CN109863630A - The manufacturing method of positive active material for lithium secondary battery - Google Patents
The manufacturing method of positive active material for lithium secondary battery Download PDFInfo
- Publication number
- CN109863630A CN109863630A CN201780062390.7A CN201780062390A CN109863630A CN 109863630 A CN109863630 A CN 109863630A CN 201780062390 A CN201780062390 A CN 201780062390A CN 109863630 A CN109863630 A CN 109863630A
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- CN
- China
- Prior art keywords
- active material
- secondary battery
- lithium secondary
- positive active
- lithium
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 152
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 143
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 117
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 137
- 239000000203 mixture Substances 0.000 claims abstract description 112
- 230000008569 process Effects 0.000 claims abstract description 111
- 238000001354 calcination Methods 0.000 claims abstract description 93
- 150000002642 lithium compounds Chemical class 0.000 claims abstract description 23
- 239000007769 metal material Substances 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 239000002243 precursor Substances 0.000 claims abstract description 15
- 239000001301 oxygen Substances 0.000 claims description 37
- 229910052760 oxygen Inorganic materials 0.000 claims description 37
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 36
- 239000007789 gas Substances 0.000 claims description 27
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 24
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 23
- 229910052804 chromium Inorganic materials 0.000 claims description 23
- 239000011651 chromium Substances 0.000 claims description 23
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- 238000007590 electrostatic spraying Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- RRMGGYGDQCMPKP-UHFFFAOYSA-N gold lithium Chemical compound [Li].[Au] RRMGGYGDQCMPKP-UHFFFAOYSA-N 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- UHUWQCGPGPPDDT-UHFFFAOYSA-N greigite Chemical compound [S-2].[S-2].[S-2].[S-2].[Fe+2].[Fe+3].[Fe+3] UHUWQCGPGPPDDT-UHFFFAOYSA-N 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 1
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910001537 lithium tetrachloroaluminate Inorganic materials 0.000 description 1
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052960 marcasite Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910000338 selenium disulfide Inorganic materials 0.000 description 1
- 229960005265 selenium sulfide Drugs 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052959 stibnite Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- RCYJPSGNXVLIBO-UHFFFAOYSA-N sulfanylidenetitanium Chemical compound [S].[Ti] RCYJPSGNXVLIBO-UHFFFAOYSA-N 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 235000001508 sulfur Nutrition 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 229920006259 thermoplastic polyimide Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to a kind of manufacturing methods of positive active material for lithium secondary battery, it is characterized in that, including the formal calcination process that lithium compound and positive active material precursor are obtained by mixing to the mixed processes of mixture and calcined said mixture using rotary furnace, wherein, the content of the lithium compound contained in said mixture is greater than 0 and 50 mass % hereinafter, the furnace inner wall of above-mentioned rotary furnace is formed by non-metallic material.
Description
Technical field
The present invention relates to the manufacturing methods of positive active material for lithium secondary battery.
Japanese Patent Application 2016-201566 based on October 13rd, 2016 in Japanese publication of the application claims priority,
Its content is quoted herein.
Background technique
Positive active material for lithium secondary battery uses lithium composite xoide.Lithium secondary battery is not only in mobile phone
Promoted in the Miniature Power Units such as purposes, laptop purposes it is practical, and mobile applications, electric power storage applications etc. it is medium-sized or
It is also promoted in large-scale power supply practical.
The manufacturing method of positive active material for lithium secondary battery is generally comprised by lithium compound and as metal composite oxygen
The process that the precursor of compound is calcined.
In order to improve the performance of the lithium secondary batteries such as cycle characteristics, carried out positive active material for lithium secondary battery
The trial for forming homogenization, the trial for reducing the residual quantity of unreacted reactant.
For example, in patent document 1, describe and implement calcination process by using roller kilns, it can be with good production
The few positive electrode of the unevenness of rate manufacture oxidation.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2006-4724 bulletin
Summary of the invention
During the expansion of the application field of lithium secondary battery promotes, for positive electrode for lithium secondary battery active matter
Matter, in order to improve various battery behaviors, it is desirable that high crystallinity.
However, as described in Patent Document 1, if calcining needs for a long time, and crystallinity using roller kilns
It is insufficient.
The present invention is carried out in view of above-mentioned thing, and project is providing the excellent secondary lithium batteries of crystallinity just
The manufacturing method of pole active material.
That is, the present invention includes the invention of following [1]~[8].
[1] a kind of manufacturing method of positive active material for lithium secondary battery, which is characterized in that including by lithium compound and
Positive active material precursor is obtained by mixing the mixed processes of mixture and is calcined said mixture just using rotary furnace
Formula calcination process, wherein the content of the lithium compound contained in said mixture is big relative to the gross mass of said mixture
In 0 and 50 mass % hereinafter, the furnace inner wall of above-mentioned rotary furnace is formed by non-metallic material.
[2] manufacturing method of the positive active material for lithium secondary battery according to [1], wherein 750 DEG C~1000
DEG C carry out above-mentioned formal calcination process.
[3] manufacturing method of the positive active material for lithium secondary battery according to [1] or [2], wherein above-mentioned lithium two
Primary cell contains the lithium metal composite oxides that logical formula (I) below indicates with positive active material.
Li[Lix(Ni(1-y-z-w)CoyMnzMw)1-x]O2···(I)
(in logical formula (I), -0.1≤x≤0.2,0 < y≤0.5,0 < z≤0.8,0≤w≤0.1, y+z+w < 1, M are indicated
Element selected from one or more of Cu, Ti, Mg, Al, W, B, Mo, Nb, Zn, Sn, Zr, Ga and V.)
[4] manufacturing method of the positive active material for lithium secondary battery according to any one of [1]~[3], wherein
After above-mentioned mixed processes, before above-mentioned formal calcination process, including in the temperature lower than the above-mentioned calcination temperature formally calcined
The lower pre-burning process calcined of degree.
[5] manufacturing method of the positive active material for lithium secondary battery according to any one of [1]~[4], wherein
By with 15Nm3/h/m3The above flow circulation oxygen-containing gas and carry out in above-mentioned formal calcination process and above-mentioned pre-burning process
Either or both.
[6] manufacturing method of the positive active material for lithium secondary battery according to [5], wherein above-mentioned oxygen-containing gas
In oxygen concentration relative to oxygen-containing gas total volume be 21 volume % or more.
[7] manufacturing method of the positive active material for lithium secondary battery according to any one of [1]~[6], wherein
The content of the chromium contained in above-mentioned positive active material for lithium secondary battery is relative to above-mentioned positive electrode for lithium secondary battery active matter
The gross mass of matter is 50ppm or less.
[8] manufacturing method of the positive active material for lithium secondary battery according to any one of [1]~[7], wherein
The content of the lithium carbonate contained in above-mentioned positive active material for lithium secondary battery is living relative to above-mentioned positive electrode for lithium secondary battery
Property substance gross mass be 1.0 mass % or less.
In accordance with the invention it is possible to provide a kind of manufacturer of positive active material for lithium secondary battery that crystallinity is excellent
Method.
Detailed description of the invention
Figure 1A is the structural schematic diagram for indicating an example of lithium ion secondary battery.
Figure 1B is the structural schematic diagram for indicating an example of lithium ion secondary battery.
Fig. 2 is the schematic diagram for indicating an example of rotary furnace.
Fig. 3 is the schematic cross-section for indicating the direction vertical with the longitudinal direction of rotary furnace.
Fig. 4 is the schematic cross-section of the longitudinal direction of rotary furnace.
Specific embodiment
The manufacturing method > of < positive active material for lithium secondary battery
The manufacturer of positive active material for lithium secondary battery (being also recorded as " positive active material " below) of the invention
Method, which is characterized in that being includes being obtained by mixing lithium compound and positive active material precursor (being also recorded as " precursor " below)
To the mixed processes of mixture and the secondary lithium batteries for the formal calcination process for being calcined said mixture using rotary furnace
The manufacturing method of positive active material, total matter of the content of the lithium compound contained in said mixture relative to said mixture
Amount is greater than 0 and is 50 mass % hereinafter, the furnace inner wall of above-mentioned rotary furnace is formed by non-metallic material.
In the calcination process of lithium compound and precursor, in the past using equipment such as continuous tunnel furnace, roller kilns, rotary furnaces.
Continuous tunnel furnace, roller kilns because in saggar filling mixture calcined, so that there are calcination efficiencies is low, and calcine
Need long-time such problems.
In addition, metal is dissolved out from component when there is calcining at high temperature, just if the furnace inner wall of rotary furnace is made of metal
The problem of metal component that pole active material is dissolved is polluted.
