JP2018503238A - Multi-component material having an inclined structure for lithium ion battery, preparation method thereof, positive electrode of lithium ion battery and lithium ion battery - Google Patents
Multi-component material having an inclined structure for lithium ion battery, preparation method thereof, positive electrode of lithium ion battery and lithium ion battery Download PDFInfo
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- JP2018503238A JP2018503238A JP2017553292A JP2017553292A JP2018503238A JP 2018503238 A JP2018503238 A JP 2018503238A JP 2017553292 A JP2017553292 A JP 2017553292A JP 2017553292 A JP2017553292 A JP 2017553292A JP 2018503238 A JP2018503238 A JP 2018503238A
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- JP
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- Prior art keywords
- lithium ion
- ion battery
- salt solution
- component material
- lithium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 128
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 35
- 230000007423 decrease Effects 0.000 claims abstract description 19
- 239000002245 particle Substances 0.000 claims abstract description 19
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 12
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 4
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 4
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 4
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 4
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 4
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 4
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 4
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 4
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 4
- 239000012266 salt solution Substances 0.000 claims description 97
- 239000002243 precursor Substances 0.000 claims description 73
- 229910052751 metal Inorganic materials 0.000 claims description 55
- 239000002184 metal Substances 0.000 claims description 55
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 47
- 238000006243 chemical reaction Methods 0.000 claims description 39
- 150000003839 salts Chemical class 0.000 claims description 35
- 239000008139 complexing agent Substances 0.000 claims description 34
- 239000002244 precipitate Substances 0.000 claims description 34
- 239000003795 chemical substances by application Substances 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000012298 atmosphere Substances 0.000 claims description 24
- 230000001376 precipitating effect Effects 0.000 claims description 24
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 19
- 229910001882 dioxygen Inorganic materials 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- 229910052759 nickel Inorganic materials 0.000 claims description 17
- 229910013716 LiNi Inorganic materials 0.000 claims description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 14
- 229910052744 lithium Inorganic materials 0.000 claims description 14
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 11
- 230000035484 reaction time Effects 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- 229910052748 manganese Inorganic materials 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000002033 PVDF binder Substances 0.000 claims description 9
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 5
- 239000001099 ammonium carbonate Substances 0.000 claims description 5
- 239000006229 carbon black Substances 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims 2
- 238000010304 firing Methods 0.000 claims 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims 1
- 235000017557 sodium bicarbonate Nutrition 0.000 claims 1
- 229910052721 tungsten Inorganic materials 0.000 abstract description 3
- 229910052738 indium Inorganic materials 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 62
- 239000011572 manganese Substances 0.000 description 22
- 230000014759 maintenance of location Effects 0.000 description 20
- 239000000243 solution Substances 0.000 description 19
- 238000001816 cooling Methods 0.000 description 18
- 238000007873 sieving Methods 0.000 description 18
- 239000007774 positive electrode material Substances 0.000 description 16
- 239000008187 granular material Substances 0.000 description 15
- 238000003860 storage Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 9
- 229940044175 cobalt sulfate Drugs 0.000 description 9
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 9
- 238000005336 cracking Methods 0.000 description 9
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 238000000227 grinding Methods 0.000 description 8
- 229940099596 manganese sulfate Drugs 0.000 description 8
- 239000011702 manganese sulphate Substances 0.000 description 8
- 235000007079 manganese sulphate Nutrition 0.000 description 8
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 8
