CN1848491A - Lithium secondary battery anode active matter, production method thereof, and lithium secondary battery - Google Patents

Lithium secondary battery anode active matter, production method thereof, and lithium secondary battery Download PDF

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Publication number
CN1848491A
CN1848491A CNA200610072060XA CN200610072060A CN1848491A CN 1848491 A CN1848491 A CN 1848491A CN A200610072060X A CNA200610072060X A CN A200610072060XA CN 200610072060 A CN200610072060 A CN 200610072060A CN 1848491 A CN1848491 A CN 1848491A
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lithium
average grain
grain diameter
powder
secondary battery
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粟野英明
大石义英
根岸克幸
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Nippon Chemical Industrial Co Ltd
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Nippon Chemical Industrial Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • 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
    • 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
    • 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
    • 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
    • H01M4/48—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
    • 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
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The present invention provides active material for lithium secondary batteries, a method of manufacturing the same and a lithium secondary battery all of which can improve cycle characteristics and battery capacity at low temperatures of lithium secondary batteries even if an inexpensive material, such as cobalt, is used. This positive active material for lithium secondary batteries is a mixed powder produced by mixing together: a lithium cobaltate particle powder (A) that has an average particle diameter of 5 to 30 mum and is produced by calcining a mixed powder of oxyhydoxide cobalt and a lithium compound; and a lithium cobaltate particle powder (B) that has an average particle diameter of 0.1 to 10 mum and less than the above average particle diameter (A) and is produced by calcining a mixed powder of tricoblt tetraoxide and a lithium compound; wherein a mixing ratio of the component (A) to the component (B) is (A):(B)=95:5 to 60:40 in terms of a weight ratio, and a tap density is 1.8-3.0 g/cm<SP>3</SP>.

Description

Cathode active material for lithium secondary battery, its manufacture method and lithium secondary battery
Technical field
The present invention relates to cathode active material for lithium secondary battery, its manufacture method and cycle characteristics excellence, also have a lithium secondary battery of high battery capacity at low temperatures.
Background technology
In recent years, along with the portability of household electrical appliance, the develop rapidly of wireless penetration, lithium rechargeable battery is applied to the power supply of small-sized electronic products such as laptop PC, mobile phone, video camera.(" マ テ リ ア Le リ サ one チ Block レ テ イ Application " (MaterialResearch Bulletin) Vol 15 since people such as water island in 1980 have disclosed cobalt acid lithium can effectively be used as the positive active material of lithium rechargeable battery, P783～789 (1980)), in field of lithium ion secondary, correlative study exploitation to the lithium system complex oxide just becomes very active, and people have proposed a lot of technical schemes up to now.
In following patent documentation 1, proposed to contain average grain diameter D50 and be the slightly spherical cobalt acid lithium of 7～20 μ m and average grain diameter D50 and be the technical scheme of the positive active material of 1/2～9/1 mixture for the mass ratio of 10～30% the cobalt acid lithium small size particle of the D50 of this cobalt acid lithium large-size particles and the former with the latter.In addition, the average grain diameter that the inventor etc. have proposed a kind of lithium composite xoide particle is in the scope of 0.1～50 μ m, and the positive active material (patent documentation 2) that has the peak more than 2 in the particle size distribution of this lithium composite xoide particle, or a kind of containing comprise tap density 1.8g/cm 3More than, add percent consolidation 3.5～4.0g/cm 3The bulky grain powder and the positive active material (patent documentation 3) of the cobalt of small particle powder acid lithium powder mixed-powder each other.
[patent documentation 1] Japan Patent spy opens the 2004-119218 communique
[patent documentation 2] Japan Patent spy opens the 2000-82466 communique
[patent documentation 3] Japan Patent spy opens the 2004-182564 communique
According to said method, a kind of lithium secondary battery with excellent initial capacity and capability retention can be provided, but the also more remaining problems in aspect such as battery capacity reduction under cycle characteristics and low temperature.On the other hand, exist problems such as the cost of material of cobalt raw material cobalt oxide etc. is surging, very big hope is arranged so people, can reach the cathode active material for lithium secondary battery of excellent battery behavior to using cheap cobalt raw material.
Summary of the invention
Therefore, the object of the present invention is to provide a kind of cobalt raw material of cheapness that uses also can improve the cycle characteristics of lithium secondary battery and the cathode active material for lithium secondary battery and the manufacture method thereof of the battery capacity under the low temperature, in addition, also provide a kind of lithium secondary battery this positive active material, that the cycle characteristics excellence also has very high battery capacity at low temperatures that uses.
The inventor etc. are for after addressing the above problem further investigation repeatedly, found that, in the powder that the cobalt acid lithium powder that contains bulky grain powder and small particle powder is mixed with each other, the bulky grain powder is to utilize the cobalt acid lithium particle powder of the average grain diameter of cheap cobalt raw material hydroxy cobalt oxide (Cobalt Oxyhydroxide) generation at particular range, and small particle powder is to utilize the cobalt acid lithium particle powder of the average grain diameter of cobaltosic oxide generation at particular range, and above-mentioned bulky grain powder cooperates ratio and tap density in particular range with small particle powder, this mixed-powder is used as positive active material, then such lithium secondary battery has solved the problems referred to above, cycle characteristics is good, particularly also have high battery capacity under the low temperature, thereby finished the present invention.
That is, first invention proposed by the invention relates to cathode active material for lithium secondary battery, it is characterized in that this cathode active material for lithium secondary battery is following powder (A) and mixed-powder (B):
(A) mixture of hydroxy cobalt oxide and lithium compound being carried out the average grain diameter that sintering generates is the cobalt acid lithium particle powder of 5～30 μ m;
(B) mixture of cobaltosic oxide and lithium compound being carried out the average grain diameter that sintering generates is 0.1～10 μ m, and average grain diameter is less than the cobalt acid lithium particle powder of the average grain diameter of above-mentioned (A),
Wherein, the cooperation ratio of above-mentioned bulky grain powder (A) and small particle powder (B) is counted (A) with weight ratio: (B)=95: 5～60: 40, and tap density is 1.8～3.0g/cm 3
Second invention proposed by the invention relates to the manufacture method of cathode active material for lithium secondary battery, it is characterized in that, mixes following powder (A) and (B):
(A) mixture of hydroxy cobalt oxide and lithium compound being carried out the average grain diameter that sintering generates is the cobalt acid lithium particle powder of 5～30 μ m;
(B) mixture of cobaltosic oxide and lithium compound being carried out the average grain diameter that sintering generates is 0.1～10 μ m, and average grain diameter is less than the cobalt acid lithium particle powder of the average grain diameter of above-mentioned (A),
Make the cooperation ratio of above-mentioned bulky grain powder (A) and small particle powder (B) count (A) with weight ratio: (B)=95: 5～60: 40, obtaining tap density is 1.8～3.0g/cm 3Cobalt acid lithium mixed-powder.
