CN1311574C - Nonaqueous electrolyte secondary battery-use anode active matter, prodn. method therefor, nonaqueous electrolyte secondary battery, and prodn, method for anode - Google Patents

Nonaqueous electrolyte secondary battery-use anode active matter, prodn. method therefor, nonaqueous electrolyte secondary battery, and prodn, method for anode Download PDF

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CN1311574C
CN1311574C CNB02812992XA CN02812992A CN1311574C CN 1311574 C CN1311574 C CN 1311574C CN B02812992X A CNB02812992X A CN B02812992XA CN 02812992 A CN02812992 A CN 02812992A CN 1311574 C CN1311574 C CN 1311574C
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active material
particle
composite oxide
positive active
secondary battery
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CN1520621A (en
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藤原哲
小野茂
室田忠俊
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Santoku Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/139—Processes of manufacture
    • 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
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • 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

A nonaqueous electrolyte secondary battery-use active matter capable of effectively improving load characteristics in a nonaqueous electrolyte secondary battery and being increased in capacity, and being high in pack efficiency and large in pack density; and a production method therefor; wherein the anode active matter consists of complex oxide particles containing Li and at least one kind of transition element selected from a group consisting of Co, Ni, Mn and Fe, and the complex oxide particles contain at least 90% of spherical and/or ellipsoidal particles having a ratio D1/D2 that ranges from 1.0 to 2.0 when the longest diameter is D1 and the shortest diameter D2.

Description

Nonaqueous electrolytic solution secondary battery positive active material, its manufacture method, nonaqueous electrolytic solution secondary battery and anodal manufacture method
Technical field
The present invention relates to non-aqueous solution as effective in the electrolytical secondary cell improved load characteristic, can high capacity the nonaqueous electrolytic solution secondary battery positive active material, its manufacture method is used the nonaqueous electrolytic solution secondary battery of this positive active material and the manufacture method that this nonaqueous electrolytic solution secondary battery is used positive pole.
Background technology
In recent years, portable miniaturization with e-machine, lightweight, high performances such as video camera, portable CD, portable phone, PDA, notebook personal computer are carrying out always.For portable power supply, need high power capacity and the secondary cell heavy load characteristic good, safe with e-machine.As satisfying the above-mentioned purpose secondary cell, can use sealed lead accumulator, cadmium-nickel storage cell, as the higher battery of energy density, nickel-hydrogen accumulator has been realized practicability, as nonaqueous electrolytic solution secondary battery, lithium rechargeable battery has been realized practicability.
Lithium rechargeable battery is to use the composite oxides of Li and transition metal such as Co, Ni, Mn as positive active material, the secondary cell of the carbonaceous materials such as carbon of insertion lithium ion as negative electrode active material can be inserted, be taken off to use, compare with nickel-hydrogen accumulator etc., have the feature that capacity is big and voltage is high.But, at the further requirement of high capacity and big electric currentization recently, needing by improving the packed density of positive active material, the amount that reduces the conductive auxiliary agent that mixes with positive active material increases countermeasures such as positive active material weight.
In order to respond this needs, various researchs have been carried out, wherein carried out following trial, that is,, improve charging efficiency by positive active material is made sphere, increase active material contact area each other by improving charging efficiency, thereby raising conductivity reduces the conductive auxiliary agent in the positive pole, increases the trial of active material weight in fact.
For example, open in the flat 10-74516 communique, disclose positive active material is made hollow spheres, when improving charging efficiency, increase specific area, the contact area of increase and electrolyte, the reactive technology when improving heavy load the spy.But, adopt this method, because active material is hollow spheres, even thereby expect that owing to the spherical charging efficiency that improved but the reduction of the amount of the active material that unit volume can be filled can't wish to obtain high power capacity.
Disclose cobalt source in the Te Kaiping 11-273678 communique, used spherical or axiolitic hydroxy cobalt oxide, hydroxy cobalt oxide and lithium compound have been mixed, sintering, the technology of manufacturing spherical cathode active material as the lithium cobaltate cathode active material.Open in the flat 11-288716 communique the spy, disclose primary particle is mixed with the spherical or axiolitic nickel hydroxide cobalt of radial gathering and lithium compound, sintering is made the technology of spherical positive active material.