- 238000003801 milling Methods 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- 230000035939 shock Effects 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 7
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 6
- 238000001000 micrograph Methods 0.000 description 6
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 description 5
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 5
- 229940053662 nickel sulfate Drugs 0.000 description 5
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 5
- 230000000717 retained effect Effects 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 4
- 235000019341 magnesium sulphate Nutrition 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 3
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 3
- 229910021383 artificial graphite Inorganic materials 0.000 description 3
- 230000009172 bursting Effects 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000003411 electrode reaction Methods 0.000 description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 2
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 2
- 229910011328 LiNi0.6Co0.2Mn0.2O2 Inorganic materials 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 238000010280 constant potential charging Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000011565 manganese chloride Substances 0.000 description 2
- 235000002867 manganese chloride Nutrition 0.000 description 2
- 229940099607 manganese chloride Drugs 0.000 description 2
- KNLQKHUBPCXPQD-UHFFFAOYSA-N manganese;sulfuric acid Chemical compound [Mn].OS(O)(=O)=O KNLQKHUBPCXPQD-UHFFFAOYSA-N 0.000 description 2
- 238000013517 stratification Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 210000001217 buttock Anatomy 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229960002713 calcium chloride Drugs 0.000 description 1
- 235000011148 calcium chloride Nutrition 0.000 description 1
- 238000007600 charging Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229960003390 magnesium sulfate Drugs 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
- -1 nitric acid Aluminum Chemical compound 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-BJUDXGSMSA-N oxygen-15 atom Chemical compound [15O] QVGXLLKOCUKJST-BJUDXGSMSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- 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
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/11—Powder tap density
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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
本発明は、リチウムイオン電池用の傾斜構造を有する多成分材料、その調製方法、リチウムイオン電池の正極、およびリチウムイオン電池を提供する。本発明により提供されるリチウムイオン電池用の傾斜構造を有する多成分材料は、式（Ｉ）：ＬｉＮｉｘＣｏｙＭｎｚＧｄＯ２式（Ｉ）（式中、０．４≦ｘ≦０．９，０≦ｙ＋ｚ≦０．６，０≦ｄ≦０．１，ｘ＋ｙ＋ｚ＋ｄ＝１，ＧはＬｉ、Ｃｒ、Ｆｅ、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｂ、Ａｌ、Ｙ、Ｓｍ、Ｔｉ、Ｚｎ、Ｚｒ、Ｖ、Ｎｂ、Ｔａ、Ｍｏ及びＷ元素の１種以上である。）で示される平均組成を有し、リチウムイオン電池用の傾斜構造を有する多成分材料において、Ｎｉ元素の含有量は粒子の中心から表面まで連続的に減少する。本発明により提供されるリチウムイオン電池用の傾斜構造を有する多成分材料を使用するリチウムイオン電池は、高容量、改善されたサイクル性能及び安全性能を有し、比較的低コストである。【選択図】図４The present invention provides a multi-component material having an inclined structure for a lithium ion battery, a preparation method thereof, a positive electrode of a lithium ion battery, and a lithium ion battery. The multi-component material having a graded structure for a lithium ion battery provided by the present invention has the formula (I): LiNixCoyMnzGdO2 formula (I) (where 0.4 ≦ x ≦ 0.9, 0 ≦ y + z ≦ 0. 6, 0 ≦ d ≦ 0.1, x + y + z + d = 1, G is Li, Cr, Fe, Mg, Ca, Sr, Ba, B, Al, Y, Sm, Ti, Zn, Zr, V, Nb, Ta, In a multi-component material having an average composition represented by (1) Mo and W elements) and having an inclined structure for a lithium ion battery, the Ni element content is continuously from the center to the surface of the particles. Decrease. A lithium ion battery using a multi-component material having a graded structure for a lithium ion battery provided by the present invention has a high capacity, improved cycle performance and safety performance, and is relatively low cost. [Selection] Figure 4
Description
本発明は、リチウムイオン電池の技術分野に属する、リチウムイオン電池用の傾斜構造を有する多成分材料、その製造方法、リチウムイオン電池の正極、及びリチウムイオン電池に関する。 The present invention relates to a multi-component material having an inclined structure for a lithium ion battery, a manufacturing method thereof, a positive electrode of a lithium ion battery, and a lithium ion battery, which belong to the technical field of lithium ion batteries.
リチウムイオン電池は、現代社会においてますます広く適用され、現在、携帯電話、ラップトップコンピュータ、電動工具および電気自動車の分野で主に使用されている。大容量リチウムイオン電池に対する需要の増加に伴い、高い安全性、高エネルギー密度、高出力、長寿命、環境適合性を有し、低コストであるリチウムイオン電池の開発が急務となっている。 Lithium ion batteries are increasingly applied in modern society and are currently used mainly in the field of mobile phones, laptop computers, power tools and electric vehicles. As demand for large-capacity lithium-ion batteries increases, there is an urgent need to develop a low-cost lithium-ion battery that has high safety, high energy density, high output, long life, and environmental compatibility.
