve, alchlor, the monomer of conductive polymer electrodes active material, TEF, trialkyl phosphine, morpholine, aryl compound with carbonyl, hexamethylphosphorictriamide and 4-alkyl morpholine, the tertiary amine of dicyclo, oil Phosphonium root salt and Shu Phosphonium root salt, phosphonitrile, carbonic ester etc.In addition, for electrolyte being made non-flammability, can in electrolyte, contain halogen-containing solvent, for example carbon tetrachloride, trifluoro-ethylene.In addition, preserve adaptability, can in electrolyte, contain carbon dioxide in order to make it to have high temperature.
Lithium secondary battery of the present invention is battery performance, the particularly lithium secondary battery of cycle characteristics excellence, and the shape of battery also can be the arbitrary shape of button, sheet, cylinder, side, Coin shape etc.
There is no particular limitation for the purposes of lithium secondary battery of the present invention, can enumerate the daily life electronic apparatus of the electronic apparatus, automobile, motor vehicle, game machine etc. of for example notebook-sized personal computer, portable personal computer, pocket Word message processor, portable phone, the handset of Wireless electrical appliance, portable CD-audio player, broadcast receiver, liquid crystal TV set, back-up source, electric razor, storage card, video tape recorder etc.
In with the lithium secondary battery of lithium-cobalt composite oxides powder of the present invention as positive active material, particularly the reason of cycle characteristics raising is not understood, as the compound that contains above-mentioned metallic atom in the past, can think the lithium-cobalt composite oxides powder that uses these metal oxides or carbonate to obtain, this metal is to exist in the solid-state equably dissolving in lithium-cobalt composite oxides particle inside, but the compound that contains metallic atom as the present invention like that, can think because use the phosphate of these metals or/and hydrophosphate, sintering contains the compound of this metallic atom, the material of the mixture of lithium compound and cobalt compound, the metal ingredient that makes it to contain energetically are by the opposing party's composition PO
4Effect etc., preferentially exist at the particle surface of this lithium-cobalt composite oxides with oxide, again by the delicate balance of the amount of the metallic atom that contains it, suppress the Co in the lithium-cobalt composite oxides of one of lithium secondary battery cycle characteristics variation reason effectively
4+Stripping.
Embodiment
Below, illustrate in greater detail the present invention by embodiment, but the present invention is not limited by these.
Embodiment 1～3 and reference examples 1
Become the molar ratio weighing Co of atom of Co shown in the table 1 and Li atom
3O
4(average grain diameter 2 μ m), Li
2CO
3(average grain diameter 7 μ m) with the Mg atomic molar ratio shown in the table 1, fully mix commercially available Mg with dry type again
3(PO
4)
28H
2Behind the O (average grain diameter 10.6 μ m), carry out sintering with the temperature and time shown in the table 1.Pulverize this sinter, classification, obtain containing the lithium-cobalt composite oxides of Mg atom.
Reference examples 2
Molar ratio weighing Co with atom of Co shown in the table 1 and Li atom
3O
4(average grain diameter 2 μ m), Li
2CO
3(average grain diameter 9 μ m), again with the Mg atomic molar ratio shown in the table 1, fully mix commercially available MgO (average grain diameter 8 μ m) with dry type after, carry out sintering with the temperature and time shown in the table 1.Pulverize this sinter, classification, obtain containing the lithium-cobalt composite oxides of Mg atom.
Reference examples 3
With the mol ratio of atom of Co shown in the table 1 and Li atom, weighing Co
3O
4(average grain diameter 4.3 μ m), Li
2CO
3(average grain diameter 13 μ m) with the Mg atomic molar ratio shown in the table 1, fully mix commercially available MgCO with dry type again
3After (average grain diameter 5.2 μ m), carry out sintering with the temperature and time shown in the table 1.Pulverize this sinter, classification, obtain containing the lithium-cobalt composite oxides of Mg atom.