The furnace inner wall at the position that the present invention is contacted using mixture implements lithiumation conjunction by the rotary furnace that non-metallic material is formed
The calcination process of the mixture of object and precursor.Therefore, even if metal will not be molten from furnace inner wall in the case where calcining at high temperature
Out, positive active material will not be polluted.In addition, the gross mass in the present invention by the content of lithium compound relative to said mixture
Calcined for 50 mass % mixtures below, so even calcine at high temperature can also mixture and calcined material only
Degree is calcined in the case where being attached to rotary furnace.
Hereinafter, being illustrated to the manufacturing method of positive active material for lithium secondary battery of the invention.
[mixed processes]
This process is the process that lithium compound and precursor are obtained by mixing mixture.
In this process, with the content of the lithium compound in the mixture of lithium compound and precursor relative to said mixture
Gross mass is greater than 0 and mixes for 50 mass % modes below.
The lower limit value of the content of the lithium compound of gross mass relative to said mixture is preferably 10 mass % or more, more
Preferably 15 mass % or more, particularly preferably 20 mass % or more.
The upper limit value of the content of the lithium compound of gross mass relative to said mixture is preferably 49 mass % hereinafter, more
Preferably 48 mass % are hereinafter, particularly preferably 47 mass % or less.
Above-mentioned upper limit value and lower limit value can be combined arbitrarily.
For example, the content of the above-mentioned lithium compound of the gross mass relative to said mixture is preferably 10 matter of mass %~49
Measure %, the more preferably 15 mass % of mass %~48, further preferably 20 mass of mass %~47 %.
In the present invention, in the content of lithium compound by making the gross mass relative to said mixture in mixture
Specific content is stated, the attachment of mixture and calcined material to the furnace inner wall of rotary furnace can be reduced.Therefore, in aftermentioned calciner
It in sequence, can calcine at high temperature, the high positive active material of crystallinity can be obtained.
Lithium compound
Lithium compound used in the present invention is illustrated.
Lithium compound used in the present invention is not particularly limited, and lithium carbonate, lithium nitrate, lithium acetate, hydrogen-oxygen can be used
Change lithium, lithium hydroxide monohydrate, any one of lithia or is used in mixed way two kinds or more.In these, preferred hydroxide
Any one of lithium and lithium carbonate or both.
Precursor
Precursor is preferably transistion metal compound.Precursor is preferably the metal contained in addition to lithium, that is, as essential metal
Ni and the arbitrary element selected from one or more of Co, Mn, Cu, Ti, Mg, Al, W, B, Mo, Nb, Zn, Sn, Zr, Ga and V mistake
Cross metallic compound.Transistion metal compound is preferably transition metal hydroxide or transition metal oxide, specifically,
Preferably nickel cobalt manganese composite hydroxide or cobalt-nickel-manganese oxide compound.
Precursor can use generally well-known batch process or coprecipitation manufacture.
[formal calcination process]
It, can by that can be calcined at high temperature in calcination process as above-mentioned specific mixing condition in the present invention
Carry out the growth of crystal well.
What formal calcination process was formed using the furnace inner wall as the position contacted with said mixture by non-metallic material
Rotary furnace carries out.
Rotary furnace used in present embodiment is illustrated using Fig. 2~Fig. 4.
Rotary furnace 40 includes: cylindric furnace core tube 42, the rotating device (not shown) for rotating above-mentioned furnace core tube 42, covers
Cover heater (not shown), the Xiang Shangshu furnace heart of the heat-insulating material (not shown) for stating furnace core tube 42, the above-mentioned furnace core tube 42 of heating
The discharge unit (not shown) of raw material investment device (not shown) of investment calcining raw materials and discharge calcined material in pipe 42.Such as Fig. 4
Shown, furnace core tube 42 forms inclination in the outlet side mode lower than the entrance side for putting into calcining raw materials and is arranged.It is above-mentioned by making
Furnace core tube 42 rotates, so that calcining raw materials side is mixed, while being sent to outlet side from the entrance side of furnace core tube 42, and is forged
It burns.In addition, oxygen-containing gas usually circulates (ventilation) from outlet side to entrance side as shown in the dotted arrow of Fig. 4.
Formal calcination process supplies said mixture in particular by rotary furnace 40, makes the furnace core for constituting rotary furnace 40
Pipe 42 rotates, so that side mixes said mixture, while will turn round stove heating in such a way that said mixture becomes predetermined temperature
And carry out.In the present invention, furnace inner wall 41 refers to the wall of the inside of furnace core tube 42.
As non-metallic material, preferably silicon nitride (Si3N4), aluminium oxide (Al2O3；Also referred to as alumina), silica
(SiO2), zirconium dioxide (ZrO2), magnesia (MgO), the ceramic materials such as silicon carbide (SiC), relative to above-mentioned non-metallic material
Gross mass, the particularly preferably aluminium oxide containing 50 mass % or more.
The loading of the said mixture of full content product relative to rotary furnace is preferably the 1 volume % of volume %~50,
The more preferably 3 volume % of volume %~30, further preferably 5 volume of volume %~20 %.
Formal calcination process is preferably carried out at 750 DEG C~1000 DEG C.
By making 750 DEG C~1000 DEG C of calcination temperature of high temperature range, the high positive electrode active material of crystallinity can be made
Matter.
In present embodiment, the temperature of calcination process refers to the temperature for the mixture being calcined.
[pre-burning process]
In the present invention, after above-mentioned mixed processes, before above-mentioned formal calcination process, it is preferably included in more formal than above-mentioned
The pre-burning process of the low temperature lower calcination of the calcination temperature of calcining.As long as pre-burning is lower than the above-mentioned temperature formally calcined, with
The calcination temperature formally calcined is compared, preferably low 80 DEG C~200 DEG C of temperature, preferably low 100 DEG C~150 DEG C of temperature.
By carrying out pre-burning, the positive electrode active material containing the lithium metal composite oxides with high crystalline can be obtained
Matter, in addition, unreacting substance can be reduced.
The calcining furnace of pre-burning process is not particularly limited, it is preferable to use rotary furnace.Formal calcination process and pre-burning process can
Think identical rotary furnace, or different rotary furnaces, from the viewpoint of it can carry out continuous calcining process, it is preferable to use
Identical rotary furnace is implemented.
The position of calcining furnace used in pre-burning process contacted with said mixture can be inconel
(INCONEL) metal materials, or silicon nitride (Si such as3N4), aluminium oxide (Al2O3；Also referred to as alumina) etc. non-metallic materials
Matter.
Any one of above-mentioned formal calcination process and above-mentioned pre-burning process or both are preferably by with 15Nm3/h/m3More than
Flow circulation oxygen-containing gas and carry out, more preferably 16Nm3/h/m3More than.Upper limit value is not particularly limited, for example, can enumerate
150Nm3/h/m3Below, 130Nm3/h/m3Below, 120Nm3/h/m3Below.
Above-mentioned upper limit value and lower limit value can be in any combination.
For example, above-mentioned flow is preferably 15Nm3/h/m3~150Nm3/h/m3, more preferably 16Nm3/h/m3~130Nm3/
h/m3, further preferably 16Nm3/h/m3~120Nm3/h/m3。
As the another side of present embodiment, above-mentioned flow is preferably 40Nm3/h/m3~200Nm3/h/m3, more preferably
For 80Nm3/h/m3~180Nm3/h/m3, further preferably 130Nm3/h/m3~160Nm3/h/m3。
The oxygen concentration phase of any one of above-mentioned formal calcination process and above-mentioned pre-burning process or both preferably in oxygen
Total volume for oxygen-containing gas is implemented under conditions of being 21 volume % or more.The system of oxygen-containing gas as above-mentioned oxygen concentration
Make method, can by by other than oxygen gas and oxygen be obtained by mixing in defined ratio.Gas and oxygen other than oxygen
Flow can use the control of well known flowmeter.Furthermore it is possible to directly use air.
In the present invention, preferably implement formal calcination process under above-mentioned aeration condition.
Calcination time, i.e., the total ascent time until temperature keeps terminating after arrival temperature since heating is preferably 1 hour
~10 hours, more preferably 1 hour~8 hours, particularly preferably 1 hour~5 hours.
In the present invention, implement pre-burning when, make since pre-burning process heating until formal calcination process terminates when
Between be to implement within the above-mentioned time.
More specifically, pre-burning process is preferably 30 minutes~3 hours, more preferably 1 hour~2.5 hours.
In addition, formal calcination process is preferably 30 minutes~3 hours, more preferably 1 hour~2.5 hours.
As another side of the invention, the retention time reached after target temperature in calcination process is preferably 1 hour
~10 hours, more preferably 1 hour~8 hours, further preferably 1 hour~6 hours.In addition, until reaching target temperature
Heating rate be preferably 20 DEG C/h~2000 DEG C/h, more preferably 50 DEG C/h~1000 DEG C/h, further
Preferably 100 DEG C/h~800 DEG C/h.