正極材料は、リチウムイオン電池の性能およびその価格の重要な要素である。現在、正極材料としては、ＬｉＣｏＯ２、ＬｉＮｉＯ２、ＬｉＮｉｘＣｏ１−ｘＯ２、ＬｉＮｉｘＣｏｙＭｎ１−ｘ−ｙＯ２、ＬｉＭｎ２Ｏ４，およびＬｉＦｅＰＯ４が主に挙げられ、その中でＬｉＣｏＯ２は、その安定した性能と容易な合成方法により商業化を実現した最初のもので、現在でも広く使用されている正極材料であるが、限られたＣｏ資源は材料の高コスト化につながり、いくつかの新興市場ではその適用に制限を課してしまう。ＬｉＮｉＯ２は、高容量であるが製造が困難であり、その性能は一貫性および再現性が低く、安全性の重大な問題がある。ＬｉＮｉｘＣｏ１−ｘＯ２は、ＬｉＮｉＯ２とＬｉＣｏＯ２の固溶体と考えられ、一時期、ＬｉＣｏＯ２を、ＬｉＮｉＯ２とＬｉＣｏＯ２の両方の利点で置き換えられる可能性が最も高い、新しい正極材料とされていたが、合成が難しい、安全性に劣る等の欠点があり、その総合的な特性が改善されるべきである。立方晶スピネル構造のＬｉＭｎ２Ｏ４は、低コストであるが、低容量および劣化しやすいなどの欠点を有する。また、オリビン構造のＬｉＦｅＰＯ４は、低電圧および低密度などの欠点を有する。
The positive electrode material is an important factor in the performance of a lithium ion battery and its price. Currently, as the cathode material, LiCoO 2, LiNiO 2, LiNi x Co 1-x
層状構造は、Ｌｉ＋の可逆的インターカレーション／デインターカレーションに有利であるため、低コスト、より高い環境適合性、および、より良い性能を有する層状構造の正極材料を開発することが望まれる。近年、ＬｉＮｉＯ２、ＬｉＣｏＯ２、ＬｉＭｎ２Ｏ４および他の材料の利点（例えば、高容量、良好なサイクル性能、優れたレート特性および熱安定性）を組み合わせるために、ニッケルリッチな正極材料（層状ＬｉＮｉｘＣｏｙＭｎ１−ｘ−ｙＯ２）に関する研究がますます脚光を浴びており、広範な商業的用途に使用される価値が高い。 Since the layered structure is advantageous for the reversible intercalation / deintercalation of Li + , it is desirable to develop a cathode material with a layered structure that has lower cost, higher environmental compatibility, and better performance. It is. In recent years, nickel-rich cathode materials (layered) have been combined to combine the advantages of LiNiO 2 , LiCoO 2 , LiMn 2 O 4 and other materials (eg, high capacity, good cycle performance, excellent rate characteristics and thermal stability). Research on LiNi x Co y Mn 1-xy O 2 ) is increasingly in the spotlight and is of great value for use in a wide range of commercial applications.
層状のＬｉＮｉｘＣｏｙＭｎ１−ｘ−ｙＯ２において、Ｎｉ含有量の増加は、比容量を改善することができ、例えば、ＬｉＮｉ０．８Ｃｏ０．１Ｍｎ０．１Ｏ２の可逆容量は、ＬｉＣｏＯ２の比容量（約１４５ｍＡｈ／ｇ）をはるかに上回る約１９０ｍＡｈ／ｇまであり得る。しかし、そのサイクル性能と安全性能は幾分低下し、実用上の制限が課される。 In layered LiNi x Co y Mn 1-xy O 2 , increasing the Ni content can improve the specific capacity, for example, reversibility of LiNi 0.8 Co 0.1 Mn 0.1 O 2 . The capacity can be up to about 190 mAh / g, far exceeding the specific capacity of LiCoO 2 (about 145 mAh / g). However, its cycle performance and safety performance are somewhat degraded and impose practical limitations.
第１に、上記ニッケルリッチな正極材料は、充放電の繰返しが進む間に、体積変化に伴う結晶構造の大きな相転移を起こしやすく、結果的に結晶層の空間が部分的に崩壊し、リチウムイオンのインターカレーション／デインターカレーションを阻害し、分極抵抗が増大するとともにサイクル性能が低下する。従来技術において、ニッケルリッチな正極材料の合成条件を最適化することにより上記の問題を解決する試みがなされているが、結果として満足できるものではない。これは、作製したニッケルリッチな正極材料が、結晶構造の相転移とともに、加熱時のリチウム欠乏相の相転移および分解とを根本的に防ぐことができず、繰返しの充放電サイクルによるサイクル性能の激しい劣化の問題に対応できないためである。 First, the nickel-rich positive electrode material is likely to undergo a large phase transition of the crystal structure accompanying volume change during repeated charge and discharge, resulting in partial collapse of the crystal layer space, Ion intercalation / deintercalation is inhibited, and the polarization resistance increases and the cycle performance decreases. In the prior art, attempts have been made to solve the above problems by optimizing the synthesis conditions of the nickel-rich positive electrode material, but this is not satisfactory as a result. This is because the produced nickel-rich positive electrode material cannot fundamentally prevent the phase transition and decomposition of the lithium-deficient phase during heating together with the phase transition of the crystal structure, and the cycle performance due to repeated charge and discharge cycles This is because the problem of severe deterioration cannot be dealt with.