Reference examples 4
With the mol ratio of atom of Co shown in the table 1 and Li atom, weighing Co
3O
4(average grain diameter 12.1 μ m), Li
2CO
3(average grain diameter 13 μ m) are after fully mixing with dry type, 1080 ℃ of following sintering 5 hours.Pulverize this sinter, classification, obtain LiCoO
2
Table 1
| The kind of raw material Mg compound | The mol ratio of the Li of raw mix: Co: Mg | Sintering temperature (℃) | Sintering time (hour) | |
| Embodiment 1 | Magnesium phosphate | 1.030∶1.00∶0.001 | 1000 | 3 |
| | Magnesium phosphate | 1.045∶1.00∶0.005 | 1080 | 5 |
| Embodiment 3 | Magnesium phosphate | 1.010∶1.00∶0.04 | 1050 | 2 |
| Reference examples 1 | Magnesium phosphate | 1.010∶1.00∶0.06 | 1000 | 3 |
| Reference examples 2 | Magnesium oxide | 1.030∶1.00∶0.002 | 1000 | 3 |
| Reference examples 3 | Magnesium carbonate | 1.045∶1.00∶0.005 | 1080 | 5 |
| Reference examples 4 | - | 1.045∶1.00∶- | 1080 | 5 |
(evaluation of physical property of lithium-cobalt composite oxides)
The lithium-cobalt composite oxides powder that embodiment 1～3 and reference examples 1～4 are obtained is measured the PO of average grain diameter, BET specific area and stripping
4 2-Amount, its result shown in the table 2.In addition, average grain diameter is obtained by laser particle size measure of spread method, the PO of stripping
4 2-Amount is obtained with following method.
(1) PO of stripping
4 2-Mensuration
Make the 30g lithium-cobalt composite oxides powder with 5 minutes, under 25 ℃, be distributed in the 100ml pure water, make PO
4 2-From the particle surface stripping, by the PO in quantitative this solution of chromatography of ions
4 2-Amount.
Table 2
| Mg content (weight %) | Average grain diameter (μ m) | BET specific area (m 2/g) | PO 4 2-Amount (ppm) | |
| Embodiment 1 | 0.0253 | 8.0 | 0.45 | 55 |
| | 0.1238 | 19.3 | 0.25 | 619 |
| Embodiment 3 | 0.9940 | 7.2 | 0.48 | 2321 |
| Reference examples 1 | 1.2450 | 6.5 | 0.51 | 2798 |
| Reference examples 2 | 0.0505 | 9.2 | 0.35 | 5 |
| Reference examples 3 | 0.1250 | 17.2 | 0.38 | 4 |
| Reference examples 4 | 0.0025 | 16.5 | 0.28 | 1 |
Mg content is with acid dissolving test portion in (notes) table, measures the value that its lysate is tried to achieve by ICP.
＜battery performance test 〉
(1) making of lithium secondary battery
The Kynoar of powdered graphite, 3 weight % that mixes the embodiment 1～3 of 91 weight % and lithium-cobalt composite oxides powder that reference examples 1～4 obtains, 6 weight % is dispersed in the N-N-methyl-2-2-pyrrolidone N-it as anodal agent, prepares mixing paste.This mixing paste back of coating is dry on aluminium foil, and die mould is die-cut into the disk that diameter is 15mm, obtains positive plate.
Utilize this positive plate, use each member of spacer, negative pole, positive pole, collector plate, installation accessory, outside terminal, electrolyte etc., make lithium secondary battery.Wherein, negative pole uses metallic lithium foil, and electrolyte uses 1 mole of LiPF of dissolving in 1: 1 mixing liquid of 1 liter of ethylene carbonate and Methylethyl carbonic ester
6Solution.
(2) evaluation of battery performance
Make the lithium secondary battery work of making under the room temperature with following condition, estimate following battery performance.
The evaluation of＜cycle characteristics 〉
The active material of electrode coating embodiment 1～3 and reference examples 1～4 preparation is with 2.7V～4.3V (vs.Li/Li
+) determine that electric current discharges and recharges test.Fig. 1～7 these results' of expression flash-over characteristic figure.In addition, charging and discharging currents carries out with 0.2C.
By the result of Fig. 1～7 as can be known, the active material that the active material that embodiment 1～3 obtains obtains than reference examples 1～4 can obtain good cycle characteristics.Can think that this is that the Mg that contains remains in surface, coating surface as oxide, suppresses cycle characteristics is imposed the cause of dysgenic Co ion stripping in cobalt acid lithium.
Claims (10)
1. lithium-cobalt composite oxides powder is characterized in that:
The metallic atom more than at least a kind that is selected from Mg, Al, Zr, Ca and Ti that contains 0.025～1.0 weight %, and by mixed lithiated compound, cobalt compound and be selected from the phosphate of described metal or the compound that contains metallic atom of hydrophosphate, this mixture of sintering and generating.
2. lithium-cobalt composite oxides powder as claimed in claim 1 is characterized in that:
Average grain diameter is 0.5～30 μ m.
3. lithium-cobalt composite oxides powder as claimed in claim 1 is characterized in that:
The BET specific area is 0.05～1m
2/ g.
4. lithium-cobalt composite oxides powder as claimed in claim 1 is characterized in that:
The PO of stripping in water
4 2-Amount be below the 1 weight %.
5. as the described lithium-cobalt composite oxides powder of claim 1～4, it is characterized in that:
Described metallic atom is the Mg atom.
