CN104701525B - Lithium secondary battery and positive electrode active substance for lithium secondary battery - Google Patents
Lithium secondary battery and positive electrode active substance for lithium secondary battery Download PDFInfo
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- CN104701525B CN104701525B CN201510112023.6A CN201510112023A CN104701525B CN 104701525 B CN104701525 B CN 104701525B CN 201510112023 A CN201510112023 A CN 201510112023A CN 104701525 B CN104701525 B CN 104701525B
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- oxide
- secondary battery
- lithium secondary
- complex
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- 239000013543 active substance Substances 0.000 title claims abstract description 12
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- 239000007774 positive electrode material Substances 0.000 claims description 74
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- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 1
- 229940114079 arachidonic acid Drugs 0.000 description 1
- 235000021342 arachidonic acid Nutrition 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- SAEBCFDIJRQJQB-UHFFFAOYSA-N carbonic acid;nickel Chemical compound [Ni].OC(O)=O SAEBCFDIJRQJQB-UHFFFAOYSA-N 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- NZSLBYVEIXCMBT-UHFFFAOYSA-N chloro hypochlorite;zirconium Chemical compound [Zr].ClOCl NZSLBYVEIXCMBT-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- UQPHVQVXLPRNCX-UHFFFAOYSA-N erythrulose Chemical compound OCC(O)C(=O)CO UQPHVQVXLPRNCX-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 229930182830 galactose Natural products 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- DLHSXQSAISCVNN-UHFFFAOYSA-M hydroxy(oxo)cobalt Chemical compound O[Co]=O DLHSXQSAISCVNN-UHFFFAOYSA-M 0.000 description 1
- VUFYPLUHTVSSGR-UHFFFAOYSA-M hydroxy(oxo)nickel Chemical compound O[Ni]=O VUFYPLUHTVSSGR-UHFFFAOYSA-M 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
- ODBLHEXUDAPZAU-UHFFFAOYSA-N isocitric acid Chemical compound OC(=O)C(O)C(C(O)=O)CC(O)=O ODBLHEXUDAPZAU-UHFFFAOYSA-N 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- BJHIKXHVCXFQLS-PQLUHFTBSA-N keto-D-tagatose Chemical compound OC[C@@H](O)[C@H](O)[C@H](O)C(=O)CO BJHIKXHVCXFQLS-PQLUHFTBSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002584 ketoses Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000008101 lactose Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 210000004508 polar body Anatomy 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 150000003214 pyranose derivatives Chemical class 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 235000011044 succinic acid Nutrition 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- GKLVYJBZJHMRIY-UHFFFAOYSA-N technetium atom Chemical compound [Tc] GKLVYJBZJHMRIY-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a lithium secondary battery with a positive electrode active substance in a positive electrode. The lithium secondary batter is characterized in that the positive electrode active substance comprises a Li-Mn composite oxide shown by a general formula (1): Lix(MnaCobNic)(2-x-y)MyO2 (1), wherein in the formula (1), a is more than 0 and less than 0.65, b is more than or equal to 0, and c is more than or equal to 0, x is more than 0 and less than 1.3, and y is more than 0 and less than 0.05, and compared with Mn, Co and Ni, the element M in the formula (1) is high in binding energy with oxygen.
Description
It is on March 19th, 2010, entitled " lithium two that the application is the Application No. 201080065502.2, applying date
The divisional application of the patent application of primary cell and positive active material for lithium secondary battery ".
Technical field
The present invention relates to the lithium secondary battery of lithium ion battery etc. and the positive pole of the lithium secondary battery can be performed well in
Positive active material.In addition, being related to the method for manufacturing the positive active material.In detail, it is related to a kind of positive active material
And possessing the lithium secondary battery of the positive active material in positive pole, the positive active material is comprising with rocksalt-type
The lithium-contained composite oxide of crystal structure.
Background technology
In recent years, the secondary cell of lithium secondary battery, Ni-MH battery etc., as the vehicle boarded electricity consumption with electricity as driving source
The power supply carried by the electrical apparatus product in source or personal computer and portable terminal device etc. etc., its importance are improved constantly.Particularly weigh
Amount is light and the lithium secondary battery (typically lithium ion battery) of high-energy-density is obtained, and is expected to conduct and is preferably used as car
Carry with the battery of high-output power power supply.
Lithium secondary battery, possesses and maintains on electroconductive member (electrode collector) and reversibly occlusion and release can become
The electrode of the composition of the material (electrode active material) for the lithium ion of charge carrier, in order to realize further high-energy-density
Change and high-output power, carry out the investigation of electrode activity thing material.As the positive pole for lithium secondary battery just
Pole active substance, can enumerate the knot of the crystal with rocksalt-type (layered rocksalt) and spinel-type (spinel) etc.
The lithium-contained composite oxide of structure.Can illustrate for example, containing lithium (Li) and at least one transition metal, lithium nickel composite oxygen
Compound, lithium cobalt composite oxide, complex Li-Mn-oxide or the metal lattice point beyond the lithium of above-mentioned crystal structure are configured with
Nickel, cobalt, the lithium nickel cobalt manganese oxide of each atom of manganese.Particularly lithium nickel cobalt manganese oxide is excellent as heat stability
It is different, and the material of high-energy-density be obtained receive publicity.As the positive active material phase with such secondary lithium batteries
The prior art of pass, for the various lithium-contained composite oxides of the crystal structure with rocksalt-type in patent documentation 1 and 2
Disclosed.
Prior art literature
Patent documentation 1：Japanese Patent Application Publication 2008-288112 publications
Patent documentation 2：Japanese Patent Application Publication 2008-243661 publications
The content of the invention
Among the purposes of lithium secondary battery, have imagination as it is vehicle boarded with power supply, in high speed discharge and recharge (institute repeatedly
The high current charge-discharge of meaning) mode under the purposes that chronically uses.But, using with stratiform as positive active material
In the lithium secondary battery of the complex Li-Mn-oxide of the crystal structure of rock salt, if in the side of such high speed discharge and recharge repeatedly
Use under formula, heat is produced in inside battery, then there is the Mn dissolutions in lattice.If Mn dissolutions, cause positive pole work
The reduction and/or the delay of the electric charge mobile response between positive pole and electrolyte of the translational speed of the lithium in property material, capacity urgency
Reduce acutely.Even if therefore, it is intended that using under high speed discharge and recharge, not making the translational speed of lithium reduce and high power capacity can be maintained yet
Positive active material.
The present invention is in view of the situation is completed, even if its main purpose is to provide one kind making under high speed discharge and recharge
With capacity is also difficult to the positive active material of the secondary lithium batteries for reducing and the manufacture method of the positive active material.In addition,
Another object is to provide a kind of lithium secondary battery for possessing such positive active material in positive pole.
To achieve these goals, by the present invention, there is provided a kind of positive active material, it is characterised in that above-mentioned positive pole
The complex Li-Mn-oxide that active substance is represented comprising formula (1),
Lix(MnaCobNic)2-x-yMyO2 (1)
(a, b, the c in formula (1) be
0 ＜ a ＜ 0.65,
0≤b、
0≤c,
X, y in formula (1) be
0 ＜ x ＜ 1.3,
0 ＜ y ＜ 0.05.Typically a+b+c=2-x-y.)
Element M in above-mentioned formula (1) is that, compared with Mn, Co, Ni, and the combination of oxygen can big element.
In addition, the present invention provides a kind of lithium secondary battery for possessing above-mentioned positive active material in positive pole.
Furthermore, so-called in this manual " lithium secondary battery " is referred to by the use of lithium ion as electrolyte ion, can be passed through
The movement of the electric charge associated with the lithium ion of positive and negative interpolar is realizing the secondary cell of discharge and recharge.Commonly referred to as lithium ion battery
Secondary cell be included in the typical case in the lithium secondary battery of this specification.