In the present invention, the rotary furnace that is formed by non-metallic material of furnace inner wall at the position used as said mixture contact
Implement formal calcination process.
Metal rotary furnace is needed in the temperature lower calcination that metal dissolving will not occur, but used as said mixture
It, can be by calcining temperature without considering the dissolution of metal when the rotary furnace that the furnace inner wall at the position of contact is formed by non-metallic material
Degree is set as high temperature.Therefore, compared with the case where using furnace inner wall to be metal rotary furnace, using furnace inner wall by non-metallic material
In the case where the rotary furnace that matter is formed, calcination process can be implemented with higher temperature.Therefore, pass through the calcination process of short time
It can obtain the positive active material containing the high lithium metal composite oxides of crystallinity.
It is suitably classified after being pulverized by calcining obtained lithium metal composite oxides, is made and can be used for the secondary electricity of lithium
The positive active material for lithium secondary battery in pond.Pass through above-mentioned classification process, positive active material for lithium secondary battery usually quilt
It is classified into 200~400 mesh.
It further comprises powder that a side of the invention, which is on the basis of above-mentioned mixed processes, formal calcination process,
The manufacturing method of broken, classification process positive active material for lithium secondary battery.
< positive active material for lithium secondary battery >
Just to the secondary lithium batteries for utilizing the manufacturing method of positive active material for lithium secondary battery of the invention to manufacture
Pole active material is illustrated.
From the aspect of the energy density for improving lithium secondary battery, preferred lithium secondary batteries positive active material contains
The lithium metal composite oxides that consisting of formula (I) indicates.
Li[Lix(Ni(1-y-z-w)CoyMnzMw)1-x]O2···(I)
(in logical formula (I), -0.1≤x≤0.2,0 < y≤0.5,0 < z≤0.8,0≤w≤0.1, y+z+w < 1, M are indicated
Element selected from one or more of Cu, Ti, Mg, Al, W, B, Mo, Nb, Zn, Sn, Zr, Ga and V.)
From the aspect of obtaining the high lithium secondary battery of cycle characteristics, the x in above-mentioned composition formula (I) is preferably 0 or more,
More preferably 0.01 or more, further preferably 0.02 or more.In addition, from the higher lithium secondary battery of coulombic efficiency for the first time is obtained
From the aspect of, the x in above-mentioned composition formula (I) is preferably 0.18 hereinafter, more preferably 0.15 hereinafter, further preferably 0.1
Below.
The upper limit value and lower limit value of x can be combined arbitrarily.
For example, above-mentioned x is preferably 0~0.18, more preferably 0.01~0.15, further preferably 0.02~0.1.
In this specification, " cycle characteristics is high " refers to that discharge capacity sustainment rate is high.
In addition, the y in above-mentioned composition formula (I) is preferably 0.13 from the aspect of the high lithium secondary battery of cycle characteristics
More than, more preferably 0.14 or more.In addition, from the aspect of obtaining the high lithium secondary battery of thermal stability, above-mentioned composition formula
(I) y in is preferably 0.35 hereinafter, more preferably 0.3 hereinafter, further preferably 0.25 or less.
The upper limit value and lower limit value of y can be combined arbitrarily.
For example, above-mentioned y is preferably 0.13~0.35, more preferably 0.14~0.3, further preferably 0.14~0.25.
In addition, from the aspect of obtaining the high lithium secondary battery of cycle characteristics, the z in above-mentioned composition formula (I) is preferably
0.1 or more, more preferably 0.15 or more, more preferably 0.2 or more.In addition, from obtaining under high temperature (such as under 60 DEG C of environment)
From the aspect of the high lithium secondary battery of preservation characteristics, the z in above-mentioned composition formula (I) is preferably 0.35 hereinafter, more preferably
0.32 hereinafter, further preferably 0.30 or less.
The upper limit value and lower limit value of z can be combined arbitrarily.
For example, above-mentioned z is preferably 0.1~0.35, more preferably 0.15~0.32, further preferably 0.2~0.30.
From the aspect of the operability for improving positive active material for lithium secondary battery, the w in above-mentioned composition formula (I) is excellent
Choosing is greater than 0, more preferably 0.001 or more, further preferably 0.005 or more.In addition, from the electric discharge under high current multiplying power is obtained
From the aspect of the high lithium secondary battery of capacity, the w in above-mentioned composition formula (I) be preferably 0.04 hereinafter, more preferably 0.03 with
Under, further preferably 0.02 or less.
The upper limit value and lower limit value of w can be combined arbitrarily.
For example, above-mentioned w is preferably greater than 0 and for 0.04 hereinafter, more preferably 0.001~0.03, further preferably 0.005
~0.02.
M in above-mentioned composition formula (I) be a kind in Cu, Ti, Mg, Al, W, B, Mo, Nb, Zn, Sn, Zr, Ga and V with
On element.
In the present invention, with the positive active material for lithium secondary battery of manufacture contain it is above-mentioned form that formula (I) indicates wish
The mode of the lithium metal composite oxides of the composition of prestige mixes lithium compound and positive active material precursor.
(layer structure)
The crystal structure of positive active material is layer structure, the more preferably crystal structure or monoclinic crystal of hexagonal structure
The crystal structure of type.
The crystal structure of hexagonal structure is belonged to selected from P3, P31、P32, R3, P-3, R-3, P312, P321, P3112、
P3121、P3212、P3221, R32, P3m1, P31m, P3c1, P31c, R3m, R3c, P-31m, P-31c, P-3m1, P-3c1,
R-3m, R-3c, P6, P61、P65、P62、P64、P63, P-6, P6/m, P63/m、P622、P6122、P6522、P6222、P6422、
P6322、P6mm、P6cc、P63cm、P63Mc, P-6m2, P-6c2, P-62m, P-62c, P6/mmm, P6/mcc, P63/mcm、
P63Any one space group in/mmc.
In addition, the crystal structure of monoclinic form is belonged to selected from P2, P21、C2、Pm、Pc、Cm、Cc、P2/m、P21/m、C2/
m、P2/c、P21Any one space group in/c, C2/c.
In these, from the aspect of obtaining the high lithium secondary battery of discharge capacity, crystal structure particularly preferably belongs to
In the hexagonal structure of space group R-3m crystal structure or belong to C2/m monoclinic form crystal structure.
In present embodiment, the crystallinity of positive active material be can use by using the Alpha-ray X-ray diffraction of CuK
Measure half-peak breadth and 2 θ=44.4 ± 1 ° of diffraction maximum in the range of obtained 2 θ=18.7 ± 1 ° of X-ray diffraction pattern
The half-peak breadth of diffraction maximum in range is evaluated.
The range of half-peak breadth as the diffraction maximum in the range of 2 θ=18.7 ± 1 °, preferably 0.01~0.20, it is more excellent
It is selected as 0.02~0.19, further preferably 0.03~0.18.
The range of half-peak breadth as the diffraction maximum in the range of 2 θ=44.4 ± 1 °, preferably 0.01~0.25, it is more excellent
It is selected as 0.02~0.22, further preferably 0.03~0.20.
The rotary furnace that the furnace inner wall at the position contacted used as mixture due to the present invention is formed by non-metallic material is real
Formal calcination process is applied, even if so in order to improve the crystallinity of positive active material and the height as 750 DEG C~1000 DEG C
The lower calcining of temperature, can also reduce metal from the dissolution in the material of calcining furnace.Therefore, it is conceived to one kind as metal impurities
When chromium, the positive active material of the content reduction of chromium can be manufactured.
Contain in the positive active material for lithium secondary battery manufactured through the invention relative to above-mentioned lithium secondary battery
Content with the chromium of the gross mass of positive active material is preferably 50ppm hereinafter, more preferably 45ppm is hereinafter, particularly preferably
40ppm or less.
Contain in positive active material for lithium secondary battery relative to above-mentioned positive active material for lithium secondary battery
The measurement of the content of the chromium of gross mass can be by contacting the powder of above-mentioned positive active material for lithium secondary battery with hydrochloric acid
It handles after dissolution, is carried out using inductive coupling plasma emission spectrograph.
The manufacturing method of positive active material for lithium secondary battery of the invention is because contacting used as said mixture
The furnace inner wall at position is implemented by the rotary furnace that non-metallic material is formed, so can calcine at high temperature.Therefore, promote in raw material
Lithium carbonate decomposition, the residual quantity of the lithium carbonate in the positive active material of manufacture reduces.
Contain in the positive active material for lithium secondary battery manufactured through the invention relative to positive active material
The content of the lithium carbonate of gross mass is preferably 1.0 mass % hereinafter, more preferably 0.99 mass % is hereinafter, particularly preferably 0.95
Quality % or less.The lower limit value of the content of the lithium carbonate of gross mass relative to positive active material is not particularly limited, for example,
0.05 mass % or more, 0.10 mass % or more, 0.2 mass % or more can be enumerated.