第２に、上記ニッケルリッチな正極材料を作製する工程の間に、ニッケルとリチウムとが混在して配置される可能性が高く、反応後に粒子の表面上および粒子間に残存するＬｉの量が増加し；Ｌｉ２ＣＯ３およびＬｉＯＨの形で存在する残存したＬｉは、貯蔵またはリサイクル中に分解してＣＯ２などのガスを生成し、電池が膨張して高温になる場合、安全性の低下につながる可能性がある。 Secondly, during the step of producing the nickel-rich positive electrode material, there is a high possibility that nickel and lithium are mixed and the amount of Li remaining on the surface of the particles and between the particles after the reaction is small. Increased; remaining Li present in the form of Li 2 CO 3 and LiOH decomposes during storage or recycling to produce gases such as CO 2 , reducing safety when the battery expands to high temperatures May lead to
特許出願ＣＮ１７７８００３は、式Ｌｉｙ（ＮｉｘＣｏ１−２ｘＭｎｘ）Ｏ２（式中、０．０２５≦ｘ≦０．５）で示される組成を有する正極材料を開示しており、サイクル性能および安全性能は良好であるが、ニッケル含有量が低いため、比容量が低い。特許出願ＣＮ１０１３００６９６は、式Ｌｉｘ（Ｎｉ１−ａ−ｂ（Ｎｉ１／２Ｍｎ１／２）ａＣｏｂＡｋ）ｙＯ２（式中、０．４≦Ｎｉ≦０．７，０．１≦Ｃｏ≦０．４，０．０５≦Ｍｎ≦０．６）で示される組成を有する別の正極材料を開示しており、ニッケル含有量および比容量の両方がある程度改善されるが、サイクル性能および安全性能は劣る。
Patent application CN 1777003 discloses a positive electrode material having a composition represented by the formula Li y (Ni x Co 1-2x Mn x ) O 2 , where 0.025 ≦ x ≦ 0.5, and cycle performance And the safety performance is good, but the specific capacity is low due to the low nickel content. Patent CN101300696 has the formula Li x (Ni 1-a- b (
本発明は、リチウムイオン電池用の傾斜構造を有する多成分材料を提供する。多成分材料を用いて製造されたリチウムイオン電池は、高容量、改善されたサイクル性能、及び安全性能を有し、比較的低コストである。 The present invention provides a multi-component material having an inclined structure for a lithium ion battery. Lithium ion batteries made using multi-component materials have high capacity, improved cycle performance, and safety performance, and are relatively low cost.
また、本発明は、上記リチウムイオン電池用の傾斜構造を有する多成分材料の調製方法を提供し、これは、単純なプロセス、比較的低コストで、かつ連続性を有し、したがって工業生産に好適である。 The present invention also provides a method for preparing a multi-component material having a graded structure for the lithium ion battery, which has a simple process, a relatively low cost, and has continuity, and thus is suitable for industrial production. Is preferred.
また、本発明は、リチウムイオン電池用の傾斜構造を有する上記多成分材料から作製されたリチウムイオン電池の正極を提供する。 Moreover, this invention provides the positive electrode of the lithium ion battery produced from the said multi-component material which has the inclination structure for lithium ion batteries.
また、本発明は、上記リチウムイオン電池の正極を含み、高容量であるとともに、優れたサイクル性能及び安全性能を有するリチウムイオン電池を提供する。 Moreover, this invention provides the lithium ion battery which has the positive electrode of the said lithium ion battery, is high capacity | capacitance, and has the outstanding cycling performance and safety | security performance.