Furthermore, so-called in this manual " positive active material ", refer in the secondary battery can reversibly occlusion and
Release (typically insert and depart from) is changed into the active substance of the side of the positive electrode of the chemical seed (such as lithium ion) of charge carrier.
The positive active material comprising complex Li-Mn-oxide possessed in the positive pole of lithium secondary battery disclosed herein, its
It is characterised by, by formula (1) Lix(MnaCobNic)2-x-yMyO2Represent, the element M in the formula (1) is compared with Mn, Co, Ni, with oxygen
Combination can big element.
Here, as positive active material, lithium-contained composite oxide, the so-called lithium containing manganese (content ratio of manganese is big)
Manganese composite oxide, compared with the other lithium composite xoides containing cobalt, nickel as main body, if produced in inside battery
Heat, the then easy dissolutions of the Mn in lattice worry the reduction of discharge capacity.But, it is big using the content ratio as cheap manganese
Complex Li-Mn-oxide can suppress manufacturing cost as the lithium secondary battery of positive active material.Even if therefore, it is intended that
Also the positive active material for lithium secondary battery comprising complex Li-Mn-oxide for reducing is difficult under high speed discharge and recharge using capacity.
Therefore, the inventors have found that element M in complex Li-Mn-oxide as pettiness amount, with the addition of compared with Mn, Co, Ni with
The combination of oxygen can be big element, even if using under high speed discharge and recharge, the Mn in lattice is also difficult to dissolution.Thus, the secondary electricity of lithium
The heat stability in pond is improved, the translational speed of the lithium in positive active material, the electric charge mobile response between positive pole and electrolyte
Become to be difficult to reduce, therefore the reduction of discharge capacity can be suppressed.Therefore, by using positive active material disclosed herein, can
To provide the lithium secondary battery with excellent battery behavior (such as high-rate characteristics or cycle characteristics).Possess with here
The lithium secondary battery of the positive pole of disclosed positive active material, even if using can also become under the mode of high speed discharge and recharge repeatedly
Inhibit the battery of the reduction of discharge capacity.
In a preferred mode of lithium secondary battery disclosed herein, as above-mentioned positive active material, possess in formula (1)
A be meet 0.33 ＜ a ＜ 0.65 number positive active material.
By formula (1) Lix(MnaCobNic)2-x-yMyO2The manganese contained in the complex Li-Mn-oxide of expression, compared to cobalt, nickel
Content ratio more contain and the positive active material that constitutes, heat stability is more excellent.Thus, lived using the positive pole
Property material build lithium secondary battery, even if under high speed discharge and recharge use, it is also possible to do not reduce the lithium in positive active material
Translational speed and the electric charge mobile response between positive pole and electrolyte and maintain high power capacity.
Furthermore, complex Li-Mn-oxide disclosed herein, in the X determined using powder x-ray diffraction analysis device (XRD)
In x ray diffration pattern x, it is typical that the position of (such as 22 ° ± 1 °) near 2 θ values about 22 °, can confirm that belong to containing
The peak of the compound of Mn.In addition, according to the location confirmation of (such as 18 ° ± 1 °, 65 ° ± 1 °) near being about 18 ° or 65 ° in 2 θ values
Peak, can confirm that whether complex Li-Mn-oxide defines solid solution.
Additionally, in a preferred mode of lithium secondary battery disclosed herein, as above-mentioned positive active material, possess on
It is selected from Al, Si, Ca, Sc, Ti, V, Cr, Fe, Ge, Sr, Y, Zr, Nb, Mo, Tc, Ru, Rh, rare earths to state the element M in formula (1)
The positive active material of at least one element above in lanthanide series and rare earths actinidess.In addition, preferred
In one mode of lithium secondary battery, as above-mentioned positive active material, possess the element M in above-mentioned formula (1) be selected from Al, Ca,
The positive active material of at least one element above in Fe and Zr.
As the element M in above-mentioned formula (1), the complex Li-Mn-oxide containing the above-mentioned element enumerated has been used as just
The lithium secondary battery of pole active substance, and using not containing the complex Li-Mn-oxide of element M as positive active material
Lithium secondary battery is compared, discharge capacity increase about 30%.Even if it is, therefore, possible to provide high using also having under high speed discharge and recharge
The positive active material for lithium secondary battery of capacity.
In addition, making another aspect for achieving the above object, the present invention provides manufacture and is just including complex Li-Mn-oxide
The method of pole active substance.Manufacture method disclosed herein includes following operation.That is, include：To be used for constituting lithium manganese and be combined
The operation of the initiation material and organic acid hybrid modulation raw mixture in water solvent of oxide, above-mentioned lithium manganese combined oxidation
Thing is characterised by, by formula (1) expression,
Lix(MnaCobNic)2-x-yMyO2 (1)
(a, b, the c in formula (1) be
0 ＜ a ＜ 0.65,
0≤b、
0≤c,
X, y in formula (1) be
0 ＜ x ＜ 1.3,
0 ＜ y ＜ 0.05.Typically a+b+c=2-x-y.)
Element M in above-mentioned formula (1) is that, compared with Mn, Co, Ni, and the combination of oxygen can big element；Heating above-mentioned raw materials
Mixture makes the operation that above-mentioned water solvent is dried；To making the dried raw mixture of above-mentioned water solvent carry out the work of false burning
Sequence；The false operation burnt thing, burnt till at a temperature of higher than above-mentioned false burning temperature above-mentioned with crushing.
In above-mentioned modulating process, as the element M of the pettiness amount of initiation material, prepare compared with Mn, Co, Ni, with oxygen
Combination can big element, thus, the complex Li-Mn-oxide obtained by said method can be changed into the positive pole of excellent heat stability
Active substance.Therefore, the complex Li-Mn-oxide has been used as the lithium secondary battery of positive active material, even if filling in high speed
Electric discharge is lower to be used, and the Mn in lattice is also difficult to dissolution.Therefore, according to the manufacture method of the present invention, even if can manufacture at a high speed
Use under discharge and recharge, can also promote the translational speed of the lithium in positive active material, the electric charge between positive pole and electrolyte to move
Reaction, it is suppressed that the lithium secondary battery of the reduction of capacity.
In addition, in the preferred another way of manufacture method provided by the present invention, in the tune of above-mentioned raw materials mixture
In operation processed, prepare above-mentioned initiation material so that a in above-mentioned formula (1) becomes the number for meeting 0.33 ＜ a ＜ 0.65.
Prepare initiation material by way of being changed into the scope with the composition ratio of manganese, even if can manufacture filling in high speed
The lower use of electric discharge can also maintain the positive active material comprising complex Li-Mn-oxide of high power capacity.
It is preferred that：Prepare above-mentioned initiation material so that as the element M in above-mentioned formula (1), containing selected from Al, Si, Ca, Sc,
In Ti, V, Cr, Fe, Ge, Sr, Y, Zr, Nb, Mo, Tc, Ru, Rh, rare earths lanthanide series and rare earths actinidess at least one
Plant the element of the above.
Complex Li-Mn-oxide containing the above-mentioned element M enumerated, with the complex Li-Mn-oxide phase for not containing element M
Than using the lithium secondary battery of the composite oxides, discharge capacity becomes about 30%.Therefore, according to the manufacture method, can make
Even if making under high speed discharge and recharge using the also positive active material for lithium secondary battery with high power capacity.
In addition, in preferred another way, in above-mentioned false burning operation, false burning is carried out at 400～600 DEG C.Additionally,
It is preferred that：In above-mentioned firing process, burnt till in the temperature higher than above-mentioned false burning temperature and below 1000 DEG C.