Above-mentioned upper limit value and lower limit value can be combined arbitrarily.
For example, the content of the above-mentioned lithium carbonate of the gross mass relative to above-mentioned positive active material is preferably 0.05 mass %
~1.0 mass %, the more preferably 0.10 mass % of mass %~0.99, further preferably 0.2 mass of mass %~0.95 %.
The content of the lithium carbonate ingredient contained in positive active material for lithium secondary battery can be by using acid solution
Acid-base titration find out.Specifically, carrying out contact treatment to positive active material for lithium secondary battery with pure water, make lithium carbonate
Ingredient is dissolved out into pure water.Acid-base titration is carried out to above-mentioned dissolution fluid with acid solutions such as hydrochloric acid, finds out containing for lithium carbonate ingredient
Amount.The calculation method etc. of the more specifically content of operation and lithium carbonate ingredient is illustrated in embodiment.
With the present invention in contrast be filling mixture and to be calcined in formal calcining into saggars such as roller kilns
In the case where, since oxygen-containing gas is unable to fully reach the mixture for being filled into saggar bottom, the decomposition of lithium carbonate is not uniform
Ground carries out, so in the presence of the trend for remaining many lithium carbonates in the positive active material of manufacture.
< lithium secondary battery >
Next, the composition to lithium secondary battery is illustrated, while to using by secondary lithium batteries of the invention just
The anode and lithium with the anode of the positive active material for lithium secondary battery of the manufacturing method manufacture of pole active material are secondary
Battery is illustrated.
One example of the lithium secondary battery of present embodiment has anode and cathode, is held between positive electrode and negative electrode
Separator, the electrolyte being configured between positive electrode and negative electrode.
Figure 1A and Figure 1B is the schematic diagram for indicating an example of lithium secondary battery for present embodiment.Present embodiment
The lithium secondary battery 10 of cylinder type manufactures as follows.
Firstly, as shown in Figure 1A, by band-like a pair of of separator 1, at one end with positive wire 21 it is band-like just
Pole 2 and the at one end band-like cathode 3 with negative wire 31 are laminated by the sequence of separator 1, anode 2, separator 1, cathode 3
And wind, so that electrode group 4 be made.
Next, as shown in Figure 1B, after electrode group 4 and insulator (not shown) are contained in battery can 5, hermetically sealed can bottom,
So that electrolyte 6 is infiltrated in electrode group 4, configures electrolyte between anode 2 and cathode 3.Further with top insulator 7 and sealing
The top of 8 sealed cell tank 5 of body, so as to manufacture lithium secondary battery 10.
As the shape of electrode group 4, such as the section by electrode group 4 when the direction vertical with wireline reel is cut off can be enumerated
Shape becomes columnar shape as the rectangle of circle, ellipse, rectangle, fillet.
In addition, the shape as the lithium secondary battery with such electrode group 4, can use International Electrotechnical Commission
(IEC) shape specified in standard, that is, IEC60086 or JIS C 8500 as defined in battery.For example, can enumerate cylinder type,
The shapes such as square.
In addition, lithium secondary battery is not limited to above-mentioned winding-type composition, be also possible to be overlapped repeatedly anode, separator,
The composition of the laminated type of the stepped construction of cathode, separator.As the lithium secondary battery of laminated type, so-called Coin shape can be illustrated
Battery, button-type battery, paper mold (or piece type) battery.
Hereinafter, being successively illustrated to each composition.
(anode)
The anode of present embodiment can be by preparing first containing positive active material, conductive material and binder just
Pole mixture supports anode mixture and manufactures in positive electrode collector.
(conductive material)
Carbon material can be used in conductive material possessed by anode as present embodiment.As carbon material, stone can be enumerated
Ink powder end, carbon black (such as acetylene black), fibrous carbon material etc..Carbon black is since for particle, surface area is big, therefore by anode
The electric conductivity that just can be improved inside anode on a small quantity is added in mixture, efficiency for charge-discharge and output characteristics is improved, if but too much
It is added, then it is equal as the cohesive force inside the cohesive force and anode mixture of the anode mixture and positive electrode collector generated by binder
Decline increases the reason of internal resistance instead.
The ratio of conductive material in anode mixture relative to 100 mass parts of positive active material be preferably 5 mass parts~
20 mass parts.When using the fibrous carbons such as graphitized carbon fibre, carbon nanotube material as conductive material, the ratio can also be reduced
Example.
(binder)
Binder possessed by anode as present embodiment, can be used thermoplastic resin.
As the thermoplastic resin, Kynoar (hereinafter sometimes referred to PVdF) can be enumerated, polytetrafluoroethylene (PTFE) (has below
When referred to as PTFE), tetrafluoroethene hexafluoropropene vinylidene based copolymer, hexafluoropropene vinylidene based copolymer,
The fluororesin such as tetrafluoroethene perfluoroalkyl vinyl ether based copolymer；The polyolefin resins such as polyethylene, polypropylene.
These thermoplastic resins can also be mixed with two or more.By using fluororesin and polyolefin resin as viscous
Tie agent, and make fluororesin relative to the quality of anode mixture entirety 1 mass of mass %~10 % of ratio, make polyolefin resin
Ratio be the 0.1 mass % of mass %~2, the binding force inside the closing force and anode mixture with positive electrode collector can be obtained
High anode mixture.
(positive electrode collector)
Positive electrode collector possessed by anode as present embodiment can be used with Al, Ni, stainless steel and other metal materials
For the band-like component of forming material.Wherein, from the aspect of being easily worked, is cheap, preferably as forming material and added using Al
Work at film-form collector.
As making anode mixture support the method in positive electrode collector, it can enumerate and add anode mixture on positive electrode collector
Molded method.Further, it is possible to use organic solvent makes anode mixture paste, the paste of obtained anode mixture is coated with
In positive electrode collector at least one side side and make it dry, carry out pressurization make its consolidation, so that anode mixture be made to support in anode
Collector.
When making anode mixture paste, as workable organic solvent, N can be enumerated, N- dimethylamino propylamine,
The amine series solvents such as diethylenetriamine；The ether series solvents such as tetrahydrofuran；The ketone series solvents such as methyl ethyl ketone；The ester series solvents such as methyl acetate；
Acid amides series solvents such as dimethyl acetamide, n-methyl-2-pyrrolidone (hereinafter sometimes referred to NMP) etc..
As the method that the paste of anode mixture is coated on positive electrode collector, such as slit mold coating method, silk can be enumerated
Net rubbing method, curtain coating processes, scraper for coating method, gravure coating process and electrostatic spraying processes.
Method by enumerating above can manufacture anode.
(cathode)
As long as cathode possessed by the lithium secondary battery of present embodiment can be to carry out lithium ion than just extremely low current potential
Doping and dedoping, the cathode agent containing negative electrode active material can be enumerated and supported the electricity made of negative electrode collector
Pole and the electrode being separately formed by negative electrode active material.
(negative electrode active material)
As negative electrode active material possessed by cathode, carbon material, chalcogenide (oxide, sulfide can be enumerated
Deng), nitride, can be to carry out the doping of lithium ion and the material of dedoping than just extremely low current potential in metal or alloy.
As the carbon material that can be used as negative electrode active material, can enumerate the graphite such as natural graphite, artificial graphite, coke class,
Carbon black, thermal cracking carbons, carbon fiber and organic high molecular compound calcined body.
As the oxide that can be used as negative electrode active material, SiO can be enumerated2, SiO etc. is by formula SiOx(wherein, the reality that x is positive
Number) indicate silicon oxide；TiO2, TiO etc. is by formula TiOxThe titanyl compound that (wherein, the real number that x is positive) indicates；V2O5、
VO2Deng by Formula V OxThe oxide for the vanadium that (wherein, the real number that x is positive) indicates；Fe3O4、Fe2O3, FeO etc. is by formula FeOx(wherein, x
The real number being positive) indicate iron oxide；SnO2, SnO etc. is by formula SnOxThe oxidation for the tin that (wherein, the real number that x is positive) indicates
Object；WO3、WO2Deng by general formula WOxThe oxide for the tungsten that (wherein, the real number that x is positive) indicates；Li4Ti5O12、LiVO2Etc. containing lithium
With the metal composite oxide of titanium or vanadium.