本発明によって提供される、リチウムイオン電池用の傾斜構造を有する多成分材料は、式（Ｉ）： A multi-component material having a graded structure for a lithium ion battery provided by the present invention has the formula (I):
ＬｉＮｉｘＣｏｙＭｎｚＧｄＯ２ 式（Ｉ） LiNi x Co y Mn z G d O 2 Formula (I)
（式中、０．４≦ｘ≦０．９，０≦ｙ＋ｚ≦０．６，０≦ｄ≦０．１，ｘ＋ｙ＋ｚ＋ｄ＝１，Ｇは、Ｌｉ、Ｃｒ、Ｆｅ、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｂ、Ａｌ、Ｙ、Ｓｍ、Ｔｉ、Ｚｎ、Ｚｒ、Ｖ、Ｎｂ、Ｔａ、Ｍｏ、Ｗ元素の１種以上である。）で示される平均組成を有し、リチウムイオン電池用の傾斜構造を有する多成分材料において、Ｎｉ元素の含有量が粒子の中心から表面に向かって連続的に減少する。 (In the formula, 0.4 ≦ x ≦ 0.9, 0 ≦ y + z ≦ 0.6, 0 ≦ d ≦ 0.1, x + y + z + d = 1, G is Li, Cr, Fe, Mg, Ca, Sr, Ba , B, Al, Y, Sm, Ti, Zn, Zr, V, Nb, Ta, Mo, and W elements)), and an inclined structure for a lithium ion battery. In the multicomponent material, the Ni element content continuously decreases from the center of the particle toward the surface.
本発明によって提供される、リチウムイオン電池用の傾斜構造を有する多成分材料は、球状粒子であり；Ｎｉ元素の含有量は粒子の中心から表面に向かって連続的かつ単調に減少する。このＮｉ含有量の傾斜を有する粒状の正極材料は、その中心部が高いＮｉ含有量を有し、正極材料の高い比容量という要望を達成でき；一方、粒子表面のＮｉの含有量が比較的少ないことから、原料粒子表面の電極反応が弱く、そのため、正極材料のサイクル性能と安全性能の要求を同時に満たすことができる。また、粒状材料中のＮｉ元素の含有量が中心から表面にかけて連続的に変化するため、電極反応において、Ｎｉ元素の含有量の急激な低下による層状化が起こらず、正極材料から作製された電極の安全性能をさらに保障する。 The multi-component material having a graded structure for lithium ion batteries provided by the present invention is a spherical particle; the content of Ni element decreases continuously and monotonically from the center of the particle toward the surface. This granular positive electrode material having a Ni content gradient has a high Ni content at the center, and can achieve the demand for a high specific capacity of the positive electrode material; Therefore, the electrode reaction on the surface of the raw material particles is weak, so that the requirements for the cycle performance and safety performance of the positive electrode material can be satisfied at the same time. Further, since the content of Ni element in the granular material continuously changes from the center to the surface, the electrode reaction does not cause stratification due to a rapid decrease in the Ni element content, and the electrode is made from the positive electrode material. Further ensure the safety performance.
また、リチウムイオン電池用の傾斜構造を有する多成分材料のメジアン径は、３〜２５μｍであり、メジアン径は、粒子径、すなわち、５０％の分布率に対応する粒子径を意味し、それは実際に要求されるように具体的に調整することができる。リチウムイオン電池用の傾斜構造を有する多成分材料のタップ密度は、１．５〜３．０ｇ／ｃｍ３である。また、本発明の正極材料から作製した電池は、従来の正極材料と比較して、同じ電池体積でより大きな容量を有し、これはリチウムイオン電池の軽量化に寄与する。 Moreover, the median diameter of the multi-component material having an inclined structure for a lithium ion battery is 3 to 25 μm, and the median diameter means a particle diameter, that is, a particle diameter corresponding to a distribution ratio of 50%. Can be specifically adjusted as required. The tap density of the multicomponent material having an inclined structure for a lithium ion battery is 1.5 to 3.0 g / cm 3 . Moreover, the battery produced from the positive electrode material of this invention has a larger capacity | capacitance with the same battery volume compared with the conventional positive electrode material, and this contributes to the weight reduction of a lithium ion battery.
本発明により提供されるリチウムイオン電池用の傾斜構造を有する多成分材料は、Ｎｉ、Ｃｏ、ＭｎおよびＧ元素の１種以上を含む金属塩をＮｉ含有金属塩溶液に徐々に添加して、沈殿剤および錯化剤と沈殿反応させ、その後酸素ガスを含む雰囲気中で沈殿生成物とリチウム源とを焼結する。 The multi-component material having an inclined structure for a lithium ion battery provided by the present invention is obtained by gradually adding a metal salt containing one or more of Ni, Co, Mn and G elements to a Ni-containing metal salt solution, Then, the precipitation product and the lithium source are sintered in an atmosphere containing oxygen gas.