Burn in operation or firing process false, by heating in said temperature region, lithium manganese can be improved well and be combined
The density of the crystal structure of oxide.As a result, the complex Li-Mn-oxide for having used crystallinity high is used as positive active material
Lithium secondary battery, even if being changed into using under high speed discharge and recharge, the Mn in lattice is also difficult to the battery of dissolution.Thus, lithium two
The heat stability of primary cell is improved, and can maintain high power capacity.
Additionally, in the preferred another way of manufacture method disclosed herein, what is obtained after above-mentioned firing process burns till
The mean diameter (central diameter) based on laser diffraction formula particle size distribution of thing is 1 μm～10 μm.In addition, in a preferred mode
In, the BET specific surface area of the burned material obtained after above-mentioned firing process is 2m2/ more than g.
Mean diameter or BET specific surface area have the burned material of above range, used as the mode in high speed discharge and recharge repeatedly
Under the positive active material that used of the battery that chronically uses, excellent performance (capacity, high-energy-density) can be played.
Additionally, according to the present invention, there is provided possess the vehicle of lithium secondary battery disclosed herein.Lithium provided by the present invention two
Primary cell, can show power supply suitable performance (such as high-rate characteristics or circulation as the battery for being especially mounted in vehicle
Characteristic) battery.Therefore, lithium secondary battery disclosed herein, can function well as hybrid vehicle, electric automobile etc
Possesses the power supply of the motor (motor) carried by the vehicle of the automobile of motor etc..
Description of the drawings
Fig. 1 is the axonometric chart of the profile of the lithium secondary battery for schematically representing that an embodiment is related to.
Fig. 2 is II-II line sectional view in Fig. 1.
Fig. 3 is the side view for schematically representing the vehicle (automobile) for possessing the lithium secondary battery that an embodiment is related to.
Fig. 4 is the figure of the X-ray diffractogram for representing each complex Li-Mn-oxide.
Fig. 5 is to represent the combination energy of the element M and oxygen that are added to complex Li-Mn-oxide and built using the oxide
The figure of the relation of the discharge capacity of lithium secondary battery.
Specific embodiment
Hereinafter, illustrate the present invention preferred embodiment.In addition, beyond the item that should be particularly mentioned that in this manual
, the present invention enforcement necessary to item, can be based on the prior art in the field, setting as those skilled in the art
Count item to grasp.The present invention can be implemented based on the technology general knowledge in content disclosed in this specification and the field.
The positive active material comprising complex Li-Mn-oxide that the present invention is provided, be with manganese be must constitution element contain
Lithium composite xoide, is the positive active material of the secondary lithium batteries of the crystal structure with rocksalt-type.Hereinafter, in detail
The manufacture method of the above-mentioned positive active material of ground explanation and the active substance, in the lump explanation possess the lithium two of the positive active material
Primary cell preferred embodiment, but is not intended to limit the invention in the embodiment.
Illustrate firstly, for the positive active material comprising complex Li-Mn-oxide of the present embodiment.
Positive active material disclosed herein, is represented by formula (1).
Lix(MnaCobNic)2-x-yMyO2 (1)
A, b, c in formula (1) is 0 ＜ a ＜ 0.65,0≤b, 0≤c, and x, the y in formula (1) is 0 ＜ x ＜ 1.3,0 ＜ y ＜
0.05。
In addition, it is typical that a+b+c=2-x-y or a+b+c≤2-x-y.Preferably a+b+c≤1.
Positive active material disclosed herein, the crystal structure with rocksalt-type represented comprising above-mentioned formula (1)
Complex Li-Mn-oxide.In addition, it is characterised in that the element M in above-mentioned formula (1) is and the combination of oxygen compared with Mn, Co, Ni
The big element of energy.
Complex Li-Mn-oxide disclosed herein, the content ratio of manganese are bigger than the content ratio of cobalt, nickel.As manganese ratio of components
Rate is preferably 0 ＜ a ＜ 0.65, more preferably 0.33 ＜ a ＜ 0.65, suitably about 0.5 ＜ a ＜ 0.65.Conduct is used
The larger lithium-contained composite oxide (typically complex Li-Mn-oxide) of the content ratio of cheap manganese is used as positive electrode active material
The lithium secondary battery of matter, can suppress manufacturing cost etc., and advantage is more.
On the other hand, the complex Li-Mn-oxide of the high crystal structure with rocksalt-type of such manganese containing ratio, with
Compare containing the other lithium composite xoides of cobalt and/or nickel as main body, if heat is produced in inside battery in lattice
The easy dissolutions of Mn, worry the reduction of discharge capacity.But, to complex Li-Mn-oxide disclosed herein such as by above-mentioned formula (1) table
Show like that, as the element M of pettiness amount, with the addition of compared with Mn, Co, Ni and oxygen combination can be big element.Thus, lithium is secondary
The heat stability of battery is improved, even if Reusability Mn is also difficult to dissolution under high speed discharge and recharge.As a result, positive pole can be promoted to live
The translational speed of the lithium in property material, the electric charge mobile response between positive pole and electrolyte, can suppress the reduction of discharge capacity.
Characterized in that, the element M in above-mentioned formula (1) is compared with Mn, Co, Ni, and the element that the combination of oxygen can be big.
That is, it is possible to select combination energy (about 402.9 ± 41.8kJ/ mole) compared to Mn-O, the combination of Co-O can (about
384.5 ± 13.4kJ/ mole), the combination of Ni-O can (about 382.0 ± 16.7kJ/ mole), the unit that the combination of M-O can be larger
Plain M.
Specifically, as the element M in above-mentioned formula (1), aluminum (Al), silicon (Si), calcium (Ca), scandium (Sc), titanium can be enumerated
(Ti), vanadium (V), chromium (Cr), ferrum (Fe), germanium (Ge), strontium (Sr), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium
(Ru) any one element, included in rhodium (Rh), rare earths lanthanide series, any one included in rare earths actinidess
Element.It is preferred that at least one element above among adding them.As particularly preferred element can enumerate Al, Ca, Fe,
Zr.It is preferred that at least one element above among adding these four elements.For example, the combination energy of each element and oxygen, Al-O
Combination can (511 ± 3kJ/ mole), Ca-O combination can (402.1 ± 16.7kJ/ mole), all compared with Mn, Co, Ni with
The combination of oxygen can be larger.
Additionally, it is preferred that：The composition ratio (y) of above-mentioned element M is configured to, it is typical that 0 ＜ y ＜ 0.05, preferably 0.001
＜ y ＜ 0.03, particularly preferably 0.003 ＜ y ＜ 0.01.The complex Li-Mn-oxide of element M, layer are added with the composition ratio
The crystal structure of shape rock salt is stable, even if the Mn at high temperature in lattice is also difficult to dissolution.
The complex Li-Mn-oxide, can be in the X-ray diffraction determined using powder x-ray diffraction analysis device (XRD)
Confirm in figure.Typically near the 2 θ values about 22 ° (such as 22 ° ± 1 °) position, can confirm that and belong to containing Mn's
The peak of compound.In addition, according to the location confirmation of (such as 18 ° ± 1 °, 65 ° ± 1 °) near being about 18 ° or 65 ° in 2 θ values
Peak, can confirm that whether complex Li-Mn-oxide defines solid solution.
Furthermore, the positive active material comprising complex Li-Mn-oxide disclosed herein, or except manganese and element M
In addition, the oxide also containing nickel and/or cobalt.The composition ratio (c) of the composition ratio (b) and/or cobalt of nickel is not particularly limited, but
It is preferred that the ratio with the composition ratio (a) less than manganese contains.
Then, for the method for positive active material of the manufacture comprising complex Li-Mn-oxide is illustrated.
