CN103296272B - Positive active material for lithium secondary battery and its manufacture method and lithium secondary battery - Google Patents

Positive active material for lithium secondary battery and its manufacture method and lithium secondary battery Download PDF

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CN103296272B
CN103296272B CN201310064962.9A CN201310064962A CN103296272B CN 103296272 B CN103296272 B CN 103296272B CN 201310064962 A CN201310064962 A CN 201310064962A CN 103296272 B CN103296272 B CN 103296272B
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lithium
secondary battery
active material
lithium secondary
positive active
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CN103296272A (en
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成桥智真
渡部豪
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Nippon Chemical Industrial Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • 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
    • H01M4/36—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
    • 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
    • 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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Secondary Cells (AREA)

Abstract

The present invention provide the security and cycle characteristics that a kind of packed density is high, can improve lithium secondary battery, the positive active material for lithium secondary battery of operating voltage, its industrial favourable manufacture method and using its unit volume for obtaining capacity is high, security, cycle characteristics and the also excellent lithium secondary battery of operating voltage.The positive active material for lithium secondary battery is characterised by：Comprising the lithium cobalt composite oxide containing Sr atoms and Ti atoms obtained from being fired to the mixture containing lithium compound, cobalt compound and strontium titanates.

Description

Positive active material for lithium secondary battery and its manufacture method and lithium secondary battery
Technical field
The present invention relates to positive active material for lithium secondary battery and its manufacture method and lithium secondary battery.
Background technology
In recent years, with the rapidly development of portability, wirelessization in household electrical appliance, lithium rechargeable battery is used as on knee The power supply of the small electronic apparatus of computer, portable phone, digital camera etc. has obtained practical.For lithium ion secondary electricity Pond, since 1980 Nian Shui islands etc. delivered reported as cobalt acid lithium can be used as the positive active material of lithium rechargeable battery with Come, the research and development on lithium cobalt composite oxide are just in actively carrying out.
With the high performance of electronic instrument, the high capacity of further requirement battery.In order that the battery of specified volume High capacity, it is proposed that use packed density positive active material high as the scheme of positive pole.
As packed density positive active material high, for example, in following patent documents 1, it is proposed that will be in lithium transition In composite oxide of metal containing strontium, tungsten, antimony at least one and lithium-cobalt composite oxides containing molybdenum lived as positive pole The scheme of property substance migration.In addition, in following patent documents 2, it is proposed that molybdenum, vanadium, tungsten, boron, in fluorine at least one will be mixed Kind compound, lithium raw material and transition metal raw material and be fired and obtain lithium-transition metal composite oxide and lived as positive pole The scheme of property substance migration.
In addition, proposed in following patent documents 3 coating the lithium secondary battery that lithium composite xoide is obtained with strontium titanates With the scheme of positive active material, but, the positive active material obtained in patent document 3 is difficult to obtain packed density high.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2007-299668 publications
Patent document 2：Japanese Unexamined Patent Publication 2005-251716 publications
Patent document 3：Japanese Unexamined Patent Publication 2003-17053 publications
The content of the invention
Invent problem to be solved
In recent years, expect to develop the positive pole for also contemplating security on the basis of the high capacity of lithium secondary battery work Property material.
Therefore, it is an object of the invention to provide a kind of packed density it is high, can improve the security of lithium secondary battery and Cycle characteristics, the positive active material for lithium secondary battery of operating voltage, its industrial favourable manufacture method and use it The capacity of the unit volume for obtaining is high, security, cycle characteristics and the also excellent lithium secondary battery of operating voltage.
Method for solving problem
In view of above-mentioned actual conditions, conduct in-depth research, its result finds the present inventor etc., will contain lithium The mixture of compound, cobalt compound and strontium titanates be fired obtained from the lithium cobalt composite oxygen containing Sr atoms and Ti atoms Compound, packed density is high, and using the lithium cobalt composite oxide as positive active material lithium secondary battery, unit volume Capacity is high, and security, cycle characteristics and operating voltage are also excellent, so as to complete the present invention.
That is, the present invention the first technical scheme to be provided is positive active material for lithium secondary battery, it is characterised in that： Comprising obtained from being fired to the mixture containing lithium compound, cobalt compound and strontium titanates contain Sr atoms and Ti atoms Lithium cobalt composite oxide.
In addition, the present invention the second technical scheme to be provided is the manufacturer of positive active material for lithium secondary battery Method, it is characterised in that including：Obtain the raw material mixed processes of the mixture containing lithium compound, cobalt compound and strontium titanates；Connect The ablating work procedure that lithium cobalt composite oxide is fired and generated to the mixture.
In addition, the present invention the 3rd technical scheme to be provided is lithium secondary battery, it is characterised in that：It is using above-mentioned What the positive active material for lithium secondary battery of the first technical scheme was obtained.
The effect of invention
Positive active material for lithium secondary battery of the invention, packed density is high, it is possible to increase the safety of lithium secondary battery The capacity of property, cycle characteristics, operating voltage and unit volume.
In addition, manufacturing method according to the invention, can provide the secondary lithium batteries just with industrial advantageous approach Pole active material.
Brief description of the drawings
Fig. 1 is the amount of strontium atom in the depth direction for represent the positive active material obtained in embodiment 3 and embodiment 4 Figure.
Fig. 2 is the amount of titanium atom in the depth direction for represent the positive active material obtained in embodiment 3 and embodiment 4 Figure.
Fig. 3 is represented after lithium deintercalation from the positive active material obtained by embodiment 7, embodiment 9 and comparative example 1 The figure of the differential thermal change of positive active material.
Fig. 4 is represented from the positive active material obtained by embodiment 10, embodiment 11, embodiment 13 and comparative example 1 By the figure of the differential thermal change of the positive active material after lithium deintercalation.
Specific embodiment
Hereinafter, based on the preferred embodiment explanation present invention.
Positive active material for lithium secondary battery involved in the present invention（Hereinafter, " positive electrode active material is also referred to simply as sometimes Matter "）Comprising containing obtained from by being fired to the mixture substantially containing lithium compound, cobalt compound and strontium titanates The lithium cobalt composite oxide of Sr atoms and Ti atoms（Hereinafter, also it is referred to simply as sometimes " lithium cobalt composite oxide "）.
It is improved from tap density and the lithium cobalt composite oxide for generating is secondary as the lithium of positive active material The unit volume capacity of battery is high, cycle characteristics, operating voltage and security it is also excellent from the viewpoint of, the addition of strontium titanates Lithium cobalt composite oxide preferably with respect to generation is 0.01~0.2 mole of %, preferably 0.05~1 mole %.Additionally, making metatitanic acid The addition of strontium be above range the reasons why be：When the addition of strontium titanates is less than 0.01 mole of %, the jolt ramming of positive active material Density step-down, in addition, the effect for improving the security of lithium secondary battery, cycle characteristics and operating voltage has becoming for step-down Gesture, on the other hand, when the addition of strontium titanates is more than 2 moles of %, there is the trend for reducing in the capacity of Unit Weight.