6. the manufacture method of a lithium-cobalt composite oxides powder is characterized in that:
By mixed lithiated compound, cobalt compound with contain the compound of the metallic atom more than at least a kind that is selected from Mg, Al, Zr, Ca and Ti, and carry out sintering and make lithium-cobalt composite oxides, wherein, as the compound that contains described metallic atom, use the phosphate or the hydrophosphate of this metal, make lithium compound, cobalt compound and contain the compound of described metallic atom, mol ratio with relative Co atom is that Li atom 0.90～1.20, metallic atom 0.001～0.04 mix, and the mixture that obtains of sintering.
7. the manufacture method of lithium-cobalt composite oxides powder as claimed in claim 6, it is characterized in that: described sintering carries out under 800～1150 ℃.
8. as the manufacture method of claim 6 or 7 described lithium-cobalt composite oxides powders, it is characterized in that: the compound that contains described metallic atom is a magnesium phosphate.
9. cathode active material for lithium secondary battery is characterized in that:
Contain each described lithium-cobalt composite oxides powder of claim 1～5.
10. lithium secondary battery is characterized in that:
Use the described cathode active material for lithium secondary battery of claim 9.
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| CN103999279A (en) * | 2011-12-22 | 2014-08-20 | 国立大学法人东京工业大学 | Sulfide solid electrolyte material, battery, and method for producing sulfide solid electrolyte material |
| CN105609868A (en) * | 2010-08-26 | 2016-05-25 | 丰田自动车株式会社 | Sulfide solid electrolyte material and lithium solid state battery |
| US10008735B2 (en) | 2009-12-16 | 2018-06-26 | Toyota Jidosha Kabushiki Kaisha | Method of producing a sulfide solid electrolyte material, sulfide solid electrolyte material, and lithium battery |
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| US8137844B2 (en) | 2006-11-17 | 2012-03-20 | Nippon Chemical Industrial Co., Ltd. | Cathode active material for lithium rechargeable battery, manufacturing method thereof and lithium rechargeable battery |
| KR100814831B1 (en) | 2006-11-20 | 2008-03-20 | 삼성에스디아이 주식회사 | Lithium secondary battery |
| KR101330616B1 (en) * | 2007-04-04 | 2013-11-18 | 삼성에스디아이 주식회사 | Positive electrode for rechargable lithium battery and rechargable lithium battery comprising same |
| JP5172231B2 (en) | 2007-07-20 | 2013-03-27 | 日本化学工業株式会社 | Positive electrode active material for lithium secondary battery, method for producing the same, and lithium secondary battery |
| JP5678826B2 (en) * | 2011-07-13 | 2015-03-04 | 日亜化学工業株式会社 | Method for producing positive electrode active material for non-aqueous electrolyte secondary battery |
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| JP3162437B2 (en) * | 1990-11-02 | 2001-04-25 | セイコーインスツルメンツ株式会社 | Non-aqueous electrolyte secondary battery |
| JP3212639B2 (en) * | 1991-07-31 | 2001-09-25 | 株式会社東芝 | Non-aqueous solvent secondary battery |
| JPH06243897A (en) * | 1992-12-24 | 1994-09-02 | Fuji Photo Film Co Ltd | Nonaqueous secondary battery |
| JPH08111218A (en) * | 1994-10-07 | 1996-04-30 | Honda Motor Co Ltd | Positive electrode material for lithium secondary battery and manufacture of the positive electrode material |
| JP3633223B2 (en) * | 1997-04-25 | 2005-03-30 | ソニー株式会社 | Positive electrode active material, method for producing the same, and nonaqueous electrolyte secondary battery |
| JP2000200607A (en) * | 1998-07-13 | 2000-07-18 | Ngk Insulators Ltd | Lithium secondary battery |
| JP4963532B2 (en) * | 2001-06-01 | 2012-06-27 | 日本化学工業株式会社 | Lithium secondary battery positive electrode active material and lithium secondary battery |
| US7135251B2 (en) * | 2001-06-14 | 2006-11-14 | Samsung Sdi Co., Ltd. | Active material for battery and method of preparing the same |
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| KR100437339B1 (en) * | 2002-05-13 | 2004-06-25 | 삼성에스디아이 주식회사 | A method of preparing active material for battery and active material prepared therefrom |
| JP4502664B2 (en) * | 2004-02-24 | 2010-07-14 | 三洋電機株式会社 | Non-aqueous electrolyte secondary battery |
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-
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| CN105609868B (en) * | 2010-08-26 | 2018-08-31 | 丰田自动车株式会社 | Sulfide solid electrolyte material and lithium solid state battery |
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| JP2006169048A (en) | 2006-06-29 |
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| KR20060069283A (en) | 2006-06-21 |
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