The 3rd invention proposed by the invention is a kind of lithium secondary battery, it is characterized in that, uses the cathode active material for lithium secondary battery of above-mentioned first invention.
The present invention relates to the cathode active material for lithium secondary battery that a kind of main use cheap raw material hydroxy cobalt oxide is made, adopt the lithium secondary battery of this positive active material cobalt acid lithium to be compared as the lithium secondary battery of positive active material with existing, can form the battery that has excellent cycle characteristics, also has high power capacity at low temperatures, be a kind of cycle characteristics excellence, also have a lithium secondary battery of very high battery capacity at low temperatures.
Description of drawings
Single SEM photo that disperses cobalt acid lithium grain shape that Fig. 1 is obtained by Production Example 5 for expression.
The SEM photo of the grain shape of the cobalt acid lithium of the second particle that the primary particle aggegation that Fig. 2 is obtained by Production Example 12 for expression contains forms.
Embodiment
The following describes the cathode active material for lithium secondary battery of embodiment of the present invention.
The bulky grain powder (A) of first component
The bulky grain powder of the present invention's first component is a kind of cobalt acid lithium particle powder, it is generated by the mixture sintering of hydroxyl oxidize lithium and lithium compound, is 5～30 μ m in the average grain diameter of trying to achieve according to laser method particle size distribution measurement method, is preferably 10～28 μ m, is preferably in the particle size distribution of 11.5～20 μ m and has 1 peak especially.In the present invention, the reason that the average grain diameter of bulky grain powder is set in the above-mentioned scope is: when average grain diameter during greater than 30 μ m, can not obtain enough cycle characteristicss, and when average grain diameter during less than 5 μ m, can not obtain enough electrode densities again.
The bulky grain powder of above-mentioned first component also is an essential condition by the mixture sintering generation of hydroxyl oxidize lithium and lithium compound, compare as the bulky grain powder with the cobalt acid lithium of average grain diameter in above-mentioned scope that the mixture sintering that adopts cobaltosic oxide and lithium compound generates, use cheap raw material, can improve the cycle characteristics of the lithium secondary battery that helps commercial Application, the performances such as battery capacity under the low temperature again.
In the present invention, the bulky grain powder of first component is if form second particle by the primary particle aggegation, then electrode density can reduce, and the effect of the battery performances such as battery capacity under the low temperature that can not be improved, therefore being preferably primary particle especially has its original grain shape, promptly non-compendency monodisperse particles.Concrete grain shape can be confirmed by observing scanning electron microscope (SEM) photo.What in addition, this monodisperse status was represented is to convert, be more than 50% the state of monodisperse particles with number under the visual field of SEM.Fig. 1 is for representing the SEM photo (multiplying power * 3000) of the monodispersed cobalt acid lithium particle that Production Example 5 obtains.In addition, in the present invention, the average grain diameter of above-mentioned bulky grain powder is meant the average grain diameter of being tried to achieve by laser method particle size distribution measurement method basically.
Available hydroxy cobalt oxide is not particularly limited, the average grain diameter of trying to achieve according to laser method particle size distribution measurement method is 5～30 μ m, be preferably 10～20 μ m, in addition, hydroxy cobalt oxide in most of the cases forms second particle by the primary particle aggegation of 0.1～1 μ m, contain the following microparticle of the above 3 μ m of 20 volume %, but in the present invention, except being has the hydroxyl oxidize cobalt granule of above-mentioned average grain diameter, the content that also is preferably the following particle of 3 μ m is below 20 volume %, be preferably the hydroxyl oxidize cobalt granule that the following particulate of 15 volume % partly reduces, the hydroxy cobalt oxide and the lithium compound that use this particulate partly to reduce react the cobalt acid lithium that generates, and can further improve cycle characteristics, battery performances such as battery capacity under the low temperature.The inventor thinks that this is that this particulate partly promotes the stripping of the Co in the cobalt acid lithium, is the major reason that is easy to cause lithium secondary battery cycle characteristics variation owing to the particulate part from hydroxy cobalt oxide has sintering remnants on the particle surface of the cobalt acid lithium that generates.In addition, the content of the particle below the above-mentioned 3 μ m is tried to achieve by laser particle distribution measuring method.
This hydroxy cobalt oxide that does not contain particulate part in fact can adopt the known method manufacturing, if lift an example explanation, then can adopt and leave standstill after being distributed to commercially available hydroxy cobalt oxide in the water, removes the technical scheme of the particulate part that is present in the supernatant etc.
The lithium compound of method for making that is used for the cobalt acid lithium of this first component can be enumerated oxide, hydroxide, carbonate, nitrate and the acylate etc. of lithium, wherein, is preferably the lithium carbonate of industrial cheapness.In addition, when this lithium compound average grain diameter be 0.1～200 μ m, when being preferably 2～50 μ m especially, because of reactivity good, so preferred especially.
The reaction condition of above-mentioned hydroxy cobalt oxide and lithium compound, be that this hydroxy cobalt oxide and lithium compound are 0.90～1.10, are preferably 0.95～1.05 and mix with the mol ratio (Li/Co) of lithium and cobalt, obtain the mixture of homodisperse hydroxy cobalt oxide and lithium compound, then 700～1200 ℃, be preferably under 800～1100 ℃ to this mixture carry out sintering 0.5～10 hour, be preferably 0.5～5 hour.Sintering can carry out under the arbitrary environment in atmosphere or under the oxygen environment, is not particularly limited.And this sintering can be implemented several times as required.
Behind sintering, carry out the appropriateness cooling, pulverize as required, obtain cobalt acid lithium particle powder after the classification.In addition, the pulverizing of Shi Shiing can be carried out under the situations such as block that the sour lithium particle powder of cobalt that sintering obtains is the embrittlement combination as one sees fit as required, and cobalt acid lithium particle powder itself has specific average grain diameter and BET specific area.That is, gained cobalt acid lithium particle powder average grain diameter under the situation of monodisperse particles is 5～30 μ m, is preferably 10～28 μ m, is preferably 11.5～20 μ m especially, and the BET specific area is 0.05～1m 2/ g, be preferably 0.05～0.55m 2/ g.