But, in these methods, when the reaction that generates positive active material takes place, cause the decomposition reaction of lithium compound and the decomposition reaction of transistion metal compound simultaneously.These decomposition reactions are accompanied by the generation of gases such as steam and carbon dioxide, and therefore, though the active material of generation keeps spherical, the space is very many, and the amount of the active material that unit volume can be filled reduces, and can't expect high power capacity.
Disclosure of the Invention
The purpose of this invention is to provide effective load characteristic of improving in the nonaqueous electrolytic solution secondary battery, can high capacity, the charging efficiency height, the big nonaqueous electrolytic solution secondary battery of packed density is with positive active material and manufacture method thereof.
Another object of the present invention provides the nonaqueous electrolytic solution secondary battery and the anodal manufacture method of this nonaqueous electrolytic solution secondary battery that can obtain good discharge capacity.
According to the present invention, a kind of nonaqueous electrolytic solution secondary battery positive active material is provided, it comprises the composite oxide particle that contains Li and be selected from least a transition elements among Co, Ni, Mn and the Fe, it is D1 that this composite oxide particle contains major diameter more than 90%, when minor axis is D2 D1/D2 at the spherical of 1.0～2.0 scopes and/or ellipsoid shape particle.
In addition, according to the present invention, the manufacture method of a kind of nonaqueous electrolytic solution secondary battery with positive active material is provided, comprise: the raw material that will be selected from the compound particles of at least a transition elements among Co, Ni, Mn and the Fe and contain lithium compound mix, prepare the operation (A) of raw mix, the operation (B) of the temperature calcining more than the fusing point of the lithium compound in raw mix, and the operation (C) of the above sintering of decomposition temperature of the lithium compound in raw mix.
And, according to the present invention, also providing a kind of nonaqueous electrolytic solution secondary battery, it possesses positive pole, negative pole and the electrolyte with positive electrode active material powder, and this positive electrode active material powder contains above-mentioned nonaqueous electrolytic solution secondary battery positive active material.
And, according to the present invention, the manufacture method of nonaqueous electrolytic solution secondary battery with positive pole also is provided, this method is that the positive active material that will contain composite oxide particle shapes the method for making the positive pole that uses in the above-mentioned nonaqueous electrolytic solution secondary battery, comprise: operation (a), preparation is in following composite oxide particle, average grain diameter differs at least two kinds of composite oxide particles more than 10%, wherein, described composite oxide particle mainly comprises the particle of particle diameter 2～100 μ m, and average grain diameter is 5～80 μ m, contain Li and be selected from Co, Ni, at least a transition elements among Mn and the Fe, the major diameter that contains more than 90% is D1, D1/D2 was at the spherical of 1.0～2.0 scopes and/or ellipsoid shape particle when minor axis was D2; And operation (b), the composite oxide particle mixing of preparing in the operation (a) is obtained positive active material.
Description of drawings
Fig. 1 is the SEM image of positive active material 1000 multiplying powers of embodiment 1 manufacturing.
Fig. 2 is the SEM image of positive active material 5000 multiplying powers of embodiment 1 manufacturing.
Invention preferred embodiment
Below, the present invention will be described in more detail.
Nonaqueous electrolytic solution secondary battery of the present invention comprises the specific composite oxide particle that contains Li and be selected from least a transition elements among Co, Ni, Mn and the Fe with positive active material (below be called positive active material of the present invention).
As above-mentioned composite oxides, can enumerate for example LiCoO 2, LiNiO 2, LiMn 2O 4, LiFeO 2And LiCo 0.8Ni 0.2O 2, LiCo 0.5Ni 0.5O 2, LiCo 0.1Ni 0.9O 2Deng LiCo xNi 1-xO 2The oxide of (0≤X≤1) expression.
Positive active material of the present invention can also contain and is selected from least a of alkali metal, alkaline-earth metal, Ti, Zr, Hf, Y, Sc and rare earth metal etc. except above-mentioned composition.These metallic elements have the lattice spacing that enlarges positive active material of the present invention, and the increase capacity perhaps improves efficiency for charge-discharge, perhaps improves the agglutinating property of positive active material, improve effects such as density.
