CN106129328A - Positive active material - Google Patents

Positive active material Download PDF

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Publication number
CN106129328A
CN106129328A CN201610533779.2A CN201610533779A CN106129328A CN 106129328 A CN106129328 A CN 106129328A CN 201610533779 A CN201610533779 A CN 201610533779A CN 106129328 A CN106129328 A CN 106129328A
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Prior art keywords
lithium
active material
compound
ratio
transition metal
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CN201610533779.2A
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CN106129328B (en
Inventor
森田耕诗
细谷洋介
藤木聪
本桥成
本桥一成
李国华
远藤显
远藤一显
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Murata Northeast China
Murata Manufacturing Co Ltd
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Sony Corp
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Priority claimed from JP2010105025A external-priority patent/JP5644176B2/en
Priority claimed from JP2010105024A external-priority patent/JP5589536B2/en
Application filed by Sony Corp filed Critical Sony Corp
Priority claimed from CN201010279232.7A external-priority patent/CN102024950B/en
Publication of CN106129328A publication Critical patent/CN106129328A/en
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/006—Compounds containing, besides cobalt, two or more other elements, with the exception of oxygen or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/40—Cobaltates
    • C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—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
    • H01M4/1315—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx containing halogen atoms, e.g. 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/54—Particles characterised by their aspect ratio, i.e. the ratio of sizes in the longest to the shortest dimension
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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
    • 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

nullThe invention provides a kind of positive active material，Including lithium-transition metal composite oxide，This lithium-transition metal composite oxide comprises lithium、Primary transition metal M1 and the metallic element M2 being different from primary transition metal M1，Wherein metallic element M2 has the Concentraton gradient from the center of each granule to the described metallic element M2 on surface，Meet in the range of 0.020≤d≤0.050 at the ratio d (%) from surface to certain depth，Molar fraction r (%) meets formula 0.20≤r≤0.80，Wherein，Ratio d (%)=[(quality of described primary transition metal M1)+(quality of metallic element M2)]/(quality that granule is overall)，Molar fraction r=(the material amount of metallic element M2)/[(the material amount of primary transition metal M1)+(the material amount of metallic element M2)]，Wherein，Primary transition metal M1 is selected from nickel、Cobalt、At least one in manganese and ferrum，Metallic element M2 is selected from manganese、Magnesium、Aluminum、Nickel、Boron、Titanium、At least one element in cobalt and ferrum.

Description

Positive active material
The application is filing date JIUYUE in 2010 9 days, Application No. 201410014566.X, invention entitled " positive pole is lived Property material " divisional application, and the application of Application No. 201410014566.X is filing date JIUYUE in 2010 9 days, application number Be 201010279232.7, invention entitled " positive active material and preparation method thereof, positive pole and nonaqueous electrolyte battery " The divisional application of application for a patent for invention.
Technical field
The present invention relates to a kind of positive active material, positive pole, nonaqueous electrolyte battery and prepare positive active material Method.More particularly it relates to an be capable of having by it when charging and discharging in hot environment High-performance and present the positive active material of nonaqueous electrolyte battery of very low capacity deterioration, positive pole, nonaqueous electrolyte battery with And the method preparing positive active material.In particular it relates to a kind of positive pole including lithium-compound transition metal oxide Active substance.
Background technology
In recent years, with portable set, popularizing, to small-sized Gao Rong of such as video camera and notebook personal computer The demand of amount secondary cell and battery increases the most day by day.Currently used secondary cell include use alkaline electrolyte nickel- Cadmium cell and nickel-hydrogen cell.But, the shortcoming of these secondary cells is cell voltage the most about 1.2V and is difficult to improve energy Metric density.Therefore, nowadays the lithium rechargeable battery that voltage is higher higher than other battery system and energy density has obtained extensively General utilization.
But, owing to having higher charging voltage, therefore, asking of lithium rechargeable battery compared with other battery system Topic is, when using in the way of keeping the long period in the charge state, and the longevity that its capacity can be deteriorated and it is useful Life can be shortened.During additionally, use lithium rechargeable battery under in high ambient conditions, the rising of internal resistance can be produced, It is made to be very difficult to guarantee enough capacity.Strongly need to solve the scheme of these problems.
LiCoO2、LiNiO2It is widely used as lithium rechargeable battery with other lithium-compound transition metal oxide granule Positive active material.Recently, it has been proposed that by forming coat at the surface of the particles or making some materials from particle surface Diffusion improves the state of particle surface to obtain the various technology of the more preferable performance of lithium-compound transition metal oxide granule.
Such as, in Japanese Patent No. 3197763 (hereinafter, referred to as patent documentation 1), it is shown that slaine or hydrogen Oxide joins the method in positive pole.(hereinafter, the referred to as patent literary composition additionally, Japanese Patent Publication Hei 5-47383 Offer 2) show one phosphorus (P) cobalt-coating acid lithium (LiCoO2) the technology on surface.Japanese Patent No. 3172388 is (under Wen Zhong, referred to as patent documentation 3) and Japanese Patent No. 3691279 (hereinafter, referred to as patent documentation 4) show a kind of use The method on the surface of metal oxide-coated positive active material or positive pole.
Japanese Patent Publication Hei 7-235292 (hereinafter, referred to as patent documentation 5), Japanese Patent Publication No. 2000-149950 (hereinafter, referred to as patent documentation 6), Japanese Patent Publication the 2000-156227th (hereinafter, claim Make patent documentation 7), Japanese Patent Publication the 2000-164214th (hereinafter, referred to as patent documentation 8), Japanese Patent Publication No. 2000-195517 (hereinafter, referred to as patent documentation 9), Japanese Patent Publication the 2001-196063rd are (hereinafter, Be referred to as patent documentation 10), Japanese Patent Publication the 2002-231227th (hereinafter, referred to as patent documentation 11) etc. shows Wherein be evenly coated with lithium-compound transition metal oxide the surface of granule method and wherein composite oxides from granule The method of diffusion into the surface.(hereinafter, referred to as patent documentation 12) is shown additionally, Japanese Patent Publication the 2001-256979th Go out the positive active material that the block of wherein metal-oxide is deposited on metal oxide layer.Japanese Patent Publication 2002- No. 164053 (hereinafter, referred to as patent documentation 13) are shown in which to be formed on the surface of the core comprising lithium compound to comprise The positive active material of at least one surface-treated layer of at least two coating element.
Japanese Patent Publication the 3157413rd (hereinafter, referred to as patent documentation 14) discloses one wherein at granule Surface on the positive active material of coating including metal fluoride is set, and Japanese Patent Publication the 3141858th ( Hereinafter referred to as patent documentation 15) show a kind of coating including crystal metal fluoride.Additionally, Japanese Patent Publication No. 2003-221235 describes and specifies fluorine XPS (x-ray photoelectron power spectrum) energy on the surface of granule.When this The inventor of invention prepares positive pole according to the disclosure by the method for mixed metal fluoride thermally treated mixture and lives During property material, it was observed that about the actual effect of high temperature dwell sustainability, but this effect be limited to the surface to granule effect and It is insufficient based on actually used performance.And, U.S. Patent No. 7,364, No. 793 (hereinafter, referred to as patent documentations 16) disclose and a kind of for lithium, there is high-affinity and the compound of cation and lithium-transition can be supplied by wherein making The method of composite oxide of metal reaction and the material that obtains.
Summary of the invention
But, according to such as in the method for patent documentation 1, slaine or hydroxide are joined have common uniformly In the lithium-transition metal oxide of form, the resistance of electrode increases and is difficult to obtain enough capacity.At patent documentation 2 In method, the capacity caused due to coating reduces the biggest so that positive active material can not make us for actual should being used to say that Satisfied.If merely with the coating element, painting method and the coated form that disclose in document 3 and 4, then patent documentation 3 and 4 Method as being all unsafty for improving the technology of battery performance under the high temperature conditions.Moreover, it has been found that, Increase coated weight to obtain abundant effect can cause hindering the diffusion of lithium ion so that it is very difficult in practical application area In charge-discharge current value under obtain enough capacity.Therefore, the method is the discovery that unsafty.
Find that the method disclosed in patent documentation 4 to 9 is for improving cycle characteristics to the highest degree and suppressing high Resistance during temperature use is unsafty for improving, although can keep high power capacity by the method.When logical When crossing the method and structure disclosed in patent documentation 12 to prepare positive active material, it is difficult to obtain enough recharge-discharge effects Rate, and capacity is largely lowered.In the method for patent documentation 13, if individually using surface to process, then due to The effect that the method produces is limited.Additionally, when prepared by the method disclosed during positive active material is actual by the document, shape Become homogeneous multiple layer, when the most at high temperature using, do not find the effect preventing resistance from raising.
About the metal fluoride that the method according to patent documentation 15, simple electronic conductivity and lithium-ion-conducting are low Coating causes recharge-discharge performance to significantly reduce, and it is insufficient to the effect of the charge-discharge characteristics under hot environment 's.When the method disclosed during the present inventor is by patent documentation 16 prepares positive active material, occur as being coated with Cover the discontinuity of material of material addition or come off, and producing inactive compound such as oxide and lithium fluoride so that being coated with Cover function can not fully be presented.Additionally, it is difficult to obtain the recharge-discharge performance of actually used level, because charging-putting During electricity, the migration of lithium ion is interrupted at solid liquid interface.Additionally, it was additionally observed that the trend that capacity reduces, because from lithium-transition Composite oxide of metal loses lithium.Therefore, it is unsafty according to the material of the document.
Accordingly, it would be desirable to, charge-discharge cycles excellent high to capacity and present the least when being used for hot environment The positive active material of deterioration, the positive pole using such positive active material and rechargeable nonaqueous electrolytic battery and preparation The method of such positive active material.
According to the embodiment of the present invention, it is provided that a kind of positive active material prepared by following steps: lithium will be contained Compound, containing the compound of transition metal being included in solid solution and containing the metallic element being different from transition metal The compound mixing of M2, and burn till mixture to form composite oxide particle；On the surface of this composite oxide particle Deposition comprises the compound of at least one element in sulfur (S), phosphorus (P) and fluorine (F)；And burn till deposition on it and have and comprise The composite oxide particle of the compound of at least one element in sulfur (S), phosphorus (P) and fluorine (F)；The most each composite oxygen Chalcogenide particles has such Concentraton gradient: the concentration of metallic element M2 increases from the center of composite oxide particle to surface, And make at least one element in sulfur (S), phosphorus (P) and fluorine (F) to assemble (aggregate, cohesion) at combined oxidation Presented on the surface of composition granule.
According to another embodiment of the present invention, it is provided that a kind of positive active material including being prepared by following steps Positive pole: by lithium-containing compound, containing the compound of transition metal being included in solid solution and containing being different from transition gold The compound mixing of the metallic element M2 belonged to, and burn till mixture to form composite oxide particle；At these composite oxides On the surface of granule, deposition comprises the compound of at least one element in sulfur (S), phosphorus (P) and fluorine (F)；And burn till it Upper deposition has the composite oxide particle of the compound of at least one element comprised in sulfur (S), phosphorus (P) and fluorine (F)；By This each composite oxide particle has such Concentraton gradient: the concentration of metallic element M2 is from the center of composite oxide particle Increase to surface, and make at least one element in sulfur (S), phosphorus (P) and fluorine (F) to be gathered in composite oxide particle Surface on presented in.
Other according to the present invention embodiment there is provided a kind of non-aqueous solution electrolysis including positive pole, negative pole and electrolyte Electrolyte cell, wherein positive pole includes the positive active material prepared by following steps: mix lithium-containing compound, containing being included in The compound of the transition metal in solid solution and the compound containing the metallic element M2 being different from transition metal, and burn till Mixture is to form composite oxide particle；The surface of this composite oxide particle deposits and comprises selected from sulfur (S), phosphorus (P) Compound with at least one element in fluorine (F)；And burn till deposition on it and have and comprise selected from sulfur (S), phosphorus (P) and fluorine (F) In the composite oxide particle of compound of at least one element；The most each composite oxide particle has such concentration Gradient: the concentration of metallic element M2 from the center of composite oxide particle to surface increase, and make selected from sulfur (S), phosphorus (P) and Presented at least one element in fluorine (F) is on the surface being gathered in composite oxide particle.
Comprising selected from sulfur (S), phosphorus (P) and fluorine of the positive pole of the present invention and the positive active material of nonaqueous electrolyte battery (F) pyrolysis (i.e. thermal decomposition) product of the compound of at least one element in or this compound of positive active material is preferred There is the fusing point of more than 70 DEG C less than 600 DEG C, and also preferably there is the average diameter of below 30 μm.
Embodiment there is provided a kind of method preparing positive active material according to another, comprise the following steps: mixing contains Lithium compound, containing the compound of transition metal being included in solid solution and containing the metal unit being different from transition metal The compound of element M2, and burn till mixture to form composite oxide particle；The surface of this composite oxide particle sinks The compound of long-pending at least one element comprised in sulfur (S), phosphorus (P) and fluorine (F)；And burn till deposition on it and have and comprise choosing The composite oxide particle of the compound of at least one element in bin cure (S), phosphorus (P) and fluorine (F)；The most each combined oxidation Composition granule has such Concentraton gradient: the concentration of metallic element M2 increases from the center of composite oxide particle to surface, and And make at least one element in sulfur (S), phosphorus (P) and fluorine (F) with the shape being gathered on the surface of composite oxide particle Formula exists.
Be deposited on the surface of composite oxide particle comprise in sulfur (S), phosphorus (P) and fluorine (F) at least one The compound of element is melted to be uniformly present on the surface of composite oxide particle after being preferably melted or thermally decomposing.Also Preferably on the surface of composite oxide particle, remove be deposited on the surface of composite oxide particle comprise selected from sulfur (S), The cation of the compound of at least one element in phosphorus (P) and fluorine (F), and make the anion of compound be included in compound Element reaction in oxide particle.
Additionally, according to another embodiment of the present invention, it is provided that one includes lithium-compound transition metal oxide granule Positive active material, this lithium-compound transition metal oxide granule comprises lithium, primary transition metal M1 and is different from mainly mistake Crossing the metallic element M2 of metal M1, metallic element M2 has from the center of each granule to the concentration ladder of the metallic element M2 on surface Degree, wherein meets in the range of 0.020≤d≤0.050 at ratio d (%) from surface to certain depth, and molar fraction r (%) is full Foot formula 0.20≤r≤0.80, wherein ratio d (%)=[(quality of primary transition metal M1)+(matter of metallic element M2 Amount)]/(quality that granule is overall), and wherein molar fraction r=(the material amount of metallic element M2)/[(primary transition metal The material amount of M1)+(the material amount of metallic element M2)], wherein, described primary transition metal M1 be selected from nickel (Ni), cobalt (Co), At least one in manganese (Mn) and ferrum (Fe), and wherein, described metallic element M2 is selected from manganese (Mn), magnesium (Mg), aluminum (Al), at least one element in nickel (Ni), boron (B), titanium (Ti), cobalt (Co) and ferrum (Fe).