The small particle powder of second component (B)
The small particle powder of above-mentioned second component is a kind of cobalt acid lithium particle powder, generated by the mixture sintering of cobaltosic oxide and lithium compound, the average grain diameter of trying to achieve according to laser method particle size distribution measurement method is 0.1～10 μ m, be preferably 0.1～8 μ m, be preferably especially in the particle size distribution of 0.3～8 μ m and have 1 peak.In the present invention, the reason that the average grain diameter of small particle powder is set in the above-mentioned scope is: when average grain diameter during greater than 10 μ m, can not obtain enough electrode densities, and when average grain diameter during less than 0.1 μ m, will go wrong at aspects such as battery securities again.
The small particle powder of above-mentioned second component also is an essential condition by the mixture sintering generation of cobaltosic oxide and lithium compound, compare as small particle powder with the cobalt acid lithium of average grain diameter in above-mentioned scope that the mixture sintering that adopts hydroxy cobalt oxide and lithium compound generates, can improve the battery performances such as battery capacity under cycle characteristics, the low temperature.
In the present invention, the bulky grain powder of second component forms secondary by the primary particle aggegation and obtains, and fillibility is good, can improve electrode density, and also has the effect that improves the battery performances such as battery capacity under the low temperature significantly, and is therefore preferred especially.What so-called primary particle aggegation formation second particle was represented is the attraction that smallest particles is subjected to Van der Waals force and surface charge power, forms the state of grain shape, and concrete grain shape can be by observing the affirmation of scanning electron microscope (SEM) photo.Can be called that powder to 80% above aggegation under the visual field of SEM carries out aggegation and the powder that forms.Fig. 2 is the SEM photo (multiplying power * 3000) of the cobalt acid lithium grain structure of the primary particle aggegation of expression Production Example 12.In addition, in the present invention, the average grain diameter of above-mentioned small particle powder is meant the average grain diameter of the second particle of being tried to achieve by laser method particle size distribution measurement method basically.
Used cobaltosic oxide is not particularly limited, and its average grain diameter of trying to achieve according to laser method particle size distribution measurement method is 0.1～10.0 μ m, is preferably 0.1～8.0 μ m that this cobaltosic oxide can adopt commercially available product.
The lithium compound of method for making that is used for the cobalt acid lithium of this second component can use the lithium compound identical with above-mentioned lithium compound, specifically can enumerate oxide, hydroxide, carbonate, nitrate and the acylate etc. of lithium, wherein, be preferably the lithium carbonate of industrial cheapness.In addition, when this lithium compound average grain diameter be 0.1～200 μ m, when being preferably 2～50 μ m especially, because reactive good, so preferred especially.
The reaction condition of above-mentioned cobaltosic oxide and lithium compound, be that this cobaltosic oxide and lithium compound are counted 0.90～1.10, are preferably 0.95～1.05 and mix with the mol ratio (Li/Co) of lithium and cobalt, obtain after the mixture of homodisperse cobaltosic oxide and lithium compound, 700～1200 ℃, be preferably under 800～1100 ℃ this mixture sintering 0.5～5 hour, be preferably 0.5～10 hour.Sintering can carry out under the arbitrary environment in atmosphere or under the oxygen environment, is not particularly limited.And this sintering can be implemented several times as required.
Behind sintering, carry out the appropriateness cooling, pulverize as required, obtain cobalt acid lithium particle powder after the classification.In addition, the pulverizing of Shi Shiing can be carried out under the situations such as block that the sour lithium particle powder of cobalt that sintering obtains is the embrittlement combination as one sees fit as required, and cobalt acid lithium particle powder itself has specific average grain diameter and BET specific area.That is, gained cobalt acid lithium particle powder has the form that the primary particle aggegation forms second particle, and the average grain diameter of this second particle is 0.1～10 μ m, is preferably 0.1～8 μ m that the BET specific area is 0.3～3.5m 2/ g, be preferably 0.3～1.5m 2/ g.
Cathode active material for lithium secondary battery
Cathode active material for lithium secondary battery of the present invention is the bulky grain powder (A) of above-mentioned first component and the mixed uniformly mixed-powder of small particle powder (B) of second component.The cooperation ratio of above-mentioned bulky grain powder (A) and small particle powder (B) is counted (A) with weight ratio: (B)=95: 5～60: 40, be preferably 90: 10～70: 30.And in the present invention, except that above-mentioned cooperation ratio, tap density is 1.8～3.0g/cm 3, be preferably 2.0～3.0g/cm 3Also be one of essential condition, the cathode active material for lithium secondary battery of the present invention with this composition can be given the cycle characteristics of the lithium secondary battery excellence of using this positive active material, and can make the battery that also has high power capacity at low temperatures.In addition, cathode active material for lithium secondary battery of the present invention is 11.5～28.0 μ m in the average grain diameter of above-mentioned (A) preferably, the average grain diameter of above-mentioned (B) is in the particle size distribution of 0.1～10 μ m, the mixed-powder that has 2 peaks, and the ratio (A)/(B) of the average grain diameter of the average grain diameter of above-mentioned (A) and above-mentioned (B) is more than 2.0, is preferably 2.5～36.0, why like this, be because can give the cycle characteristics of the lithium secondary battery excellence of using this positive active material, form the battery that also has high power capacity at low temperatures.
Above-mentioned tap density is represented be bulky grain powder (A) and small particle powder (B) special under the situation of not exerting pressure the filling characteristic of natural admixture, it is that the 70g test portion is added graduated cylinder, graduated cylinder is installed on the automatic T.D measurement mechanism, (with ASTM:B527-93,85 is standard) of trying to achieve according to the measuring condition of vibration number 500 times, vibration height 3.2mm, vibration frequency 200 times/minute.
The reason that tap density of the present invention is set in the above-mentioned scope is, when tap density is lower than 1.8g/cm 3The time, be difficult to obtain enough electrode densities, be higher than 3.0g/cm and work as tap density 3The time, the effect that then improves the battery performances such as battery capacity under the low temperature is relatively poor.