These additions of adding element are preferably below the 1 weight % of total amount, below the preferred especially 0.5 weight %, further below the preferred 0.3 weight %.Surpass 1 weight %,, can't expect that also density improves even add, and, worry that the capacity of positive active material of the present invention reduces, therefore undesirable.
Shape as the composite oxide particle of positive active material of the present invention mainly is spherical or the ellipsoid shape.Adopt needle-like, spindle shape, tabular or unbodied shape therefore not preferred owing to can't improve charging efficiency, even the ellipsoid shape, if length-width ratio is big and near spindle, then since charging efficiency reduce, therefore not preferred.
Therefore, to contain the major diameter more than 90% be D1 to above-mentioned composite oxide particle, D1/D2 (length-width ratio) was 1.0～2.0 when minor axis was D2, the spherical and/or axiolitic particle of preferred 1.0～1.5 scopes.
The tap density height of positive active material of the present invention is more suitable.If tap density is low, then therefore the charging efficiency variation of positive active material, can't fill many active materials in the volume of limited pole plate, and capacity reduces.In positive active material of the present invention, preferred tap density is 2.9g/cm 3More than, be preferably 3.0g/cm especially 3More than, more preferably 3.1g/cm 3More than.There is no particular limitation for the upper limit of tap density, is generally 5.0g/cm 3About.
Improve above-mentioned tap density, the particle size distribution of particle and average grain diameter have important effect.If viscosity profile is wide or narrow, the charging efficiency variation of particle then, if average grain diameter is too small, then the surface energy quantitative change of particle is big, therefore, this situation also can cause charging efficiency to reduce.If average grain diameter is excessive, then when making electrode, on collector body, be difficult to evenly apply active material.
Therefore, the particle diameter that constitutes the composite oxide particle of positive active material of the present invention mainly is preferably 2～100 microns, and preferred especially 10～100 microns scope is particularly wished more than 80%, further more than 85%, further more than 90% in above-mentioned scope.In addition, preferred average grain diameter is 5～80 microns, preferred especially 30～80 microns, is more preferably 30～60 microns.If 5 microns of average grain diameter less thaies, perhaps greater than 80 microns, even then the scope of particle diameter is in above-mentioned preferable range, it is narrow that particle size distribution also becomes, and charging efficiency reduces, therefore not preferred.
Here, the particle diameter of composite oxides is the values that adopt laser diffraction formula particle size distribution meter (HoneyWell corporate system マ イ Network ロ ト ラ Star Network HRA) to measure, and average grain diameter is the D50 value.
The specific area of above-mentioned composite oxides is preferably 0.05～0.24m 2/ g, preferred especially 0.1～0.2m 2/ g.The not enough 0.05m of specific area 2During/g, the internal resistance of the positive pole that obtains increases, and the efficient discharge characteristic reduces, and is therefore not preferred, on the other hand, surpassing 0.24m 2Under the situation of/g, improve with the reactivity of electrolyte etc., the thermal stability of the positive pole that obtains reduces, and is therefore undesirable.
In addition, when adopting the actual manufacturing of the composite oxide particle that constitutes positive active material of the present invention anodal,, preferably use the mixture of at least two kinds of different above-mentioned composite oxide particles of above-mentioned average grain diameter in order to improve the charging efficiency of positive active material.At this moment, the preferred average grain diameter of the composite oxide particle of mixing differs more than 10%.
Make the method for positive active material of the present invention, as long as can access positive active material of the present invention, there is no particular limitation.For example, lithium compound that can be by will becoming the lithium source and become the compound of the transition elements of transition metal source is set suitable condition and is carried out the method etc. of sintering and obtain.As preferable methods can enumerate below shown in manufacture method of the present invention.
Manufacture method of the present invention is at first carried out operation (A), that is, will contain the compound particles of the transition elements that becomes specific transition metal source and the raw material of the lithium compound that becomes the lithium source and mix, and prepares raw mix.
The above-mentioned preferred fusing point of lithium compound that becomes the lithium source is below 800 ℃, and heat decomposition temperature for example can be enumerated inorganic salts such as lithium hydroxide, lithium chloride, lithium nitrate, lithium carbonate, lithium sulfate at the compound below 1100 ℃; Organic salts such as lithium formate, lithium acetate, lithium oxalate etc.