また、本発明は、リチウムイオン電池用の傾斜構造を有する上記多成分材料の調製方法であって、以下の工程： The present invention is also a method for preparing the multi-component material having an inclined structure for a lithium ion battery, which comprises the following steps:
（１）Ｎｉ含有金属塩を水に溶解して第１塩溶液を調製し、Ｎｉ、Ｃｏ、ＭｎおよびＧ元素の１種以上を含む金属塩を水に溶解して第２塩溶液を調製する工程； (1) A first salt solution is prepared by dissolving a Ni-containing metal salt in water, and a second salt solution is prepared by dissolving a metal salt containing one or more of Ni, Co, Mn and G elements in water. Process;
（２）混合塩溶液を得るために、撹拌しながら第２塩溶液を第１塩溶液中に徐々に添加して、次いで、混合塩溶液、錯化剤および沈殿剤を反応器に同時に注入し、ｐＨ値を８〜１３、反応温度を４０〜８０℃、反応時間を５〜５０時間に制御することにより前駆体沈殿物を得、前駆体沈殿物を濾過、洗浄、熱処理した後、傾斜構造を有する多成分材料の前駆体を得る工程； (2) To obtain a mixed salt solution, the second salt solution is gradually added into the first salt solution with stirring, and then the mixed salt solution, complexing agent and precipitating agent are simultaneously injected into the reactor. The precursor precipitate is obtained by controlling the pH value to 8 to 13, the reaction temperature to 40 to 80 ° C., and the reaction time to 5 to 50 hours, and after the precursor precipitate is filtered, washed, and heat-treated, a gradient structure is obtained. Obtaining a precursor of a multi-component material having:
（３）傾斜構造を有する多成分材料の前駆体とリチウム源とを均一に混合し、空気または酸素ガスの反応雰囲気中で、５００〜１１００℃で４〜３０時間焼結し、好ましくは７００〜１０００℃で７〜２０時間焼結し、粉砕を行い、リチウム電池用の傾斜構造を有する多成分材料を得る工程
を含む。
(3) A precursor of a multi-component material having an inclined structure and a lithium source are uniformly mixed and sintered in a reaction atmosphere of air or oxygen gas at 500 to 1100 ° C. for 4 to 30 hours, preferably 700 to It includes a step of sintering at 1000 ° C. for 7 to 20 hours, pulverizing, and obtaining a multicomponent material having an inclined structure for a lithium battery.
この際、混合塩溶液中のＮｉ元素の濃度は、第２塩溶液の添加に伴って徐々に減少し、錯化剤と沈殿剤の作用により、粒状の沈殿物が生成し、ここで、最初に反応したＮｉが粒子の中心部に析出し、その後に反応した金属元素は粒子の周辺に沿って徐々に成長しながら、リチウムイオン電池用の傾斜構造を有する上記多成分材料を形成する。第２塩溶液を徐々に添加すると、Ｎｉ濃度が徐々に低下し、調製された材料中のＮｉ元素の含有量が粒子の中心から表面に向かって連続的に減少する。 At this time, the concentration of Ni element in the mixed salt solution gradually decreases with the addition of the second salt solution, and a granular precipitate is formed by the action of the complexing agent and the precipitating agent. Ni reacting with (1) precipitates in the center of the particle, and the metal element reacted thereafter gradually grows along the periphery of the particle to form the multi-component material having an inclined structure for a lithium ion battery. When the second salt solution is gradually added, the Ni concentration gradually decreases, and the content of Ni element in the prepared material continuously decreases from the center of the particle toward the surface.
さらに、第１塩溶液Ｒ１は、Ｎｉ以外の元素、例えば、Ｃｏ、ＭｎおよびＧ元素の１種以上を含んでいてもよい。 Furthermore, the first salt solution R1 may contain one or more elements other than Ni, for example, Co, Mn, and G elements.