In addition, the mix proportion of bulky grain powder (A) and small particle powder (B) is for example really outside above-mentioned scope in the present invention, then the raising effect of the battery performances such as battery capacity under cycle characteristics and the low temperature is low, and when the content of bulky grain powder during less than above-mentioned scope, then be difficult to obtain the effect of enough raising density, on the other hand, if greater than above-mentioned scope, just be difficult to obtain enough rate characteristic.
Cathode active material for lithium secondary battery of the present invention is 3.5～4.5g/cm when expression adds the percent consolidation that adds of depressing the characteristic index that bulky grain powder (A) and small particle powder (B) fill with which kind of state except that above-mentioned characteristic 3, be preferably 3.7～4.5g/cm 3The time, can also improve the battery performances such as battery capacity under electrode density characteristic and cycle characteristics, the low temperature.
In addition, adding percent consolidation and be by test portion being added in the mould of diameter 15mm, carried out size in 1 minute is 1.96 * 10 8Pa (2ton/cm 2) mold pressing, obtain pellet, measure the pellet weight and volume then, and count particles density is tried to achieve.
Cathode active material for lithium secondary battery of the present invention contains the bulky grain powder (A) of above-mentioned first component of ormal weight and the even mixed-powder of the second component small particle powder (B) basically, the bulky grain powder (A) of above-mentioned first component of even mixing and the method for the second component small particle powder (B) be thing so long as the method for industrial enforcement also can be uniformly mixed, and just is not particularly limited.Specifically can enumerate containers such as usage level cylindrical shape, V-arrangement, double cone shape rotation shape mixers, band shape, flat spin shape, blade shape, perpendicular band shape, grind the fixedly method of shape mixer etc. of containers such as shape, planetary motion shape, static mixer, single-screw rotor shape, Henschel mixer, fluid injection-type mixer, but be not limited to use the method for above-mentioned mixer.
Lithium secondary battery
Lithium secondary battery of the present invention uses above-mentioned cathode active material for lithium secondary battery, comprises positive pole, negative pole, slider and contains the nonaqueous electrolyte of lithium salts.Positive pole is for example anode mixture to be coated in the positive pole that carries out formation such as drying on the positive electrode collector, and anode mixture comprises the filler of positive active material, conductive agent, adhesive and interpolation as required etc.Lithium secondary battery of the present invention evenly is coated with on positive pole as containing of positive active material above-mentioned bulky grain powder and the cobalt of small particle powder acid lithium mixed-powder.Therefore, lithium secondary battery of the present invention especially is difficult to take place the reduction of part throttle characteristics and cycle characteristics.
Positive electrode collector is not so long as can cause the electric conductor of chemical change in the battery that forms, just be not particularly limited, for example can enumerate stainless steel, nickel, aluminium, titanium, sintering charcoal and surface treatment be carried out on the surface of aluminium, stainless steel etc. and the collector body that forms etc. with carbon, nickel, titanium, silver.These materials can use behind surface oxidation, also can bring concavo-convex re-using for the collector body surface by surface treatment.In addition, the form of collector body can be enumerated shape, lath body, porous body, foaming body, fibre bundle, nonwoven fabrics formed body of foil shape (foil), membranaceous, sheet, netted, tape punching etc.The thickness of collector body is not particularly limited, and is preferably 1～500 μ m.
Conductive agent is not so long as can cause the electrically conductive material of chemical change and just be not particularly limited in the battery that forms.For example, can enumerate graphite such as native graphite or electrographite, carbon black classes such as carbon black, acetylene black, Ketjen black (Ketjen black), channel black, furnace black, dim (lamp black), thermal black, conductive fiber such as carbon fiber, metallic fiber, metal dust classes such as fluorocarbons, aluminium, nickel powder, electric conducting materials such as conducting metal oxides such as conductive whiskers such as zinc oxide, potassium titanate class, titanium oxide or polyphenylene (polyphenylene) derivative, native graphite can be enumerated for example flaky graphite, flaky graphite and amorphous graphite etc.These conductive agents both can use wherein a kind separately, also can mix use more than 2 kinds.The cooperation ratio of conductive agent is 1～50 weight % in anode mixture, is preferably 2～30 weight %.
Adhesive can be enumerated for example starch, polyvinylidene fluoride (polyvinylidene fluoride), polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, regenerated cellulose, cellulose diacetate, PVP, tetrafluoroethene, polyethylene, polypropylene, the ter-polymers of ethylene-propylene-alkadienes (EPDM), sulfonated epdm, styrene butadiene rubbers, fluorubber, tetrafluoroethene-hexafluoroethylene copolymer, tetrafluoraoethylene-hexafluoropropylene copolymer, tetrafluoroethene-perfluoroalkyl vinyl ether copolymer, vinylidene difluoride-hexafluoropropylene copolymer, vinylidene fluoride-chlorotrifluoroethylcopolymer copolymer, ethylene-tetrafluoroethylene copolymer, polychlorotrifluoroethylene, vinylidene fluoride-five fluorine propylene copolymer, propylene-TFE copolymer, ethylene-chlorotrifluoro-ethylene copolymer, vinylidene fluoride-hexafluoropropylene-TFE copolymer, vinylidene fluoride-methyl fluoride vinethene-TFE copolymer, ethylene-acrylic acid copolymer or its (Na +) ionomer compound, ethylene-methacrylic acid copolymer or its (Na +) ionomer compound, ethylene-methyl acrylate copolymer or its (Na +) ionomer compound, ethylene-methyl methacrylate methyl terpolymer or its (Na +) polysaccharide, thermoplastic resin such as ionomer compound, polyethylene glycol oxide, having the polymer of caoutchouc elasticity etc., these adhesives both can use wherein a kind separately, also can mix use more than 2 kinds.In addition, when use contains just like polysaccharide, can be with the functional group's of lithium reaction compound the time, be preferably compounds such as for example adding NCO above-mentioned functional group is lost activity.The cooperation ratio of adhesive is 1～50 weight % in anode mixture, is preferably 5～15 weight %.
Filler is the material that suppresses anodal volumetric expansion in anode mixture, adds as required.Filler is so long as can not cause the fibrous material of chemical change in the battery that forms just passable.For example can use olefin polymers such as polypropylene, polyethylene, the fiber of glass fibre, carbon etc.Addition to filler is not particularly limited, and preferably is 0～30 weight % in anode mixture.