Manufacture method disclosed herein, is the method for positive active material of the manufacture comprising complex Li-Mn-oxide, and which is special
Levy and be, above-mentioned complex Li-Mn-oxide is represented by formula (1),
Lix(MnaCobNic)2-x-yMyO2 (1)
(a, b, the c in formula (1) be
0 ＜ a ＜ 0.65,
0≤b、
0≤c,
X, y in formula (1) be
0 ＜ x ＜ 1.3,
0 ＜ y ＜ 0.05.Typically a+b+c=2-x-y.)
Element M in above-mentioned formula (1) is that, compared with Mn, Co, Ni, and the combination of oxygen can big element.
The manufacture method, taking it by and large, including：The various initiation materials and organic acid that above-mentioned formula (1) will be used for constituting are mixed
Close the operation of brewable material mixture；Heating above-mentioned raw materials mixture makes the operation that above-mentioned water solvent is dried；To making above-mentioned water
The dried raw mixture of series solvent carries out the operation of false burning；Thing is burnt with above-mentioned vacation is crushed, burning temperature higher than above-mentioned vacation
At a temperature of the operation burnt till.
＜ initiation material ＞
First, prepare for constituting the initiation material of the complex Li-Mn-oxide that above-mentioned formula (1) is related to.It is former as the starting
Material, prepares the supply source of the lithium supply source, manganese supply source and element M as required constitution element, and alternatively property is constituted
The cobalt supply source and nickel supply source of element.
As comprising lithium supply source compound, as long as the compound that can be dissolved in water solvent or be uniformly dispersed
Various lithium compounds can be used with being not particularly limited just.Preferably use for example, the lithium organic acid chemical combination of Quilonorm (SKB), lithium oxalate etc.
The lithium inorganic acid compound of thing, lithium carbonate, Lithium hydrate, lithium phosphate etc..As more preferred example, can enumerate easily in water
Quilonorm (SKB) dihydrate [Li (the CH dissolved in series solvent3COO)·2H2O]。
In addition, as comprising above-mentioned manganese supply source compound, it is possible to use for example, manganese acetate, manganese oxalate, manganese carbonate,
The manganese compound of manganese oxide, manganese sulfate, manganese nitrate, manganous hydroxide, hydroxyl oxidize manganese (manganese oxyhydroxide) etc..
As more preferred example, manganese acetate (II) tetrahydrate [Mn for easily dissolving in water solvent can be enumerated
(CH3COO)2·4H2O]。
Additionally, as initiation material, prepare containing compared with Mn, Co, Ni, and the chemical combination of the element M that the combination of oxygen can be big
Thing.As the concrete example of element M, can enumerate Al, Si, Ca, Sc, Ti, V, Cr, Fe, Ge, Sr, Y, Zr, Nb, Mo, Tc, Ru, Rh,
Any one element included in any one element, rare earths actinidess included in rare earths lanthanide series.It is preferred that containing
Have in these elements it is at least one more than element M compound.Particularly preferably comprising the one kind among Al, Ca, Fe and Zr
The compound of element M above.As long as the compound containing the element M can dissolve in water solvent or be uniformly dispersed just not
It is particularly limited to, such as acetate comprising above-mentioned element M, oxalates can be enumerated as preference.By adding to initiation material
Compound containing the above-mentioned element M enumerated, can also maintain high power capacity, heat even if can manufacture and use under high speed discharge and recharge
Stablize excellent positive active material for lithium secondary battery.Furthermore, addition form according to the compound containing the element M not
Together, the form to form solid solution and/or coating surface can be taken, but is not particularly limited.
As the compound comprising the alternatively cobalt supply source of property constitution element, as long as can dissolve in water solvent
Or the compound being uniformly dispersed just can use various cobalt compounds with being not particularly limited.Preferably use for example, cobalt acetate, grass
Sour cobalt, cobalt carbonate, cobalt oxide, cobaltous sulfate, cobalt nitrate, cobalt hydroxide, hydroxy cobalt oxide etc..As more preferred example, can
Enumerate cobalt acetate (II) tetrahydrate [Co (CH for easily dissolving in water solvent3COO)2·4H2O]。
In addition, as the compound comprising above-mentioned nickel supply source, as long as can dissolve in water solvent or equably divide
Scattered compound just can use various nickel compounds with being not particularly limited.Preferably use for example, nickel acetate, nickel oxalate, carbonic acid
Nickel, nickel oxide, nickel sulfate, nickel nitrate, nickel hydroxide, hydroxy nickel oxide etc..As more preferred example, can enumerate and easily exist
Nickel acetate (II) tetrahydrate [Ni (CH dissolved in water solvent3COO)2·4H2O]。
The modulation ＞ of ＜ raw mixtures
Then, above-mentioned ready each initiation material and organic acid are weighed, the hybrid modulation raw material mixing in water solvent
Thing.
The combined amount of (weighing) each initiation material is adjusted more preferably so that what each initiation material generation formula (1) represented answers
Close oxide,
Lix(MnaCobNic)2-x-yMyO2 (1)
(a, b, the c in formula (1) be
0 ＜ a ＜ 0.65,
0≤b、
0≤c,
X, y in formula (1) be
0 ＜ x ＜ 1.3,
0 ＜ y ＜ 0.05.Typically a+b+c=2-x-y.).Now, it is preferred to weigh manganese supply source so that as manganese group
Into ratio, more preferably preferably 0 ＜ a ＜ 0.65,0.33 ＜ a ＜ 0.65, suitably about become 0.5 ＜ a ＜ 0.65.Again
Person, the composition ratio of lithium are not particularly limited, it is also possible to the x satisfactions 1 in above-mentioned formula (1) are caused in the way of the lithium comprising excess quantity
＜ x ＜ 1.3 mix each initiation material preparing above-mentioned lithium supply source.Thereby, it is possible to synthesize high power capacity and be capable of achieving high-energy it is close
The complex Li-Mn-oxide of degree.
Here, as organic acid (gel), the acid dissolved in water solvent or be uniformly dispersed can be used well.
For example, glycolic (C can be enumerated2H4O3).Furthermore it is possible to use saccharide, fatty acid, their salt well.As saccharide, can
To enumerate monosaccharide, disaccharides and polysaccharide and their derivant.For example, as monosaccharide, glucose, sweet can be enumerated
The aldose of dew sugar, galactose, allose, talose, ribose, arabinose, erythrose, threose etc., Fructose, Tagatose, Pyrusussuriensiss
The ketose of sugared ribulose, xylulose, Erythrulose etc. or the pyranose as their circulus body, furan saccharide.In addition,
As disaccharides, sucrose, Lactose, maltose etc. can be enumerated, as polysaccharide, starch, cellulose etc. can be enumerated.In addition,
As fatty acid, the unsaturated fatty acidss of the satisfied fatty acid of acetic acid, butanoic acid etc., Oleic acid, linoleic acid, arachidonic acid etc. can be enumerated
Other fat such as acid or phthalic acid, citric acid, 1-Hydroxy-1,2,3-propanetricarboxylic acid., malic acid, tartaric acid, lactic acid, oxalic acid, succinic acid
Acid.Particularly can well using the saccharide of sucrose etc..
Mix the water solvent of above-mentioned initiation material, it is typical that water, but as long as being as the overall solvent for showing aqueouss
, preferably for example contain the aqueous solution of lower alcohol (methanol, ethanol etc.).I.e., it is possible to be preferably used water or based on water
Mixed solvent.As the solvent constituted beyond the water of the mixed solvent, can suitably selectively using can equably mix with water
The organic solvent (lower alcohol, lower ketones etc.) of conjunction one or more.For example, it is preferable to use about 80 matter of water solvent
Amount more than % (more than even more preferably about 90 mass %, more than more preferably about 95 mass %) is the solvent of water.As spy
Not preferred example, can enumerate the solvent being substantially made up of water.