As the sulfide that can be used as negative electrode active material, Ti can be enumerated2S3、TiS2, TiS etc. is by formula TiSx(wherein, x is
Positive real number) indicate titanium sulfide；V3S4、VS2, VS etc. is by Formula V SxThe vulcanization for the vanadium that (wherein, the real number that x is positive) indicates
Object；Fe3S4、FeS2, FeS etc. is by formula FeSxThe sulfide for the iron that (wherein, the real number that x is positive) indicates；Mo2S3、MoS2Deng by formula
MoSxThe sulfide for the molybdenum that (wherein, the real number that x is positive) indicates；SnS2, SnS etc. is by formula SnSx(wherein, the real number that x is positive) table
The sulfide of the tin shown；WS2Deng by formula WSxThe sulfide for the tungsten that (the wherein real number that x is positive) indicates；Sb2S3Deng by formula SbSx(its
In, real number that x is positive) sulfide of antimony that indicates；Se5S3、SeS2, SeS etc. is by formula SeSx(wherein, the real number that x is positive) indicates
Selenium sulfide.
As the nitride that can be used as negative electrode active material, Li can be enumerated3N、Li3-xAx(wherein, A is in Ni and Co to N
Either or both, 0 < x < 3) etc. nitride containing lithium.
These carbon materials, oxide, sulfide, nitride can be used only a kind, and also two or more kinds may be used.In addition,
These carbon materials, oxide, sulfide, nitride can be any one of crystalloid or noncrystalline.
In addition, lithium metal, silicon metal and tin metal etc. can be enumerated as the metal that can be used as negative electrode active material.
As the alloy that can be used as negative electrode active material, Li-Al, Li-Ni, Li-Si, Li-Sn, Li- can also be enumerated
The lithium alloys such as Sn-Ni；The silicon alloys such as Si-Zn；The tin alloys such as Sn-Mn, Sn-Co, Sn-Ni, Sn-Cu, Sn-La；
Cu2Sb、La3Ni2Sn7Equal alloys.
These metals, alloy are mainly used separately as electrode for example after being processed into foil-like.
In above-mentioned negative electrode active material, from several from uncharged state to the current potential full of cathode until electricity condition in charging
High (the cycle characteristics of capacity maintenance rate when, repeated charge low without variation (current potential flatness is good), averaged discharge current potential
It is good) etc. reasons set out, it is preferable to use using graphite such as natural graphite, artificial graphites as the carbon material of principal component.As carbon material
Shape, such as can be for as spherical, graphitized carbon fibre as flake as natural graphite, mesocarbon microspheres
Any one of condensate of threadiness or micropowder etc..
Above-mentioned cathode agent can also contain binder as needed.As binder, thermoplastic resin can be enumerated, is had
For body, PVdF, thermoplastic polyimide, carboxymethyl cellulose, polyethylene and polypropylene can be enumerated.
(negative electrode collector)
As negative electrode collector possessed by cathode, can enumerate using Cu, Ni, stainless steel and other metal materials as forming material
Band-like component.Wherein, from being difficult to form alloy with lithium and from the aspect of being easily worked, preferably using Cu as forming material and
It is processed into the collector of film-form.
As cathode agent is supported in the method for such negative electrode collector, in the same manner as the situation of anode, can enumerate
Paste and be coated on negative electrode collector using the method for extrusion forming, using solvent etc., pressurizeed after dry and
The method of crimping.
(separator)
Separator possessed by lithium secondary battery as present embodiment, such as can be used by polyethylene, polypropylene etc.
The form with perforated membrane, non-woven fabrics, woven fabric etc. that the materials such as polyolefin resin, fluororesin, nitrogenous aromatic polymer are constituted
Material.Further, it is possible to use these materials of more than two kinds form separator, these materials can also be laminated and formed every
Off member.
In present embodiment, in order to penetrate electrolyte well (when charge and discharge) when using battery, separator by
The air permeance resistance that Gurley method specified in JIS P 8117:2009 measures is preferably 50 seconds/100cc~300 second/100cc, more
Preferably 50 seconds/100cc~200 second/100cc.
In addition, the void content of separator is preferably 30 volume of volume %~80 % relative to the total volume of separator, it is more excellent
It is selected as 40 volume of volume %~70 %.Separator is also possible to will be made of the different separator stacking of void content.
(electrolyte)
Electrolyte possessed by the lithium secondary battery of present embodiment contains electrolyte and organic solvent.
As the electrolyte contained in electrolyte, LiClO can be enumerated4、LiPF6、LiAsF6、LiSbF6、LiBF4、
LiCF3SO3、LiN(SO2CF3)2、LiN(SO2C2F5)2、LiN(SO2CF3)(COCF3)、Li(C4F9SO3)、LiC(SO2CF3)3、
Li2B10Cl10, it is LiBOB (wherein, BOB is double oxalic acid borates), LiFSI (wherein FSI is bis- (fluorosulfonyl) imines), rudimentary
Aliphatic carboxylic acid lithium salts, LiAlCl4Equal lithium salts, also can be used their mixture of more than two kinds.Wherein, as electrolyte,
It is preferable to use containing selected from the LiPF containing fluorine6、LiAsF6、LiSbF6、LiBF4、LiCF3SO3、LiN(SO2CF3)2And LiC
(SO2CF3)3In at least one kind of electrolyte.
In addition, as the organic solvent contained in above-mentioned electrolyte, for example, can be used propylene carbonate, ethylene carbonate,
Dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, 4- Trifluoromethyl-1,3- dioxolan-2-one, bis- (first of 1,2-
Oxygroup carbonyloxy group) carbonates such as ethane；1,2- dimethoxy-ethane, 1,3- dimethoxy propane, pentafluoropropyl group methyl ether,
The ethers such as tetra- fluoropropyl difluoro methyl ether of 2,2,3,3-, tetrahydrofuran, 2- methyltetrahydrofuran；Methyl formate, methyl acetate,
The esters such as gamma-butyrolacton；The nitriles such as acetonitrile, butyronitrile；The amides such as N,N-dimethylformamide, DMAC N,N' dimethyl acetamide；
3- methyl -2-The carbamates such as oxazolidone；The Containing Sulfurs such as sulfolane, dimethyl sulfoxide, 1,3- propane sultone
Close object or further imported in these organic solvents it is fluorine-based made of solvent (by 1 in hydrogen atom possessed by organic solvent
Compound made of being replaced more than a with fluorine atom).
As organic solvent, it is preferably used in mixed way two or more in them.Wherein, the mixing of carbonates is preferably comprised
The mixing of solvent, the mixed solvent and cyclic carbonate and ethers of further preferred cyclic carbonate and non-cyclic carbonate is molten
Agent.As the mixed solvent of cyclic carbonate and non-cyclic carbonate, ethylene carbonate, dimethyl carbonate and carbonic acid are preferably comprised
The mixed solvent of methyl ethyl ester.Have following lot of advantages using the electrolyte of such mixed solvent: operating temperature range is wide, i.e.,
Just the charge and discharge carried out under high current multiplying power are also not easily deteriorated, and are also not easily deteriorated even if using for a long time, and even with natural
It is also hard-decomposed when active material of the graphite materials such as graphite, artificial graphite as cathode.
In addition, as electrolyte, in order to the lithium secondary battery improved safety, it is preferable to use containing LiPF6Deng
The electrolyte of fluorine-containing lithium compound and the organic solvent with fluoro substituents.Contain pentafluoropropyl group methyl ether, 2,2,3,3- tetra-
Even if there is fluoropropyl difluoro methyl ether etc. the ethers of fluoro substituents and the mixed solvent of dimethyl carbonate to carry out high current times
Charge and discharge under rate, capacity maintenance rate is also high, therefore further preferably.
Also solid electrolyte can be used instead of above-mentioned electrolyte.As solid electrolyte, such as polycyclic oxygen second can be used
The high-molecular compound of methane series contains macromolecule chemical combination more than at least one of polysiloxane chain or polyoxyalkylene chain
The organic systems polyelectrolyte such as object.In addition, nonaqueous electrolytic solution is made to be held in the so-called gel of high-molecular compound
The electrolyte of type.In addition, can enumerate containing Li2S-SiS2、Li2S-GeS2、Li2S-P2S5、Li2S-B2S3、Li2S-
SiS2- Li3PO4、Li2S-SiS2- Li2SO4、Li2S-GeS2- P2S5Inorganic system's solid electrolyte of sulfides, can also be with
Use their mixture of more than two kinds.By using these solid electrolytes, lithium secondary battery can be further improved sometimes
Safety.
In addition, when using solid electrolyte, solid electrolyte is also sent out sometimes in the lithium secondary battery of present embodiment
The effect of separator is waved, in this case, sometimes without separator.
Lithium-contained composite metal oxide of the positive active material because using above-mentioned present embodiment as constructed as above, so
The side reaction generated in inside battery is able to suppress using the lithium secondary battery of positive active material.
In addition, it is positive because having the positive active material for lithium secondary battery of above-mentioned present embodiment as constructed as above,
So lithium secondary battery is able to suppress the side reaction generated in inside battery.