The above-mentioned compound particles that becomes the transition elements of transition metal source is the compound particles that is selected from least a transition elements of Co, Ni, Mn and Fe, preferred heat decomposition temperature is below 1100 ℃, for example can enumerate hydroxide, carbonate, if consider the purpose that improves tap density, hope is the oxide particle of the transition metal of not pyrolysis.
The preferred spherical and/or axiolitic spherical particle of the shape of particle of above-mentioned transition metal source.As the method that obtains this particle, for example can enumerate and unbodied primary particle be made spherical method by granulation, with by spray drying or spraying sintering process compound aqueous or the slurries shape is made spherical method, by the direct method of acquisition spherical particle such as sluggish precipitation.Make under the situation of spherical oxide particle, can obtain this spherical particle by sintering, if but sintering temperature at this moment is low, and tap density also can reduce, and therefore, preferably carries out sintering under the temperature more than 500 ℃.
Spherical and/or axiolitic transition metal source preferably has to a certain degree tap density in this stage.If tap density that should the stage is low, the tap density of the positive active material that then obtains also reduces.The tap density of this spherical and/or axiolitic transition metal source is preferably at 2.0g/cm 3More than, more preferably at 2.2g/cm 3More than, further preferably at 2.4g/cm 3More than.There is no particular limitation for the upper limit of tap density, is generally 5.0g/cm 3
In manufacture method of the present invention, in the above-mentioned raw material that contain lithium source and transition metal source, as required, can also contain and be selected from above-mentioned interpolation element, the i.e. at least a metallic compound of alkali metal, alkaline-earth metal, Ti, Zr, Hf, Y, Sc and rare earth metal etc.These raw-material mixing can adopt known method to carry out.
Adopt manufacture method of the present invention, the purpose of the tap density of the positive active material of the present invention that obtains based on raising is carried out the sintering of the raw mix that operation (A) prepares in specific calcination process and specific sintering circuit two stages.
Specific calcination process is the operation (B) of calcining under the temperature that is used in operation (A) more than the fusing point of lithium compound of raw mix.The purpose of this calcination process is to flood lithium compound in the compound particles as raw-material transition elements.Therefore, the upper limit that keeps temperature and wishes to be 300～950 ℃ preferably below the decomposition temperature of lithium compound, wishes to be 500～800 ℃ especially.Retention time is preferably 10～300 minutes.
Specific sintering circuit will have been passed through calcination process, for example flood the operation (C) of carrying out sintering more than the decomposition temperature of transition elements compound employed lithium compound of raw mix in operation (A) of lithium compound.The purpose of this sintering circuit is the compound reaction that makes lithium compound and transition elements, generates the positive active material of the present invention as purpose.At this moment temperature is so long as the decomposition temperature of lithium compound is above get final product, when the decomposition temperature of lithium compound is hanged down, with compound particles reaction needed time of transition elements, therefore, is preferably 700～1100 ℃, more preferably 800～1100 ℃ sometimes.If the retention time is too short, then fully, if long, solid phase reaction is not carried out excessively in reaction, and particle is attached to each other, and therefore is preferably 10～1800 minutes, more preferably 10～900 minutes.
In manufacture method of the present invention, can access positive active material of the present invention by above-mentioned operation, but as required, can also comprise other operations.
Nonaqueous electrolytic solution secondary battery of the present invention possesses positive pole, negative pole and the electrolyte that contains positive electrode active material powder, as above-mentioned positive active material, can contain positive active material of the present invention, the formation that other formations and other are additional etc. can suitably be selected from known formation etc.
In addition, make the employed positive pole of above-mentioned nonaqueous electrolytic solution secondary battery, can be by preparing in following composite oxide particle, average grain diameter differs the operation (a) of at least two kinds of composite oxide particles more than 10%, mixing the operation (b) that obtains positive active material with the composite oxide particle that will prepare in the operation (a) obtains, wherein, described composite oxide particle mainly comprises the particle of particle diameter 2～100 μ m, and average grain diameter is 5～80 μ m, contain Li and be selected from Co, Ni, at least a transition elements among Mn and the Fe, the major diameter that contains more than 90% is D1, D1/D2 was at the spherical of 1.0～2.0 scopes and/or ellipsoid shape particle when minor axis was D2.Differ the mixed proportion of at least two kinds of composite oxide particles more than 10% for average grain diameter, for example under two kinds situation, be preferably 1: 9～9: 1 scope in weight ratio.