In lithium cobalt composite oxide of the invention, as the addition element beyond strontium titanates as described later（M）, moreover it is possible to Enough contain Sr atoms and Ti atoms, it is high from the packed density of resulting lithium cobalt composite oxide and high power capacity can be formed Lithium secondary battery, make lithium secondary battery security, cycle characteristics and operating voltage further improve from the viewpoint of, preferably The content of the Sr atoms from strontium titanates is set to 0.01~1.80 mass % in terms of the conversion of Sr atoms, is preferably set to 0.04~0.90 Quality %, the content of the Ti atoms from strontium titanates is set to 0.005~1 mass % in terms of the conversion of Ti atoms, it is preferably set to 0.02~ 0.5 mass %.
One of feature of positive active material involved in the present invention be the Sr atoms that obtain of the strontium titanates by adding extremely It is present in the particle surface of lithium cobalt composite oxide less.
The present inventor etc. has found that be fired by the mixture containing strontium titanates, Sr atoms are present in lithium Cobalt composite oxide particle inside and particle surface both sides, be present in the Sr atoms of particle surface, for example, as SrO, SrTiO3、Sr3Ti2O7、Sr4Ti3O10Exist Deng strontium compound.And, the Sr atoms of addition are particularly helpful to carrying for tap density It is high.In addition, the present inventor etc. speculates, the strontium compound that this is present in particle surface is former with the Sr being present in inside particle Son, further also participates in crystallization by the cooperative effect of Ti atoms in the crystal surface of lithium composite xoide and the internal both sides of crystallization Stabilisation, therefore, the lithium secondary battery that lithium-cobalt composite oxides of the invention are used as positive active material, battery Performance, particularly high power capacity and security and cycle characteristics, operating voltage are excellent.
Be present in the Sr atoms of the particle surface of lithium cobalt composite oxide, with SrO etc. soluble strontium compound and SrTiO3、Sr3Ti2O7、Sr4Ti3O10Deng the strontium compound of slightly solubility, but be present in the Sr atoms of particle surface can be by least There is the soluble strontium compound such as SrO to confirm.
The content of the soluble strontium compound, it is excellent from the viewpoint of being high power capacity and excellent in safety from lithium secondary battery Choosing is calculated as 0.002~0.25 mass %, preferably 0.005~0.1 mass % with Sr atoms.
In the present invention, it is present in the amount of the soluble strontium compound of the particle surface of lithium cobalt composite oxide, Ke Yitong Cross by the Sr amounts of lithium cobalt composite oxide 5g dissolutions when placing 5 minutes under agitation for 25 DEG C in pure water 50ml, using inductance Coupled plasma emission spectrophotometer（ICP-AES）Quantified and obtained.
Additionally, the amount of soluble strontium compound contained in lithium cobalt composite oxide, with soluble strontium compound Sr atom meters, be 2.0~30 mass %, preferably 5~25 relative to Sr atom total amounts contained in lithium cobalt composite oxide Quality %.
On the other hand, the present inventor etc. speculates that Ti atoms contained in lithium cobalt composite oxide are particularly helpful to The raising of the cycle characteristics and operating voltage of lithium secondary battery, in addition, Ti atoms have as described above as SrTiO3、 Sr3Ti2O7、Sr4Ti3O10It is present in the Ti of the particle surface of lithium cobalt composite oxide Deng compound and is present in inside particle Ti。
Sr atoms and Ti atoms contained in lithium cobalt composite oxide, thus it is speculated that can be to pure LiCoO2Crystalline texture produce Influence.That is, pure LiCoO2C axles lattice parameter be 14.050~14.053 angstroms, in contrast, positive-active of the invention In material, the lattice parameter of C axles is 14.053~14.065 angstroms, preferably 14.055~14.062 angstroms, more than pure LiCoO2 C axles lattice parameter.
The present inventor etc. speculate this be due to be present in Sr atoms inside the particle of lithium cobalt composite oxide and The influence that Ti atoms are produced.
One of feature of positive active material involved in the present invention is that tap density is more than 2.60g/ml, preferably 2.6~3.1g/ml, more than pure LiCoO2Tap density.Positive active material of the invention has so big vibration density Degree, thus, packed density is improved, it is possible to increase the capacity of the unit volume of lithium secondary battery.
Additionally, above-mentioned tap density is to represent that positive active material sample is particularly in not pressurized natural admixture In filling characteristic value, obtain as follows：50~70g of sample is added in graduated cylinder, graduated cylinder is installed on into automatic T.D determines device In, as condition determination, tried to achieve with number of taps 500 times, jolt ramming height 3.2mm, 200 beats/min of jolt ramming speed（According to ASTM：B527-93、85）.
In positive active material of the invention, as preferred each physical property than that described above, from as positive electrode active material The fillibility of matter, the capacity of lithium secondary battery, cycle characteristics, speed characteristic, security and by positive active material coating When Stability of Slurry from the viewpoint of, the average grain diameter preferably obtained with laser diffraction, scattering method is 10~30 μm, preferably 10~25 μm.
From the security for further improving lithium secondary battery, and cycle characteristics, speed characteristic and by positive active material From the viewpoint of Stability of Slurry during coating, the BET specific surface area of positive active material preferably of the invention for 0.05~ 1m2/ g, preferably 0.1~0.3m2/g。
In addition, in positive active material of the invention, the lithium carbonate of residual is below 0.30 mass %, preferably 0.25 matter Amount below %, the lithium hydroxide of residual is below 0.15 mass %, preferably below 0.10 mass %.The lithium carbonate and hydrogen-oxygen of residual Change lithium in above range, Stability of Slurry during from the cycle characteristics of lithium secondary battery and by positive active material coating From the viewpoint of, it is more highly preferred to.
In positive active material of the invention, for the purpose of the various performances for improving lithium secondary battery, can further contain Have selected from one or more the addition element in Mn, Ni, Mg, Zr, Al, Ti, Ca, Mo, W, Bi, Nb and F（M）.Wherein, Addition element（M）When being selected from one or more in Mg, Zr, Ti, Al and F, from can further improve the secondary electricity of lithium From the viewpoint of the capacity of pond unit volume, cycle characteristics, operating voltage, security and speed characteristic etc., more preferably, especially It is preferred that and with the whole addition element containing Mg, Zr, Ti, Al and F（M）, thereby, it is possible to balance the raising secondary electricity of lithium well These performances in pond, so it is preferred that.