Negative pole carries out drying etc. by coating negative material on negative electrode collector and forms.Negative electrode collector is not so long as can cause the electric conductor of chemical change and just be not particularly limited in the battery that forms, for example can enumerate stainless steel, nickel, copper, titanium, aluminium, sintering charcoal, the collector body that surface treatment forms afterwards be carried out on the surface of copper, stainless steel etc. with carbon, nickel, titanium, silver, and aluminium-cadmium alloy etc.These materials can use behind surface oxidation, also can bring concavo-convex re-using for the collector body surface by surface treatment.In addition, the form of collector body can be enumerated shape, lath body, porous body, foaming body, fibre bundle, nonwoven fabrics formed body of metal foil sheet, membranaceous, sheet, netted, tape punching etc.The thickness of collector body is not particularly limited, and is preferably 1～500 μ m.
The anticathode material is not particularly limited, and for example can enumerating, carbonaceous material, composite oxide of metal, lithium metal, lithium alloy, Si system alloy, tin are alloy, metal oxide, electroconductive polymer, chalcogenide, Li-Co-Ni based material etc.Carbonaceous material can enumerate for example be difficult to graphited material with carbon element, graphite is material with carbon element etc.Composite oxide of metal can be enumerated for example Sn pM 1 1-pM 2 qO r(in the formula, M 1Expression is selected from the element more than a kind of Mn, Fe, Pb and Ge, M 2Expression is selected from the element more than a kind of Al, B, P, Si, periodic table the 1st family, the 2nd family, the 3rd family and halogen, 0＜p≤1,1≤q≤3,1≤r≤8), Li xFe 2O 3(0≤x≤1), Li xWO 2The compound such as grade of (0≤x≤1).Metal oxide can be enumerated 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.Electroconductive polymer can be enumerated polyacetylene, polyphenyl (poly-p-phenylene) etc.
Slider adopts the insulating properties film that has bigger ion permeability, has the mechanical strength of regulation.Can adopt tablet that polyolefin polymers such as polypropylene or glass fibre or polyethylene etc. make, nonwoven fabrics etc. with organic solvent resistance and hydrophobicity etc.The scope useful as long as aperture of slider can be used as common batteries is interior, for example 0.01～10 μ m.The thickness of slider needs only in the scope of using as common batteries, for example 5～300 μ m.In addition, during solid electrolytes such as aftermentioned electrolyte employing polymer, solid electrolyte also can be also used as slider.
The nonaqueous electrolyte that contains lithium salts is the material that contains nonaqueous electrolyte and lithium salts.Nonaqueous electrolyte can adopt nonaqueous electrolytic solution, organic solid electrolyte based, inorganic solid electrolyte.Nonaqueous electrolytic solution for example can be enumerated the N-N-methyl-2-2-pyrrolidone N-, propene carbonate (propylenecarbonate), ethylene carbonate, butylene, dimethyl carbonate, diethyl carbonate, gamma-butyrolacton, 1, the 2-dimethoxy-ethane, oxolane, the 2-methyltetrahydrofuran, methyl-sulfoxide, 1, the 3-dioxolanes, formamide, dimethyl formamide, dioxolanes, acetonitrile, nitromethane, methyl formate, ethyl acetate, triethyl phosphate, trimethoxy-methane, dioxolane derivatives, sulfolane, methyl sulfolane, 3-methyl-2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, the propylene carbonate ester derivant, tetrahydrofuran derivatives, diethyl ether, 1, the 3-N-morpholinopropanesulfonic acid lactone, methyl propionate, 1 kind of non-proton organic solvents such as ethyl propionate or mix solvent more than 2 kinds.
Organic solid electrolyte based can be enumerated for example polythene derivative, polyethylene oxide derivatives or the polymer, phosphate ester polymer, polyphosphazene, polyaziridine, poly-cured ethylene, polyvinyl alcohol, polyvinylidene fluoride, polyhexafluoropropylene etc. that contain polymer, the polypropylene oxide derivatives of polyethylene oxide derivatives or contain polypropylene oxide derivatives contain the polymer of ionic disassociation base, and contains the polymer of ionic disassociation base and the mixture of above-mentioned nonaqueous electrolytic solution etc.
Inorganic solid electrolyte can adopt nitride, halide, oxysalt, sulfide of Li etc., for example, can enumerate 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 3In more than at least a kind) etc.
In addition, when inorganic solid electrolyte is noncrystalline (glass), also can contain lithium phosphate (Li in the inorganic solid electrolyte 3PO 4), lithia (Li 2O), lithium sulfate (Li 2SO 4), phosphorus pentoxide (P 2O 5), lithium borate (Li 3BO 3) wait oxygenatedchemicals, Li 3PO 4-xN 2x/3(x satisfies 0＜x＜4), Li 4SiO 4-xN 2x/3(x satisfies 0＜x＜4), Li 4GeO 4-xN 2x/3(x satisfies 0＜x＜4), Li 3BO 3-xN 2x/3Nitrogen-containing compounds such as (x satisfy 0＜x＜3).By adding these oxygenatedchemicalss or nitrogen-containing compound, can enlarge the gap of the noncrystalline skeleton that forms, reduce the obstruction that lithium ion is moved, further improve the conductibility of ion.
Lithium salts can adopt the lithium salts that can be dissolved in above-mentioned nonaqueous electrolyte, for example can enumerate 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) 2The salt that mixes more than a kind or 2 kinds of NLi, chloroboration lithium, lower aliphatic carboxylic acid lithium, tetraphenyl lithium borate, acid imide etc.
In addition, for the purpose of improving flash-over characteristic, charge characteristic, anti-flammability etc., can also add following compound in the nonaqueous electrolyte.Pyridine for example, triethyl phosphine (triethylphosphite), triethanolamine, cyclic ethers, ethylenediamine, positive glyme, six phosphoric acid triamines, nitrobenzene derivative, sulphur, quinoneimine dye, the N-substituted oxazolidinone, N, N-substituted imidazole alkane (imidazolidine), the ethylene glycol bisthioglycolate alkyl ether, ammonium salt, polyethylene glycol, the pyrroles, 2-methyl cellosolve, the tri-chlorination ammonium, the monomer of conductive polymer electrodes active material, triethylene phosphine amine, trialkyl phosphine, morpholine, the aryl compound of band carbonyl, hexamethyl phosphine triamine, the 4-alkyl morpholine, the dicyclo tertiary amine, oil phosphonium salt and San Ji phosphonium salt, the phosphine nitrile, carbonic ester etc.In addition, have noninflammability, also can contain halogen-containing solvent in the electrolyte, for example carbon tetrachloride, trifluoro-ethylene in order to make electrolyte.In addition, for having the high temperature keeping quality of appropriateness, also can contain carbon dioxide in the electrolyte.