Nonaqueous electrolytic solution secondary battery positive active material of the present invention is spherical and/or the composite oxides of ellipsoid shape particle, and the length-width ratio of this particle is 1.0～2.0 scope, and tap density is 2.9g/cm 3More than, therefore, when using it to make electrode, can make electrode density is 3.4～3.7g/cm 3, can effectively improve the discharge capacity and the load characteristic of nonaqueous electrolytic solution secondary battery unit volume.In addition, adopt manufacture method of the present invention, can easily obtain above-mentioned positive active material.And nonaqueous electrolytic solution secondary battery of the present invention uses positive active material of the present invention, therefore, can improve discharge capacity and load characteristic.
Embodiment
Illustrate in greater detail the present invention below by embodiment, but the present invention is not limited to this.
Embodiment 1
After being dissolved in the cobalt metal 100g of purity 99.8% in the nitric acid,, become 1650ml with the pure water dilution.Then, add 4N sodium hydroxide solution 820ml, filter after stirring, obtain hydroxide filter cake spherical or that ellipsoid shape particle constitutes.This filter cake 850 ℃ of following sintering 4 hours, is obtained the cobalt/cobalt oxide particle of the spherical or ellipsoid shape particle of 137g.Behind the cobalt/cobalt oxide particle 137g and the even mixing of lithium carbonate 65g that obtain, the mixture that obtains is carried out presintering 240 minutes under 700 ℃, then, under 850 ℃, carried out main sintering 300 minutes again, obtain spherical or ellipsoid shape particle.
Adopt ICP ICP Atomic Emission Spectrophotometer device, X-ray diffraction device, electron microscope, Star プ デ Application サ-device (セ イ シ Application enterprise system, XYT-2000) particle that obtains is studied, it is that the particle diameter of primary particle is 0.2～10 micron that the result is judged as, the particle diameter of offspring is 10～100 microns a compound particle, be that to have length-width ratio be 1～1.5, tap density is 3.2g/cm 3The LiCoO of above shape 2Particle.In addition, can judge the particle specific area is 0.15m 2/ g.
In addition, the mensuration of tap density is to collect in the 20ml graduated cylinder by the particle 10.0g that will obtain, and measures for 200 times with the high 2cm that shakes, shake frequency.In addition, the mensuration of specific area is to take by weighing the particle 1g that obtains, 200 ℃ carry out the degassing in 20 minutes after, with the trade name " NOVA2000 " of カ Application Network ロ system corporate system, pass through N 2Absorption BET method is carried out.The result is as shown in table 1.
In addition, as 1000 times SEM photo of the particle of the positive active material that obtains as shown in Figure 1,5000 times SEM photo as shown in Figure 2.
Further, with the particle that obtains, mix at 50: 40: 10 with weight ratio as the acetylene black of conductive auxiliary agent with as the PTFE of sticker, the preparation anode mixture, making with the corrosion resistant plate is the positive pole of collector body.In addition, making with the corrosion resistant plate is the negative pole of the lithium metal of collector body.Again in the solution that ethylene carbonate and dimethyl carbonate are obtained with 1: 1 mixed of volume ratio, with the ratio dissolving lithium perchlorate of 1 mole/L, preparation electrolyte.The positive pole that employing obtains, negative pole, electrolyte are made lithium rechargeable battery.
To the battery that obtains, at density of charging current 3mA/cm 2Condition under, make the charging upper voltage limit be 4.3V, discharge lower voltage limit is 3V, mensuration the initial stage discharge capacity.In addition, with the particle that obtains, as the graphite of conductive auxiliary agent, as the PVDF of binding agent with 90: 5: 5 mixed of weight ratio, by scraping the skill in using a kitchen knife in cookery, on the Al of 20 micron thickness collector body, apply, with pressure 3t/cm 2Electrode is made in compacting.The volume and weight of the electrode that mensuration obtains, the volume and weight of deduction Al collector body is calculated electrode density.The result is as shown in table 1.