In positive active material of the invention, addition element（M）Content, relative to positive active material, preferably 0.03~5 mass %, particularly preferably 0.065~2.60 mass %.By making addition element（M）Content in above range, energy Enough suppress the reduction of the discharge capacity of Unit Weight, and can further improve cycle characteristics, speed characteristic, security etc. Battery performance.
In addition, in positive active material of the invention, as addition element（M）Addition is selected from Mg, Zr, Ti, Al and F When more than one or two kinds of, the content of Mg atoms is preferably 0.005~1 mass % relative to positive active material, particularly preferably It is 0.015~0.35 mass %.By making the content of Mg atoms in above range, cycle characteristics, security can be further improved Deng battery performance.
In addition, the content of Zr atoms is preferably 0.005~1.5 mass % relative to positive active material, particularly preferably 0.009~1 mass %.By making the content of Zr atoms in above range, the battery performances such as speed characteristic can be further improved.
In addition, the content of Ti atoms is preferably 0.005~0.5 mass % relative to positive active material, particularly preferably 0.005~0.5 mass %.By making the content of Ti atoms in above range, speed characteristic, operating voltage can be further improved Deng battery performance.Additionally, the addition element（M）Ti atoms, be not derived from addition strontium titanates Ti.
In addition, the content of Al atoms is preferably 0.005~1.2 mass % relative to positive active material, particularly preferably 0.03~0.65 mass %.By making the content of Al atoms in above range, security, cycle characteristics etc. can be further improved Battery performance.
In addition, the content of F atom is preferably 0.01~1 mass % relative to positive active material, particularly preferably 0.01~ 0.25 mass %.By making the content of F atom in above range, the battery performances such as cycle characteristics can be further improved.
Additionally, these addition element（M）Can be as oxide, composite oxides, sulfate, phosphate, fluoride etc. Form is present in the particle surface of lithium cobalt composite oxide, it is also possible to which solid solution is simultaneously present in the particle of lithium cobalt composite oxide Portion, is also present in particle inside and particle surface both sides.
Hereinafter, the manufacture method to positive active material involved in the present invention is illustrated.
The manufacture method of positive active material of the invention is characterised by, including：Obtain containing lithium compound, cobalt chemical combination The raw material mixed processes of the mixture of thing and strontium titanates；Then the mixture is fired and generates lithium cobalt composite oxide Ablating work procedure.
Raw material mixed processes are mixed lithiated compound, cobalt compound and strontium titanates and obtain the operation of raw mixture.
Lithium compound in raw material mixed processes, as long as the raw material for being commonly used as manufacturing lithium cobalt composite oxide makes Lithium compound, is not particularly limited, and can enumerate the oxide of lithium, hydroxide, carbonate, nitrate and organic Hydrochlorate etc., among these, preferably industrial cheap lithium carbonate.
The average grain diameter of lithium compound is 0.1~200 μm, preferably 2~50 μm, because now reactivity is good, so Particularly preferably.
Cobalt compound in raw material mixed processes, as long as the raw material for being commonly used as manufacturing lithium cobalt composite oxide makes Cobalt compound, is not particularly limited, and can enumerate oxide, the oxyhydroxide of cobalt（oxyhydroxide）, hydrogen Oxide, carbonate, nitrate and acylate etc., wherein, cobalt oxide is industrially readily available and inexpensively, so it is preferred that. In addition, the average grain diameter of cobalt compound is 0.5~40.0 μm, and preferably 2~35.0 μm, because now reactivity is good, so Particularly preferably.Especially with cobalt compound average grain diameter be 10~25 μm, more preferably 15~25 μm of cobalt compound when, The excess rate of lithium compound can be reduced, the lithium compound of remaining is reduced, from such a viewpoint, be more highly preferred to.
As the strontium titanates in raw material mixed processes, as long as being industrially obtained in that, it is not particularly limited, metatitanic acid When the average grain diameter of strontium is 0.05~5 μm, reactivity is good, so particularly preferably.
In raw material mixed processes, the mixed proportion of lithium compound and cobalt compound, the positive pole from obtained by can improve is lived Property the tap density of material, size controlling, reduce the lithium carbonate and lithium hydroxide of residual from the viewpoint of, preferably atom conversion The molal quantity of lithium is relative to the ratio between molal quantity of cobalt that atom converts（Li/Co mixes mol ratio）It is 0.990~1.100, preferably It is 1.000~1.080, particularly preferably 1.010~1.060.
In addition, the mixed proportion of strontium titanates, is 0.01~2 mole of % relative to the lithium cobalt composite oxide of generation, preferably 0.05~1 mole of %.The reason for this is that as described above, the addition of strontium titanates be less than 0.01 mole of % when, positive active material Tap density step-down, in addition, the effect for improving the security of lithium secondary battery and cycle characteristics, speed characteristic has step-down Trend, on the other hand, when the addition of strontium titanates is more than 2 moles of %, there is the trend of the capacity reduction of Unit Weight.
In raw material mixed processes, as the method for mixed lithiated compound, cobalt compound and strontium titanates, for example, can enumerate Use propeller mixer（Ribbon Mixer）, Henschel mixer, superhigh speed mixing machine（Super Mixer）, Nuo Ta Mixer（Nautamixer）Deng mixed method.
In addition, in raw material mixed processes, beyond lithium compound, cobalt compound and strontium titanates, additionally it is possible to which addition is containing adding Added elements（M）Compound mixed.Containing addition element（M）Compound be to contain addition element as described above（M）'s Compound, specifically, can enumerate addition element（M）Oxide, hydroxide, sulfate, carbonate, phosphate, halogen Compound, acylate etc..With addition element（M）Compound can also contain two or more addition element（M）Chemical combination Thing, or, for a kind of addition element（M）It is not limited to a kind of compound, it is also possible to and with two or more diverseization Compound is used.Containing addition element（M）Compound average grain diameter for 0.05~100 μm, be preferably 0.1~90 μm when, reaction Property it is good, so particularly preferably.
As containing addition element（M）Compound, preferably comprise the compound of magnesium atom, the chemical combination containing titanium atom Thing, the compound containing zirconium atom, the compound containing aluminium atom, the compound containing fluorine atom, especially through using being selected from MgF2、MgO、TiO2、ZrO2、Al(OH)3And AlF3In one or more, can further improve various battery performances. For example, MgF2The capacity sustainment rate of lithium secondary battery can be effectively improved, MgO can effectively improve the peace of lithium secondary battery Quan Xing, TiO2The average working voltage of lithium secondary battery, ZrO can be effectively improved2Lithium secondary battery can be effectively improved Security, speed characteristic, Al (OH)3The security of lithium secondary battery, AlF can be effectively improved3Lithium two can be effectively improved The capacity sustainment rate of primary cell.