Lithium secondary battery of the present invention is battery performance and cycle characteristics excellence, even also have the lithium secondary battery of high power capacity under the low temperature, the shape of this battery can be any shapes such as button-type, sheet, cylindric, square, coin shape.
Purposes to lithium secondary battery of the present invention is not particularly limited, for example, can enumerate electronic products such as notebook computer, laptop personal computer, pocket word processor, mobile phone, wireless interspeaker, portable CD Player, broadcast receiver, LCD TV, stand-by power supply, electric shaver, storage card, video camera, consumer electronic products such as automobile, electric motor car, game machine.
Embodiment
Below, be described more specifically the present invention by enumerating embodiment, but the present invention is not limited in illustrated embodiment.
The modulation hydroxy cobalt oxide
Test portion 1
In the commercially available hydroxy cobalt oxide of 30g (average grain diameter 10.5 μ m, the content 25.1 volume % of the particle that 3 μ m are following), add the 100ml pure water, left standstill 2 hours.Remove the supernatant that contains the molecule component then, reclaim hydroxy cobalt oxide and dry, with it as the hydroxy cobalt oxide test portion.
Test portion 2
In the commercially available hydroxy cobalt oxide of 30g (average grain diameter 14.1 μ m, the content 21.8 volume % of the particle that 3 μ m are following), add the 100ml pure water, left standstill 2 hours.Remove the supernatant that contains the molecule component then, reclaim hydroxy cobalt oxide and dry, with it as the hydroxy cobalt oxide test portion.
Table 1
Average grain diameter (μ m) The content (volume %) that 3 μ m are following BET specific area (m 2/g)
Test portion 1 12.5 15.2 1.0
Test portion 2 18.0 9.0 2.1
The modulation of cobalt acid lithium
Production Example 1
Being 1.01 atomic ratio according to Li/Co mixes lithium carbonate (average grain diameter 10 μ m) with hydroxy cobalt oxide test portion 1 according to the such scheme modulation, be modulated into uniform mixture, 850 ℃ of following sintering 10 hours, with this sinter pulverize, classification, obtain the cobalt acid lithium of average grain diameter 12.2 μ m.
Production Example 2
The hydroxyl-removal cobalt oxide does not adopt test portion 1 but adopts outside the test portion 2, and other is the same with Production Example 1, obtains the cobalt acid lithium of average grain diameter 17.7 μ m.
Production Example 3
Being 1.05 atomic ratio according to Li/Co mixes lithium carbonate (average grain diameter 10 μ m) with hydroxy cobalt oxide test portion 1 according to the such scheme modulation, be modulated into uniform mixture, 950 ℃ of following sintering 10 hours, with this sinter pulverize, classification, obtain the cobalt acid lithium of average grain diameter 14.1 μ m.
Production Example 4
The hydroxyl-removal cobalt oxide does not adopt test portion 1 but adopts outside the test portion 2, and other is the same with Production Example 3, obtains the cobalt acid lithium of average grain diameter 19.1 μ m.
Production Example 5
Being 1.04 atomic ratio according to Li/Co mixes lithium carbonate (average grain diameter 10 μ m) with hydroxy cobalt oxide test portion 1 according to the such scheme modulation, be modulated into uniform mixture, 1000 ℃ of following sintering 3 hours, with this sinter pulverize, classification, obtain the cobalt acid lithium of average grain diameter 15.0 μ m.
Production Example 6
The hydroxyl-removal cobalt oxide does not adopt test portion 1 but adopts outside the test portion 2, and other is the same with Production Example 5, obtains the cobalt acid lithium of average grain diameter 19.8 μ m.
Production Example 7
Being 0.98 atomic ratio according to Li/Co mixes lithium carbonate (average grain diameter 10 μ m) with hydroxy cobalt oxide test portion 1 according to the such scheme modulation, be modulated into uniform mixture, 1080 ℃ of following sintering 10 hours, with this sinter pulverize, classification, obtain the cobalt acid lithium of average grain diameter 12.0 μ m.
Production Example 8
The hydroxyl-removal cobalt oxide does not adopt test portion 1 but adopts outside the test portion 2, and other is the same with Production Example 7, obtains the cobalt acid lithium of average grain diameter 17.2 μ m.
Production Example 9
Being 1.06 atomic ratio according to Li/Co mixes lithium carbonate (average grain diameter 10 μ m) with hydroxy cobalt oxide test portion 1 according to the such scheme modulation, be modulated into uniform mixture, 1050 ℃ of following sintering 10 hours, with this sinter pulverize, classification, obtain the cobalt acid lithium of average grain diameter 24.2 μ m.
Production Example 10
The hydroxyl-removal cobalt oxide does not adopt test portion 1 but adopts outside the test portion 2, and other is the same with Production Example 9, obtains the cobalt acid lithium of average grain diameter 27.1 μ m.
Production Example 11
Be that 0.90 atomic ratio mixes lithium carbonate (average grain diameter 0.1 μ m) with commercially available cobaltosic oxide (average grain diameter 0.1 μ m) according to Li/Co, be modulated into uniform mixture, 700 ℃ of following sintering 10 hours, with this sinter pulverize, classification, obtain the cobalt acid lithium of average grain diameter 0.5 μ m.
Production Example 12
Be that 1.00 atomic ratio mixes lithium carbonate (average grain diameter 10 μ m) with commercially available cobaltosic oxide (average grain diameter 0.1 μ m) according to Li/Co, be modulated into uniform mixture, 770 ℃ of following sintering 10 hours, with this sinter pulverize, classification, obtain the cobalt acid lithium of average grain diameter 1.7 μ m.
Production Example 13
Be that 1.01 atomic ratio mixes lithium carbonate (average grain diameter 10 μ m) with commercially available cobaltosic oxide (average grain diameter 2.0 μ m) according to Li/Co, be modulated into uniform mixture, 830 ℃ of following sintering 10 hours, with this sinter pulverize, classification, obtain the cobalt acid lithium of average grain diameter 3.3 μ m.