In addition, lithium secondary battery is because having above-mentioned anode as constructed as above, so becoming inhibition compared with the past in electricity
The lithium secondary battery of the side reaction generated inside pond.
Embodiment
Next, being further described in detail by embodiment to mode of the invention.
The evaluation of calcining raw materials and positive active material for lithium secondary battery is carried out in the present embodiment as follows.
(1) composition analysis in positive active material for lithium secondary battery (ICP emission spectrographic analysis)
Oxidize metal object powder be dissolved in hydrochloric acid after, use Inductively coupled plasma optical emission spectrometer (PerkinElmer
System, Optima 7300DV) carry out positive active material for lithium secondary battery composition analysis.It is calculated by chromium content obtained above
The content of chromium as impurity.In addition, being subtracted from lithium amount obtained above using the measurement of aftermentioned method from lithium carbonate
Lithium amount, the lithium amount as lithium metal composite oxides.By nickel amount obtained above, cobalt amount, manganese amount, the amount of M and above-mentioned lithium gold
The lithium amount for belonging to composite oxides finds out x, y, z, the value of w in above-mentioned logical formula (I).
(2) the residual lithium carbonate in positive active material for lithium secondary battery is quantitative (acid-base titration)
Positive active material for lithium secondary battery 20g and pure water 100g is added in 100mL beaker, stirs 5 minutes.Stirring
Afterwards, positive active material for lithium secondary battery is filtered, 0.1mol/L hydrochloric acid is added dropwise in the 60g of remaining filtrate, uses pH meter
Measure the pH of filtrate.The titer of hydrochloric acid when by ± 0.1 pH=8.3 is set as AmL, the drop of hydrochloric acid when by ± 0.1 pH=4.5
It is quantitatively set as BmL, remaining lithium carbonate concentration in positive active material for lithium secondary battery is calculated by following calculating formulas.Under
It states in formula, each atomic weight is set as Li:6.941, C:12, O:16 and calculates the molecular weight of lithium carbonate.
Lithium carbonate concentration (%)=0.1 × (B-A)/1000 × 73.882/ (20 × 60/100) × 100
(3) the powder x-ray diffraction measurement of positive active material for lithium secondary battery
The powder x-ray diffraction measurement of positive active material for lithium secondary battery uses powder x-ray diffraction device
(Rigaku Co. Ltd. system, Ultima IV, sample horizontal type) carries out.The positive active material for lithium secondary battery that will be obtained
It is filled into dedicated substrate, using Cu-K alpha ray source, is measured with the range of 2 θ=10 °~90 ° of the angle of diffraction, is thus obtained
X-ray diffractogram of powder shape.It is (following according to the peak in the range of 2 θ=18.7 ± 1 ° of above-mentioned x-ray diffractogram of powder shape calculating
Otherwise referred to as peak A), the half-peak breadth at peak (following otherwise referred to as peak B) in the range of 2 θ=44.6 ± 1 °.
(embodiment 1)
[mixed processes]
Lithium carbonate (Li is weighed in such a way that the molar ratio of Li:Ni:Co:Mn becomes 1.05:0.55:0.21:0.242CO3) and
Nickel cobalt manganese complex metal hydroxide (Ni0.55Co0.21Mn0.24(OH)2), they are subjected to dry type mixing and obtains mixture.It answers
Explanation is given, it is 29.7 mass % that the carbonic acid lithium content contained in said mixture is calculated by mixing ratio.
[pre-burning process]
Next, said mixture is put into the rotary furnace that furnace inner wall is aluminium oxide, forge within 2 hours at 790 DEG C
It burns.
[formal calcination process]
Then, calcined material obtained in pre-burning process is put into above-mentioned rotary furnace, while with every 1m3Furnace volume is
108.7Nm3The gas of oxygen of the flow circulation containing 21 volume % of/h, calcining in 2 hours is carried out at 900 DEG C of Bian.
Thereafter, it is cooled to room temperature, is crushed, obtain positive active material for lithium secondary battery.To secondary lithium batteries
Positive active material carries out ICP emission spectrographic analysis, and as a result chromium content is 2ppm.In addition, carrying out acid-base titration, as a result lithium carbonate
Content is 0.25 mass %.In addition, the x of above-mentioned logical formula (I) is 0.03, y 0.21, z 0.24, w 0.In addition, carrying out powder
The half-peak breadth of X-ray diffraction, results peaks A and peak B are respectively 0.129,0.152.
(embodiment 2)
[mixed processes]
Lithium carbonate (Li is weighed in such a way that the molar ratio of Li:Ni:Co:Mn becomes 2.20:0.55:0.21:0.242CO3) and
Nickel cobalt manganese complex metal hydroxide (Ni0.55Co0.21Mn0.24(OH)2), they are subjected to dry type mixing and obtains mixture.It answers
Explanation is given, it is 46.6 mass % that the carbonic acid lithium content contained in said mixture is calculated by mixing ratio.
[pre-burning process]
Next, said mixture is put into the rotary furnace that furnace inner wall is aluminium oxide, forge within 2 hours at 790 DEG C
It burns.
[formal calcination process]
Then, calcined material is put into above-mentioned rotary furnace, while with every 1m3Furnace volume is 150.1Nm3The flow of/h circulates
The gas of oxygen containing 100 volume %, carries out at 850 DEG C of Bian calcining for 2 hours.Thereafter, it is cooled to room temperature, is crushed, obtained
To positive active material for lithium secondary battery.ICP emission spectrographic analysis is carried out to positive active material for lithium secondary battery, as a result
Chromium content is 4ppm.In addition, carrying out acid-base titration, as a result carbonic acid lithium content is 0.92 mass %.In addition, the x of above-mentioned logical formula (I)
For 0.37, y 0.21, z 0.24, w 0.In addition, carrying out powder x-ray diffraction, the half-peak breadth of results peaks A and peak B are respectively
0.160、0.208。
(embodiment 3)
[mixed processes]
Using the method being the same as in example 1 above, mixture is obtained.
[pre-burning process]
The mixture recorded in embodiment 1 is put into the rotary furnace that furnace inner wall is inconel, is carried out at 730 DEG C
It calcines within 2 hours.
[formal calcination process]
Then, calcined material is put into the rotary furnace that furnace inner wall is aluminium oxide, while with every 1m3Furnace volume is 107.2Nm3/
The gas of oxygen of the flow circulation containing 21 volume % of h, calcining in 2 hours is carried out at 850 DEG C of Bian.Thereafter, it is cooled to room temperature, it will
It is crushed, and obtains positive active material for lithium secondary battery.ICP emission spectrum is carried out to positive active material for lithium secondary battery
Analysis, as a result chromium content is 10ppm.In addition, carrying out acid-base titration, as a result carbonic acid lithium content is 0.16 mass %.In addition, above-mentioned
The x of logical formula (I) is 0.03, y 0.21, z 0.24, w 0.In addition, powder x-ray diffraction is carried out, the half of results peaks A and peak B
Peak width is respectively 0.152,0.185.
(embodiment 4)
[mixed processes]
Using the method being the same as in example 1 above, mixture is obtained.
[pre-burning process]
The mixture recorded in embodiment 1 is put into the rotary furnace that furnace inner wall is inconel, is carried out at 730 DEG C
It calcines within 2 hours.
[formal calcination process]
Then, calcined material is put into the rotary furnace that furnace inner wall is aluminium oxide, while with every 1m3Furnace volume is 107.2Nm3/
The gas of oxygen of the flow circulation containing 60 volume % of h, calcining in 2 hours is carried out at 850 DEG C of Bian.Thereafter, it is cooled to room temperature, it will
It is crushed, and obtains positive active material for lithium secondary battery.ICP emission spectrum is carried out to positive active material for lithium secondary battery
Analysis, as a result chromium content is 31ppm.In addition, carrying out acid-base titration, as a result carbonic acid lithium content is 0.19 mass %.In addition, above-mentioned
The x of logical formula (I) is 0.04, y 0.21, z 0.24, w 0.In addition, powder x-ray diffraction is carried out, the half of results peaks A and peak B
Peak width is respectively 0.153,0.194.
(embodiment 5)
[mixed processes]
Using the method being the same as in example 1 above, mixture is obtained.
[pre-burning process]
The mixture recorded in embodiment 1 is put into the rotary furnace that furnace inner wall is inconel, is carried out at 730 DEG C
It calcines within 2 hours.