After have adjusted the mixing quality ratio of each initiation material, the initiation material and organic acid are added in water solvent simultaneously
Mixed so as to fully spread or permeate, brewable material mixture.When being mixed, it is also possible to carry out as needed
Stirring (includes mixing, crushes).It is not particularly limited as the device for mixing, by using such as planetary-type mixer
(Planetary Mixer), planetary agitating device, disperser, ball mill, kneading machine, mixer etc., above-mentioned raw materials mixture
Equably spread or permeate, stable admixture can be formed.
＜ drying process ＞
Then, for drying process is illustrated.In drying process, the above-mentioned raw mixture for modulating of drying makes
The water solvent evaporation contained in raw mixture.By being dried using the operation before raw mixture is burnt till, from
Raw mixture only make water solvent (or a part) evaporation, the growth for suppressing crystal and each composition equably spread or
Permeate for suitable state.Thus, each composition is mixed with the ratio for being close to stoichiometric composition, as a result, can obtain crystallinity
High complex Li-Mn-oxide.
In addition, as long as the temperature of baking temperature water solvent evaporation is just not particularly limited, but can be at preferably 50 DEG C
～100 DEG C, more preferably 60～90 DEG C, be dried at a temperature of such as 80 DEG C or so.By in the humidity province less than 100 DEG C
Domain dry feed mixture, water solvent evaporation, can become and turn to the gel state for not having mobility.
Furthermore, drying time is typically sufficiently carried out can the diffusion or infiltration of each composition by keeping longlyer, but
Retention time is not particularly limited.I.e., it is possible to while the drying regime of confirmation solvent, appropriate adjustment retention time.In addition, making
For drying meanss, the appropriate of such as natural drying, hot blast, low wet wind, vacuum, infrared ray, far infrared etc. can be adopted to do
Dry means are dried well.
＜ is false to burn operation ＞
Then, for false burning is illustrated.The raw mixture gone out with water solvent hybrid modulation is carried out into false burning.It is false to burn
When heating-up temperature, it is typical that 400 DEG C～600 DEG C, preferably 450 DEG C～550 DEG C, suitably about 500 DEG C or so.Pass through
False burning is carried out in the temperature province heating, the drastically growth of crystal can be suppressed, and gelatinous raw mixture can be made equal
Spread evenly.Also, it is combined by burning till in higher temperature region described later, stoichiometric composition or lithium manganese proximate to it
The crystalchecked ground growth of the tiny crystal grains of oxide.
＜ crushes ＞
After above-mentioned false burning, false burning thing is crushed using appropriate means.By crushing and entering at a higher temperature the false thing that burns
Row burns till, and can obtain the burned material with desired mean diameter and/or BET specific surface area.Furthermore, as crushing
Device is not particularly limited, but can enumerate such as mortar, ball mill, rotating disintegrator, kneading machine etc..Wet type or dry can also be used
Formula any one or be combined and crushed.
＜ burns till ＞
Then, by false the chippy false thing that burns is being burnt at a temperature of temperature heating being burnt till higher than above-mentioned.Make
For firing temperature, heated higher than the above-mentioned false temperature province for burning temperature.Typically, higher than 600 DEG C temperature and
Less than 1000 DEG C of temperature province, preferably 700～950 DEG C, heating is carried out at 800～900 DEG C more preferably is suitable.Allusion quotation
Type, temperature when than false burning is high more than 100 DEG C, preferably more than 200 DEG C, more preferably more than 400 DEG C of temperature province enters
Row heating.By being heated under the firing temperature, can more promote crystal growth, with stoichiometric composition or proximate to it
Ratio of components formed complex Li-Mn-oxide rocksalt-type crystal structure.
In addition, the average grain based on laser diffraction formula particle size distribution of the burned material obtained after above-mentioned firing process
Footpath (central diameter), can be typically 1 μm～10 μm, such as 1 μm～8 μm or so of particulate form.Additionally, the BET of the burned material
Specific surface area, can be typically 2m2/ more than g, preferably 2m2/ g～10m2/g.Compare table with such mean diameter or BET
The burned material of area, as the positive active material used by the battery that can be used under the mode of high speed discharge and recharge repeatedly, can
Play excellent performance (capacity, high-energy-density).Furthermore, mean diameter (D50) refers to the central diameter (D50 of volume reference：50%
Volume average particle size), determined using general commercially available hondrometer (laser diffraction formula particle size distribution device).In addition, BET ratios
Surface area is determined using commercially available measure device (such as the full-automatic BET specific surface area determinators of computer controls).
Furthermore, it is also possible to burned material is further crushed as needed.By being crushed above-mentioned burned material with appropriate means,
Pelletize and classification, can obtain the granular complex Li-Mn-oxide with desired mean diameter and/or BET specific surface area
Powder.
Hereinafter, to using the complex Li-Mn-oxide obtained by manufacture method disclosed herein as positive active material
Positive pole and possess the positive pole lithium secondary battery an embodiment, see figures.1.and.2 shown in ideograph enter
Row explanation, but be not intended to limit the invention to the embodiment.
In addition, in this manual it should be particularly mentioned that item beyond, the present invention enforcement necessary to item (for example,
Possesses the electricity of the composition and preparation method, lithium secondary battery of composition and preparation method, dividing plate and the electrolyte of the electrode body of positive pole and negative pole etc.
General technology that the structure in pond is related to etc.), can be based on the prior art in the field, setting as those skilled in the art
Count item to grasp.
Furthermore, in figures in the following, sometimes to the subsidiary same tag of component and position for playing phase same-action, repeat
Explanation is omitted or simplified.In addition, the size relationship (length, width, thickness etc.) in each figure does not reflect actual size relationship.
Fig. 1 is the axonometric chart of the lithium secondary battery of the angle-style shape for schematically representing that an embodiment is related to, and Fig. 2 is Fig. 1
In II-II line sectional view.As depicted in figs. 1 and 2, lithium secondary battery of the present embodiment 100, possesses rectangular shape
Angle-style battery container 10, and the inaccessible housing 10 peristome 12 lid 14.Can be from the peristome 12 by flat pattern
Electrode body (rolled electrode bodies 20) and electrolyte be contained in inside battery container 10.In addition, being provided with outside on lid 14
The positive terminal 38 and negative terminal 48 of connection, a part for these terminals 38,48 are prominent to the face side of lid 14.Separately
Outward, a part for outside terminal 38,48 is connected to internal positive terminal 37 or internal negative terminal 47 in enclosure interior.
As shown in Fig. 2 in the present embodiment, rolled electrode bodies 20 are housed in the housing 10.The electrode body 20 is wrapped
Include：The positive plate 30 of positive electrode active material layer 34 is formed with the surface of the positive electrode collector 32 of long lamellar；In the negative of long lamellar
The surface of electrode current collector 42 is formed with the negative plate 40 of negative electrode active material layer 44；With the dividing plate 50 of long lamellar.And, by positive pole
Piece 30 and negative plate 40 and 2 pieces of dividing plates 50 together overlap winding, flatten and press the rolled electrode bodies obtained by pushing away from the side
20, thus it is configured to flat pattern.
In addition, in the positive plate 30 for being wound, the end 35 along a side of its longitudinal direction has and does not form positive-active
Material layer 34 and expose the part (positive electrode active material layer non-formation portion 36) of positive electrode collector 32, in the negative plate for being wound
In 40, the end 45 along a side of its longitudinal direction exposes the portion of negative electrode collector 42 with negative electrode active material 44 is not formed
Point (negative electrode active material layer non-formation portion 46).Also, connect in the non-formation portion of the positive electrode active material layer of positive electrode collector 32 36
Conjunction has internal positive terminal 37, is bonded to internal negative terminal in the non-formation portion of the negative electrode active material layer of negative electrode collector 42 46
47, electrically connect with the positive plate 30 or negative plate 40 of the above-mentioned rolled electrode bodies 20 for being formed flat pattern.Anode and cathode terminals
37th, 47 and positive and negative electrode current collector 32,42 can be engaged for example, by ultrasonic bonding, resistance welding etc. respectively.