Production Example 14
Be that 1.02 atomic ratio mixes lithium carbonate (average grain diameter 10 μ m) with commercially available cobaltosic oxide (average grain diameter 4.0 μ m) according to Li/Co, be modulated into uniform mixture, 880 ℃ of following sintering 10 hours, with this sinter pulverize, classification, obtain the cobalt acid lithium of average grain diameter 7.8 μ m.
Production Example 15
Be that 1.045 atomic ratio mixes lithium carbonate (average grain diameter 10 μ m) with commercially available cobaltosic oxide (average grain diameter 5.1 μ m) according to Li/Co, be modulated into uniform mixture, 980 ℃ of following sintering 10 hours, with this sinter pulverize, classification, obtain the cobalt acid lithium of average grain diameter 9.8 μ m.
Production Example 16
Being 1.05 atomic ratio according to Li/Co mixes lithium carbonate (average grain diameter 10 μ m) with hydroxy cobalt oxide test portion 2 according to the such scheme modulation, be modulated into uniform mixture, 850 ℃ of following sintering 10 hours, with this sinter pulverize, classification, obtain the cobalt acid lithium of average grain diameter 6.8 μ m.
Table 2
Test portion The cobalt raw material that uses The rerum natura of cobalt acid lithium
Average grain diameter (μ m) BET specific area (m 2/g)
Production Example 1 A-1 Hydroxy cobalt oxide test portion 1 12.2 0.51
Production Example 2 A-2 Hydroxy cobalt oxide test portion 2 17.7 0.40
Production Example 3 B-1 Hydroxy cobalt oxide test portion 1 14.1 0.25
Production Example 4 B-2 Hydroxy cobalt oxide test portion 2 19.1 0.20
Production Example 5 C-1 Hydroxy cobalt oxide test portion 1 15.0 0.23
Production Example 6 C-2 Hydroxy cobalt oxide test portion 2 19.8 0.18
Production Example 7 D-1 Hydroxy cobalt oxide test portion 1 12.0 0.52
Production Example 8 D-2 Hydroxy cobalt oxide test portion 2 17.2 0.38
Production Example 9 E-1 Hydroxy cobalt oxide test portion 1 24.2 0.15
Production Example 10 E-2 Hydroxy cobalt oxide test portion 2 27.1 0.14
Production Example 11 F Cobaltosic oxide 0.5 3.20
Production Example 12 G Cobaltosic oxide 1.7 1.00
Production Example 13 H Cobaltosic oxide 3.3 0.82
Production Example 14 I Cobaltosic oxide 7.8 0.41
Production Example 15 J Cobaltosic oxide 9.8 0.22
Production Example 16 K-2 Hydroxy cobalt oxide test portion 2 6.8 0.61
Embodiment 1～10 and comparative example 1～9
Cooperation ratio according to table 3 will evenly be mixed in the miniature belt type blender according to each cobalt acid lithium test portion of such scheme modulation, and modulation positive active material test portion is measured tap density and added percent consolidation according to following method, and its result is as shown in table 3.
The method of measurement of tap density
With the graduated cylinder bone dry, measure the weight of empty graduated cylinder.With the about 70g test portion of test portion paper weighing.Use funnel that test portion is moved in the graduated cylinder.Graduated cylinder is installed on the automatic T.D measurement mechanism (YUASA-IONICS Co., Ltd. system, DUAL AUTOTAP), and regulating vibration number is 500 times, vibrates, and reads the scale of test portion face, measures the graduated cylinder weight that has added test portion, calculates tap density.Vibration is 200 times/minute (with ASTM:B527-93,85 is standard) for 3.2mm, vibration frequency highly.
The method of measurement that adds percent consolidation
Test portion is added in the mould of diameter 15mm, with 1.96 * 10 8Pa (2ton/cm 2) pressure (manual pressure machine, Japan merchant worker corporate system, model: WPN-10) handle 1 minute, obtain pellet.Measure the weight and volume of pellet then, calculate pellet density, as adding percent consolidation.
Table 3
The bulky grain powder Small particle powder Mixed-powder average grain diameter (μ m) Tap density (g/cm 3) Add percent consolidation (g/cm 3)
Kind Use level (weight portion) Kind Use level (weight portion)
Embodiment 1 A-1 70 F 30 8.9 1.80 3.51
Embodiment 2 A-2 70 F 30 12.8 1.85 3.62
Embodiment 3 B-1 85 G 15 11.9 2.00 3.70
Embodiment 4 B-2 85 G 15 16.0 2.05 3.75
Embodiment 5 C-1 90 H 10 13.6 2.21 3.70
Embodiment 6 C-2 90 H 10 18.0 2.28 3.82
Embodiment 7 D-1 80 I 20 11.5 2.31 3.73
Embodiment 8 D-2 80 I 20 15.3 2.62 3.75
Embodiment 9 E-1 75 J 25 20.7 2.81 3.91
Embodiment 10 E-2 75 J 25 23.1 2.87 3.93
Comparative example 1 - - I 100 7.8 2.18 3.23
Comparative example 2 - - J 100 9.8 2.45 3.42
Comparative example 3 A-1 100 - - 12.2 2.55 3.40
Comparative example 4 A-2 100 - - 17.7 2.71 3.49
Comparative example 5 B-1 100 - - 14.1 2.62 3.45
Comparative example 6 B-2 100 - - 19.1 2.78 3.49
Comparative example 7 K-2 40 F 60 6.8 2.11 3.21
Comparative example 8 K-2 98 F 2 6.8 2.05 3.22
Comparative example 9 I 80 F 20 7.8 2.22 3.30
Battery performance test
(1) makes lithium secondary battery
Positive electrode active material powder 91 weight %, powdered graphite 6 weight %, the polyvinylidene fluoride 3 weight % of embodiment 1～10 and comparative example 1～9 gained are mixed, make anode mixture, this anode mixture is distributed to the mixing cream of modulation in the N-N-methyl-2-2-pyrrolidone N-.Should be coated in dry back pressurization on the aluminium foil by mixing cream, strike out the disk of diameter 15mm, obtain positive plate.
Use this positive plate, and use various parts such as slider, negative pole, positive pole, collector plate, installation part, outside terminal, electrolyte to make lithium secondary battery.Wherein, negative pole adopts metallic lithium foil, and it is to be dissolved with 1 mole of LiPF in 1: 1 the mixing liquid that electrolyte uses 1 liter of ethylene carbonate and methyl ethyl carbonate 6Solution.
(2) battery performance evaluation
Make the lithium secondary battery that makes under 25 ℃ of room temperatures or-20 ℃, work under the following conditions, estimate following battery performance.