[formal calcination process]
Then, calcined material is put into the rotary furnace that furnace inner wall is aluminium oxide, while with every 1m3Furnace volume is 46.5Nm3/h
Oxygen of the flow circulation containing 100 volume % gas, calcining in 2 hours is carried out at 850 DEG C of Bian.Thereafter, it is cooled to room temperature, it will
It is crushed, and obtains positive active material for lithium secondary battery.ICP emission spectrum is carried out to positive active material for lithium secondary battery
Analysis, as a result chromium content is 49ppm.In addition, carrying out acid-base titration, as a result carbonic acid lithium content is 0.15 mass %.In addition, above-mentioned
The x of logical formula (I) is 0.04, y 0.22, z 0.24, w 0.In addition, powder x-ray diffraction is carried out, the half of results peaks A and peak B
Peak width is respectively 0.152,0.178.
(embodiment 6)
[mixed processes]
Using the method being the same as in example 1 above, mixture is obtained.
[pre-burning process]
The mixture recorded in embodiment 1 is put into the rotary furnace that furnace inner wall is inconel, is carried out at 730 DEG C
It calcines within 2 hours.
[formal calcination process]
Then, calcined material is put into the rotary furnace that furnace inner wall is aluminium oxide, while with every 1m3Furnace volume is 46.5Nm3/h
Oxygen of the flow circulation containing 21 volume % gas, calcining in 2 hours is carried out at 850 DEG C of Bian.Thereafter, it is cooled to room temperature, it will
It is crushed, and obtains positive active material for lithium secondary battery.ICP emission spectrum is carried out to positive active material for lithium secondary battery
Analysis, as a result chromium content is 20ppm.In addition, carrying out acid-base titration, as a result carbonic acid lithium content is 0.51 mass %.In addition, above-mentioned
The x of logical formula (I) is 0.04, y 0.21, z 0.24, w 0.In addition, powder x-ray diffraction is carried out, the half of results peaks A and peak B
Peak width is respectively 0.149,0.182.
(embodiment 7)
[mixed processes]
Using the method being the same as in example 1 above, mixture is obtained.
[pre-burning process]
The mixture recorded in embodiment 1 is put into the rotary furnace that furnace inner wall is inconel, is carried out at 730 DEG C
It calcines within 2 hours.
[formal calcination process]
Then, calcined material is put into the rotary furnace that furnace inner wall is aluminium oxide, while with every 1m3Furnace volume is 17.9Nm3/h
Oxygen of the flow circulation containing 21 volume % gas, calcining in 2 hours is carried out at 850 DEG C of Bian.Thereafter, it is cooled to room temperature, it will
It is crushed, and obtains positive active material for lithium secondary battery.ICP emission spectrum is carried out to positive active material for lithium secondary battery
Analysis, as a result chromium content is 19ppm.In addition, carrying out acid-base titration, as a result carbonic acid lithium content is 0.90 mass %.In addition, above-mentioned
The x of logical formula (I) is 0.03, y 0.21, z 0.24, w 0.In addition, powder x-ray diffraction is carried out, the half of results peaks A and peak B
Peak width is respectively 0.161,0.200.
(embodiment 8)
[mixed processes]
Using the method being the same as in example 1 above, mixture is obtained.
[pre-burning process]
The mixture recorded in embodiment 1 is put into the rotary furnace that furnace inner wall is inconel, is carried out at 730 DEG C
It calcines within 2 hours.
[formal calcination process]
Then, calcined material is put into the rotary furnace that furnace inner wall is aluminium oxide, while with every 1m3Furnace volume is 17.9Nm3/h
Oxygen of the flow circulation containing 100 volume % gas, calcining in 2 hours is carried out at 850 DEG C of Bian.Thereafter, it is cooled to room temperature, it will
It is crushed, and obtains positive active material for lithium secondary battery.ICP emission spectrum is carried out to positive active material for lithium secondary battery
Analysis, as a result chromium content is 45ppm.In addition, carrying out acid-base titration, as a result carbonic acid lithium content is 0.53 mass %.In addition, above-mentioned
The x of logical formula (I) is 0.03, y 0.21, z 0.24, w 0.In addition, powder x-ray diffraction is carried out, the half of results peaks A and peak B
Peak width is respectively 0.151,0.184.
(comparative example 1)
[mixed processes]
Using the method being the same as in example 1 above, mixture is obtained.
[pre-burning process]
The mixture recorded in embodiment 1 is put into the rotary furnace that furnace inner wall is inconel, is carried out at 730 DEG C
It calcines within 2 hours.
[formal calcination process]
Then, calcined material is put into the rotary furnace that furnace inner wall is inconel, while with every 1m3Furnace volume is
22.6Nm3The gas of oxygen of the flow circulation containing 21 volume % of/h, calcining in 2 hours is carried out at 730 DEG C of Bian.Thereafter, cooling
It to room temperature, is crushed, obtains positive active material for lithium secondary battery.Positive active material for lithium secondary battery is carried out
ICP emission spectrographic analysis, as a result chromium content is 55ppm.In addition, carrying out acid-base titration, as a result carbonic acid lithium content is 5.31 matter
Measure %.In addition, the x of above-mentioned logical formula (I) is 0.02, y 0.21, z 0.24, w 0.In addition, powder x-ray diffraction is carried out, knot
The half-peak breadth of fruit peak A and peak B are respectively 0.458,0.639.
(comparative example 2)
[mixed processes]
Using the method being the same as in example 1 above, mixture is obtained.
[pre-burning process]
The mixture recorded in embodiment 1 is put into the rotary furnace that furnace inner wall is inconel, is carried out at 730 DEG C
It calcines within 2 hours.
[formal calcination process]
Then, calcined material is put into the rotary furnace that furnace inner wall is inconel, while with every 1m3Furnace volume is
22.6Nm3The gas of oxygen of the flow circulation containing 21 volume % of/h, calcining in 4 hours is carried out at 730 DEG C of Bian.Thereafter, cooling
It to room temperature, is crushed, obtains positive active material for lithium secondary battery.Positive active material for lithium secondary battery is carried out
ICP emission spectrographic analysis, as a result chromium content is 60ppm.In addition, carrying out acid-base titration, as a result carbonic acid lithium content is 3.43 matter
Measure %.In addition, the x of above-mentioned logical formula (I) is 0.03, y 0.22, z 0.24, w 0.In addition, powder x-ray diffraction is carried out, knot
The half-peak breadth of fruit peak A and peak B are respectively 0.415,0.578.
(comparative example 3)
[mixed processes]
Using the method being the same as in example 1 above, mixture is obtained.
[pre-burning process]
The mixture recorded in embodiment 1 is put into the rotary furnace that furnace inner wall is inconel, is carried out at 730 DEG C
It calcines within 2 hours.
[formal calcination process]
Then, calcined material is put into the rotary furnace that furnace inner wall is SUS310, while with every 1m3Furnace volume is 22.6Nm3/h
Oxygen of the flow circulation containing 21 volume % gas, calcining in 5 hours is carried out at 730 DEG C of Bian.Thereafter, it is cooled to room temperature, it will
It is crushed, and obtains positive active material for lithium secondary battery.ICP emission spectrum is carried out to positive active material for lithium secondary battery
Analysis, as a result chromium content is 320ppm.In addition, carrying out acid-base titration, as a result carbonic acid lithium content is 1.13 mass %.On in addition,
The x for stating logical formula (I) is 0.02, y 0.21, z 0.24, w 0.In addition, progress powder x-ray diffraction, results peaks A and peak B
Half-peak breadth is respectively 0.214,0.261.
(comparative example 4)
[mixed processes]
Using the method being the same as in example 1 above, mixture is obtained.
[pre-burning process]
The mixture recorded in embodiment 1 is put into the rotary furnace that furnace inner wall is inconel, is carried out at 730 DEG C
It calcines within 2 hours.
[formal calcination process]
Then, calcined material is filled into the saggar that furnace inner wall is aluminium oxide, in roller kilns, while with every 1m3Furnace content
Product is 29.7Nm3The gas of oxygen of the flow circulation containing 21 volume % of/h, calcining in 2 hours is carried out at 850 DEG C of Bian.Thereafter,
It is cooled to room temperature, is crushed, obtain positive active material for lithium secondary battery.To positive active material for lithium secondary battery into
Row ICP emission spectrographic analysis, as a result chromium content is 10ppm.In addition, carrying out acid-base titration, as a result carbonic acid lithium content is 1.01 matter
Measure %.In addition, the x of above-mentioned logical formula (I) is 0.04, y 0.21, z 0.24, w 0.In addition, powder x-ray diffraction is carried out, knot
The half-peak breadth of fruit peak A and peak B are respectively 0.225,0.278.
(comparative example 5)
[mixed processes]
Using the method being the same as in example 1 above, mixture is obtained.
[pre-burning process]
The mixture recorded in embodiment 1 is put into the rotary furnace that furnace inner wall is inconel, is carried out at 730 DEG C
It calcines within 2 hours.