According to another embodiment of the invention, it is provided that a kind of positive pole, this positive pole includes that comprising lithium-transition metal is combined The positive active material of oxide particle, this lithium-compound transition metal oxide granule comprises lithium, primary transition metal M1 and not Being same as the metallic element M2 of primary transition metal M1, metallic element M2 has from the center of each granule to the metallic element on surface The Concentraton gradient of M2, wherein meets in the range of 0.020≤d≤0.050 at the ratio d (%) from surface to certain depth, rubs You mark r (%) meets formula 0.20≤r≤0.80, wherein ratio d (%)=[(quality of primary transition metal M1)+(metal The quality of element M 2)]/(quality that granule is overall), and wherein molar fraction r=(the material amount of metallic element M2)/[(master Want the material amount of transition metal M 1)+(the material amount of metallic element M2)].
According to another embodiment of the invention, it is provided that a kind of nonaqueous electrolyte including positive pole, negative pole and electrolyte Battery, positive pole includes the positive active material comprising lithium-compound transition metal oxide granule, this lithium-transition metal composite oxygen Chalcogenide particles comprises lithium, primary transition metal M1 and is different from the metallic element M2 of primary transition metal M1, and metallic element M2 has There is the Concentraton gradient to the metallic element M2 on surface from the center of each granule, wherein at the ratio d from surface to certain depth (%) meeting in the range of 0.020≤d≤0.050, molar fraction r (%) meets formula 0.20≤r≤0.80, wherein ratio d (%)=[(quality of primary transition metal M1)+(quality of metallic element M2)]/(quality that granule is overall), and wherein rub That mark r=(the material amount of metallic element M2)/[(the material amount of primary transition metal M1)+(material of metallic element M2 Amount)].
According to the present invention, by meeting the scope of 0.020≤d≤0.050 at the ratio d (%) from surface to certain depth Interior control molar fraction r (%) meets formula 0.20≤r≤0.80 to suppress the anti-of positive active material-electrolyte boundary Should.
In the present invention, each composite oxide particle has such Concentraton gradient: the concentration of metallic element M2 is from multiple The center closing oxide particle increases to surface, and at least one element in sulfur (S), phosphorus (P) and fluorine (F) is to assemble Presented on the surface of composite oxide particle on the surface of composite oxide particle.It may therefore be assured that positive pole Stable and the stablizing in interface of active substance.
According to the present invention it is possible to realize high power capacity, charge/discharge cycles excellent and when being used for hot environment Present the battery of the least deterioration.
Accompanying drawing explanation
Fig. 1 shows the perspective view of the configuration example of nonaqueous electrolyte battery according to the embodiment of the present invention；
Fig. 2 is the sectional view of the line II-II along Fig. 1 of the rolled electrode bodies shown in Fig. 1；
Fig. 3 shows the sectional view of the configuration example of nonaqueous electrolyte battery according to the embodiment of the present invention；
Fig. 4 is the sectional view of the part being illustrated in exaggerated form the rolled electrode bodies shown in Fig. 3；And
Fig. 5 shows the sectional view of the configuration example of nonaqueous electrolyte battery according to the embodiment of the present invention.
Detailed description of the invention
Now, embodiments of the present invention are described below with reference to accompanying drawings.Embodiments described below is the present invention Instantiation, and provide simultaneously and be technically considered preferred various restriction.But, unless given in the following description Go out and represent the description of specific restriction for the present invention, otherwise the scope of the present invention being not restricted by the embodiments.It addition, To be described in the following sequence.
1. the first embodiment (the first example of nonaqueous electrolyte battery)
2. the second embodiment (the second example of nonaqueous electrolyte battery)
3. the 3rd embodiment (the 3rd example of nonaqueous electrolyte battery)
4. the 4th embodiment (the 4th example of nonaqueous electrolyte battery)
5. the 5th embodiment (the 5th example of nonaqueous electrolyte battery)
6. other embodiment
[summary of the present invention]
Such as cobalt acid lithium (LiCoO2) and lithium nickelate (LiNiO2) lithium-containing transition metal oxide be widely used as lithium ion Positive active material in secondary cell.But, the problem that they exist the stability under their charged state.Especially It is that, due to the reactive rising of the interface between positive active material and electrolyte, transiting metal component can be from positive pole Dissolution, causes the deterioration of active substance or the metal of dissolution to separate out in negative side.As a result, the occlusion that can hinder lithium (Li) is (embedding Enter) and release (deintercalation).
Additionally, such positive active material as mentioned above is considered to accelerate the decomposition reaction of interface electrolyte, lead Causing form coating at the electrode surface or produce gas, it causes the deterioration of battery behavior.Meanwhile, be suitably designed positive pole- Under conditions of negative pole ratio, by reaching the maximum charge electricity of at least 4.20V (preferably at least 4.35V, more preferably at least 4.40V) The mode of pressure is charged, the energy density of battery when can improve charging.But, it is clear that at charging voltage liter High and under the high charge voltage conditions of more than 4.25V in the case of recharge-discharge cycles, active substance or electrolyte Above-mentioned deterioration accelerate, cause charge-discharge cycle life reduce or High temperature storage after performance degradation.
Therefore, the present inventor carries out extensive careful research.Through research, they send out and currently use tool Have improvement particle surface containing lithium-metal composite oxides in the case of, the existence of the metallic compound on particle surface is to electricity Improving of pond characteristic produces high synergy or new effect.Based on this discovery make it is desirable to provide one is for pole The positive active material of the lithium rechargeable battery of the big characteristic improving battery and stability.
1. the first embodiment (the first example of nonaqueous electrolyte battery)
Fig. 1 shows the perspective view of the configuration example of nonaqueous electrolyte battery according to the first embodiment of the invention. This nonaqueous electrolyte battery is such as rechargeable nonaqueous electrolytic battery.This nonaqueous electrolyte battery that global shape is flat has Such structure, the rolled electrode bodies 10 being wherein provided with positive wire 11 and negative wire 12 is contained in membranaceous package (outward Mould component) in 1.
The shape of positive wire 11 and negative wire 12 the most for example, rectangular plate-like, and they are such as from package 1 Inside is drawn in the same direction towards outside.Such as, positive wire 11 is made up of the metal material of such as aluminum (Al), and example As, negative wire 12 is made up of the metal material of such as nickel (Ni).
Package 1 is stacked with this order by such as having insulating barrier, metal level and outermost layer and passes through lamination etc. each other The laminated film of the structure adhered to is constituted.Such as, package 1 is configured to insulating barrier side and is arranged on inner side, and every pair of outer edge leads to Cross melted or be fixed to one another by use binding agent.
Insulating barrier by such as vistanex such as polyethylene, polypropylene, modified poly ethylene, modified polypropene and they Copolymer is constituted.Such vistanex ensures that low water penetration and air-tightness are excellent.Metal level is by aluminum, stainless The foil-like of steel, nickel, ferrum etc. or tabular component are constituted.Outermost layer can be such as made up of or by Buddhist nun the resin being similar to insulating barrier Dragons etc. are constituted.Such material ensures have the high intensity preventing rupturing or pierce through.Package 1 can also have except above-mentioned absolutely Edge layer, metal level and other layer outermost.
Between each in package 1 and positive wire 11 and negative wire 12, insert adhesive film 2 for just improving Each in pole lead-in wire 11 and negative wire 12 adhesion strength with the inside of package 1 and be used for preventing oozing of extraneous air Thoroughly.Adhesive film 2 is by the material with each in negative wire 12 positive wire 11 with adhesion strength (fix and contact) performance Formed.In the case of positive wire 11 and negative wire 12 are made up of above-mentioned metal material, adhesive film 2 is the most such as by polyene Hydrocarbon resin such as polyethylene, polypropylene, modified poly ethylene, modified polypropene etc. are formed.
Fig. 2 is the sectional view along the line II-II of Fig. 1 of the rolled electrode bodies 10 shown in Fig. 1.Rolled electrode bodies 10 has wherein The structure that positive pole 13 and negative pole 14 are stacked by barrier film 15 therebetween and electrolyte 16, and its outermost perimembranous is by protecting Protecting band 17 is protected.
[positive pole]
Positive pole 13 such as have positive electrode collector 13A and be separately positioned on positive electrode collector 13A both sides on positive pole Active material layer 13B.Positive electrode active material layer can be provided only on the side of positive electrode collector 13A.As positive electrode collector 13A, it is, for example possible to use the metal forming of such as aluminium foil.
Positive electrode active material layer 13B include as positive active material one or more can occlusion and release The positive electrode of electrode reaction thing.Positive electrode active material layer 13B farther includes the conductive auxiliary agent of such as material with carbon element and such as gathers Vinylidene or the binding agent of politef.
[positive active material]
Positive active material is such as composite oxide particle, comprises and be different from major shift in this composite oxide particle Metal M1 also has from the center of each granule the metallic element M2 to the Concentraton gradient of the metallic element M2 on surface.Described concentration Gradient refers to along with close to particle surface, the concentration of metallic element M2 increases.This composite oxide particle is wherein selected from sulfur (S), at least one element X in phosphorus (P) and fluorine (F) with aggregated forms be present on the surface of composite oxide particle containing lithium The granule of compound transition metal oxide.Incidentally, the state on lithium-compound transition metal oxide surface can be passed through The powder observing acquisition under SEM/EDX (scanning electron microscope/energy dispersion-type X-ray spectrometer) confirms.
Metallic element M2 is not particularly limited.It is preferable, however, that composite oxide particle is prepared by such method The granule of lithium-containing transition metal composite oxides, wherein makes metallic element M2 preexist in inside composite oxide particle, and And make metallic element M2 with the compound of at least one element X comprised in sulfur (S), phosphorus (P) and fluorine (F) and react so that The concentration of the metallic element M2 at particle surface raises.
Therefore, metallic element M2 is evenly distributed in inside composite oxide particle in advance, then metallic element M2 The concentration on grain surface raises, and metallic element M2 thus can be made to be uniformly present in particle surface.As a result, metallic element M2 Modified effect on grain surface can be presented to greatest extent.
Metallic element M2 preferably, based on solid solution, can replace the major shift gold in composite oxide particle inside Belong at least one element of element M 1.It is highly preferred that metallic element M2 is to select free manganese (Mn), magnesium (Mg), aluminum (Al), nickel (Ni), at least one element in the group that boron (B), titanium (Ti), cobalt (Co) and ferrum (Fe) form.Metallic element M2 is main in displacement Be present in particle surface under the state of transition metal A or when being diffused into the inner side near particle surface thus in Now to the continuous Concentraton gradient of each granular center be effective.
Incidentally, the concentration of magnesium can be by cutting the cross section of lithium-compound transition metal oxide and by Auger electricity The distribution that sub-power spectrum art is measured radially confirms.
Additionally, for improve metallic element M2 the concentration of particle surface metallic element M2 with comprise selected from sulfur (S), phosphorus (P) reaction of the compound of at least one element and in fluorine (F) is preferably carried out under lithium (Li) compound coexists.At Li chemical combination Thing coexists down in the case of reacting, and can regulate the amount of Li in lithium-contained composite oxide and suppress owing to surface modification is drawn The capacity risen reduces.
As the lithium-compound transition metal oxide within granule, it is possible to use one of various known substances.But, excellent Selection of land, lithium-compound transition metal oxide is to have layered rock salt structure and the primary transition metal elements A constituted as it It it is the material of at least one in nickel (Ni), cobalt (Co), manganese (Mn) and ferrum (Fe).Such material guarantee high power capacity.This Outward, it is possible to use wherein have been incorporated into the known substance of a small amount of addition element alternatively thing based on solid solution.
Incidentally, with the composite oxide particle of the base material acting on positive pole be such as have layered rock salt structure and The average lithium composite xoide granule formed represented by below formula (chemical formula 1).
(chemical formula 1)
LiaAbM1-bOc
In the formula, M be preferably selected from manganese (Mn), magnesium (Mg), aluminum (Al), nickel (Ni), boron (B), titanium (Ti), cobalt (Co) and At least one element in ferrum (Fe)；A, b and c are in the range of 0.2≤a≤1.4,0≤b≤1.0 and 1.8≤c≤2.2 Numeral；It addition, the component ratio of lithium changes with charge/discharge state, the value of a shown herein represents under complete discharge condition Value.
In chemical formula (chemical formula 1), the scope of the value of a is such as 0.2≤a≤1.4.If the value of a is the least, then conduct The layered rock salt structure of the basic crystal structure of lithium composite xoide can destroy, so that be difficult to recharge and hold Amount can significantly reduce.On the other hand, if the value of a is too big, then lithium can diffuse to the outside of composite oxide particle, hinders subsequently Process the control of basicity in step, and in the kneading process of anode sizing agent, finally cause the problem promoting gelation.
Incidentally, the lithium composite xoide in above formula (chemical formula 1) is arranged to have and exceedes correlation technique Containing lithium amount.Specifically, represent that in the lithium composite xoide in above formula (chemical formula 1), the value of a of the ratio of lithium can be more than 1.2.Herein, the value of 1.2 component ratio as the lithium in the lithium composite xoide of the type the most in the related is carried out Disclose, and due to have with a=1 in the case of identical crystal structure, obtain working effect (reference same as the present application The earlier application of such as the applicant: Japanese Patent Publication the 2008-251434th).
Even if notationally in the lithium composite xoide of formula (chemical formula 1), the value of a of the composition of lithium is more than 1.2, The crystal structure of lithium composite xoide is identical in the case of being also not more than 1.2 with the value of a.Even if additionally, notationally formula is (chemical Formula 1) in the value of a of composition of lithium more than 1.2 time, if this value is not more than 1.4, then with charge-discharge cycles The chemical state of the transition metal constituting lithium composite xoide in redox reaction is not more than the difference in the case of 1.2 with a value The most little.
B value scope is such as 0≤b≤1.0.If the value of b decreases below this scope, the then electric discharge of positive active material Capacity can reduce.On the other hand, if the value of b increases above this value, then the stablizing of the crystal structure of composite oxide particle Property can reduce, cause positive active material recharge-discharge keep capacity reduce and safety reduce.
C value scope is such as 1.8≤c≤2.2.Higher than this model in the case of the value of c is less than this scope and in this value In the case of enclosing, the stability of the crystal structure of composite oxide particle can reduce, and causes the recharge-discharge of positive active material Keep capacity to reduce and safety reduces, and cause the discharge capacity of positive active material to reduce.