In the present invention, from from the viewpoint of can balance the above-mentioned performance of raising lithium secondary battery well, preferably comprise Addition element（M）Compound and use MgF2、MgO、TiO2、ZrO2、Al(OH)3And AlF3Whole use.
In raw material mixed processes, mixing contains addition element（M）Compound when, contain addition element（M）Compound Combined amount, relative to the lithium cobalt composite oxide of generation, preferably addition element（M）It is the combined amount of 0.03~5 mass %, it is special Not preferred addition element（M）It is the combined amount of 0.065~2.6 mass %.By making to contain addition element（M）Compound it is mixed Resultant from the reduction of the discharge capacity of the Unit Weight that can suppress lithium secondary battery, and improves capacity dimension in above range From the viewpoint of the battery performance of holdup, operating voltage, speed characteristic, security etc., it is more highly preferred to.
Additionally, conduct contains addition element（M）Compound, using selected from MgF2、MgO、TiO2、ZrO2、Al(OH)3With AlF3In one or two kinds of more than when, MgF2Lithium cobalt composite oxide of the addition relative to generation rub for 0.01~1 The addition of your %, preferably 0.01~0.25 mole %, MgO rubs for 0.01~2.50 relative to the lithium cobalt composite oxide of generation You are %, preferably 0.05~1.00 mole %.In addition, TiO2Lithium cobalt composite oxide of the addition relative to generation for 0.01~ 1 mole of %, preferably 0.01~1 mole %, ZrO2Addition relative to generation lithium cobalt composite oxide be 0.01~1.50 Mole %, preferably 0.10~1 mole %, Al (OH)3Lithium cobalt composite oxide of the addition relative to generation rub for 0.01~3 You are %, preferably 0.1~2 mole %, AlF3Addition relative to generation lithium cobalt composite oxide be 0.01~1 mole of %, it is excellent Elect 0.01~0.25 mole of % as.
Additionally, the lithium compound of raw material, cobalt compound, strontium titanates and be added as needed on containing addition element（M）Change Compound is unrelated with manufacture experience, but in order to manufacture the lithium cobalt composite oxide powder of high-purity, is preferably reduced as far as impurity Content.
Ablating work procedure in the manufacture method of positive active material of the invention is, by that will be obtained in raw material mixed processes To lithium compound, cobalt compound, strontium titanates and mix as needed containing addition element（M）Compound raw mixture It is fired, obtains the operation of lithium cobalt composite oxide.
In ablating work procedure, raw mixture is fired and makes lithium compound, cobalt compound, strontium titanates and according to need To be mixed containing addition element（M）Compound react when firing temperature be 1000 DEG C~1100 DEG C, preferably 1050~ 1080℃.Itself reason for this is that：The tap density of then lithium cobalt composite oxide has the trend of reduction when firing temperature is less than 1000 DEG C, On the other hand, when firing temperature is higher than 1100 DEG C, then the sintering of the burned product obtained by having becomes strong, the stone and broken place of hardness Reason, pulverization process become difficult trend.
In addition, the reaction time is 1~30 hour, preferably 5~20 hours.In addition, firing atmosphere is in air, in oxygen Deng oxidizing atmosphere.
The lithium cobalt composite oxide containing Sr atoms and Ti atoms for obtaining is operated as above, can be carried out as needed repeatedly Ablating work procedure.
For the lithium cobalt composite oxide containing Sr atoms and Ti atoms for obtaining after firing, broken place is carried out as needed Reason and/or pulverization process, are further classified, and obtain positive active material for lithium secondary battery.
So, resulting positive active material of the invention includes the lithium cobalt combined oxidation containing Sr atoms and Ti atoms Thing, used as preferred physical property, average grain diameter is 10~30 μm, and preferably 10~25 μm, tap density is more than 2.6g/ml, excellent 2.6~3.1g/ml, and Sr atoms are elected as present at least at the particle surface of lithium cobalt composite oxide.
In addition, lithium secondary battery of the invention is obtained using positive active material of the invention, the lithium secondary battery Including positive pole, negative pole, barrier film and nonaqueous electrolyte containing lithium salts.
Positive pole in lithium secondary battery of the invention is, for example, that anode mixture is coated with positive electrode collector and it is dried Deng and formed.Anode mixture includes positive active material, conductive agent, binding agent and the filler for being added as needed etc..This In the lithium secondary battery of invention, positive active material for lithium secondary battery of the invention is coated uniformly with positive pole.Therefore, originally The battery performance of the lithium secondary battery of invention is high, particularly high power capacity and safe.
The content of the positive active material contained by anode mixture in lithium secondary battery of the invention is desired for 70~100 Quality %, preferably 90~98 mass %.
As the positive electrode collector in lithium secondary battery of the invention, as long as do not cause chemistry in the battery for being constituted The electronic conductor of change, is not particularly limited, for example, can enumerate stainless steel, nickel, aluminium, titanium, fire carbon, in aluminium or The surface of stainless steel carried out material of surface treatment etc. with carbon, nickel, titanium, silver.The surface oxidation of these materials can be made With, it is also possible to assign concavo-convex use on collector surface by being surface-treated.In addition, as the form of collector, for example, can To enumerate paper tinsel, film, sheet material, mesh, perforation（punching）Material, lath-shaped thing, porous plastid, foaming body, groups of fibers, Formed body of non-woven fabrics etc..The thickness of collector is not particularly limited, and is preferably set to 1~500 μm.
As the conductive agent in lithium secondary battery of the invention, as long as do not cause chemical change in the battery for being constituted Electrically conductive material, be not particularly limited, for example, can enumerate the blacklead of natural graphite and artificial blacklead etc., carbon black, The carbon black class of acetylene black, Ketjen black, channel black, furnace black, lampblack, pyrolytic carbon black etc., carbon fiber or metallic fiber etc. The electric conductivity whisker class of metal dust class, zinc oxide, the potassium titanate of conducting fibre class, fluorocarbons, aluminium, nickel powder etc. etc., oxidation The conductive material of the conductive metal oxide or polyphenylene derivatives of titanium etc. etc., as natural graphite, for example, can arrange Lift squamous blacklead, flakey blacklead and earthy blacklead etc..They can use a kind of or be used in combination of two or more.Conductive agent Mixing ratio, in anode mixture be 1~50 mass %, preferably 2~30 mass %.