The evaluation of cycle characteristics
The Coin shape rechargeable nonaqueous electrolytic battery that makes is being worked at each temperature, estimate the capacity sustainment rate.At first, to positive pole charging, charging to 4.3V with the electric weight of 0.5C through 5 hours under constant current constant voltage (CCCV), be discharged to 2.7V with discharge rate 0.2C then, is a circulation with said process, measures the discharge capacity of each circulation.Then, under the situation of measuring above-mentioned discharge capacity, carry out discharging and recharging of 20 circulations, calculate the capacity sustainment rate according to following formula.The results are shown in table 4.
Capacity sustainment rate (%)=(discharge capacity of the 20th circulation) * 100/ (discharge capacity of circulation for the first time)
The evaluation of low-temperature characteristics
Make the Coin shape rechargeable nonaqueous electrolytic battery that makes in 25 ℃ of work down of room temperature, estimate discharge capacity.At first, under constant current constant voltage (CCCV),, charged to 4.3V through 5 hours, under-20 ℃, be discharged to 2.7V with discharge rate 0.2C then, measure discharge capacity with the electric weight of 0.5C to positive pole charging.The results are shown in table 4.
Table 4
25 ℃ capacity sustainment rate (%) -20 ℃ discharge capacity (mAh/g)
Embodiment 1 96 152
Embodiment 2 98 145
Embodiment 3 93 138
Embodiment 4 94 135
Embodiment 5 98 130
Embodiment 6 94 131
Embodiment 7 93 128
Embodiment 8 92 135
Embodiment 9 90 132
Embodiment 10 91 135
Comparative example 1 82 99
Comparative example 2 80 84
Comparative example 3 72 90
Comparative example 4 84 95
Comparative example 5 83 93
Comparative example 6 82 85
Comparative example 7 81 100
Comparative example 8 85 84
Comparative example 9 83 87
Comparing embodiment 1～10 gained active material and comparative example 1～9 gained active material as can be known, embodiment gained active material also has high power capacity under low temperature region.

Claims (6)

1. a cathode active material for lithium secondary battery is characterized in that,
This cathode active material for lithium secondary battery is following powder (A) and mixed-powder (B):
(A) mixture of hydroxy cobalt oxide and lithium compound being carried out the average grain diameter that sintering generates is the cobalt acid lithium particle powder of 5～30 μ m;
(B) mixture of cobaltosic oxide and lithium compound being carried out the average grain diameter that sintering generates is 0.1～10 μ m, and average grain diameter is less than the cobalt acid lithium particle powder of the average grain diameter of described (A),
Wherein, the cooperation ratio of described bulky grain powder (A) and small particle powder (B) is counted (A) with weight ratio: (B)=95: 5～60: 40, and tap density is 1.8～3.0g/cm 3
2. cathode active material for lithium secondary battery as claimed in claim 1 is characterized in that:
Described hydroxy cobalt oxide is that average grain diameter is the particle powder of content below 20 volume % of the following particle of 5～30 μ m and 3 μ m.
3. cathode active material for lithium secondary battery as claimed in claim 1 or 2 is characterized in that: adding percent consolidation is 3.5～4.5g/cm 3
4. the manufacture method of a cathode active material for lithium secondary battery is characterized in that,
Mix following powder (A) and (B):
(A) mixture of hydroxy cobalt oxide and lithium compound being carried out the average grain diameter that sintering generates is the cobalt acid lithium particle powder of 5～30 μ m;
(B) mixture of cobaltosic oxide and lithium compound being carried out the average grain diameter that sintering generates is 0.1～10 μ m, and average grain diameter is less than the cobalt acid lithium particle powder of the average grain diameter of described (A),
Make the cooperation ratio of described bulky grain powder (A) and small particle powder (B) count (A) with weight ratio: (B)=95: 5～60: 40, obtaining tap density is 1.8～3.0g/cm 3Cobalt acid lithium mixed-powder.
5. the manufacture method of cathode active material for lithium secondary battery as claimed in claim 4 is characterized in that: described hydroxy cobalt oxide is that average grain diameter is the particle powder of content below 20 volume % of the following particle of 5～30 μ m and 3 μ m.
6. lithium secondary battery is characterized in that:
Use each described cathode active material for lithium secondary battery of claim 1～3.
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Publication number Priority date Publication date Assignee Title
CN101284681B (en) * 2007-04-11 2010-11-17 北京当升材料科技有限公司 Super-size and high-density lithium cobalt oxide and method for preparing the same
EP3511298A1 (en) 2007-06-29 2019-07-17 Umicore High density lithium cobalt oxide for rechargeable batteries
US8337727B2 (en) 2007-06-29 2012-12-25 Umicore High density lithium cobalt oxide for rechargeable batteries
US8608987B2 (en) 2007-06-29 2013-12-17 Umicore High density lithium cobalt oxide for rechargeable batteries
CN103259011B (en) * 2008-03-28 2015-06-03 户田工业株式会社 Oxycobalt hydroxide particulate powder and manufacturing method therefor
CN101945825A (en) * 2008-03-28 2011-01-12 户田工业株式会社 Oxycobalt hydroxide particulate powder and manufacturing method therefor, as well as lithium cobaltate particulate powder, manufacturing method therefor, and non-aqueous electrolyte secondary battery using the same
CN101945825B (en) * 2008-03-28 2014-07-02 户田工业株式会社 Oxycobalt hydroxide particulate powder and manufacturing method therefor, as well as lithium cobaltate particulate powder, manufacturing method therefor, and non-aqueous electrolyte secondary battery using the same
US10044035B2 (en) 2011-06-17 2018-08-07 Umicore Lithium cobalt oxide based compounds with a cubic secondary phase
US9979021B2 (en) 2011-06-17 2018-05-22 Umicore Stoichiometrically controlled lithium cobalt oxide based compounds
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
CN102779976A (en) * 2011-10-10 2012-11-14 北大先行科技产业有限公司 Preparation method of cathode material of LCO (lithium cobaltate)-based lithium ion battery
CN110739485A (en) * 2019-10-30 2020-01-31 东莞维科电池有限公司 low-temperature lithium ion batteries
CN111029529A (en) * 2019-12-24 2020-04-17 北京汽车集团越野车有限公司 Preparation method of positive electrode material structure, battery positive electrode, battery and automobile

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