[particle diameter]
Positive active material preferably has 2.0 μm average particulate diameter to 50 μm.If average particulate diameter is less than 2.0 μm, then can occur the stripping of positive electrode active material layer in manufacturing anode process when suppressing positive electrode active material layer.Additionally, by Surface area in the increase of positive active material, it is therefore necessary to increase conductive auxiliary agent and the addition of binding agent so that often single The energy density of position weight is tended to be lowered.On the other hand, if average particulate diameter is more than 50 μm, then granule tends to thorn Wear barrier film, cause short circuit.
As above preferably positive pole 13 has the thickness of no more than 250 μm.
[negative pole]
Negative pole 14 such as has negative electrode collector 14A and the negative pole being separately positioned on the both sides of negative electrode collector 14A is lived Property material layer 14B.Negative electrode active material layer 14B can be arranged on the only side of negative electrode collector 14A.Negative electrode collector 14A It is made up of the metal forming of the most such as Copper Foil.
Such as, negative electrode active material layer 14B be configured to contain as negative electrode active material can occlusion and release lithium At least one negative material, and if need can comprise conductive auxiliary agent and/or binding agent.
Occlusion can include material with carbon element such as graphite, difficult graphitized carbon or easy graphite with the example of the negative material of release lithium Changing carbon, it can individually or use with the two or more mixture in them.Additionally, two kinds that average particulate diameter is different Above such material can use with mixture.
Can other example of negative material of occlusion and release lithium include those comprise as constitution element can be with Lithium forms metal or the material of semimetallic elements of alloy.The instantiation of such material includes to form alloy with lithium The simple substance of metallic element, alloy and compound and can with lithium formed alloy the simple substance of semimetallic elements, alloy and chemical combination Thing, and its at least partly in there is the material of more than one phase in these simple substance, alloy and compound.
The example of such metal or semimetallic elements includes stannum (Sn), lead (Pb), aluminum, indium (In), silicon (Si), zinc (Zn), antimony (Sb), bismuth (Bi), cadmium (Cd), magnesium (Mg), boron (B), gallium (Ga), germanium (Ge), arsenic (As), silver (Ag), zirconium (Zr), yttrium And hafnium (Hf) (Y), wherein it is preferred that metal or the semimetallic elements of 14 races in long period type periodic chart, and particularly preferably Be silicon (Si) and stannum (Sn).Silicon (Si) and stannum (Sn) have high occlusion and the ability of release lithium, thereby ensure that high-energy is close Degree.
The example of the alloy of silicon (Si) includes that those comprise the free stannum of choosing (Sn), nickel (Ni), copper (Cu), ferrum (Fe), cobalt (Co), manganese (Mn), zinc (Zn), indium (In), silver (Ag), titanium (Ti), germanium (Ge), bismuth (Bi), antimony (Sb) and chromium (Cr) form At least one in group is as the alloy of the second constitution element in addition to silicon (Si).The example of the alloy of stannum (Sn) includes that Comprise the free silicon of choosing (Si), nickel (Ni), copper (Cu), ferrum (Fe), cobalt (Co), manganese (Mn), zinc (Zn), indium (In), silver (Ag), titanium (Ti), at least one in the group that germanium (Ge), bismuth (Bi), antimony (Sb) and chromium (Cr) form is as in addition to stannum (Sn) The alloy of two constitution elements.
The example of the compound of silicon (Si) or stannum (Sn) includes that those comprise oxygen (O) or the compound of carbon (C), and this change Compound can comprise one or more in above-mentioned second constitution element in addition to silicon (Si) or stannum (Sn).
[barrier film]
Barrier film 15 can be the most stable, relative to positive active material, negative electrode active material and solvent by using Chemically stable and nonconducting any material is formed.The example of the material that herein can use includes macromolecule nonwoven The paper-like plate of cloth, perforated membrane and glass or ceramic fibre, it can use with the form of multilayer laminated body.The most Hole polyolefin film, it can be to have the shape of the complex of the heat proof material formed by polyimides, glass or ceramic fibre etc. Formula uses.
[electrolyte]
Electrolyte 16 includes electrolyte and can be used for keeping the holding body of electrolyte, and this holding body includes macromolecule chemical combination Thing, and be so-called gelation state.Electrolyte comprises electrolytic salt and can be used for dissolving the solvent of electrolytic salt.Electrolyte The example of salt includes such as LiPF6、LiClO4、LiBF4、LiN(SO2CF3)2、LiN(SO2C2F5)2And LiAsF6Lithium salts, it can Individually or to use with the two or more mixture in them.
The example of solvent includes the lactone of such as gamma-butyrolacton, gamma-valerolactone, δ-valerolactone, 6-caprolactone etc., such as Ethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate, dimethyl carbonate, Ethyl methyl carbonate, carbonic acid diethyl The carbonate solvent of ester etc., such as 1,2-dimethoxy-ethane, 1-ethyoxyl-2-Ethyl Methyl Ether, 1,2-diethoxyethane, The ether solvents of oxolane, 2-methyltetrahydrofuran etc., the nonaqueous solvent of the nitrile solvent such as such as acetonitrile, such as sulfolane solvent, The nonaqueous solvent of phosphoric acid class, phosphate ester solvent and ketopyrrolidine.These solvents can two or more individually or with in them Mixture use.
Additionally, solvent preferably comprises the compound having a structure in which, in described structure, cyclic ester or ol ester Hydrogen moiety or be all fluorinated (being replaced by fluorine atom).Preferably as fluorinated compound is carbonic acid two fluoroethylene (4,5-bis-fluoro-1,3-dioxolan-2-one).Thus, even if include the chemical combination of silicon (Si), stannum (Sn), germanium (Ge) etc. in use In the case of thing is as the negative pole 14 of negative electrode active material, it is also possible to improve charge-discharge cycles characteristic.Particularly, carbonic acid two Fluoroethylene has the improvement effect of excellence to cycle characteristics.
Macromolecular compound can be any by lyosoption by the macromolecular compound of gelatine.Macromolecule chemical combination The example of thing includes fluoro macromolecular compound such as Kynoar, vinylidene fluoride-hexafluoropropylene copolymer etc., ether producing high-molecular Compound such as poly(ethylene oxide), cross linked polymer etc. containing poly(ethylene oxide), and comprise polyacrylonitrile, poly(propylene oxide) or poly-first Base acrylic acid methyl ester. is as the macromolecular compound of repetitive.These macromolecular compounds can be individually or with in them Two or more mixture uses.
Particularly, from the viewpoint of oxidation-reduction stability, fluoro macromolecular compound is desired, wherein comprises partially Fluorothene and hexafluoropropene are preferred as the copolymer of component.And, copolymer can comprise the list of unsaturated dibasic acid The ethylene halide of ester such as monomethyl maleate etc., such as trifluoro-ethylene etc., the ring of such as vinylene carbonate unsaturated compound Shape carbonic ester or the acryloyl group vinyl monomer containing epoxide group are as component, so that it can obtain higher spy Property.
Additionally, as solid electrolyte, it is possible to use inorganic solid electrolyte and polymer solid electrolyte, as long as this is solid Body electrolyte has lithium-ion-conducting.The example of inorganic solid electrolyte includes lithium nitride and lithium iodide.Macromolecular solid Body electrolyte all includes electrolytic salt and can be used for dissolving the macromolecular compound of this electrolytic salt.The example of macromolecular compound Including ether macromolecule the most poly-(oxirane), its cross-linking products etc., poly-(methacrylate) macromolecule, acrylate polymeric Deng, they can be used alone or as the two or more copolymer in them or with two or more the mixing in them Compound uses.
[method manufacturing positive pole]
First, the synthesis present invention comprises the composite oxide particle of metallic element M1.For synthesizing composite oxide The mode of grain is not particularly limited.And, as being used for making composite oxide particle and comprising selected from sulfur (S), phosphorus (P) and fluorine (F) the compound reaction of at least one element in makes the method raised in the concentration of the metallic element M2 of particle surface, can Use known various methods.
Additionally, the method on the surface for coating composite oxide particle includes such method, wherein by using ball Grinding machine, crusher, pulverizer etc. make the lithium-compound transition metal oxide containing metallic element M2 and comprise selected from sulfur (S), phosphorus (P) compound of at least one element and in fluorine (F) is pulverized, and mixes and coats (deposition).In carrying out this operation, add one Quantitative liquid component (can be such as water) is effective.In addition it is also possible to use the coating processed by mechanochemistry (heavy Long-pending) or by the vapor phase method such as coating (deposition) of metallic compound such as sputtering, CVD (chemical gaseous phase deposition).
And, by mixing raw material in water or in the solvent of such as ethanol, by via the knot neutralized in the liquid phase Brilliant or by other similar approach can the upper formation of lithium-compound transition metal oxide comprise selected from sulfur (S), phosphorus (P) and The surface of at least one element in fluorine (F).Thus making at least one element in sulfur (S), phosphorus (P) and fluorine (F) It is present in after comprising on the lithium-compound transition metal oxide of metallic element M2, preferably carries out heat treatment and make metallic element M2 raises in the concentration of particle surface.For example, it is possible to carry out heat treatment at 350 DEG C to 900 DEG C.Lithium-the transition metal obtained Composite oxides can be composite oxides by the known technical finesse for controlling powder property.
Subsequently, mix to prepare positive pole by the conductive auxiliary agent of positive active material, binding agent and such as material with carbon element Compositions.This positive electrode composition is dispersed in the solvent of such as METHYLPYRROLIDONE, to prepare positive electrode composition slurry Material.Binding agent can be Kynoar, politef etc..
Then, this positive electrode composition slurry is applied to positive electrode collector 13A, and is dried.Afterwards, roll squeezer etc. is used It is compressed molding to form positive electrode active material layer 13B, is derived from positive pole 13.Incidentally, if it is desired, in preparation just The conductive auxiliary agent of such as material with carbon element is mixed during the compositions of pole.
[method manufacturing negative pole]
Then, negative pole 14 is manufactured in the following manner.First, negative electrode active material and binding agent are mixed with each other with Prepare cathode composition, and this cathode composition is dispersed in the solvent of such as METHYLPYRROLIDONE, negative with preparation Pole combination pulp.Subsequently, this cathode composition slurry is applied to negative electrode collector 14A, and makes solvent evaporate.It After, use roll squeezer etc. to be compressed molding to form negative electrode active material layer 14B, be derived from negative pole 14.
[method manufacturing nonaqueous electrolyte battery]
For example, it is possible to manufacture nonaqueous electrolyte battery in the following manner.First, electrolyte, macromolecule chemical combination will be comprised The precursor solution of thing and mixed solvent is applied in each in positive pole 13 and negative pole 14, and evaporates mixed solvent, with Form electrode 16.Afterwards, by positive wire 11 by being welded to connect the end to positive electrode collector 13A, and by negative wire 12 by being welded to connect the end to negative electrode collector 14A.
Then, by be formed with the positive pole 13 of electrolyte 16 and negative pole 14 by barrier film 15 therebetween be stacked with Form stacked body, this stacked body is wound along the longitudinal direction, and by protection with the 17 outermost perimembranous adhering to coiling body, with shape Become rolled electrode bodies 10.Finally, such as, rolled electrode bodies 10 is clipped between package 1, and makes the peripheral part of package 1 lead to Cross heat fusing etc. to be adhering to each other, to be sealed in package 1 by rolled electrode bodies 10.In this case, adhesive film 2 is inserted Between each in each and package 1 in positive wire 11 and negative wire 12.So, complete such as Fig. 1 and Nonaqueous electrolyte battery shown in Fig. 2.
Further, it is also possible to manufacture nonaqueous electrolyte battery in the following manner.First, positive pole 13 He is manufactured in the above described manner Negative pole 14, and positive wire 11 and negative wire 12 are adhered to positive pole 11 and negative pole 12 respectively.Then, by positive pole 13 with negative Pole 14 is stacked to form stacked body by barrier film 15 therebetween, winds this stacked body, and is adhered to by protection band 17 The outermost perimembranous of coiling body, to form the coiling body of the precursor as rolled electrode bodies 10.Then, this coiling body is clipped in packaging Between part 1, the edge, periphery in addition to a side of package 1 is carried out heat fused to obtain bag shape, thus will volume It is contained in package 1 around body.Subsequently, preparation is containing electrolyte, the monomer as the raw material for macromolecular compound, polymerization Initiator and other material (the need to) such as the electrolyte composition of polymerization inhibitor, this electrolyte composition is introduced In package 1.
After introducing electrolyte composition, by the peristome of the incompatible sealed package of hot melt 1 under vacuum atmosphere.Connect , heat will be applied so that a kind of monomer or various of monomer are polymerized to form macromolecular compound, and be consequently formed gel electrolyte 16, And assemble nonaqueous electrolyte battery as depicted in figs. 1 and 2.
The improvement details of cycle characteristics etc. is the most unclear, but it is believed that this improvement is realized by following mechanism.Filling In the lithium rechargeable battery of electricity condition, positive pole is in Strong oxdiative state, and is in easy sending out with the electrolyte of positive contact The environment of raw oxidation Decomposition, the most in high temperature environments.When electrolyte is decomposed, on the surface of positive active material Form torpescence film, thus stop electronics and/or the migration of lithium ion.
And, the component of decomposition produces the molecule that activity is high in electrolyte present in the hole of electrode, thus accelerates electricity Solve the deterioration of liquid or attack (corrosion) positive active material, thus dissolve the constitution element of positive active material or reduce capacity. In order to suppress such phenomenon, it is insufficient for only stablizing the interface between positive active material granule and electrolyte, above-mentioned surely It is set for using and stablize the outside of positive active material granule and its neighbouring bioactive molecule must be carried out cooperatively.
In lithium-containing transition metal oxide in embodiments of the present invention, make the master being different within oxide particle The metallic element M2 wanting transition metal is present on particle surface so that the interface between active material particle and electrolyte is steady Fixed.Additionally, make the lithium-compound transition metal oxide comprising at least one element in sulfur (S), phosphorus (P) and fluorine (F) with Aggregated forms is present in the vicinity of granule so that bioactive molecule stabilisation.It is believed that due to the collaborative effect of these Stabilization Really, battery performance is improved considerably.
Furthermore, it is believed that owing to making metallic element M2 be uniformly present in the inside of granule in advance, then make metallic element M2 Concentration at particle surface raises, to guarantee that metallic element M2 is uniformly present in particle surface, so metallic element M2 Stablizing effect can present to greatest extent, thus successfully improves battery performance.