As the binding agent in lithium secondary battery of the invention, for example, starch, Kynoar, polyethylene can be enumerated Alcohol, carboxymethylcellulose calcium, hydroxypropyl cellulose, regenerated cellulose, diacetyl cellulose, polyvinylpyrrolidone, tetrafluoro second Alkene, polyethylene, polypropylene, ethylene/propylene/diene terpolymer（EPDM）, sulfonated epdm, styrene butadiene ribber, Fluorubber, tetrafluoroethene-hexafluoroethylene copolymer, tetrafluoraoethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoro alkyl vinyl Base ether copolymer, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene-chlorotrifluoroethylcopolymer copolymer, ethylene-tetrafluoroethylene are common Polymers, polychlorotrifluoroethylene, vinylidene fluoride pentafluor propylene copolymer, vinylidene fluoride-pentafluoropropylenecopolymer copolymer, ethylene chlorotrifluoro Copolymer, biasfluoroethylene-hexafluoropropylene-TFE copolymer, vinylidene-perfluoro methyl vinyl ether-tetrafluoroethene are common Polymers, ethylene-acrylic acid copolymer or its（Na+）Ionomer body, ethylene-methacrylic acid copolymer or its（Na+）Ion is handed over Conjuncted, ethylene-methyl acrylate copolymer or its（Na+）Ionomer body, ethylene methyl methacrylate copolymer or its （Na+）Polysaccharide, thermoplastic resin, the polymer with caoutchouc elasticity of ionomer body, PEO etc. etc., their energy It is enough to use a kind of or be used in combination of two or more.Additionally, containing and the functional group of lithium reaction using as polysaccharide During compound, its functional group is inactivated for example, it is preferable to add compound as isocyanates.The mixing ratio of binding agent, It is 1~50 mass %, preferably 5~15 mass % in anode mixture.
Filler in lithium secondary battery of the invention is the material for suppressing the volumetric expansion of positive pole in anode mixture etc., Can be added as needed on.As filler, as long as do not cause the fibrous material of chemical change in the battery for being constituted i.e. Can, any one can be used, it is, for example possible to use the fibre of the polyolefin polymers of polypropylene, polyethylene etc., glass, carbon etc. Dimension.The addition of filler is not particularly limited, and 0~30 mass % is preferably in anode mixture.
Negative pole in lithium secondary battery of the invention be on negative electrode collector be coated with negative material make its dry etc. and shape Into.As the negative electrode collector in lithium secondary battery of the invention, as long as do not cause chemical change in the battery for being constituted The electronic conductor of change, is not particularly limited, for example, can enumerate stainless steel, nickel, copper, titanium, aluminium, fire carbon, in copper or The surface of stainless steel carried out material and aluminium-cadmium alloy of surface treatment etc. with carbon, nickel, titanium, silver.Furthermore it is possible to by these The surface oxidation of material is used, it is also possible to collector surface assigned concavo-convex use by being surface-treated.In addition, as collection The form of electric body, for example, paper tinsel, film, sheet material, mesh, material, lath-shaped thing, porous plastid, the foaming of perforation can be enumerated Body, groups of fibers, formed body of non-woven fabrics etc..The thickness of collector is not particularly limited, and is preferably set to 1~500 μm.
As the negative material in lithium secondary battery of the invention, it is not particularly limited, for example, carbonaceous material can be enumerated Material, composite oxide of metal, lithium metal, lithium alloy, silicon class alloy, tin class alloy, metal oxide, electroconductive polymer, sulphur Category compound, Li-Co-Ni classes material, Li4Ti5O12Deng.As carbonaceous material, for example, can enumerate difficult blacklead carbon material, Blacklead class carbon material etc..As composite oxide of metal, for example, Sn can be enumeratedp(M1)1-p(M2)qOr（In formula, M1Expression is selected from The element of one or more of Mn, Fe, Pb and Ge, M2Represent and be selected from Al, B, P, Si, the race of the periodic table of elements the 1st, the 2nd race, the 3rd The element of one or more of race and halogen, 0<p≤1、1≤q≤3、1≤r≤8）、LitFe2O3（0≤t≤1）、LitWO2 （0≤t≤1）Deng compound.As metal oxide, GeO, GeO can be enumerated2、SnO、SnO2、PbO、PbO2、Pb2O3、 Pb3O4、Sb2O3、Sb2O4、Sb2O5、Bi2O3、Bi2O4、Bi2O5Deng.As electroconductive polymer, polyacetylene can be enumerated, gathered to benzene Deng.
As the barrier film in lithium secondary battery of the invention, it is possible to use with big ion permeability, with regulation The insulating properties film of mechanical strength.Consider to use from organic solvent resistance and hydrophobicity and be polymerized by TPOs such as polypropylene The obtained sheet material such as thing, glass fibre or polyethylene or non-woven fabrics.As the aperture of barrier film, as long as be generally used for battery have Scope, for example, being 0.01~10 μm.As the thickness of barrier film, as long as the scope of general battery, example Such as, it is 5~300 μm.Additionally, when using the solid electrolyte of polymer etc. as electrolyte described later, solid electrolyte can be with And septate function.
The nonaqueous electrolyte containing lithium salts in lithium secondary battery of the invention, including nonaqueous electrolyte and lithium salts.As Nonaqueous electrolyte in lithium battery of the invention, it is possible to use nonaqueous electrolytic solution, organic solid electrolyte, inorganic solid electrolyte Matter.As nonaqueous electrolytic solution, for example, METHYLPYRROLIDONE, propene carbonate, ethylene carbonate, carbonic acid fourth can be enumerated Alkene ester, dimethyl carbonate, diethyl carbonate, gamma-butyrolacton, 1,2- dimethoxy-ethanes, tetrahydroxy furans, 2- methyl tetrahydrochysene furans Mutter, dimethyl sulfoxide, the ring of 1,3- dioxas penta, formamide, dimethylformamide, the ring of dioxa penta, acetonitrile, nitromethane, formic acid Methyl esters, methyl acetate, phosphotriester, trimethoxy-methane, dioxolane derivatives, sulfolane, methyl sulfolane, 3- first Base -2- oxazolidones, 1,3- dimethyl-imidazols alkanone, propylene carbonate ester derivant, tetrahydrofuran derivatives, diethyl ether, 1,3- One kind in the non-proton organic solvent of the third sultone, methyl propionate, ethyl propionate etc. or mix it is two or more obtain it is molten Agent.
As the organic solid electrolyte in lithium secondary battery of the invention, for example, polythene derivative can be enumerated, gathered Epoxyethane derivative or the polymer containing it, poly propylene oxide derivative or the polymer containing it, phosphate ester polymer, Polyphosphazene, polyaziridine, polyethylene sulfide, polyvinyl alcohol, Kynoar, polyhexafluoropropylene etc. contain ionic dissociation Mixture of the polymer of base, the polymer containing ionic dissociation base and above-mentioned nonaqueous electrolytic solution etc..