Embodiment 2～5
Make the filter cake sintering temperature of embodiment 1 be respectively 500 ℃, 700 ℃, 800 ℃ or 900 ℃, the presintering time was respectively 240 minutes, 480 minutes, 360 minutes or 640 minutes, make main sintering temperature be respectively 800 ℃, 850 ℃, 900 ℃ or 950 ℃, main sintering time was respectively 600 minutes, 1200 minutes, 60 hours or 100 hours, replace lithium carbonate, use lithium oxalate 47g, lithium nitrate 35g, lithium hydroxide 100g or lithium sulfate 44g, in addition, by operation similarly to Example 1, the particle diameter of making primary particle is 0.2～10 micron, the particle diameter of offspring is 10～100 microns a compound particle, and be that length-width ratio is 1～1.5 spherical or ellipsoid shape particle, carry out various mensuration and evaluation.The result is as shown in table 1.
Embodiment 6～11
Replace hydroxide spherical or ellipsoid shape particle, using the mol ratio of nickle atom and cobalt atom is 8: 2,5: 5, the co-precipitation hydroxide of 1: 9 or 10: 0, perhaps the mol ratio of cobalt atom and manganese atom is 5: 1 a co-precipitation hydroxide, the mol ratio of manganese atom and nickle atom is 1: 1 a co-precipitation hydroxide, in addition, by operation similarly to Example 1, the particle diameter of making primary particle is 0.2～10 micron, the particle diameter of offspring is 10～100 microns a compound particle, and be that length-width ratio is 1～1.5 spherical or ellipsoid shape particle, carry out various mensuration and evaluation.The result is as shown in table 1.
Comparative example 1 and 2
Replace hydroxide spherical or ellipsoid shape particle, use needle-like or unbodied hydroxide, in addition,, make needle-like or unbodied composite oxides, measure and estimate by operation similarly to Example 1.The result is as shown in table 1.
Table 1
The kind of precursor The kind of composite oxides The kind of Li compound The sintering temperature of oxide precursor (℃) Pre-sintering temperature (℃) The presintering time (branch) Main sintering temperature (℃) Main sintering time (branch) TD (g/cm 3) Specific area (m 2/g) 3mA/cm 2Discharge capacity mAh/cm 3 Electrode density (g/cm 3)
Embodiment 1 Spherical or ellipsoid shape LiCoO 2 Lithium carbonate 850 700 240 850 300 3.2 0.15 528.5 3.5
Embodiment 2 Spherical or ellipsoid shape LiCoO 2 Lithium oxalate 500 700 240 800 600 2.9 0.18 513.4 3.4
Embodiment 3 Spherical or ellipsoid shape LiCoO 2 Lithium nitrate 700 700 480 850 1200 3.1 0.12 513.4 3.4
Embodiment 4 Spherical or ellipsoid shape LiCoO 2 Lithium hydroxide 800 700 360 900 60 2.9 0.10 525.0 3.5
Embodiment 5 Spherical or ellipsoid shape LiCoO 2 Lithium sulfate 900 700 640 950 100 3.1 0.05 521.5 3.5
Embodiment 6 Spherical or ellipsoid shape LiCo 0.8Ni 0.2O 2 Lithium carbonate 850 700 240 850 300 3.0 0.13 521.5 3.5
Embodiment 7 Spherical or ellipsoid shape LiCo 0.5Ni 0.5O 2 Lithium carbonate 850 700 240 850 300 3.1 0.14 510.0 3.4
Embodiment 8 Spherical or ellipsoid shape LiCo 0.1Ni 0.9O 2 Lithium carbonate 850 700 240 850 300 3.1 0.15 520.2 3.4
Embodiment 9 Spherical or ellipsoid shape LiNiO 2 Lithium carbonate 850 700 240 850 300 3.1 0.13 528.5 3.5
Embodiment 10 Spherical or ellipsoid shape LiCo 0.8Mn 0.2O 2 Lithium carbonate 850 700 240 850 300 3.1 0.20 506.6 3.4
Embodiment 11 Spherical or ellipsoid shape LiMn 0.5Ni 0.5O 2 Lithium carbonate 850 700 240 850 300 3.1 0.24 516.8 3.5
Comparative example 1 Needle-like LiCoO 2 Lithium carbonate 850 700 240 850 300 2.5 0.60 414.4 2.8
Comparative example 2 Amorphous LiCoO 2 Lithium carbonate 850 700 240 850 300 2.6 1.00 417.2 2.8
Embodiment 12～14
Particle to embodiment 1 preparation carries out classification, the macroparticle group that is divided into 70 microns of the small-particle group of 10 microns of average grain diameters and average grain diameters, they are mixed with 1: 1 (embodiment 12) of weight ratio, 3: 7 (embodiment 13) or 1: 9 (embodiment 14), obtain positive active material, and then make electrode similarly to Example 1, carry out various mensuration and evaluation.The result is as shown in table 2.