[effect]
According to the first embodiment of the invention the nonaqueous electrolyte battery in, can suppress the deterioration of cycle characteristics, press down Make the internal resistance owing to charge-discharge cycles causes in high temperature environments to raise, and thus can realize raising simultaneously Capacity and the battery behavior of improvement.
2. the second embodiment (the second example of nonaqueous electrolyte battery)
Second embodiment of the present invention will be described.Nonaqueous electrolyte battery second embodiment of the invention makes With the positive active material with evenly coating.
Owing to other material is identical with the first embodiment with structure, therefore omit the explanation about them.
[positive active material]
Positive active material is wherein to comprise be different from primary transition metal M1 and have the center from each granule The composite oxide particle of metallic element M2 of Concentraton gradient towards the metallic element M2 on surface.Concentraton gradient refers to along with connecing The concentration of nearly particle surface metallic element M2 increases.Composite oxide particle is the granule of lithium-containing transition metal composite oxides, Wherein at least one element X in sulfur (S), phosphorus (P) and fluorine (F) is present in the table of composite oxide particle with aggregated forms Face.
In this second embodiment, comprise at least one element in sulfur (S), phosphorus (P) and fluorine (F) compound or The catabolite of this compound has the fusing point of more than 70 DEG C less than 600 DEG C.Such as utilized ball mill to be positioned at by certain way This compound or the catabolite of this compound on the surface of composite oxides are melted by heating, thus are evenly coated with The surface of composite oxides.Hereafter, the catabolite making heating and melted compound or this compound is anti-with composite oxides Should.Make coating than the first embodiment more effectively and evenly.
When heating the catabolite of this compound or this compound at a temperature of higher than 600 DEG C, composite oxygen will be caused The structure reacting and can changing composite oxides in compound.But in the present embodiment, make maybe this change of this compound The catabolite of compound melt and coat composite oxides before changing in the structure of composite oxides with the answering of steady statue Conjunction oxide reacts.
If the fusing point of the catabolite of this compound or this compound is higher than 600 DEG C, then at compound or product melt And start coating reaction before coating the surface of composite oxide particle, and compound or described product and composite oxides it Between reaction start, it only provides part coating reaction with composite oxides at position that compound or described product contact, this Cause the disadvantageous non-homogeneous coating on composite oxides.
Heating at a temperature of more than 600 DEG C also results in the structure change of composite oxides.
If the fusing point of this compound or this catabolite is less than 70 DEG C, then this compound or this product are passing through ball mill Deng deposition process in will adversely melt or decompose.
The catabolite of this compound or this compound preferably has the average diameter of below 30 μm.Being somebody's turn to do of such diameter Compound or this catabolite will realize the uniform coating of composite oxides.When this compound or this catabolite diameter are the biggest Time, they can not mix with composite oxides well to utilize ball mill etc., and it causes the nonuniform deposition on composite oxides. The diameter of this compound or this catabolite does not has lower limit.Less diameter will provide coating evenly.But diameter is actual On be ground into about 1 μm by this compound or this catabolite and limited.
The example of compound is diammonium phosphate ((NH4)2HPO4), ammonium dihydrogen phosphate (NH4H2PO4), ammonium sulfate ((NH4)2HPO4), phosphoric acid (H3PO4) etc..The cation of these compounds is removed by evaporating the most when heated, therefore can obtain There is no the positive active material of impurity, its reduction that can avoid capacity and other deleterious effects.
As being different from the metallic element M2 of primary transition metal M1, the metal identical with embodiment 1 can be used Element M 2.
[method manufacturing positive active material]
For example, it is possible to prepare the positive active material of the second embodiment according to following procedure.
First, the surface of composite oxide particle is coated with coating material.About being used for coating composite oxide particle The illustrative methods on surface, the method identical with the first embodiment can be used, wherein by using ball mill, pulverizing Machine, pulverizer etc. are pulverized the lithium-compound transition metal oxide comprising metallic element M1 and comprise selected from sulfur (S), phosphorus (P) and fluorine (F) compound of at least one element X in, mixes and coats (deposition).
In carrying out this operation, it is effective for adding a certain amount of liquid component (can be such as water).In addition it is also possible to Use the coating (deposition) processed by mechanochemistry or use metal by vapor phase method such as sputtering, CVD (chemical gaseous phase deposition) etc. The coating (deposition) of compound.
Metallic element M1 is comprised making at least one element X in sulfur (S), phosphorus (P) and fluorine (F) thus be present in Lithium-compound transition metal oxide on after, preferably carry out heat treatment and make metallic element M2 concentration at particle surface Raise.For example, it is possible to carry out heat treatment at 700 to 900 DEG C.Lithium-the compound transition metal oxide that can make acquisition stands For controlling the process of the known technology of powder property or some other purposes.
In heat treatment process, the compound being positioned on the surface of composite oxides is melt into liquid condition and makes The combined thing in surface of composite oxides uniformly coats.After further heat treatment, compound decomposes and cation quilt Remove, and anion is reacted with the metallic element M2 being included in composite oxides.Compound melts with coating material The temperature of heat treatment can be raised after reaction.
[effect]
According to the second embodiment, combined oxidation can be coated with coating material before the structure of composite oxides changes Thing.Therefore, it can improve the function of positive active material, it causes the better performance of rechargeable nonaqueous electrolytic battery.
3. the 3rd embodiment (the 3rd example of nonaqueous electrolyte battery)
Third embodiment of the present invention will be described.Nonaqueous electrolyte battery according to third embodiment of the present invention makes The gel electrolyte 16 in nonaqueous electrolyte battery according to the first embodiment of the invention is replaced with electrolyte.In this feelings Under condition, by using electrolyte with its dipping barrier film 15.As electrolyte, it is possible to use identical with the first embodiment Electrolyte.
For example, it is possible to manufacture the nonaqueous electrolyte battery thus constructed in the following manner.First, manufacture positive pole 13 and bear Pole 14.Positive pole 13 and negative pole 14 can be manufactured in the way of identical with above-mentioned first embodiment, omit system the most herein The detailed description made.
Then, after positive wire 11 and negative wire 12 are respectively connecting to positive pole 13 and negative pole 14, by positive pole 13 He Negative pole 14 stacks to be formed stacked body, winding layer laminate together by barrier film 15 therebetween, and protection band 17 is adhered to volume Outermost perimembranous around body.
Result, it is thus achieved that the rolled electrode bodies identical with the structure of above-mentioned rolled electrode bodies 10, difference is, omits Electrolyte 16.After being clipped between package 1 by coiling body, electrolyte is incorporated into the inside of package 1, and sealed bundle Piece installing 1.By this way, it is thus achieved that according to the nonaqueous electrolyte battery of third embodiment of the present invention.
[effect]
According to third embodiment of the present invention, it is possible to obtain the effect identical with the first embodiment.Specifically, permissible The deterioration of suppression cycle characteristics, suppresses the rising due to the internal resistance that charge-discharge cycles causes in high temperature environments, and Thus can realize capacity and the battery behavior of improvement improved simultaneously.
4. the 4th embodiment (the 4th example of nonaqueous electrolyte battery)
Then, the structure of the nonaqueous electrolyte battery of the 4th embodiment according to the present invention will be described with reference to Fig. 3 and Fig. 4 Make.Fig. 3 shows the structure of the nonaqueous electrolyte battery of the 4th embodiment according to the present invention.
This nonaqueous electrolyte battery is so-called cylindrical battery, wherein winding banding positive pole 31 and banding negative pole 32 and Barrier film 33 between them forms rolled electrode bodies 30, and this rolled electrode bodies 30 is arranged on substantially hollow cylindrical battery shell The inside of 21.
Barrier film 33 is impregnated with the electrolyte as liquid electrolyte.Battery case 21 is by ferrum (Fe) shape of such as nickel plating (Ni) Become.Battery case 21 is closed at its end, and is unlimited at its other end.In the inside of battery case 21, by a pair insulation board 22 and 23 outer peripheral faces being respectively perpendicular to rolled electrode bodies 30 are arranged on the two opposite sides of rolled electrode bodies 30.
At the opening of battery case 21, battery cover 24 and be arranged on relief valve mechanism 25 He inside this battery cover 24 PTC (positive temperature coefficient) thermistor element 26 is installed by utilizing packing ring 27 caulked.Thus, sealed cell shell 21 is interior Portion.
Battery cover 24 is made up of such as identical with battery case 21 material.Relief valve mechanism 25 is by thermistor element 26 And electrically connect with battery cover 24.This relief valve mechanism 25 is configured in making battery due to internal short-circuit or external heat When portion's pressure exceedes predetermined value, discoid plate 25A upset is to cut off the electrical connection between battery cover 24 and rolled electrode bodies 30.
When the temperature increases, thermistor element 26 limits electric current by increasing its resistance, thus prevents by big electric current The abnormal heating caused.Packing ring 27 is formed by such as insulant, and its surface-coated has Colophonium.
Such as, rolled electrode bodies 30 winds centered by centrepin 34.In rolled electrode bodies 30, will be by shapes such as aluminum (Al) The positive wire 35 become is connected to positive pole 31, and the negative wire 36 formed by nickel (Ni) etc. is connected to negative pole 32.Make positive pole Lead-in wire 35 is electrically connected to battery cover 24 by being soldered to relief valve mechanism 25, and makes negative wire 36 by being soldered to battery case 21 and be electrically connected to battery case 21.
Fig. 4 is the sectional view of the part showing the electric collective 30 of the winding shown in Fig. 3 in the way to enlarge.Winding electricity collection Body 30 has a structure in which, wherein positive pole 31 and negative pole 32 are stacked to form stacking by barrier film 33 therebetween Body, and wind this stacked body.
Positive pole 31 includes that such as positive electrode collector 31A and the positive pole being separately positioned on the both sides of positive electrode collector 31A are lived Property material layer 31B.It is negative be separately positioned on the both sides of negative electrode collector 31A that negative pole 32 includes such as negative electrode collector 32A Pole active material layer 32B.Positive electrode collector 31A, positive electrode active material layer 31B, negative electrode collector 32A, negative electrode active material layer The composition of 32B, barrier film 33 and electrolyte is respectively equivalent to the positive electrode collector 13A in above-mentioned first battery, positive electrode active material Those of matter layer 13B, negative electrode collector 14A, negative electrode active material layer 14B, barrier film 15 and electrolyte are constituted.
[method manufacturing nonaqueous electrolyte battery]
Now, the method that will be described below the nonaqueous electrolyte battery manufacturing the 4th embodiment according to the present invention. Positive pole 31 is manufactured as got off.First, it is mixed with each other to prepare positive electrode composition by positive active material and binding agent, by this positive pole Compositions is dispersed in the solvent of such as METHYLPYRROLIDONE, to prepare positive electrode composition slurry.Then, by this positive pole Combination pulp is applied to positive electrode collector 31A, and is dried.Afterwards, roll squeezer etc. is used to be compressed molding just to be formed Pole active material layer 31B, is derived from positive pole 31.
Manufacture negative pole 32 in the following manner.First, negative electrode active material and binding agent are mixed with each other with preparation Cathode composition, is dispersed in this cathode composition in the solvent of such as METHYLPYRROLIDONE, to prepare cathode composition Slurry.Then, this cathode composition slurry is applied to negative electrode collector 32A, and makes solvent evaporate.Afterwards, roll-in is used Machines etc. are compressed molding to form negative electrode active material layer 32B, are derived from negative pole 32.
Subsequently, positive wire 35 is connected to positive electrode collector 31A by welding etc., and by negative wire 36 by welding Etc. being connected to negative electrode collector 32A.Afterwards, winding positive pole 31 and negative pole 32 and the stacked body of the barrier film between them 33, will The top ends of positive wire 35 is soldered to relief valve mechanism 25, and the top ends of negative wire 36 is soldered to battery case 21.
Then, the stacked body of positive pole 31 and negative pole 32 is clipped between a pair insulation board 22 and 23, and is contained in battery In shell 21.After positive pole 31 and negative pole 32 being contained in battery case 21, electrolyte is incorporated into the inside of battery case 21 so that Barrier film 33 impregnates electrolyte.
Afterwards, by battery cover 24, relief valve mechanism 25 and thermistor element 26 by being fixed to packing ring 27 caulked The open end of battery case 21.By this way, the nonaqueous electrolyte battery shown in Fig. 3 has been manufactured.
[effect]
In the nonaqueous electrolyte battery of the 4th embodiment according to the present invention, gas can be suppressed to generate, and prevent Only raise, due to internal pressure, the cell fracture caused.
5. the 5th embodiment (the 5th example of nonaqueous electrolyte battery)
The nonaqueous electrolyte battery of the 5th embodiment according to the present invention uses the positive-active with evenly coating Material, replaces the positive active material in the nonaqueous electrolyte battery of the 4th embodiment.
Owing to other material is identical with the 4th embodiment with composition, therefore omit the explanation about them.
[positive active material]
Meet in the range of 0.020≤d≤0.050 at the ratio d (%) from surface to certain depth, the 5th embodiment Molar fraction r (%) of positive active material meet formula 0.20≤r≤0.80.Ratio d and molar fraction r are according to following Formula determines.
Ratio d (%)=[(quality of primary transition metal M1)+(quality of metallic element M2)]/(matter that granule is overall Amount) (I)
Molar fraction r=(the material amount of metallic element M2)/[(the material amount of primary transition metal M1)+(metallic element M2 Material amount)] (II)
In addition to above-mentioned point, the positive active material of the 5th embodiment and the 4th embodiment identical.
The quality of primary transition metal M1 and the quality of metallic element M2 can be known as follows: be combined by lithium-transition metal The surface of oxide is dissolved in buffer solvent, analyzes the primary transition metal M1 and metallic element M2 being dissolved in buffer solvent Mass content.
Specifically, ratio d (%) and molar fraction ratio r can determine as got off.First, buffer solvent is joined In lithium-compound transition metal oxide granule and mix them.Then, Sample buffer solvent the most at regular intervals, and mistake Filter solvent.The quality of the primary transition metal M1 being included in each buffer solvent by inductively coupled plasma method measurement and The quality of metallic element M2.
Calculate the amount [mol] of metal M1 and metallic element M2 according to described quality, and obtain according to formula (I) and (II) Ratio d and molar fraction r.Herein, granule is assumed to spherical, and exists at the diameter supposing the granule being dissolved in buffer solvent Keep becoming under spherical state less under conditions of calculate.
The above-mentioned analysis on the surface of positive active material is three-dimensional, and can provide the quantitative analysis of Concentraton gradient, It is difficult to be realized by the conventional method of analysis of the apparent condition of positive active material.
Under conditions of molar fraction ratio r (%) falls in the range of 0.20≤r≤0.80, wherein, from surface to one The ratio d (%) of depthkeeping degree meets 0.020≤d≤0.050, and capability retention and High temperature storage capacity are higher.