Positive plate (typically positive plate 30) possesses the formation on the positive electrode collector 32 of long shape and contains positive pole
The composition of the positive electrode active material layer 34 of active substance.Positive electrode collector 32 can well using the positive pole that is suitable for of aluminium foil etc.
Metal forming.In addition, positive active material can be using the complex Li-Mn-oxide obtained using manufacture method disclosed herein.
, in addition to above-mentioned positive active material, can also contain as needed can be general for positive electrode active material layer 34
One or more the binding agent coordinated in lithium secondary battery and conductive material etc..As the conductive material, preferably make
With the electroconductive powder material of carbon dust, carbon fiber etc..For example, it is preferable to acetylene black, furnace black, Ketjen black, powdered graphite
Deng can only using the one kind among them, it is also possible to and with two or more.
The positive electrode active material layer 34 can pass through：Positive active material, binding agent and conductive material etc. are added to suitable
When solvent (water, organic solvent and their mixed solvent) in, by the paste for dispersing or dissolving which and modulating or pulpous state
Compositionss coat on positive electrode collector 32, make solvent seasoning and be compressed, so as to make well.
On the other hand, negative pole (typically negative plate 40), can be 42 (such as copper of negative electrode collector in long shape
Paper tinsel) on be formed with the composition of negative electrode active material layer 44.Negative electrode active material can be used all the time in which be not particularly limited
The material for using in the lithium secondary battery one or more.As preference, carbon particle can be enumerated.Preferably use
Granular material with carbon element (carbon particle) containing graphite-structure (layer structure) at least a portion.The material with carbon element of so-called graphite
(graphite), the material with carbon element (hard carbon) of difficult graphitization carbonaceous, the material with carbon element (soft carbon) of easy graphitization carbonaceous, with they are combined with
Any one material with carbon element of material with carbon element of structure can be preferably used.
In addition, negative electrode active material layer 44 is in addition to above-mentioned negative electrode active material, can also as needed containing can be
The material of one or more the binding agent coordinated in general lithium secondary battery etc..Furthermore, it is possible to pass through：Negative pole is lived
Property material and binding agent etc. are added in appropriate solvent (water, organic solvent and their mixed solvent), disperse will which
Or the compositionss of dissolving and the paste that modulates or pulpous state are coated on negative electrode collector 42, are made solvent seasoning and are compressed, from
And make well.
In addition, as the suitable separator sheets 50 used between positive/negative plate 30,40, can enumerate by Porous polyolefin
The separator sheets that resin is constituted.For example, it may be preferred to which ground uses synthetic resin system (the polyolefin system of such as polyethylene etc.) Porous
Separator sheets.Furthermore, in the case where solid electrolyte or gel-like electrolyte are used as electrolyte, do not need sometimes dividing plate
(i.e. in this case electrolyte itself can be used as dividing plate function).
In addition, electrolyte can be used and the nonaqueous electrolytic solution for being used for lithium secondary battery in which be not particularly limited all the time
Same electrolyte.As the nonaqueous electrolytic solution, typically, with the group containing supporting electrolyte in appropriate nonaqueous solvent
Into.As above-mentioned nonaqueous solvent, propylene carbonate (PC), ethylene carbonate (EC), diethyl carbonate (DEC), carbonic acid can be enumerated
Dimethyl ester (DMC), ethyl methyl carbonate (EMC) etc..Can use they among one or more.In addition, as upper
State supporting electrolyte, it is possible to use such as LiPF6、LiBF4、LiClO4、LiAsF6Deng lithium compound (lithium salts).
In addition, the structure explanation of the lithium secondary battery 100 is related to by an embodiment substantially the step of.By will be above-mentioned
Made by positive plate 30 and negative plate 40 and 2 pieces of dividing plates 50 be together laminated, wind, and flatten from stack direction and press and push away, by electricity
Polar body 20 is configured to flat pattern, houses in battery container 10 and injects after electrolyte, installs lid in the shell nozzle portion 12
Body 14 is simultaneously packaged, it is possible thereby to build the lithium secondary battery 100 of present embodiment.In addition, for the knot of battery container 10
Structure, size, material (can be such as metal system or laminated film system), and based on both positive and negative polarity the electrode body of element structure
(such as winding-structure, laminated construction) etc. is not particularly limited.
The lithium secondary battery 100 for so building, can also suppress discharge capacity even if can become and use under high speed discharge and recharge
Reduction battery.Therefore, lithium secondary battery according to the present invention 100 can be used as vehicle boarded use high-output power power supply, spy
It is not to be used with power supply well as the motor (motor) carried by the vehicle of automobile etc..Schematically represent such as Fig. 3 that
Sample, there is provided it (can be by the lithium secondary battery more than the 100 individual set of cells for being connected in series and being formed to possess the lithium secondary battery 100
Form) as vehicle (typically automobile, particularly hybrid vehicle, electric automobile, fuel cell car etc of power supply
The automobile for possessing motor) 1.
Hereinafter, for test example according to the present invention is illustrated, but it is not intended to limit the invention to the concrete example institute
The form shown.
1 ＞ of ＜ test examples
Formula：Lix(MnaCobNic)2-x-yMyO2 (1)
It is respectively synthesized：As the element M in above-mentioned formula (1), containing compared with Mn, Co, Ni, and the combination of oxygen can be big
The complex Li-Mn-oxide of element (Al, Ca, Fe or Zr)；As the element M in above-mentioned formula (1), containing compared with Mn, Co, Ni,
And the combination of oxygen can be little element (Zn or Mg) complex Li-Mn-oxide；With the complex Li-Mn-oxide for not containing element M.