Table 2
The kind of precursor The kind of composite oxides The kind of Li compound The small-particle group of composite oxide particle: the ratio of macroparticle group TD (g/cm 3) Specific area (m 2/g) Electrode density (g/cm 3)
Embodiment 12 Spherical or ellipsoid shape LiCoO 2 Lithium carbonate 1∶1 3.1 0.10 3.5
Embodiment 13 Spherical or ellipsoid shape LiCoO 2 Lithium carbonate 3∶7 3.3 0.10 3.7
Embodiment 14 Spherical or ellipsoid shape LiCoO 2 Lithium carbonate 1∶9 3.1 0.12 3.4

Claims (9)

1, a kind of nonaqueous electrolytic solution secondary battery positive active material, comprise the composite oxide particle that contains Li and be selected from least a transition elements among Co, Ni, Mn and the Fe, it is D1 that above-mentioned composite oxide particle contains major diameter more than 90%, when minor axis is D2 D1/D2 at the spherical of 1.0～2.0 scopes and/or ellipsoid shape particle, described composite oxide particle mainly comprises the particle of 10～100 microns of particle diameters, and average grain diameter is 30～80 microns.
2, the positive active material of claim 1, wherein, the tap density of composite oxide particle is 2.9g/cm 3More than.
3, the positive active material of claim 1, wherein, composite oxide particle contains and is selected from least a in alkali metal, alkaline-earth metal, Ti, Zr, Hf, Y, Sc and the rare earth metal.
4, the positive active material of claim 1, wherein, the specific area of composite oxide particle is 0.05～0.24m 2/ g.
5, the manufacture method of the positive active material of claim 1, comprise: will contain the compound particles of at least a transition elements that is selected from Co, Ni, Mn and Fe and the raw material of lithium compound and mix, prepare the operation (A) of raw mix, more than the fusing point of the lithium compound in raw mix, more than the decomposition temperature of the operation (B) of calcining under 500～800 ℃ of temperature and the lithium compound in raw mix, carry out the operation (C) of sintering under 800～1100 ℃ of temperature.
6, the manufacture method of claim 5, wherein, the compound particles of above-mentioned transition elements is the oxide particle of transition metal, it is shaped as spherical and/or the ellipsoid shape, and tap density is 2.0g/cm 3More than.
7, the manufacture method of claim 5, wherein, the retention time of calcining is 10～300 minutes in the operation (B), the retention time of sintering is 10～1800 minutes in the above-mentioned operation (C).
8, nonaqueous electrolytic solution secondary battery, it possesses positive pole, negative pole and the electrolyte with positive electrode active material powder, and this positive electrode active material powder contains the positive active material of claim 1.
9, the anodal manufacture method of nonaqueous electrolytic solution secondary battery, this method is the method that the positive active material that will contain composite oxide particle shapes the positive pole that uses in the nonaqueous electrolytic solution secondary battery of making claim 8, comprise: operation (a), prepare in the following composite oxide particle, average grain diameter differs at least two kinds of composite oxide particles more than 10%, wherein, described composite oxide particle mainly comprises the particle of particle diameter 2～100 μ m, and average grain diameter is 5～80 μ m, contain Li and be selected from Co, Ni, at least a transition elements among Mn and the Fe, the major diameter that contains more than 90% is D1, spherical and/or the ellipsoid shape particle of D1/D2 in 1.0～2.0 scopes when minor axis is D2; Operation (b) obtains positive active material with the composite oxide particle mixing of preparing in the operation (a), and at least a kind of positive active material that comprises claim 1 of the composite oxide particle of preparing in operation (a).
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