As the inorganic solid electrolyte in lithium secondary battery of the invention, can using the nitride of Li, halide, contain Oxygen hydrochlorate, sulfide etc., for example, Li can be enumerated3N、LiI、Li5NI2、Li3N-LiI-LiOH、LiSiO4、LiSiO4-LiI- LiOH、Li2SiS3、Li4SiO4、Li4SiO4-LiI-LiOH、P2S5、Li2S or Li2S-P2S5、Li2S-SiS2、Li2S-GeS2、 Li2S-Ga2S3、Li2S-B2S3、Li2S-P2S5-X、Li2S-SiS2-X、Li2S-GeS2-X、Li2S-Ga2S3-X、Li2S-B2S3-X （In formula, X is selected from LiI, B2S3Or Al2S3In at least one more than）.
In addition, inorganic solid electrolyte is noncrystal（Glass）When, lithium phosphate can be contained in inorganic solid electrolyte （Li3PO4）, lithia（Li2O）, lithium sulfate（Li2SO4）, phosphorous oxide（P2O5）, lithium borate（Li3BO3）Deng oxygenatedchemicals, Li3PO4-uN2u/3（U is 0 ＜ u ＜ 4）、Li3SiO4-uN2u/3（U is 0 ＜ u ＜ 4）、Li3GeO4-uN2u/3（U is 0 ＜ u ＜ 4）、 Li3BO3-uN2u/3（U is 0 ＜ u ＜ 3）Deng nitrogen-containing compound.By the addition of the oxygenatedchemicals or nitrogen-containing compound, can The gap of the noncrystal skeleton that expansion is formed, mitigates the obstruction to lithium ion mobility, further improves ionic conductivity.
As the lithium salts in lithium secondary battery of the invention, it is possible to use the lithium salts dissolved in above-mentioned nonaqueous electrolyte, For example, LiCl, LiBr, LiI, LiClO can be enumerated4、LiBF4、LiB10Cl10、LiPF6、LiCF3SO3、LiCF3CO2、LiAsF6、 LiSbF6、LiB10Cl10、LiAlCl4、CH3SO3Li、CF3SO3Li、(CF3SO2)2NLi, chloroborane lithium, lower aliphatic carboxylic acid A kind of or two or more salt for obtaining of mixing in lithium, tetraphenyl borate lithium, acid imide etc..
In addition, in nonaqueous electrolyte, for the purpose of improveing charge-discharge characteristic, anti-flammability, can add as shown below Compound.For example, pyridine, triethyl phosphite, triethanolamine, cyclic ethers, ethylenediamine, n- glymes can be enumerated （glyme）, six phosphoric triamides, nitrobenzene derivative, sulphur, quinoneimine dye, N- substituted oxazolidinones and N, N- substituted imidazole Alkanone, glycol dialkyl ether, ammonium salt, polyethylene glycol, pyrroles, 2-methyl cellosolve, tri-chlorination ammonium, conductive polymer electrodes The monomer of active material, triethylene phosphoramide (TEPA), trialkyl phosphine, morpholine, the aryl compound with carbonyl, HMPA With 4- alkyl morpholines, the tertiary amine of two rings, You, phosphonium salts He tertiary phosphonium salt, phosphonitrile, carbonic ester etc..In addition, in order that electrolyte possesses Noninflammability, can in the electrolytic solution contain halogen solvent, for example, carbon tetrachloride, trifluoro-ethylene.In addition, in order to have for height The adaptability that temperature is preserved, can in the electrolytic solution contain carbon dioxide.
Lithium secondary battery of the invention be unit volume capacity is high, security, cycle characteristics and operating voltage are also excellent Lithium secondary battery, the shape of battery can be any one shape such as button-like, sheet material, tubular, square, Coin shape.
The purposes of lithium secondary battery of the invention is not particularly limited, for example, notebook computer, laptop electricity can be enumerated Brain, portable word processor, portable phone, Subset of cordless telephone, portable CD Player, radio, LCD TV, standby electricity Electronic instrument, automobile, electric vehicle, game machine, the electric tool of source, electric shaver, RAM card, video camera etc. etc. it is civilian Electronic instrument.
Embodiment
Hereinafter, the present invention is explained according to embodiment, but the present invention is not limited to these embodiments.
{ embodiment 1~9 }
With Co atoms and the mol ratio of Li atoms shown in table 1, cobaltosic oxide is weighed（25.0 μm of average grain diameter）, carbon Sour lithium（7.0 μm of average grain diameter）, then weigh strontium titanates（0.9 μm of average grain diameter）, used with the ratio shown in table 1 home-use mixed Conjunction machine with 60 seconds fully dry type mixing and obtain raw mixture.Then, with shown in table 1 in the bowl of oxidation aluminum Temperature and time is fired to resulting raw mixture in an atmosphere.After firing terminates, the firing thing is crushed, Classification, obtains the lithium cobalt composite oxide containing Sr atoms and Ti atoms, as positive active material sample.
{ comparative example 1~2 }
With Co atoms and the mol ratio of Li atoms shown in table 1, cobaltosic oxide is weighed（25.0 μm of average grain diameter）, carbon Sour lithium（7.0 μm of average grain diameter）, using home-use mixer with 60 seconds fully dry type mixing and obtain raw mixture. Then, resulting raw mixture is carried out in an atmosphere with the temperature and time shown in table 1 in the bowl of oxidation aluminum Fire.After firing terminates, the firing thing is crushed, is classified, lithium-transition metal composite oxide is obtained, as positive pole Active material sample.
Table 1
Note）SrTiO3Addition represent relative to generation lithium cobalt composite oxide mole %.
<The evaluation of physical property of positive active material sample>
To the positive active material sample obtained in embodiment and comparative example, obtain average grain diameter, BET specific surface area, Tap density, in water the amount of the strontium of dissolution, the lattice parameter of C axles and remaining LiOH and Li2CO3Content.And in table 2 Middle its result of expression.
<Average grain diameter>
Using laser diffraction, scattering method average grain diameter.
<Tap density>
For tap density, based on apparent density or the method for apparent specific volume described in JIS-K-5101,50ml's 50~70g of sample is added in graduated cylinder, is installed in Yuasa-Ionics company systems, DUAL AUTOTAP devices, with number of taps 500 times, jolt ramming height 3.2mm carry out jolt ramming, read capacity, apparent density is calculated, as tap density.