Even if but molar fraction ratio r (%) falls in the range of 0.20≤r≤0.80, wherein, from surface to necessarily The ratio d (%) of the degree of depth is also unsatisfactory for 0.020≤d≤0.050, exists and not necessarily has capability retention and high temperature dwell sustainability Improve the trend of effect.
Preferably, the ratio d (%) from surface to certain depth meets in the range of 0.020≤d≤0.050, molar ratio r (%) reduce from surface to inside, because capability retention and the reduction of high temperature dwell sustainability can be avoided, especially can be notable Avoid the reduction of capability retention.
Except the molar fraction ratio r when the ratio d (%) from surface to certain depth meets 0.020≤d≤0.050 (%), outside falling in the range of 0.20≤r≤0.80, further preferably 0.010 is met at the ratio d (%) from surface to certain depth ≤ d < in the range of 0.020, molar ratio r meets 0.55≤r≤1.0 because can avoid discharge capacity reduction and can To improve cycle performance and High temperature storage performance.
[method manufacturing battery]
The method of the rechargeable nonaqueous electrolytic battery manufacturing the 5th embodiment is as follows.
First, the lithium-compound transition metal oxide granule making to comprise lithium, primary transition metal M1 and metallic element M2 with The compound comprising at least one element X in sulfur (S), phosphorus (P) and fluorine (F) mixes.Preferably further mixing comprises lithium Compound.Then, at least one unit realizing comprising in sulfur (S), phosphorus (P) and fluorine (F) is processed by mechanochemistry The compound of element X and preferably comprise the compound of the lithium deposition on the surface of lithium-compound transition metal oxide.To mixing Thing mechanochemistry processes more than 5 minutes less than 2 hours.When mechanochemistry processes and is shorter than 5 minutes, coating is not enough, and just Pole active material particle is ground into the less granule with too minor diameter.
Then, lithium-compound transition metal oxide granule is fired, to obtain positive active material.For the temperature fired It is preferably 500 DEG C to 1500 DEG C.If temperature is less than 500 DEG C, then lithium-compound transition metal oxide granule can not be fully coated with Cover.But, if temperature is higher than 1500 DEG C, then particle aggregation becomes second particle, and it causes the coating on collector body to be deteriorated.
After burning till, lithium-compound transition metal oxide granule has the metal on the centrally directed surface from each granule The Concentraton gradient of element M 2.Granule comprise with aggregated forms be deposited on the surface of composite oxide particle selected from sulfur (S), phosphorus (P) at least one element X and in fluorine (F).
Generally, molar ratio r can comprise at least one element X in sulfur (S), phosphorus (P) and fluorine (F) by employing The addition of compound regulate.When compound adds very little, reaction is so small that and can not obtain enough coatings, and Molar ratio r reduces.When addition is bigger, molar ratio r becomes relatively big, but is not more than 1 in r principle.Reaction is from table Face is carried out to inside, therefore when addition is bigger, the part bigger for ratio d (%) from surface to certain depth obtains height Molar ratio.
When coating material (i.e. compound or catabolite) and base material (i.e. lithium-compound transition metal oxide) are the most fine During mixing, molar fraction ratio r reduces.Such as, more than a diameter of 100 μm of compound, it is more than positive active material 5 μm extremely The average diameter of 30 μm, and non-homogeneous dispersion.Therefore, there is no preferred coating state, and molar fraction ratio r has Time become relatively low.About the technology of mixing, any technology can be used, as long as base material and coating material mix well, The preliminary technology etc. of the mixture in such as planetary-type mixer, shake bag.
After obtaining positive active material, the program identical with the 4th embodiment can be taked to obtain the 5th enforcement The nonaqueous electrolyte battery of mode.
The upper limit of the charging voltage of the battery of the 4th embodiment can be 4.2V, but is preferably designed to higher than 4.2V. Particularly, design battery makes the upper limit of charging voltage be preferably 4.25V to 4.80V, more excellent from the viewpoint of discharge capacity Select more than 4.35V, be below 4.65V from a security point of view.The lower limit of the discharge voltage of battery is preferably 2.00V extremely 3.30V.Design high cell voltage and cause high-energy-density.
6. other embodiment (deformation)
The present invention is not limited to the above-mentioned embodiment of the present invention, and the most various deformation and application It is possible.Such as, the shape of nonaqueous electrolyte battery is not limited to the above-mentioned type (column type), and can be such as coin Type.
Additionally, it is, for example possible to use include the polymer solid electrolyte of ionic conductive high molecular material or include ion The inorganic solid electrolyte of conducting inorganic material is as electrolyte.The example of ionic conductive high molecular material includes polyethers, gathers Esters, polyphosphazene and polysiloxanes.The example of inorganic solid electrolyte includes ionic conductivity ceramics, ion conductive crystal and ion Electro-conductive glass.
The positive active material of the 5th embodiment can be used in the battery of the first to the 3rd embodiment.
[embodiment]
Now, will be specifically described the present invention by the embodiment illustrated, these embodiments are not construed as this Bright restriction.
In embodiment 1-1 to 1-13 and comparative example 1-1 to 1-9, change the interpolation volume of coating material, and determine tool There is the battery performance of the positive electrode that the distribution of coating material is different on the surface of composite oxides.
<embodiment 1-1>
[manufacture of positive pole]
At the molar ratio mixed carbonic acid lithium (Li with Li:Co:Al:Mg=1.00:0.98:0.01:0.012CO3), oxidation Cobalt (Co3O4), aluminium hydroxide (Al (OH)3) and magnesium carbonate (MgCO3After), at 900 DEG C, burn till mixture in atmosphere 5 hours, To obtain lithium-cobalt composite oxide (LiCo0.98Al0.01Mg0.01O2).The average particulate diameter of lithium-cobalt composite oxide is by swashing Light scattering method is measured, and is 13 μm.
Subsequently, lithium carbonate (Li is weighed2CO3) and diammonium phosphate ((NH4)2HPO4) and and lithium-cobalt composite oxide (LiCo0.98Al0.01Mg0.01O2) mixing, in order to obtain the atom ratio of Co:Li:P=98:1:1.Then, mechanochemistry is passed through System processes the mixing material 1 hour comprising lithium-cobalt composite oxide.Result, it is thus achieved that the precursor before firing, wherein lithium-cobalt The granule of composite oxides exists as center material, and lithium carbonate and diammonium phosphate deposit at the surface of the particles.
With the speed of 3 DEG C/min, the precursor before firing is heated up, and be maintained at 900 DEG C 3 hours, the most slowly Cooling, to obtain the lithium-compound transition metal oxide belonging to the present invention.This lithium-compound transition metal oxide has uniformly The magnesium (Mg) being distributed on the surface of lithium-cobalt composite oxide granule.Additionally, the concentration of magnesium (Mg) ratio on the surface of granule exists Height, and lithium phosphate (Li are wanted in the inside of granule3PO4) spread at the surface of the particles.
Incidentally, the apparent condition of lithium-compound transition metal oxide is by observing the powder of acquisition under SEM/EDX Confirm.It was confirmed magnesium (Mg) being uniformly distributed at the surface of the particles behind the surface observing lithium-compound transition metal oxide With phosphorus distribution at the surface of the particles.Additionally, the concentration of magnesium is by cutting the cross section of lithium-compound transition metal oxide, and lead to Cross auger electron spectrometry Elemental redistribution radially to confirm.In the cross section measuring lithium-compound transition metal oxide After Elemental redistribution, the concentration of magnesium is proved to be from the surface of granule internally consecutive variations.
Additionally, when by using measurement that CuK α carries out x-ray diffractogram of powder case to powder, except being equivalent to have The LiCoO of layered rock salt structure2Diffraction maximum outside, have also demonstrated and be equivalent to Li3PO4Diffraction maximum.
By using lithium-compound transition metal oxide obtained as described above as positive active material, manufacture non-water power Solve electrolitc secondary cell, and the high-temperature cycle that have rated battery as described below and internal resistance change.
By mixing the above-mentioned positive active material of 98wt%, the amorphous carbon powder (Ketjen black) of 0.8wt% and The Kynoar (PVdF) of 1.2wt% prepares positive electrode composition.This positive electrode composition is dispersed in N-methyl-2-pyrrolidine To prepare positive electrode composition slurry in ketone (NMP), then it is applied to equably the positive electrode collector being made up of banding aluminium foil Both sides.Subsequently, current of warm air is dried the positive electrode composition slurry on the surface of positive electrode collector, and uses roll squeezer to enter Row compression forming, to form positive electrode composition layer.
[manufacture of negative pole]
Cathode composition is prepared by the powdered graphite of mixing 95wt% and the PVdF of 5wt%.By this cathode composition It is dispersed in METHYLPYRROLIDONE to prepare cathode composition slurry, then it is applied to equably by banding Copper Foil The both sides of the negative electrode collector constituted, are pressed, the most under heating to form cathode composition layer.
[preparation of electrolyte]
At the mixed solvent by obtaining with the volume mixture ethylene carbonate (EC) of 1:1 and Ethyl methyl carbonate (MEC) In, dissolve lithium hexafluoro phosphate (LiPF6) to obtain 1mol/dm3Concentration, thus prepare nonaqueous electrolytic solution.
[assembling of battery]
By banding positive pole manufactured as above and negative pole and the barrier film being made up of porous polyolefin between them to be stacked on State together winds repeatedly, thus manufactures spiral wound electrode body.Be contained in by this rolled electrode bodies by nickel plating is iron In the battery case become, and insulation board is arranged on rolled electrode bodies above and below.Then, will be connected with negative electrode collector The negative terminal of nickel be soldered to the bottom of battery case.Additionally, the positive terminal of the aluminum being connected with positive electrode collector is welded It is connected to guarantee the protuberance of the relief valve with battery cover conductivity.
Finally, nonaqueous electrolytic solution is incorporated into the most it is combined with in the battery case of rolled electrode bodies.Afterwards, can pass through Insulated enclosure packing ring is used to carry out caulked battery case, with standing valve, PTC thermistor element and battery cover.By this way, manufacture There is 18mm external diameter and the cylindrical battery of 65mm height.
[evaluation of battery]
(a) initial capacity
In the environment of the environment temperature of 45 DEG C, cylindrical battery manufactured as above is carried out perseverance with the charging current of 1.5A Electric current charging is until the charging voltage of 4.35V.Then, constant current charge conversion is charged to constant voltage, and when always charging Between reach 2.5 little complete charge constantly.With the discharge current of 2.0A, battery is discharged the most immediately, and work as cell voltage It is reduced to during 3.0V terminate electric discharge.Measurement discharge capacity in this case, as initial capacity, is found to be 9.1Wh.
(b) capability retention
With with repeat to fill to battery for measuring recharge-discharge condition identical in the above-mentioned situation of initial capacity Electricity-discharge cycles.After circulating at 300 times, measure discharge capacity, and determine capability retention based on initial capacity.Capacity Conservation rate is 82%.
<embodiment 1-2>
Manufacturing rechargeable nonaqueous electrolytic battery in the way of identical with embodiment 1-1, difference is, during charging Cell voltage be 4.20V.When evaluating battery, discovery initial capacity is 8.0Wh, and capability retention is 82%.In passing Mention, the concentration distribution of the element in positive active material in embodiment 1-2 and latter embodiments and comparative example and living The apparent condition of the granule of property material is shown in table 1 below.
<embodiment 1-3>
Manufacturing rechargeable nonaqueous electrolytic battery in the way of identical with embodiment 1-1, difference is, during charging Cell voltage be 4.4V.When evaluating battery, discovery initial capacity is 9.4Wh, and capability retention is 80%.
<embodiment 1-4>
Manufacturing rechargeable nonaqueous electrolytic battery in the way of identical with embodiment 1-1, difference is, during charging Cell voltage be 4.5V.When evaluating battery, discovery initial capacity is 10.0Wh, and capability retention is 61%.
<embodiment 1-5>
Manufacturing rechargeable nonaqueous electrolytic battery in the way of identical with embodiment 1-1, difference is, to be deposited At lithium-cobalt composite oxide (LiCo0.98Al0.01Mg0.01O2Coating material on) is ammonium dihydrogen phosphate (NH4H2PO4).Evaluating During battery, discovery initial capacity is 9.1Wh, and capability retention is 80%.
<embodiment 1-6>
Manufacturing rechargeable nonaqueous electrolytic battery in the way of identical with embodiment 1-1, difference is, to be deposited At lithium-cobalt composite oxide (LiCo0.98Al0.01Mg0.01O2Coating material on) is lithium hexafluoro phosphate (LiPF6) and burn till temperature Degree is 700 DEG C.When evaluating battery, discovery initial capacity is 9.1Wh, and capability retention is 81%.
<embodiment 1-7>
Manufacturing rechargeable nonaqueous electrolytic battery in the way of identical with embodiment 1-1, difference is, to be deposited At lithium-cobalt composite oxide (LiCo0.98Al0.01Mg0.01O2Coating material on) is LiBF4 (LiBF4) and burn till temperature Degree is 700 DEG C.When evaluating battery, discovery initial capacity is 9.1Wh, and capability retention is 76%.
<embodiment 1-8>
Manufacturing rechargeable nonaqueous electrolytic battery in the way of identical with embodiment 1-1, difference is, to be deposited At lithium-cobalt composite oxide (LiCo0.98Al0.01Mg0.01O2Coating material on) is sulfur (S) and firing temperature is 700 DEG C. When evaluating battery, discovery initial capacity is 9.1Wh, and capability retention is 64%.
<embodiment 1-9>
Manufacturing rechargeable nonaqueous electrolytic battery in the way of identical with embodiment 1-1, difference is, with Co: The atomic ratio mixing lithium-cobalt composite oxide (LiCo of Li:P=98:0.5:0.50.98Al0.01Mg0.01O2), lithium carbonate (Li2CO3) and diammonium phosphate ((NH4)2HPO4).When evaluating battery, discovery initial capacity is 9.1Wh, and capacity keeps Rate is 80%.
<embodiment 1-10>
Manufacturing rechargeable nonaqueous electrolytic battery in the way of identical with embodiment 1-1, difference is, with Co: The atomic ratio mixing lithium-cobalt composite oxide (LiCo of Li:P=98:2.5:2.50.98Al0.01Mg0.01O2), lithium carbonate (Li2CO3) and diammonium phosphate ((NH4)2HPO4).When evaluating battery, discovery initial capacity is 8.9Wh, and capacity keeps Rate is 75%.