さらに、第２塩溶液Ｒ２を第１塩溶液に、混合塩溶液を反応器に添加する流速の０．１〜０．６倍の流速で添加し、撹拌する。換言すれば、反応器に注入される混合塩溶液の流速をｖとすると、第１塩溶液に注入される第２塩溶液の流速は０．１ｖ〜０．６ｖである。 Further, the second salt solution R2 is added to the first salt solution and stirred at a flow rate of 0.1 to 0.6 times the flow rate at which the mixed salt solution is added to the reactor. In other words, when the flow rate of the mixed salt solution injected into the reactor is v, the flow rate of the second salt solution injected into the first salt solution is 0.1 v to 0.6 v.
上記の方法において、金属塩は、可溶性金属塩、例えば、硫酸塩、塩化物、硝酸塩および酢酸塩の１種以上である。 In the above method, the metal salt is one or more of a soluble metal salt, for example, sulfate, chloride, nitrate and acetate.
錯化剤は、ＥＤＴＡ、アンモニア水、塩化アンモニウム、硫酸アンモニウム、硝酸アンモニウム、クエン酸アンモニウムおよびエチレンジアミンのうちの１種以上である。錯化剤対総金属塩の比は、錯化平衡の原理または実際の要求に従って決定してよく、例えば錯化剤対総金属塩のモル比は通常０．１：１〜３：１であり、ここで、総金属塩とは、Ｒ１およびＲ２に含まれる金属塩の総モル数を意味する。 The complexing agent is at least one of EDTA, aqueous ammonia, ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium citrate and ethylenediamine. The ratio of complexing agent to total metal salt may be determined according to the principle of complexation equilibrium or actual requirements, for example the molar ratio of complexing agent to total metal salt is usually 0.1: 1 to 3: 1. Here, the total metal salt means the total number of moles of metal salts contained in R1 and R2.
沈殿剤は、ＯＨ−、ＣＯ３ ２−等を含む化合物であり、例えば、水酸化ナトリウム、水酸化カリウム、水酸化リチウム、重炭酸アンモニウム、炭酸アンモニウム、重炭酸ナトリウムおよび炭酸ナトリウムのうちの１種以上であり、金属と沈殿物を形成できる。沈殿剤対総金属塩の比は、反応平衡の原理または実際の需要に従って決定してよく、例えば、沈殿剤対総金属塩のモル比は、通常１：１〜２．５：１であってよく、ここで、総金属塩とは、Ｒ１およびＲ２に含まれる金属塩の総モル数を意味する。 The precipitant is a compound containing OH − , CO 3 2−, and the like, for example, one kind of sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium bicarbonate, ammonium carbonate, sodium bicarbonate, and sodium carbonate. As described above, a precipitate can be formed with the metal. The ratio of precipitant to total metal salt may be determined according to the principle of reaction equilibrium or actual demand; for example, the molar ratio of precipitant to total metal salt is usually 1: 1 to 2.5: 1. Well, here, the total metal salt means the total number of moles of metal salts contained in R1 and R2.
上記調製方法において、工程（２）の熱処理は、７０〜１５０℃で乾燥させてもよく、また、酸素ガスを含む雰囲気中で３００〜７００℃で焼成してもよい。 In the said preparation method, the heat processing of a process (2) may be dried at 70-150 degreeC, and may be baked at 300-700 degreeC in the atmosphere containing oxygen gas.
リチウム源は、リチウムイオン電池の正極材料を調製するために典型的に使用されるリチウム源であり、例えば、リチウム源は、炭酸リチウム、水酸化リチウムおよび硝酸リチウムのうちの１種以上である。 The lithium source is a lithium source typically used to prepare a positive electrode material for a lithium ion battery. For example, the lithium source is one or more of lithium carbonate, lithium hydroxide, and lithium nitrate.
また、本発明は、リチウムイオン電池用の傾斜構造を有する上記多成分材料から調製されたリチウムイオン電池の正極を提供する。調製方法は、従来技術の方法を参照してよい。例えば、上記リチウムイオン電池用の傾斜構造を有する多成分材料を、カーボンブラックとポリフッ化ビニリデン（ＰＶＤＦ）と重量比９４％：３％：３％でブレンドしてコーティングして電極板を形成することで、リチウムイオン電池の正極を作製してもよい。 Moreover, this invention provides the positive electrode of the lithium ion battery prepared from the said multi-component material which has the inclination structure for lithium ion batteries. The preparation method may refer to a prior art method. For example, a multi-component material having an inclined structure for the above lithium ion battery is blended and coated with carbon black and polyvinylidene fluoride (PVDF) at a weight ratio of 94%: 3%: 3% to form an electrode plate. Thus, a positive electrode of a lithium ion battery may be produced.