＜ embodiments 1：Synthesis (M=Al) ＞ of complex Li-Mn-oxide
Among the complex Li-Mn-oxide represented by above-mentioned formula (1), synthesized in embodiment 1 element M for Al,
Li1.2Mn0.52Co0.13Ni0.13Al0.02O2。
That is, as initiation material, Quilonorm (SKB) dihydrate [Li (CH are prepared3COO)·2H2O], nickel acetate (II) four be hydrated
Thing [Ni (CH3COO)2·4H2O], manganese acetate (II) tetrahydrate [Mn (CH3COO)2·4H2O] and aluminium acetate [Al
(CH3COO)3], carry out respectively weighing so that mixing quality ratio becomes above-mentioned composition ratio.Then, will be each starting for weighing former
Expect and as the glycolic (C of organic acid2H4O3) mix in water solvent, it is drying over night using drying machine, modulate gel
Raw mixture.Then, the raw mixture being dried is heated 5 hours at 500 DEG C, carries out false burning.After false burning, using row
Celestial body grinding machine case of wet attrition, then burnt till within 5 hours in 900 DEG C of heating, thus synthesize the lithium manganese composite oxygen that embodiment 1 is related to
Compound (Li1.2Mn0.52Co0.13Ni0.13Al0.02O2)。
＜ embodiments 2：Synthesis (M=Ca) ＞ of complex Li-Mn-oxide
Among the complex Li-Mn-oxide represented by above-mentioned formula (1), in example 2, synthesized in above-mentioned formula (1)
Element M is Ca, Li1.2Mn0.52Co0.13Ni0.13Ca0.02O2。
That is, as initiation material, using acetic acid calcium dihydrate [Ca (CH3COO)2·2H2O] substitute aluminium acetate, except this with
It is outer to adopt the step same with above-described embodiment 1, synthesize the complex Li-Mn-oxide that embodiment 2 is related to
(Li1.2Mn0.52Co0.13Ni0.13Ca0.02O2)。
＜ embodiments 3：Synthesis (M=Fe) ＞ of complex Li-Mn-oxide
Among the complex Li-Mn-oxide represented by above-mentioned formula (1), in embodiment 3, synthesized in above-mentioned formula (1)
Element M is Fe, Li1.2Mn0.52Co0.13Ni0.13Fe0.02O2。
That is, as initiation material, using ferric acetate [Fe (CH3COO)2] substitute aluminium acetate, in addition using with above-mentioned reality
The same step of example 1 is applied, has synthesized the complex Li-Mn-oxide (Li that embodiment 3 is related to1.2Mn0.52Co0.13Ni0.13Fe0.02O2)。
＜ embodiments 4：Synthesis (M=Zr) ＞ of complex Li-Mn-oxide
Among the complex Li-Mn-oxide represented by above-mentioned formula (1), in example 4, synthesized in above-mentioned formula (1)
Element M is Zr, Li1.2Mn0.52Co0.13Ni0.13Zr0.02O2。
That is, as initiation material, using eight hydrate [ZrOCl of zirconium oxychloride2·8H2O] substitute aluminium acetate, except this with
It is outer to adopt the step same with above-described embodiment 1, synthesize the complex Li-Mn-oxide that embodiment 4 is related to
(Li1.2Mn0.52Co0.13Ni0.13Zr0.02O2)。
＜ comparative examples 1：Synthesis (no M) ＞ of complex Li-Mn-oxide
Among the complex Li-Mn-oxide represented by above-mentioned formula (1), in comparative example 1, synthesize and do not contained above-mentioned formula
(1) element M, the Li in1.2Mn0.54Co0.13Ni0.13O2。
Aluminium acetate is excluded from initiation material, in addition using the step same with above-described embodiment 1, has been synthesized and has been compared
Complex Li-Mn-oxide (the Li that example 1 is related to1.2Mn0.54Co0.13Ni0.13O2)。
＜ comparative examples 2：Synthesis (M=Zn) ＞ of complex Li-Mn-oxide
Among the complex Li-Mn-oxide represented by above-mentioned formula (1), in comparative example 2, synthesize in above-mentioned formula (1)
Element M is Zn, Li1.2Mn0.52Co0.13Ni0.13Zn0.02O2。
That is, as initiation material, using zinc acetate [Zn (CH3COO)2] substitute aluminium acetate, in addition using with above-mentioned reality
The same step of example 1 is applied, has synthesized the complex Li-Mn-oxide (Li that comparative example 2 is related to1.2Mn0.52Co0.13Ni0.13Zn0.02O2)。
＜ comparative examples 3：Synthesis (M=Mg) ＞ of complex Li-Mn-oxide
Among the complex Li-Mn-oxide represented by above-mentioned formula (1), in comparative example 3, synthesize in above-mentioned formula (1)
Element M is Mg, Li1.2Mn0.52Co0.13Ni0.13Mg0.02O2。
That is, as initiation material, using magnesium acetate 4 hydrate [Mg (CH3COO)2·4H2O] substitute aluminium acetate, except this with
It is outer to adopt the step same with above-described embodiment 1, synthesize the complex Li-Mn-oxide that comparative example 3 is related to
(Li1.2Mn0.52Co0.13Ni0.13Mg0.02O2)。
[XRD analysis]
The lithium manganese that each embodiment and comparative example of above-mentioned synthesis are analyzed using powder x-ray diffraction analysis device (XRD) is multiple
Close the crystal structure of oxide.Respective X-ray diffraction is illustrated in into Fig. 4.
According to the X-ray diffractogram shown in Fig. 4, the complex Li-Mn-oxide that embodiment 1～4 and comparative example 1～3 are related to
Crystal structure, any one can confirm to belong to the peak of the compound containing Mn near 2 θ values are about 22 °.
In addition, according to the peak confirmed near being about 18 ° or 65 ° in 2 θ values, showing any one complex Li-Mn-oxide all
Define solid solution.
[measure of mean diameter and BET specific surface area]
For each embodiment and the complex Li-Mn-oxide of comparative example of above-mentioned synthesis, determined based on laser diffraction respectively
The mean diameter (central diameter) of formula particle size distribution and BET specific surface area.Measurement result is shown in into table 1.
Table 1
[structure of lithium secondary battery]
Then, build the lithium secondary battery of test.First, produce the positive pole used in the battery.That is, by making
For the complex Li-Mn-oxide of the positive active material of above-mentioned synthesis, the acetylene black as conductive material and as the poly- of binding agent
Vinylidene fluoride (PVDF), becomes 85 with the quality % ratio of these materials：10：5 mode is weighed, and add N- methyl-
2-Pyrrolidone (NMP) is mixed, and thus modulates positive electrode active material layer formation paste.
Then, above-mentioned muddle is distributed in as on the aluminium foil of positive electrode collector, makes the moisture drying (evaporation) in the paste.And
And, slabbing is stretched using roll squeezer, define active material layer on the surface of positive electrode collector.Then, using a diameter of
The drift punching of 15mm is circular, modulates positive pole.
Then, modulate the negative pole of the lithium secondary battery of test.Prepare lithium metal foil, rushed with the drift of a diameter of 15mm
Cut out, modulate negative pole.
2032 types (a diameter of 20mm, thickness are 3.2mm) button type is constructed using the above-mentioned positive pole for modulating and negative pole
Test lithium secondary battery.That is, in the circular positive pole of the inner laminated configuration of the outer tinning of the exterior for forming side of the positive electrode and leaching
Stain has the dividing plate of nonaqueous electrolytic solution, after the periphery of dividing plate is pushed down with sealing gasket, configures negative pole, the adjustment of circle on dividing plate successively
The shaping piece and leaf spring of thickness.Then, with the inside of the inaccessible above-mentioned outer tinning for having housed of outer capping, by outer tinning and exterior
The periphery sealed cans of lid, construct the lithium secondary battery of test.
Furthermore, as nonaqueous electrolytic solution, using to ethylene carbonate (EC), dimethyl carbonate (DMC) and carbonic acid ethyl first
The 3 of ester (EMC)：3：The LiPF of 1 mol/L has been dissolved in 4 (volume ratio) mixed solvent6Composition.
[measure of discharge capacity]
Determine the discharge capacity of each test lithium secondary battery of above-mentioned structure.That is, under 25 DEG C of temperature conditionss, will
Upper voltage limit of constant current charge of each battery with electric current density as 3A/g to 4.3V, is then discharged with identical electric current density
To 2.5V, the discharge capacity of each battery is thus determined.Fig. 5 represents the discharge capacity for determining and is added to lithium manganese composite oxygen
The relation of the combination energy of the element M and oxygen of compound.
As shown in figure 5, use as the element M in above-mentioned formula (1), containing compared with Mn, Co, Ni, and the combination energy of oxygen
The electric discharge of the lithium secondary battery that the complex Li-Mn-oxide that the embodiment 1～4 of big element (Al, Ca, Fe or Zr) is related to builds
Capacity, more than using containing compared with Mn, Co, Ni, and the comparative example 2,3 of the element (Zn or Mg) that the combination of oxygen can be little is related to
The discharge capacity of the lithium secondary battery that complex Li-Mn-oxide builds, shows with excellent battery behavior.In addition, using not
The discharge capacity of the lithium secondary battery that the complex Li-Mn-oxide that the comparative example 1 containing element M is related to builds, it is first with conduct is used
The discharge capacity of the lithium secondary battery that the complex Li-Mn-oxide that the embodiment 3 that plain M contains Fe is related to builds is roughly the same
Numerical value, in consideration of it, show containing and oxygen combination can the material of big element M there is bigger discharge capacity.