<embodiment 1-11>
Manufacturing rechargeable nonaqueous electrolytic battery in the way of identical with embodiment 1-1, difference is, with Co: The atomic ratio mixing lithium-cobalt composite oxide (LiCo of Li:P=98:5:50.98Al0.01Mg0.01O2), lithium carbonate (Li2CO3) and Diammonium phosphate ((NH4)2HPO4).When evaluating battery, discovery initial capacity is 8.2Wh, and capability retention is 69%.
<embodiment 1-12>
Manufacturing rechargeable nonaqueous electrolytic battery in the way of identical with embodiment 1-1, difference is, lithium-cobalt Composite oxides consist of LiCo0.97Al0.01Mg0.02O2.When evaluating battery, discovery initial capacity is 9.0Wh, and holds Amount conservation rate is 84%.
<embodiment 1-13>
Manufacturing rechargeable nonaqueous electrolytic battery in the way of identical with embodiment 1-1, difference is, lithium-cobalt Composite oxides consist of LiCo0.95Al0.01Mg0.04O2.When evaluating battery, discovery initial capacity is 8.8Wh, and holds Amount conservation rate is 82%.
<comparative example 1-1>
Manufacturing rechargeable nonaqueous electrolytic battery in the way of identical with embodiment 1-1, difference is, omits Lithium-cobalt composite oxide (LiCo0.98Al0.01Mg0.01O2) coating processing.When evaluating battery, find that initial capacity is 9.2Wh, and capability retention is 31%.
<comparative example 1-2>
Manufacturing rechargeable nonaqueous electrolytic battery in the way of identical with embodiment 1-1, difference is, omits Lithium-cobalt composite oxide (LiCo0.98Al0.01Mg0.01O2) coating processing and cell voltage when charging be 4.2V.Commenting During valency battery, discovery initial capacity is 8.1Wh, and capability retention is 71%.
<comparative example 1-3>
Manufacturing rechargeable nonaqueous electrolytic battery in the way of identical with embodiment 1-1, difference is, omits Lithium-cobalt composite oxide (LiCo0.98Al0.01Mg0.01O2) coating processing and cell voltage when charging be 4.4V.Commenting During valency battery, discovery initial capacity is 9.5Wh, and capability retention is 25%.
<comparative example 1-4>
Manufacturing rechargeable nonaqueous electrolytic battery in the way of identical with embodiment 1-1, difference is, lithium-cobalt Composite oxides consist of LiCoO2, to be deposited on lithium-cobalt composite oxide (LiCoO2Coating material on) is lithium carbonate (Li2CO3), magnesium carbonate (MgCO3) and diammonium phosphate ((NH4)2HPO4) mixture, and weigh and mix lithium-cobalt be combined Oxide (LiCoO2), lithium carbonate (Li2CO3), magnesium carbonate (MgCO3) and ammonium dihydrogen phosphate (NH4H2PO4), to obtain Co:Li: The atom ratio of Mg:P=100:1:1:1.When evaluating battery, discovery initial capacity is 9.1Wh, and capability retention is 32%.
<comparative example 1-5>
Manufacturing rechargeable nonaqueous electrolytic battery in the way of identical with embodiment 1-1, difference is, lithium-cobalt Composite oxides consist of LiCoO2, to be deposited on lithium-cobalt composite oxide (LiCoO2Coating material on) is aluminium fluoride (AlF3), and weigh and mix lithium-cobalt composite oxide (LiCoO2) and aluminium fluoride (AlF3), to obtain Co:Al=100:1 Atom ratio.When evaluating battery, discovery initial capacity is 9.1Wh, and capability retention is 30%.
<comparative example 1-6>
Manufacturing rechargeable nonaqueous electrolytic battery in the way of identical with embodiment 1-1, difference is, lithium-cobalt Composite oxides consist of LiCoO2, to be deposited on lithium-cobalt composite oxide (LiCoO2Coating material on) is aluminum phosphate (AlPO4), and weigh and mix lithium-cobalt composite oxide (LiCoO2) and aluminum phosphate (AlPO4), to obtain Co:Al=100: The atom ratio of 1.When evaluating battery, discovery initial capacity is 9.1Wh, and capability retention is 25%.
<comparative example 1-7>
Manufacturing rechargeable nonaqueous electrolytic battery in the way of identical with embodiment 1-1, difference is, lithium-cobalt Composite oxides consist of LiCoO2.When evaluating battery, discovery initial capacity is 9.1Wh, and capability retention is 20%.
<comparative example 1-8>
Manufacturing rechargeable nonaqueous electrolytic battery in the way of identical with embodiment 1-1, difference is, lithium-cobalt Composite oxides consist of LiCoO2, to be deposited on lithium-cobalt composite oxide (LiCoO2Coating material on) is lithium phosphate (Li3PO4), and weigh and mix lithium-cobalt composite oxide (LiCoO2) and lithium phosphate (Li3PO4), to obtain Co:P=100: The atom ratio of 1.When evaluating battery, discovery initial capacity is 9.1Wh, and capability retention is 15%.
<comparative example 1-9>
Manufacturing rechargeable nonaqueous electrolytic battery in the way of identical with embodiment 1-1, difference is, with phosphorus Acid hydrogen diammonium ((NH4)2HPO4) firing temperature in sintering process is 300 DEG C after the process that coats.When evaluating battery, send out Existing initial capacity is 8.6Wh, and capability retention is 35%.
Evaluation result is shown in table 1 below.
From evaluation result it can be seen that utilize positive active material to make magnesium (Mg) with from composite oxide particle wherein Inside be uniformly distributed to surface, and the mode of particle surface coats the sulfur (S) so that having spread state, phosphorus (P) etc. Embodiment can realize capability retention and good initial capacity.
On the other hand, the most do not exist in the comparative example 1-1 to 1-3 of coating material, due to battery charging capacity more Height, therefore capability retention is significantly more reduced.Additionally, the magnesium (Mg) in oxide particle wherein is pockety In comparative example 1-4 to 1-6, even if there is Concentraton gradient, high power capacity conservation rate can not be kept.And, there is not above-mentioned gold In the case of belonging to element M 2, even if sulfur (S), phosphorus (P) etc. are dispersed on the surface of oxide particle, capability retention is the lowest.
In embodiment 2-1 to 2-9, change coating material and obtain the coating with the surface at composite oxides The battery performance of the positive electrode that material is different.
<embodiment 2-1>
Manufacture the rechargeable nonaqueous electrolytic battery identical with embodiment 1-1, and with the side identical with embodiment 1-1 Formula utilizes the charging voltage of 4.35V to be evaluated, and difference is, replaces lithium carbonate and diammonium phosphate, will have and pass through The average diameter of 10 μm that laser scattering method is measured and the diammonium phosphate ((NH of the fusing point of 190 DEG C4)2HPO4) it is deposited on lithium-cobalt Composite oxides (LiCo0.98Al0.01Mg0.01O2On).Initial capacity is 9.1Wh and capability retention is 85%.< embodiment 2-2>
Manufacturing the rechargeable nonaqueous electrolytic battery identical with embodiment 2-1, difference is, will have and pass through laser The average diameter of 10 μm that scattering method is measured and the ammonium sulfate ((NH of the fusing point of 513 DEG C4)2HSO4) it is deposited on lithium-cobalt combined oxidation Thing (LiCo0.98Al0.01Mg0.01O2On).Initial capacity is 9.1Wh and capability retention is 87%.
<embodiment 2-3>
Manufacturing the rechargeable nonaqueous electrolytic battery identical with embodiment 2-1, difference is, will have and pass through laser The average diameter of 30 μm that scattering method is measured and the diammonium phosphate ((NH of the fusing point of 190 DEG C4)2HPO4) be deposited on lithium-cobalt be combined Oxide (LiCo0.98Al0.01Mg0.01O2On).Initial capacity is 9.1Wh and capability retention is 80%.
<embodiment 2-4>
Manufacturing the rechargeable nonaqueous electrolytic battery identical with embodiment 2-1, difference is, coating lithium-cobalt is combined Oxide (LiNi0.79Co0.19Al0.01Mg0.01O2).Initial capacity is 10.9Wh and capability retention is 81%.
<embodiment 2-5>
Manufacturing the rechargeable nonaqueous electrolytic battery identical with embodiment 2-1, difference is, coating lithium-cobalt is combined Oxide (LiNi0.49Co0.19Mn0.29Al0.01Mg0.01O2).Initial capacity is 9.5Wh and capability retention is 80%.
<embodiment 2-6>
Manufacturing the rechargeable nonaqueous electrolytic battery identical with embodiment 2-1, difference is, will have and pass through laser The average diameter of 10 μm that scattering method is measured and the phosphoric acid (H of the fusing point of 43 DEG C3PO4) it is deposited on lithium-cobalt composite oxide (LiCo0.98Al0.01Mg0.01O2On).Initial capacity is 9.1Wh and capability retention is 53%.
<embodiment 2-7>
Manufacturing the rechargeable nonaqueous electrolytic battery identical with embodiment 2-1, difference is, will have and pass through laser The average diameter of 10 μm that scattering method is measured and the iron sulfate (Fe of the fusing point of 480 DEG C2(SO4)3) it is deposited on lithium-cobalt combined oxidation Thing (LiCo0.98Al0.01Mg0.01O2On).Initial capacity is 8.9Wh and capability retention is 80%.
<embodiment 2-8>
Manufacturing the rechargeable nonaqueous electrolytic battery identical with embodiment 2-1, difference is, will have and pass through laser The average diameter of 100 μm that scattering method is measured and the diammonium phosphate ((NH of the fusing point of 190 DEG C4)2HPO4) to be deposited on lithium-cobalt multiple Close oxide (LiCo0.98Al0.01Mg0.01O2On).Initial capacity is 9.1Wh and capability retention is 58%.
<embodiment 2-9>
Manufacturing the rechargeable nonaqueous electrolytic battery identical with embodiment 2-1, difference is, will have and pass through laser The average diameter of 100 μm that scattering method is measured and the diammonium phosphate ((NH of the fusing point of 837 DEG C4)2HPO4) to be deposited on lithium-cobalt multiple Close oxide (LiCo0.98Al0.01Mg0.01O2On).Initial capacity is 9.0Wh and capability retention is 60%.
Evaluation result is shown in table 2 below.In table 2, further it is shown that for the result of the comparative example 1-1 of reference.
From evaluation result it can be seen that comprise wherein phosphorus P or the compound of fluorine F or pyrolysis compound have 80 DEG C to In the embodiment 2-1 to 2-5 of the fusing point of 600 DEG C, it is possible to achieve capability retention.Assume that when burning till at 900 DEG C, bag Phosphorous P or the compound of fluorine F or pyrolysis compound become liquid and are evenly coated with the surface of composite oxides.Real at these Executing in example, because ammonium evaporates and is not retained in active substance, therefore initial capacity keeps the highest.
In embodiment 2-4 and 2-5, make when using lithium-nickel-cobalt composite oxides or lithium-nickel-cobalt manganese composite oxide During for the center material of positive active material, it is possible to obtain there is the concentration so that metallic element M2 from composite oxide particle Concentraton gradient that center increases to surface and the positive active material of good capability retention.
About embodiment 2-6, capability retention is improved, but is not the biggest owing to coating the improvement caused.Cause Dissolve for phosphoric acid in mechanochemistry processing procedure and coating does not has those in embodiment 2-1 to 2-5 effective.This is because The temperature that the fusing point of phosphoric acid processes less than mechanochemistry causes.
About embodiment 2-7, owing to the fusing point of compound falls in the range of 70 DEG C to 600 DEG C, coating preferably, but divides The material solved is retained on positive electrode surface, and because this impurity is helpless to charge or discharge reaction, so initial discharge capacity Somewhat reduce.
In embodiment 2-8, because the diameter of coating material is too big, coating material does not mixes well with composite oxides Close.Therefore, capability retention improves, but is not the biggest owing to coating the improvement caused.Because the fusing point of coating material is 837 DEG C, higher than 600 DEG C and close to firing temperature, this causes melted at coating material and preferably coats these composite oxides Before, coating material reacts with the region of composite oxides, and destroys well applied.
In embodiment 3-1 to 3-14 and comparative example 3-1 to 3-14, change ratio d and molar fraction ratio r and really Determine battery behavior.
In these embodiments, ratio d obtained as below and molar fraction ratio r.
[ratio d and molar fraction ratio r]
Lithium-transition metal that the buffer solvent being prepared as pH 5.1 with citric acid and sodium citrate joins 0.2g is combined In oxide.Stirring mixture and per minute by 0.2 μm filter filtered sample.It is included in the major shift in each sample The quality of metal M1 (i.e. Co) or volumetric concentration and the quality of metallic element M2 (i.e. Mg, Mn, Ni) or volumetric concentration pass through ICP- AES: inductively coupled plasma atomic emission spectrometry [HORIBA JY238 ULTRACE] is measured and is dissolved in obtain The quality of M1 and M2 in the buffer solvent of 10mL.Utilize this result, calculate the amount [mol] of M1 and M2.According to formula (I) and (II) ratio d and molar fraction ratio r are determined.
Ratio d (%)=[(quality of primary transition metal M1)+(quality of metallic element M2)]/(matter that granule is overall Amount) (I)
Molar fraction r=(the material amount of metallic element M2)/[(the material amount of primary transition metal M1)+(metallic element M2 Material amount)] (II)
For capability retention and high temperature dwell sustainability, the coating including M2 is maximally effective, and wherein ratio d is full Foot 0.20≤r≤0.80, i.e. 10nm to the 100nm degree of depth from surface.In the examples below, molar fraction ratio r along with than Rate d changes in the range of 0.20≤r≤0.80 and have detected the battery performance of each battery.
In the examples below, metallic element M2 identified below and the distribution of element X.
[metallic element M2 and the distribution of element X]
Mg is checked, to confirm whether Mg is evenly distributed on the surface of granule or whether P is dispersed in by SEM/EDX On surface.Cut granule, and by Auger electron spectroscopy measure along diameter Elemental redistribution with observe Mg concentration company Continuous change.
<embodiment 3-1>
Prepare positive active material as follows.
The precursor that burns till in the way of identical with the embodiment 1-1 speed with 3 DEG C/min will be used for heating up, and And be maintained at 900 DEG C 3 hours, then Slow cooling, to obtain lithium-compound transition metal oxide.This lithium-transition metal is multiple Close oxide and there is the magnesium (Mg) on the surface being evenly distributed on lithium-cobalt composite oxide granule.Additionally, the concentration of magnesium (Mg) exists The surface ratio of granule wants height, and lithium phosphate (Li in the inside of granule3PO4) spread at the surface of the particles.