<The size of the lattice parameter of C axles>
For lattice parameter, using CuK alpha rays as radiographic source, using by X-ray diffraction（XRD）What analysis was obtained spreads out Penetrating pattern carries out rydberg that moral to positive active material sample（Rietveld）Parsing, becomes more meticulous and obtains lattice parameter, knot Structure parameter.Rydberg your moral parsing is, in order that extract information contained therein with X-ray diffraction pattern, by by actual survey The diffraction pattern for obtaining is compared with the diffraction pattern from crystalline texture model prediction（fitting）, carry out and crystalline texture phase The method for becoming more meticulous of the parameter of pass.
<The evaluation of the Sr amounts of the dissolution in water>
With 5 minutes, 25 DEG C of dispersion positive active material sample 5g in pure water 100ml, make Sr atoms molten from particle surface Go out, using inductively coupled plasma emission spectrophotometer（ICP-AES）The amount of the Sr in the quantitative solution.
<The LiOH and Li of remaining2CO3The evaluation of content>
Positive active material sample 5g, pure water 100g are weighed in beaker, using magnetic stirring apparatus disperse within 5 minutes. Then, the dispersion liquid is filtered, automatic titration device is used（Model C OMTITE-2500）With 0.1N-HCl, to 30ml, the filtrate is entered Row titration, calculates the LiOH and Li of residual2CO3。
<XPS is determined>
To the positive active material sample obtained in embodiment 3 and embodiment 4, x-ray photoelectron power spectrum is used（XPS）Point Analysis, is etched with argon to surface, and Sr peak values and Ti peak values are determined in depth direction, and its result is represented in fig. 1 and 2.
Additionally, etching condition is as described below.
Etching condition
Use ion gun：The differential discharge type suspended ion rifle of low energy with neutral particle removing device
Ion species：Ar+Ion
Negative electric field（extractor）Electric current：2μA
Accelerating potential：5.0kV
Etch-rate：1.84nm/ minutes（SiO2Conversion）
Table 2
{ embodiment 10 }
With Co atoms and the mol ratio of Li atoms shown in table 3, cobaltosic oxide is weighed（25.0 μm of average grain diameter）, carbon Sour lithium（7.0 μm of average grain diameter）, then strontium titanates is weighed with the ratio shown in table 3（0.9 μm of average grain diameter）、TiO2（Average grain 0.2 μm of footpath）、ZrO2（0.5 μm of average grain diameter）, using home-use mixer with 60 seconds fully dry type mixing and obtain raw material Mixture.Then, resulting raw mixture is carried out in an atmosphere with 1080 DEG C, 5 hours in the bowl of oxidation aluminum Fire.After firing terminates, the firing thing is crushed, is classified, obtained the lithium cobalt combined oxidation containing Sr atoms and Ti atoms Thing, as positive active material sample.
{ embodiment 11~13 }
With Co atoms and the mol ratio of Li atoms shown in table 3, cobaltosic oxide is weighed（25.0 μm of average grain diameter）, carbon Sour lithium（7.0 μm of average grain diameter）, then strontium titanates is weighed with the ratio shown in table 3（0.9 μm of average grain diameter）、MgF2（Average grain 22.6 μm of footpath）、MgO（Average grain diameter（3.1μm）、TiO2（0.2 μm of average grain diameter）、ZrO2（0.5 μm of average grain diameter）、Al(OH)3 （1.6 μm of average grain diameter）、AlF3（82.2 μm of average grain diameter）, using home-use mixer with 60 seconds fully dry type mixing and Obtain raw mixture.Then, resulting raw material is mixed in an atmosphere with 1080 DEG C, 5 hours in the bowl of oxidation aluminum Compound is fired.After firing terminates, the firing thing is crushed, is classified, obtained the lithium cobalt containing Sr atoms and Ti atoms Composite oxides, as positive active material sample.
Table 3
Note）SrTiO3Addition and containing addition element（M）Compound addition, represent relative to generation lithium cobalt Mole % of composite oxides.
<The evaluation of physical property of lithium cobalt composite oxide>
To the lithium cobalt composite oxide obtained in embodiment 10~13, average grain diameter, jolt ramming are obtained by the above method Density, the amount of the strontium of dissolution and the LiOH of remaining and Li in water2CO3Content.And its result is represented in table 4.
Table 4
Operation as described below, carries out battery performance test.
<The making of lithium secondary battery>
The mass % of positive active material 96, the matter of blacklead powder 2 resulting in mix embodiment 7,9~13 and comparative example 1 Amount %, the mass % of Kynoar 2 are scattered in METHYLPYRROLIDONE as anode mixture, prepare mixing paste. Aluminium foil dries it after being coated with mixing paste, is suppressed, and is punched into the disk of diameter 15mm, obtains positive plate.
Using the positive plate, each portion such as barrier film, negative pole, positive pole, collector plate, installation fitting, outside terminal, electrolyte is used Part, makes Coin shape lithium secondary battery.Wherein, negative pole uses metallic lithium foil, and electrolyte is used in ethylene carbonate and carbonic acid first 1 mole of LiPF is dissolved with the mixing liquid of 1 ︰ 1 1L of ethyl ester6Liquid.
Then, the performance evaluation of the lithium secondary battery obtained by carrying out.Its result is represented in table 5.
<The performance evaluation of battery>
Obtained Coin shape lithium secondary battery is worked with following experimental conditions at room temperature, evaluate following cell performance Energy.
（Evaluate A）
（1）The experimental condition that cycle characteristics is evaluated
First, carried out charging to 4.45V with 2 hours with 0.5C, then, carry out keeping the constant of voltage 3 hours in 4.45V Electric current-constant-potential charge（CCCV charges）.Afterwards, constant current electric discharge is carried out with 0.2C（CC discharges）Discharge and recharge until 2.7V, using these operations an as circulation, determines the discharge capacity of each circulation.Repeat 20 circulations.
（2）Initial stage discharge capacity（Unit Weight）
The discharge capacity of first circulation is used as initial stage discharge capacity in being evaluated using cycle characteristics.
（3）Initial stage discharge capacity（Unit volume）
The electrode density and initial stage discharge capacity measured when being made by positive plate（Unit Weight）Calculate.
（4）Capacity sustainment rate
The respective discharge capacity of the 1st circulation and the 20th circulation from cycle characteristics evaluation（Per unit weight）, according under Formula calculates capacity sustainment rate.
Capacity sustainment rate（%）=（The discharge capacity of the circulation of discharge capacity/1st of the 20th circulation）×100
（5）Average working voltage
20 average working voltages of circulation are used as average working voltage in being evaluated using cycle characteristics.