[formal calcination process]
Then, calcined material is filled into the saggar that furnace inner wall is aluminium oxide, in roller kilns, while with every 1m3Furnace content
Product is 29.7Nm3The gas of oxygen of the flow circulation containing 21 volume % of/h, calcining in 10 hours is carried out at 850 DEG C of Bian.Thereafter,
It is cooled to room temperature, is crushed, obtain positive active material for lithium secondary battery.To positive active material for lithium secondary battery into
Row acid-base titration, as a result carbonic acid lithium content is 0.67 mass %.In addition, the x of above-mentioned logical formula (I) is 0.02, y 0.21, z is
0.24, w 0.In addition, carrying out powder x-ray diffraction, the half-peak breadth of results peaks A and peak B are respectively 0.129,0.150.
(comparative example 6)
[mixed processes]
Lithium carbonate (Li is weighed in such a way that the molar ratio of Li:Ni:Co:Mn becomes 3.00:0.55:0.21:0.242CO3) and
Nickel cobalt manganese complex metal hydroxide (Ni0.55Co0.21Mn0.24(OH)2), they are subjected to dry type mixing and obtains mixture.It answers
Explanation is given, it is 54.3 mass % that the carbonic acid lithium content contained in said mixture is calculated by mixing ratio.In addition, the x of above-mentioned logical formula (I)
For 0.50, y 0.21, z 0.24, w 0.Side is in the rotary furnace that furnace inner wall is aluminium oxide with every 1m3Furnace volume is
17.9Nm3The gas of oxygen of the flow circulation containing 21 volume % of/h, forge within 2 hours to said mixture at 850 DEG C of Bian
It burns.But mixture and calcined material are attached on the wall of furnace heart pipe, can not be discharged.
(reference example)
[mixed processes]
Using the method being the same as in example 1 above, mixture is obtained.
[pre-burning process]
The mixture recorded in embodiment 1 is put into the rotary furnace that furnace inner wall is inconel, is carried out at 730 DEG C
It calcines within 2 hours.
[formal calcination process]
Then, calcined material is put into the rotary furnace that furnace inner wall is aluminium oxide, while with every 1m3Furnace volume is 17.9Nm3/h
Oxygen of the flow circulation containing 21 volume % gas, calcining in 4 hours is carried out at 850 DEG C of Bian.Thereafter, it is cooled to room temperature, it will
It is crushed, and obtains positive active material for lithium secondary battery.ICP emission spectrum is carried out to positive active material for lithium secondary battery
Analysis, as a result chromium content is 13ppm.In addition, carrying out acid-base titration, as a result carbonic acid lithium content is 0.10 mass %.In addition, above-mentioned
The x of logical formula (I) is 0.02, y 0.21, z 0.24, w 0.In addition, powder x-ray diffraction is carried out, the half of results peaks A and peak B
Peak width is respectively 0.149,0.183.
Hereinafter, recording embodiment and comparative example, the condition of reference example, result etc. together in table 1~3.In table, RK refers to
Rotary furnace, RHK refer to roller kilns.
As shown in the result recorded in following table 1~3, use the embodiment of the present invention 1~8 with the calcination time of short time
The half-peak breadth that can manufacture peak is small, i.e. the high positive active material of crystallinity.
In addition, the content of chromium is low using in the embodiment of the present invention 1~8.
In contrast, in the comparative example 1~3 for implementing formal calcination process with metal rotary furnace, the content of chromium is more,
The half-peak breadth at peak is also big.In addition, formal calcination process uses the half-peak at peak in the comparative example 4 of roller kilns, 2 hours calcination times
Roomy, the half-peak breadth at peak is small in comparative example 5, but formal calcination time needs 10 hours.
The furnace inner wall at the position that reference example 1 is contacted using mixture is implemented 4 hours by the rotary furnace that non-metallic material is formed
Formal calcining.By reference example 1 compared with embodiment 1, the half-peak breadth of results peaks is equal extent.That is, the short time (2
Hour) calcination time can manufacture the high positive active material of crystallinity.
[table 1]
[table 2]
[table 3]
Symbol description
1 ... separator, 2 ... anodes, 3 ... cathode, 4 ... electrode groups, 5 ... battery cans, 6 ... electrolyte, the insulation of 7 ... tops
Body, 8 ... seal bodies, 10 ... lithium secondary batteries, 21 ... positive wires, 31 ... negative wires, 40 ... rotary furnaces, 41 ... furnace inner walls,
42 ... furnace core tubes, 50 ... calcining raw materials.
Claims (8)
1. a kind of manufacturing method of positive active material for lithium secondary battery, which is characterized in that including following processes:
Lithium compound and positive active material precursor are obtained by mixing to the mixed processes of mixture, and,
The formal calcination process for being calcined the mixture using rotary furnace；
Wherein, the content of the lithium compound contained in the mixture is greater than 0 and 50 relative to the gross mass of the mixture
Quality % hereinafter,
The furnace inner wall of the rotary furnace is formed by non-metallic material.
2. the manufacturing method of positive active material for lithium secondary battery according to claim 1, wherein 750 DEG C~
1000 DEG C carry out the formal calcination process.
3. the manufacturing method of positive active material for lithium secondary battery according to claim 1 or 2, wherein the lithium two
Primary cell contains the lithium metal composite oxides that logical formula (I) below indicates with positive active material,
Li[Lix(Ni(1-y-z-w)CoyMnzMw)1-x]O2···(I)
In logical formula (I), -0.1≤x≤0.2,0 < y≤0.5,0 < z≤0.8,0≤w≤0.1, y+z+w < 1, M expression is selected from
The element of one or more of Cu, Ti, Mg, Al, W, B, Mo, Nb, Zn, Sn, Zr, Ga and V.
4. the manufacturing method of positive active material for lithium secondary battery described in any one of claim 1 to 3, wherein
After the mixed processes, before the formal calcination process, including in the temperature lower than the calcination temperature formally calcined
The lower pre-burning process calcined of degree.
5. the manufacturing method of positive active material for lithium secondary battery according to any one of claims 1 to 4, wherein
By with 15Nm3/h/m3The above flow circulation oxygen-containing gas and carry out in the formal calcination process and the pre-burning process
Either or both.
6. the manufacturing method of positive active material for lithium secondary battery according to claim 5, wherein the oxygen-containing gas
In oxygen concentration relative to oxygen-containing gas total volume be 21 volume % or more.
7. the manufacturing method of positive active material for lithium secondary battery described according to claim 1~any one of 6, wherein
The content of the chromium contained in the positive active material for lithium secondary battery is relative to the positive electrode for lithium secondary battery active matter
The gross mass of matter is 50ppm or less.
8. the manufacturing method of positive active material for lithium secondary battery according to any one of claims 1 to 7, wherein
The content of the lithium carbonate contained in the positive active material for lithium secondary battery is living relative to the positive electrode for lithium secondary battery
Property substance gross mass be 1.0 mass % or less.
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| JP2016201566A JP6857482B2 (en) | 2016-10-13 | 2016-10-13 | Manufacturing method of positive electrode active material for lithium secondary battery |
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| PCT/JP2017/037171 WO2018070517A1 (en) | 2016-10-13 | 2017-10-13 | Production method for lithium secondary battery positive electrode active material |
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| CN110444756A (en) * | 2019-08-19 | 2019-11-12 | 湖南金富力新能源股份有限公司 | The anode material for lithium-ion batteries and preparation method that are prepared with pyroreaction device and application |
| CN110459759A (en) * | 2019-08-19 | 2019-11-15 | 湖南金富力新能源股份有限公司 | The anode material for lithium-ion batteries and its preparation method that are prepared with slewing equipment and application |
| CN110935881A (en) * | 2019-12-30 | 2020-03-31 | 佛山市中研非晶科技股份有限公司 | Amorphous nanocrystalline powder baking equipment and use its magnetic powder core production line |
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| JP6673538B2 (en) | 2017-11-21 | 2020-03-25 | 日立金属株式会社 | Method for producing positive electrode active material for lithium ion secondary battery and heat treatment apparatus |
| CN109037633B (en) * | 2018-07-31 | 2022-02-22 | 湖南德景源科技有限公司 | Method for producing modified high-nickel cathode material by using rotary kiln heat treatment |
| JP6646129B1 (en) * | 2018-12-07 | 2020-02-14 | 住友化学株式会社 | Method for producing positive electrode active material for lithium secondary battery |
| KR102168640B1 (en) * | 2020-04-21 | 2020-10-21 | (주)탑전지 | Positive active material comprising spinel complex-oxide, method for preparing same, and rechargeable lithium battery comprising same |
| JP6936909B1 (en) * | 2020-08-07 | 2021-09-22 | Ｂａｓｆ戸田バッテリーマテリアルズ合同会社 | Positive electrode active material for non-aqueous electrolyte secondary battery and non-aqueous electrolyte secondary battery using it |
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Application publication date: 20190607 |