It addition, confirm the surface concentration gradient of magnesium Mg in detail.Ratio d=0.02%, under 0.05% mole point Percentage r is respectively 0.32,0.30.Be respectively 0.46 in ratio d=0.01%, molar fraction ratio r under 0.10%, 0.25。
The apparent condition of lithium-compound transition metal oxide confirms by observing the powder of acquisition under SEM/EDX.? Observe lithium-compound transition metal oxide surface time it was confirmed magnesium (Mg) at the surface of the particles be uniformly distributed with phosphorus Distribution on grain surface.By using CuK α powder to be carried out x-ray diffractogram of powder case measurement, except being equivalent to have stratiform The LiCoO of rock salt structure2Diffraction maximum outside, have also demonstrated and be equivalent to Li3PO4Diffraction maximum.Additionally, the concentration of magnesium is by cutting Open the cross section of lithium-compound transition metal oxide, and confirmed by auger electron spectrometry Elemental redistribution radially.Surveying After Elemental redistribution in the cross section of amount lithium-compound transition metal oxide, the concentration of magnesium is proved to be from the surface of granule inside Portion's consecutive variations.
By use lithium-compound transition metal oxide obtained as described above as positive active material, according to embodiment Method identical in 1-1 has manufactured rechargeable nonaqueous electrolytic battery.
Battery is carried out initial capacity, capability retention and the evaluation of High temperature storage performance.High temperature dwell sustainability identified below Energy.
In the environment of the environment temperature of 45 DEG C, battery manufactured as above is charged with the charging current of 1.5A until 4.35V charging voltage.With the discharge current of 2.0A, battery is discharged the most immediately, and when cell voltage is reduced to Electric discharge is terminated during 3.0V.Then by battery being carried out High temperature storage in 300 hours in the environment of being retained in the environment temperature of 60 DEG C. Afterwards, by measuring the discharge capacity after High temperature storage with 0.2C electric discharge.Electric discharge after utilizing initial capacity and insulation to preserve Capacity, obtains high temperature capability retention according to the following formula, i.e. high temperature dwell sustainability.High temperature capability retention [%]=(insulation preserves After discharge capacity/initial capacity) × 100.
<embodiment 3-2>
In the way of identical with embodiment 3-1, prepare rechargeable nonaqueous electrolytic battery, and with phase in embodiment 3-1 Same mode carries out initial capacity, capability retention and High temperature storage and keeps the evaluation of performance, and difference is, charging voltage For 4.2V.
<embodiment 3-3>
In the way of identical with embodiment 3-1, prepare rechargeable nonaqueous electrolytic battery, and with phase in embodiment 3-1 Same mode carries out initial capacity, capability retention and High temperature storage and keeps the evaluation of performance, and difference is, charging voltage For 4.5V.
<embodiment 3-4>
Preparing positive active material in the way of identical with embodiment 3-1, difference is, the second temperature burnt till Degree is set to 950 DEG C, and the second time burnt till was 30 minutes.At ratio d=0.02%, molar fraction ratio under 0.05% Rate r is respectively 0.22,0.21.It is respectively 0.38,0.16 in ratio d=0.01%, molar fraction ratio r under 0.10%.With The mode identical with embodiment 3-1 prepares rechargeable nonaqueous electrolytic battery, and enters in the way of identical with embodiment 3-1 Row initial capacity, capability retention and High temperature storage keep the evaluation of performance, and difference is, charging voltage is 4.5V.
<embodiment 3-5>
Preparing positive active material in the way of identical with embodiment 3-1, difference is, answering as base material Conjunction oxide is LiCo0.95Al0.01Mg0.04O2.It is respectively in ratio d=0.02%, molar fraction ratio r under 0.05% 0.73、0.52.It is respectively 0.86,0.44 in ratio d=0.01%, molar fraction ratio r under 0.10%.With with embodiment 3- Mode identical in 1 prepares rechargeable nonaqueous electrolytic battery, and initially holds in the way of identical with embodiment 3-1 Amount, capability retention and High temperature storage keep the evaluation of performance.
<embodiment 3-6>
Preparing positive active material in the way of identical with embodiment 3-1, difference is, answering as base material Conjunction oxide is LiCo0.97Al0.01Mg0.02O2.It is respectively in ratio d=0.02%, molar fraction ratio r under 0.05% 0.31、0.31.It is respectively 0.56,0.25 in ratio d=0.01%, molar fraction ratio r under 0.10%.With with embodiment 3- Mode identical in 1 prepares rechargeable nonaqueous electrolytic battery, and initially holds in the way of identical with embodiment 3-1 Amount, capability retention and High temperature storage keep the evaluation of performance.
<embodiment 3-7>
Preparing positive active material in the way of identical with embodiment 3-1, difference is, answering as base material Conjunction oxide is LiCoO3And with lithium carbonate Li2CO3, magnesium carbonate MgCO3, ammonium dihydrogen phosphate NH4H2PO4Shown in table 3 and table 4 Ratio mixing.It is respectively 0.46,0.40 in ratio d=0.02%, molar fraction ratio r under 0.05%.At ratio d= 0.01%, the molar fraction ratio r under 0.10% is respectively 0.55,0.44.Prepare in the way of identical with embodiment 3-1 Rechargeable nonaqueous electrolytic battery, and carry out initial capacity, capability retention and high temperature dwell in the way of identical with embodiment 3-1 Deposit the evaluation keeping performance.
<embodiment 3-8>
Preparing positive active material in the way of identical with embodiment 3-1, difference is, uses LiCoO2Make For the lithium-cobalt composite oxide for base material, and coat with the coating material of nickel hydroxide and manganese phosphate.In coating, system Standby and mix material and make to be respectively in ratio d=0.02%, molar fraction ratio r (Ni+Mn/Ni+Mn+Co) under 0.05% 0.35,0.34, and it is respectively 0.56,0.25 in ratio d=0.01%, molar fraction ratio r under 0.10%.With with enforcement Mode identical in example 3-1 prepares rechargeable nonaqueous electrolytic battery, and carries out initial in the way of identical with embodiment 3-1 Capacity, capability retention and the evaluation of High temperature storage characteristic.
<comparative example 3-1>
Use does not has cated composite oxides LiCo0.98Al0.01Mg0.01O2As positive active material.At ratio d= 0.02%, the molar fraction ratio r under 0.05% is respectively 0.01,0.01.Ratio d=0.01%, under 0.10% mole Fractional ratio r is respectively 0.01,0.01.Rechargeable nonaqueous electrolytic battery is prepared in the way of identical with embodiment 3-1, and Initial capacity, capability retention and the evaluation of High temperature storage characteristic is carried out in the way of identical with embodiment 3-1.
<comparative example 3-2>
Preparing positive active material in the way of identical with embodiment 3-1, difference is, LiCoO2For making For the lithium-cobalt composite oxide of base material, and with lithium carbonate Li2CO3, magnesium carbonate MgCO3With ammonium dihydrogen phosphate NH4H2PO4With Co: The molar ratio mixing of Li:Mg:P=100:1:0.5:1.Divide in ratio d=0.02%, molar fraction ratio r under 0.05% It is not 0.18,0.10.It is respectively 0.25,0.08 in ratio d=0.01%, molar fraction ratio r under 0.10%.With with enforcement Mode identical in example 3-1 prepares rechargeable nonaqueous electrolytic battery, and carries out initial in the way of identical with embodiment 3-1 Capacity, capability retention and the evaluation of High temperature storage characteristic.
<comparative example 3-3>
Preparing positive active material in the way of identical with embodiment 3-1, difference is, lithium-cobalt composite oxygen Compound LiCo0.98Al0.01Mg0.01O2, lithium carbonate Li2CO3, magnesium carbonate MgCO3With ammonium dihydrogen phosphate NH4H2PO4With Co:Li:Mg:P The molar ratio mixing of=100:1:1:4.Be respectively 0.82 in ratio d=0.02%, molar fraction ratio r under 0.05%, 0.83.It is respectively 0.80,0.85 in ratio d=0.01%, molar fraction ratio r under 0.10%.With with phase in embodiment 3-1 Same mode prepares rechargeable nonaqueous electrolytic battery, and carries out initial capacity, capacity in the way of identical with embodiment 3-1 Conservation rate and the evaluation of High temperature storage characteristic.
<comparative example 3-4>
Preparing positive active material in the way of identical with embodiment 3-1, difference is, the second temperature burnt till Degree is set to 950 DEG C, and the second time burnt till was 30 minutes.At ratio d=0.02%, molar fraction ratio under 0.05% Rate r is respectively 0.22,0.21.It is respectively 0.38,0.16 in ratio d=0.01%, molar fraction ratio r under 0.10%.With The mode identical with embodiment 3-1 prepares rechargeable nonaqueous electrolytic battery, and enters in the way of identical with embodiment 3-1 Row initial capacity, capability retention and the evaluation of High temperature storage characteristic.
<comparative example 3-5>
Preparing positive active material in the way of identical with embodiment 3-1, difference is, LiCo0.95Al0.01Mg0.04O2For the lithium-cobalt composite oxide as base material.Ratio d=0.02%, rubbing under 0.05% You are respectively 0.73,0.52 at fractional ratio r.Be respectively 0.86 in ratio d=0.01%, molar fraction ratio r under 0.10%, 0.44.Rechargeable nonaqueous electrolytic battery is prepared in the way of identical with embodiment 3-1, and with identical with embodiment 3-1 Mode carry out initial capacity, capability retention and the evaluation of High temperature storage characteristic.
<comparative example 3-6>
Rechargeable nonaqueous electrolytic battery is manufactured in the way of identical with comparative example 3-5.With identical with embodiment 3-1 Mode battery is carried out initial capacity, capability retention and the evaluation of High temperature storage characteristic, difference is, during charging Cell voltage is 4.2V.
<comparative example 3-7>
Rechargeable nonaqueous electrolytic battery is manufactured in the way of identical with comparative example 3-5.With identical with embodiment 3-1 Mode battery is carried out initial capacity, capability retention and the evaluation of High temperature storage characteristic, difference is, during charging Cell voltage is 4.5V.
<comparative example 3-8>
Preparing positive active material in the way of identical with embodiment 3-1, difference is, omits second and burns till Step.It is respectively 0.80,0.81 in ratio d=0.02%, molar fraction ratio r under 0.05%.Ratio d=0.01%, Molar fraction ratio r under 0.10% is respectively 0.82,0.79.Non-water power is manufactured in the way of identical with embodiment 3-1 Solve electrolitc secondary cell, and carry out initial capacity, capability retention and High temperature storage characteristic in the way of identical with embodiment 3-1 Evaluation.
<comparative example 3-9>
Preparing positive active material in the way of identical with embodiment 3-1, difference is, carries out mechanochemistry Process 15 minutes.It is respectively 0.21,0.16 in ratio d=0.02%, molar fraction ratio r under 0.05%.At ratio d= 0.01%, the molar fraction ratio r under 0.10% is respectively 0.31,0.14.Manufacture in the way of identical with embodiment 3-1 Rechargeable nonaqueous electrolytic battery, and carry out initial capacity, capability retention and high temperature dwell in the way of identical with embodiment 3-1 Deposit the evaluation of characteristic.
<comparative example 3-10>
Preparing positive active material in the way of identical with embodiment 3-1, difference is, LiCoO2With effect In the lithium-cobalt composite oxide of base material, and coat with the coating material of nickel hydroxide and manganese phosphate.In coating, preparation is also Mixing material makes the molar ratio=1:1:1 of the Ni:Co:Mn in whole positive active material granule, and at ratio d= 0.02%, the molar fraction ratio r (Ni+Mn/Ni+Mn+Co) under 0.05% is respectively 0.25,0.17, and at ratio d= 0.01%, the molar fraction ratio r under 0.10% is respectively 0.30,0.15.Manufacture in the way of identical with embodiment 3-1 Rechargeable nonaqueous electrolytic battery, and carry out initial capacity, capability retention and high temperature dwell in the way of identical with embodiment 3-1 Deposit the evaluation of characteristic.
The positive active material of the rechargeable nonaqueous electrolytic battery of embodiment 3-1 to 3-8 and comparative example 3-1 to 3-10 Structure and evaluation result are shown in Table 3 below and table 4.
From evaluation result it can be seen that can realize good by the decline of control initial capacity among embodiment 3-1 to 3-8 Good capability retention and High temperature storage characteristic.On the other hand, in comparative example 3-1 to 3-10, there is no these effects.
The ratio d of the positive active material of embodiment 3-1 to 3-8 meets the molar fraction under 0.02%≤d≤0.05% Ratio r falls in scope 0.20≤r≤0.80.Further, they present the model meeting 0.02%≤d≤0.05% at ratio d In enclosing, the trend that molar ratio r reduces from surface to depth direction.
When the ratio d (%) of certain depth scope (i.e. from a surface to 10nm to 100nm) meets 0.02%≤d≤0.05% Time, comparative example 3-1 to 3-2,3-4, the molar fraction ratio r of positive active material of 3-9 to 3-10 are constants or along the degree of depth Direction reduces.But molar fraction ratio r does not fall in the scope of 0.20≤r≤0.80.
The molar fraction ratio r of comparative example 3-1, not in the scope of 0.20≤r≤0.80, is because not using coating Material.The molar fraction ratio r of comparative example 3-2, not in the scope of 0.20≤r≤0.80, is because base material and coating material Mixed volume is not suitable.The molar fraction ratio r of comparative example 3-4, not in the scope of 0.20≤r≤0.80, is because Two firing temperatures are 750 DEG C.The molar fraction ratio r of comparative example 3-9, not in the scope of 0.20≤r≤0.80, is because machine The tool chemically treated time is 15 minutes, and it is the shortest compared with embodiment 3-1.The molar fraction ratio r of comparative example 3-10 does not exists In the scope of 0.20≤r≤0.80, the mixed volume being because base material and coating material is not suitable.
Ratio d (%) meet 0.02%≤d≤0.05% time, the positive active material of comparative example 3-3 and 3-8 mole Fractional ratio r falls outside the scope of 0.20≤r≤0.80.And they demonstrate such trend: in certain depth scope (i.e. 10nm to 100nm from surface) meet in the range of 0.02%≤d≤0.05% at ratio d (%), molar ratio r is from table Face increases to depth direction.
The molar fraction ratio r of the positive active material of comparative example 3-3 falls outside the scope of 0.20≤r≤0.80, be because of Mixed volume for base material and coating material is not suitable.The molar fraction ratio r of the positive active material of comparative example 3-8 falls Outside the scope of 0.20≤r≤0.80, it is because not carrying out second and burns till process.
The molar fraction ratio r of the positive active material of comparative example 3-5 to 3-7 falls in the range of 0.20≤r≤0.80. But they present such trend: when full at ratio d (%) in certain depth scope (i.e. from a surface to 10nm to 100nm) In the range of foot 0.02%≤d≤0.05%, molar fraction ratio r increases from surface to depth direction.