（Evaluate B：The evaluation of security）
Based on carriage stone, like many and field（13 on November 21 ,~23 days of Heisei is held, and the 42nd primary cell discussion, speech is plucked Collect, page 462~463）, too field, great Yan, stone wall etc.（13 on November 21 ,~23 days of Heisei holds, the 42nd primary cell discussion Meeting, speech summary collection, page 470~471）, Japanese Unexamined Patent Publication 2002-158008 publications and Japanese Unexamined Patent Publication 2003-221235 public affairs The Evaluation of Thermal Stability method of the battery of report, will use the secondary electricity of lithium of the positive active material prepared in embodiment and comparative example Pond, constant current voltage is utilized to positive pole（CCCV）Charge with 0.5C with after charging within 5 hours 4.45V, divide under an argon Solution lithium secondary battery, takes out and contains the positive plate of the positive active material after lithium deintercalation.Then, from each positive plate of the taking-up Cut and take positive active material 5.0mg, 1 mole is dissolved with 1 ︰ 1 of ethylene carbonate and methyl ethyl carbonate mixing liquid 1L LiPF65.0 μm of l of the liquid for obtaining together enclose means of differential scanning calorimetry measure（DSC）Use sealed cell（SUS cells）In, with 2 DEG C/min of programming rate determines device with means of differential scanning calorimetry（SII Epolead Service company systems, model DSC6200） Determine differential thermal change.And obtain the summation S of the thermal discharge in 180 DEG C~220 DEG C of scope（J/g）.The thermal discharge Summation S（J/g）Value it is smaller, then it represents that heat endurance, i.e. battery security are more excellent.Embodiment 7, reality are represented in Fig. 1~2 Apply the result of the differential thermal change of example 9~11 and embodiment 13.The heat of the longitudinal axis in Fig. 1~2, using divided by measuring The value that the weight of positive active material is obtained.
Table 5
Industrial utilizability
Positive active material for lithium secondary battery of the invention, packed density is high, it is possible to increase the safety of lithium secondary battery The capacity of property, cycle characteristics, operating voltage and unit volume.
In addition, manufacturing method according to the invention, can provide the secondary lithium batteries just with industrial advantageous approach Pole active material.

Claims (3)

1. a kind of manufacture method of positive active material for lithium secondary battery, it is characterised in that including：
Obtain the raw material mixed processes of the mixture containing lithium compound, cobalt compound and strontium titanates；Then the mixture is entered Row is fired and generates the ablating work procedure of lithium cobalt composite oxide,
The addition of the strontium titanates of the raw material mixed processes rubs for 0.01~2 relative to the lithium cobalt composite oxide of generation You are %.
2. the manufacture method of positive active material for lithium secondary battery as claimed in claim 1, it is characterised in that：
In raw material mixed processes, one or more the compound containing addition element (M), the addition element are also added (M) selected from one or more in Mn, Ni, Mg, Zr, Ti, Al and F.
3. the manufacture method of positive active material for lithium secondary battery as claimed in claim 2, it is characterised in that：
Compound containing addition element (M), selected from MgF2、MgO、TiO2、ZrO2、Al(OH)3And AlF3。
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TWI525889B (en) * 2013-10-31 2016-03-11 Ｌｇ化學股份有限公司 Cathode active material, preparation method thereof, cathode comprising the same, and lithium secondary battery comprising the cathode
JP6194235B2 (en) * 2013-11-20 2017-09-06 日本化学工業株式会社 Positive electrode active material for lithium secondary battery, method for producing positive electrode active material for lithium secondary battery, and lithium secondary battery
KR20160081545A (en) * 2014-12-31 2016-07-08 주식회사 에코프로 Cathod active material and manufacturing method of the same
KR20180023732A (en) * 2016-08-26 2018-03-07 삼성에스디아이 주식회사 Composite positive electrode active material for lithium ion battery, preparing method thereof, and lithium ion battery including positive electrode comprising the same
KR102229453B1 (en) * 2017-11-24 2021-03-17 주식회사 엘지화학 A carbon -surfur complex, manufacturing method thereof and lithium secondary battery comprising the same
JP6791112B2 (en) 2017-12-25 2020-11-25 日亜化学工業株式会社 Manufacturing method of positive electrode material for non-aqueous secondary batteries
CN110148711B (en) * 2018-02-11 2021-06-04 宁德新能源科技有限公司 Positive electrode material and lithium ion battery
JP6994162B2 (en) * 2018-08-24 2022-01-14 トヨタ自動車株式会社 Non-aqueous electrolyte secondary battery
JP7256950B2 (en) * 2018-09-06 2023-04-13 住友金属鉱山株式会社 Hardness measuring method and hardness measuring device for fired material, and method for judging whether crushing is possible
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JP7257847B2 (en) * 2019-03-29 2023-04-14 新日本電工株式会社 Lithium ion secondary battery positive electrode material, lithium ion secondary battery positive electrode material additive, lithium ion secondary battery, and method for producing lithium ion secondary battery positive electrode material
US11715826B2 (en) 2019-06-25 2023-08-01 Nichia Corporation Method for producing electrode for non-aqueous secondary battery
US20220293931A1 (en) * 2019-08-30 2022-09-15 Panasonic Corporation Positive electrode active material for nonaqueous electrolyte secondary batteries, and nonaqueous electrolyte secondary battery
KR20220062307A (en) 2019-09-11 2022-05-16 니폰 가가쿠 고교 가부시키가이샤 Cathode active material for lithium secondary battery and lithium secondary battery
JP7302402B2 (en) * 2019-09-13 2023-07-04 株式会社豊田中央研究所 storage device
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CN112103492B (en) * 2020-11-17 2021-03-23 湖南雅城新材料有限公司 Modified ternary cathode material of lithium ion battery and preparation method and application thereof
CN114751736B (en) * 2022-05-18 2023-06-06 合肥工业大学 SrTiO with high dielectric and high pressure resistance 3 Dielectric ceramic insulation framework regulating and controlling method

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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JP2005251716A (en) 2004-02-05 2005-09-15 Nichia Chem Ind Ltd Cathode active substance for nonaqueous electrolyte secondary battery, cathode mixture for nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery
JP4952034B2 (en) * 2005-04-20 2012-06-13 パナソニック株式会社 Nonaqueous electrolyte secondary battery
JP2007265731A (en) * 2006-03-28 2007-10-11 Hitachi Maxell Ltd Lithium ion secondary battery
JP5245210B2 (en) 2006-05-01 2013-07-24 日亜化学工業株式会社 Cathode active material for non-aqueous electrolyte battery and non-aqueous electrolyte battery using the same
JP2012138197A (en) * 2010-12-24 2012-07-19 Asahi Glass Co Ltd Positive electrode active material for lithium ion secondary battery, positive electrode, lithium ion secondary battery, and method for manufacturing positive electrode active material for lithium ion secondary battery

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