2 ＞ of ＜ test examples
Formula：Lix(MnaCobNic)2-x-yMyO2 (1)
It has been respectively synthesized as the element M in above-mentioned formula (1), containing compared with Mn, Co, Ni, and the combination of oxygen can be big
Al, and the composition ratio (y) of the Al has been carried out the complex Li-Mn-oxide of various changes.
＜ embodiments 5：Synthesis (y=0.003) ＞ of complex Li-Mn-oxide
Among the complex Li-Mn-oxide represented by above-mentioned formula (1), composition ratio y of Al in embodiment 5, is synthesized
=0.003, Li1.2Mn0.52Co0.127Ni0.13Al0.003O2。
That is, as initiation material, Quilonorm (SKB) dihydrate [Li (CH are prepared3COO)·2H2O], nickel acetate (II) four be hydrated
Thing [Ni (CH3COO)2·4H2O], manganese acetate (II) tetrahydrate [Mn (CH3COO)2·4H2O] and aluminium acetate [Al
(CH3COO)3], carry out respectively weighing so that mixing quality ratio becomes above-mentioned composition ratio.Then, will be each starting for weighing former
Expect and as the glycolic (C of organic acid2H4O3) mix in water solvent, it is drying over night using drying machine, modulate gel
Raw mixture.Then, the raw mixture being dried is heated 5 hours at 500 DEG C, carries out false burning.After false burning, using wet
Formula ball mill is crushed, then is burnt till within 5 hours in 900 DEG C of heating, has thus synthesized the complex Li-Mn-oxide that embodiment 5 is related to
(Li1.2Mn0.52Co0.127Ni0.13Al0.003O2)。
＜ embodiments 6：Synthesis (y=0.005) ＞ of complex Li-Mn-oxide
Among the complex Li-Mn-oxide represented by above-mentioned formula (1), composition ratio y of Al in embodiment 6, is synthesized
=0.005, Li1.2Mn0.52Co0.125Ni0.13Al0.005O2。
That is, as initiation material, Quilonorm (SKB) dihydrate [Li (CH are prepared3COO)·2H2O], nickel acetate (II) four be hydrated
Thing [Ni (CH3COO)2·4H2O], manganese acetate (II) tetrahydrate [Mn (CH3COO)2·4H2O] and aluminium acetate [Al
(CH3COO)3], carry out respectively weighing so that mixing quality ratio becomes above-mentioned composition ratio.Then, will be each starting for weighing former
Expect and as the glycolic (C of organic acid2H4O3) mix in water solvent, it is drying over night using drying machine, modulate gel
Raw mixture.Then, the raw mixture being dried is heated 5 hours at 600 DEG C, carries out false burning.After false burning, using dry
Formula mortar is crushed, then is burnt till within 5 hours in 800 DEG C of heating, has thus synthesized the complex Li-Mn-oxide that embodiment 6 is related to
(Li1.2Mn0.52Co0.125Ni0.13Al0.005O2)。
＜ embodiments 7：Synthesis (y=0.008) ＞ of complex Li-Mn-oxide
Among the complex Li-Mn-oxide represented by above-mentioned formula (1), composition ratio y of Al in embodiment 7, is synthesized
=0.008, Li1.2Mn0.52Co0.122Ni0.13Al0.008O2。
That is, as initiation material, aluminium acetate [Al (CH are changed3COO)3] composition ratio, in addition, using with it is upper
The same step of embodiment 5 is stated, has synthesized the complex Li-Mn-oxide that embodiment 7 is related to
(Li1.2Mn0.52Co0.122Ni0.13Al0.008O2)。
＜ embodiments 8：Synthesis (y=0.026) ＞ of complex Li-Mn-oxide
Among the complex Li-Mn-oxide represented by above-mentioned formula (1), composition ratio y of Al in embodiment 8, is synthesized
=0.026, Li1.2Mn0.52Co0.104Ni0.13Al0.026O2。
That is, as initiation material, aluminium acetate [Al (CH are changed3COO)3] composition ratio, in addition, using with it is upper
The same step of embodiment 5 is stated, has synthesized the complex Li-Mn-oxide that embodiment 8 is related to
(Li1.2Mn0.52Co0.104Ni0.13Al0.026O2)。
Using the complex Li-Mn-oxide of the positive active material as above-mentioned synthesis, in the same manner as above-mentioned test example 1
The lithium secondary battery of test is built, discharge capacity is determined.Specifically, with by each battery with electric current density as 150mA/g
Constant current charge to 4.8V upper voltage limit, then the constant current with electric current density as 50mA/g discharge into 2.5V to follow
Ring, above-mentioned circulation is carried out, after a circulation, determining the discharge capacity of each battery in the scope of 4.3V～2.5V.By measurement result
It is shown in table 2.
Table 2
As shown in table 2, confirm to use the element M as in above-mentioned formula (1), containing compared with Mn, Co, Ni, with oxygen
With reference to Al that can be big, and the lithium that the complex Li-Mn-oxide that the composition ratio (y) of the Al has carried out various changes is built is secondary
The discharge capacity of battery, any one is all discharge capacity for more than 100mAh/g, and is related to using the comparative example 1 for not containing element M
And complex Li-Mn-oxide build lithium secondary battery discharge capacity compare it is larger.In addition, showing what embodiment 5 was related to
It is high about that complex Li-Mn-oxide becomes the discharge capacity compared with the complex Li-Mn-oxide for not containing element M that comparative example 1 is related to
30% positive active material for lithium secondary battery.
More than, the present invention is described in detail by, but the above-described embodiment and examples are only illustrated, it is disclosed herein
Comprising the form for above-mentioned concrete example being carried out various modifications, change in invention.For example, it is also possible to be electrode body constituent material
And/or the battery of the different various content of electrolyte.In addition, for the size and other compositions of the battery, it is also possible to root
Suitably change according to purposes (typically vehicle-mounted).
Utilization probability in industry
Using the complex Li-Mn-oxide obtained by the method for the present invention as the secondary electricity of the lithium that positive active material builds
Pond, as described above, even if using the reduction that can also suppress discharge capacity under high speed discharge and recharge, therefore can exist as being particularly
The motor (motor) carried by the vehicle of automobile etc. is used well with power supply.Therefore, the present invention provides such as Fig. 3 pattern earth's surfaces
Show the vehicle 1 for possessing lithium secondary battery (typically multiple being connected in series and the set of cells that formed) 100 like that as power supply
(the typically vapour for possessing motor of automobile, particularly hybrid vehicle, electric automobile, fuel cell car etc
Car).
Claims (6)
1. a kind of lithium secondary battery for possessing positive active material in positive pole, it is characterised in that the positive active material bag
The complex Li-Mn-oxide that (1) containing formula represents,
LixMnaCobNicMyO2 (1)
A, b, c in formula (1) be
0.5 ＜ a ＜ 0.65,
0 ＜ b,
0≤c,
X, y in formula (1) be
1 ＜ x ＜ 1.3,
0.001 ＜ y ＜ 0.03,
A+b+c=2-x-y,
Element M in the formula (1) is at least one element in Ca, Fe and Zr,
In the X-ray diffractogram of the complex Li-Mn-oxide, 2 θ values be 22 ° near position observe belong to containing
The peak of the compound of Mn.
2. the lithium secondary battery for possessing positive active material in positive pole according to claim 1, it is characterised in that described
Element M in formula (1) is Ca.
3. the lithium secondary battery for possessing positive active material in positive pole according to claim 1, it is characterised in that described
In formula (1), element M is Fe.
4. the lithium secondary battery for possessing positive active material in positive pole according to claim 1, it is characterised in that described
Element M in formula (1) is Zr.
5. a kind of positive active material, be Claims 1 to 4 any one described in the positive pole of lithium secondary battery just possess
Pole active substance.
6. a kind of vehicle, possesses the lithium secondary battery described in any one of Claims 1 to 4.
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