The molar fraction ratio r of the positive active material of comparative example 3-5 to 3-7 increases, and is because second and burns till process Temperature is 850 DEG C.
As implied above go out, at the model meeting 0.02%≤d≤0.05% from surface to certain depth scope at ratio d In enclosing, when molar fraction ratio r falls in the range of 0.20≤r≤0.80, can be realized by the decline of suppression initial capacity Good capability retention and High temperature storage characteristic.
About the preparation method of positive active material, as embodiment 3-1 to 3-6, metallic element M2 is preferably from base Material causes surface.Preparation method makes technique simple, and the material prepared has a distribution evenly in surface, and very Keep structure well, which improve capability retention and High temperature storage characteristic.
Evaluation result from table 4 is it can be seen that have the positive pole at 0.02%≤d≤0.05% extraneous ratio d Active substance differs and improves capability retention and High temperature storage characteristic surely, even if molar fraction ratio r is in 0.20≤r≤0.80 In the range of.
About the analysis method on the surface of positive active material, be used for so far XPS (x-ray photoelectron power spectrum) and TOF-SIMS (time of flight secondary ion massspectrometry).Table 3 shows the molar fraction ratio r of measurement, wherein by these methods The ratio d corresponding with the depth bounds along depth direction measured is 0.010%, and it is corresponding to the district of a few nm degree of depth from surface Territory, and wherein measured by the method is 0.100% corresponding to the ratio d of depth bounds along depth direction, and it is corresponding In from the region more than the 100nm degree of depth on surface.
<embodiment 3-9>
Take the rechargeable nonaqueous electrolytic battery as manufactured in embodiment 3-4 apart, and from electrode, peel positive electrode collector off, From positive active material, remove binding agent by being immersed in NMP, burn conductive agent to obtain positive active material.At ratio Molar fraction ratio r under d=0.02% and 0.05% is respectively 0.29 and 0.22.
<embodiment 3-10>
Take the rechargeable nonaqueous electrolytic battery as manufactured in embodiment 3-5 apart, and from electrode, peel positive electrode collector off, From positive active material, remove binding agent by being immersed in NMP, burn conductive agent to obtain positive active material.At ratio Molar fraction ratio r under d=0.02% and 0.05% is respectively 0.79 and 0.53.
Structure and the evaluation result of the positive active material of the rechargeable nonaqueous electrolytic battery of embodiment 3-9 and 3-10 are shown in In table 5 below.
Table 5
Annotation:
U.: uniformly, nu.: uneven, pr.: exist, ab.: do not exist, int.: spread
Table 5 shows when removing positive active material from rechargeable nonaqueous electrolytic battery, ratio d 0.02% to Molar fraction ratio r under 0.05% falls 0.20, and < r is < in the range of 0.80.
<embodiment 3-11>
Prepare positive active material as follows.
With the atom ratio of Co:P=99:1 mix with embodiment 3-1 identical have measured by laser scattering method The lithium of 13 μm average diameters-cobalt/cobalt oxide LiCo0.98Al0.01Mg0.01O26 μm average diameters are become (to pass through with by jet mill comminution Laser scattering method measure) ammonium dihydrogen phosphate NH4H2PO4。
Mixture is processed 1 hour, with sedimentary phosphor acid dihydride on the surface of lithium-cobalt/cobalt oxide by mechanochemistry device Ammonium, thus obtain the precursor before firing.With the speed of 3 DEG C/min, this precursor is heated up, and holding 3 is little at 900 DEG C Time, then Slow cooling, to obtain lithium-compound transition metal oxide.This lithium-compound transition metal oxide has equably The magnesium (Mg) being distributed on the surface of lithium-compound transition metal oxide granule.Additionally, the concentration of magnesium (Mg) is at particle surface ratio Height, and lithium phosphate (Li is wanted in the inside of granule3PO4) spread at the surface of the particles.
Incidentally, the surface concentration gradient of magnesium Mg is confirmed in detail.Ratio d=0.01%, 0.015%, 0.02%, the molar fraction ratio r at 0.05% is respectively 0.82,0.73,0.62 and 0.40.
The apparent condition of the material obtained confirms by observing the powder of acquisition under SEM/EDX.When observing, it was demonstrated that Magnesium (Mg) being uniformly distributed and phosphorus distribution at the surface of the particles at the surface of the particles.By using CuK α that granule is carried out powder The measurement of end X-ray diffraction pattern, except being equivalent to the LiCoO with layered rock salt structure2Diffraction maximum outside, have also demonstrated Be equivalent to Li3PO4Diffraction maximum.Additionally, the concentration of magnesium is by cutting the cross section of lithium-compound transition metal oxide, and pass through Russia Auger electron spectroscopy is measured Elemental redistribution radially and is confirmed.Measure granule cross section in Elemental redistribution time, the concentration quilt of magnesium Turn out to be from the surface of granule towards internal consecutive variations.
By use lithium-compound transition metal oxide granule obtained as described above as positive active material, with enforcement Mode identical in example 3-1 has manufactured rechargeable nonaqueous electrolytic battery, and to battery in the way of identical with embodiment 3-1 Initial capacity, capability retention and the evaluation of High temperature storage characteristic are carried out.
<embodiment 3-12>
Preparing positive active material in the way of identical with embodiment 3-11, difference is, with Co:P= The atom ratio mixing of 98.8:1.2 has the lithium-cobalt/cobalt oxide of the 6 μm average diameters measured by laser scattering method LiCo0.98Al0.01Mg0.01O2The biphosphate of 6 μm average diameters (being measured by laser scattering method) is become with by jet mill comminution Ammonium NH4H2PO4。
Incidentally, the surface concentration gradient of magnesium Mg is confirmed in detail.Ratio d=0.01%, 0.015%, 0.02%, the molar fraction ratio r at 0.05% is respectively 0.92,0.85,0.80 and 0.65.
By use lithium-compound transition metal oxide granule obtained as described above as positive active material, with enforcement Mode identical in example 1-1 has manufactured rechargeable nonaqueous electrolytic battery.And to electricity in the way of identical with embodiment 3-11 Pond has carried out initial capacity, capability retention and the evaluation of High temperature storage characteristic.
<embodiment 3-13>
Lithium-the cobalt with 6 μm average diameters (being measured by laser scattering method) is mixed with the atom ratio of Co:S=99:1 Oxide LiCo0.98Al0.01Mg0.01O2The sulfur of 3 μm average diameters (being measured by laser scattering method) is become with by jet mill comminution Acid ammonium (NH4)2SO4.Mixture is processed 30 minutes, so that ammonium sulfate precipitation is at the table of lithium-cobalt/cobalt oxide by planetary-type mixer On face.In addition to said process, in the way of identical with embodiment 3-11, prepare positive active material.At ratio d= 0.01%, the molar fraction ratio r at 0.015%, 0.02%, 0.05% is respectively 0.80,0.71,0.58 and 0.38.
By use lithium-compound transition metal oxide granule obtained as described above as positive active material, with enforcement Mode identical in example 3-11 has manufactured rechargeable nonaqueous electrolytic battery.And to electricity in the way of identical with embodiment 3-11 Pond has carried out initial capacity, capability retention and the evaluation of High temperature storage characteristic.
<embodiment 3-14>
Preparing positive active material in the way of identical with embodiment 3-11, difference is, with Co:P=99: The atom ratio mixed phosphate ammonium dihydrogen NH of 14H2PO4With the lithium cobalt with the 100 μm average diameters measured by laser scattering method Oxide.
Incidentally, the surface concentration gradient of magnesium Mg is confirmed in detail.Ratio d=0.01%, 0.015%, 0.02%, the molar fraction ratio r at 0.05% is respectively 0.62,0.53,0.44 and 0.25.
By use lithium-compound transition metal oxide granule obtained as described above as positive active material, with enforcement Mode identical in example 3-11 has manufactured rechargeable nonaqueous electrolytic battery.And to electricity in the way of identical with embodiment 3-11 Pond has carried out initial capacity, capability retention and the evaluation of High temperature storage characteristic.
<comparative example 3-11>
Preparing positive active material in the way of identical with embodiment 3-11, difference is, with Co:P=95: The atom ratio mixed phosphate ammonium dihydrogen NH of 54H2PO4With the lithium cobalt oxide with the 6 μm average diameters measured by laser scattering method Compound.
Incidentally, the surface concentration gradient of magnesium Mg is confirmed in detail.Ratio d=0.01%, 0.015%, 0.02%, the molar fraction ratio r at 0.05% is respectively 0.98,0.95,0.92 and 0.85.
By use lithium-compound transition metal oxide granule obtained as described above as positive active material, with enforcement Mode identical in example 3-11 has manufactured rechargeable nonaqueous electrolytic battery.And to electricity in the way of identical with embodiment 3-11 Pond has carried out initial capacity, capability retention and the evaluation of High temperature storage characteristic.
<comparative example 3-12>
Preparing positive active material in the way of identical with embodiment 3-11, difference is, with Co:S=99: The atom ratio mixing ammonium sulfate (NH of 14)2SO4With the lithium cobalt oxidation with the 6 μm average diameters measured by laser scattering method Thing.
Incidentally, the surface concentration gradient of magnesium Mg is confirmed in detail.Ratio d=0.01%, 0.015%, 0.02%, the molar fraction ratio r at 0.05% is respectively 0.33,0.25,0.20 and 0.15.
By use lithium-compound transition metal oxide granule obtained as described above as positive active material, with enforcement Mode identical in example 3-11 has manufactured rechargeable nonaqueous electrolytic battery.And to electricity in the way of identical with embodiment 3-11 Pond has carried out initial capacity, capability retention and the evaluation of High temperature storage characteristic.
Embodiment 3-11 to 3-14, the positive active material of rechargeable nonaqueous electrolytic battery of comparative example 3-11 to 3-12 Structure and evaluation result are shown in table 6 below.
From the evaluation result shown in table 6 it can be seen that meet in the range of 0.02%≤d≤0.05% at ratio d, implement Example 3-11, the molar fraction ratio r of positive active material of 3-12,3-13 fall in scope 0.20≤r≤0.80.And with Time, < in the range of 0.02%, molar fraction ratio r falls at scope 0.55≤r < in 1.0 to meet 0.01%≤d at ratio d.Logical Crossing the decline of the discharge capacity suppressing them, these embodiments show the biggest holding capacity rate of improvement and High temperature storage is special Property.
Meet in the range of 0.02%≤d≤0.05% at ratio d, the positive active material of embodiment 3-14 mole point Percentage r falls in scope 0.20≤r≤0.80.But ratio d meet 0.01%≤d < in the range of 0.02%, mole point Percentage r does not fall at scope 0.55≤r < in 1.0.Embodiment 3-14 can not obtain holding capacity or the high temperature dwell that height improves Sustainability.Because the average diameter of coating material ammonium dihydrogen phosphate is 100 μm, this upsets the good admixture of ammonium dihydrogen phosphate, Thus good coating state can not be obtained on the surface of base material.
Ratio d meet 0.01%≤d < in the range of 0.02%, the positive active material of comparative example 3-11 mole point Percentage r falls at scope 0.55≤r < in 1.0.But meet in the range of 0.02%≤d≤0.05% at ratio d, mole point Percentage r falls outside scope 0.20≤r≤0.80.This is because too many coating material makes coating the thickest, its minimizing helps Positive active material in charge-discharge capacities.Therefore, the initial discharge capacity of comparative example 3-11 is the least.
Ratio d meet 0.01%≤d < in the range of 0.02%, the positive active material of comparative example 3-12 mole point Percentage r falls at scope 0.55≤r < outside 1.0.This is because coating material mixes with base material the most well and can not obtain Good coating.Therefore, the good improvement of holding capacity and High temperature storage characteristic can not be obtained by comparative example 3-12.
It will be understood by those within the art that, can according to design require and other factors carry out various change, Combination, sub-portfolio and change, as long as they are in the range of claims or its equivalent.

Claims (9)

1. a positive active material, including lithium-compound transition metal oxide, this lithium-compound transition metal oxide comprises Lithium, primary transition metal M1 and be different from the metallic element M2 of described primary transition metal M1, wherein,
Described metallic element M2 has the Concentraton gradient from the center of each granule to the described metallic element M2 on surface,
Meeting in the range of 0.020≤d≤0.050 at the ratio d (%) from surface to certain depth, molar fraction r (%) is full Foot formula 0.20≤r≤0.80,
Wherein, ratio d (%)=[(quality of described primary transition metal M1)+(quality of metallic element M2)]/(granule is overall Quality),
Molar fraction r=(the material amount of metallic element M2)/[(the material amount of primary transition metal M1)+(thing of metallic element M2 Quality)],
Wherein, described primary transition metal M1 is at least one in nickel (Ni), cobalt (Co), manganese (Mn) and ferrum (Fe), And
Wherein, described metallic element M2 is selected from manganese (Mn), magnesium (Mg), aluminum (Al), nickel (Ni), boron (B), titanium (Ti), cobalt (Co) And at least one element in ferrum (Fe).
Positive active material the most according to claim 1, wherein,
< in the range of 0.020, molar fraction r (%) meets to meet 0.010≤d at the ratio d (%) from surface to certain depth Formula 0.55≤r < 1.00.
Positive active material the most according to claim 1, wherein,
Meeting in the range of 0.020≤d≤0.050 from the ratio d (%) on surface to the described degree of depth, molar fraction ratio r from The surface of described composite oxide particle reduces to center.
Positive active material the most according to claim 2, wherein,
< in the range of 0.020, molar fraction ratio r is from institute to meet 0.010≤d at the ratio d (%) from surface to the described degree of depth The surface stating composite oxide particle reduces towards center.
Positive active material the most according to claim 2, wherein,
At least one element X in sulfur S, phosphorus P and fluorine F is present on described surface with aggregated forms.
Positive active material the most according to claim 5, wherein,
By described lithium-compound transition metal oxide granule and at least one element included in sulfur S, phosphorus P and fluorine F Reaction between compound, the concentration of described metallic element M2 increases in described surface.
Positive active material the most according to claim 6, wherein,
There is the compound comprising lithium in described course of reaction simultaneously.
Positive active material the most according to claim 6, wherein,
Comprise described compound or the thermal decomposition product of described compound of at least one element in sulfur S, phosphorus P and fluorine F There is the fusing point of more than 70 DEG C less than 600 DEG C.
Positive active material the most according to claim 6, wherein,
Comprise described compound or the thermal decomposition product of described compound of at least one element in sulfur S, phosphorus P and fluorine F There is the average diameter of below 30 μm.
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