また、本発明は、上記リチウムイオン電池の正極と、人造黒鉛を用いた負極と、正極と負極との間のセパレータを備え、これらはロールされて電解液が注入されて形成するリチウムイオン電池を提供する。作製されたリチウムイオン電池の電気化学的性能及び安全性能は、関連する規格に従って試験してよい。 The present invention also includes a positive electrode of the lithium ion battery, a negative electrode using artificial graphite, and a separator between the positive electrode and the negative electrode, which are formed by being rolled and injected with an electrolyte. provide. The electrochemical and safety performance of the fabricated lithium ion battery may be tested according to relevant standards.
本発明は以下の利点を有する： The present invention has the following advantages:
１．本発明によって提供される、リチウムイオン電池用の傾斜構造を有する多成分材料は、ニッケル、コバルト、マンガンおよび他の元素の特性を十分に利用し、Ｎｉ元素の含有量が粒子の中心から表面に向かって連続的に減少する；製造された電極は高い比容量を有し、かつ、優れた高温サイクル性能及び安全性能を有する。 1. The multi-component material having an inclined structure for a lithium ion battery provided by the present invention fully utilizes the characteristics of nickel, cobalt, manganese and other elements, and the content of Ni element is from the center of the particle to the surface. The manufactured electrode has a high specific capacity and has excellent high temperature cycle performance and safety performance.
２．本発明により提供されるリチウムイオン電池用の傾斜構造を有する多成分材料においては、粒状多成分材料のＮｉ元素の含有量が内側から外側に連続的に減少することにより、電極反応の進行中の層状化を効率的に回避することが実現される。 2. In the multi-component material having an inclined structure for a lithium ion battery provided by the present invention, the content of Ni element in the granular multi-component material continuously decreases from the inside to the outside, so that the electrode reaction is in progress. Efficient avoidance of stratification is realized.
３．本発明により提供される、リチウムイオン電池用の傾斜構造を有する多成分材料は、調製プロセスが簡単で、設備に対する要求が少なく、比較的低コストであり、したがって工業化に適している。 3. The multi-component material having a graded structure for lithium-ion batteries provided by the present invention is simple in the preparation process, requires little equipment, is relatively low cost, and is therefore suitable for industrialization.
本発明の実施形態の目的、技術的解決策および利点を、より明確に説明するために、本発明の実施形態における技術的解決策を、本発明の実施形態に伴う図面と併せて以下のように明瞭かつ完全に説明する。そして明らかに、記載された実施形態は、本発明のすべての実施形態ではなく一部に過ぎない。創造的努力をすることなく本発明の実施形態に基づいて当業者によって得られる他のすべての実施形態は、本発明の権利範囲に該当する。 In order to more clearly describe the objects, technical solutions and advantages of the embodiments of the present invention, the technical solutions in the embodiments of the present invention are described below in conjunction with the drawings accompanying the embodiments of the present invention. To be clear and complete. And clearly, the described embodiments are only a part rather than all of the embodiments of the present invention. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the scope of the present invention.
実施形態１
硫酸ニッケルを溶解して１．５ｍｏｌ／Ｌの第１塩溶液Ｒ１を３００Ｌ得；硫酸コバルトと硫酸マンガンとを０．５：０．５の金属モル比で溶解させて１．５ｍｏｌ／Ｌの第２塩溶液Ｒ２を得；錯化剤Ｃとして５．０ｍｏｌ／Ｌのアンモニアの水溶液と、沈殿剤Ｄとして８ｍｏｌ／Ｌの水酸化ナトリウム溶液を調製し；第１塩溶液Ｒ１を撹拌器を備えた容器に入れる。 Nickel sulfate is dissolved to obtain 300 L of a 1.5 mol / L first salt solution R1; cobalt sulfate and manganese sulfate are dissolved at a metal molar ratio of 0.5: 0.5 to obtain a 1.5 mol / L first salt solution R1. 2 salt solution R2 is obtained; 5.0 mol / L aqueous ammonia solution as complexing agent C and 8 mol / L sodium hydroxide solution as precipitating agent D are prepared; first salt solution R1 is equipped with a stirrer Place in a container.
混合塩溶液を得るために、第２塩溶液Ｒ２を第１塩溶液Ｒ１に６．６７Ｌ／ｈの流速で撹拌しながら添加し；次いで、混合塩溶液、沈殿剤Ｄおよび錯化剤Ｃを同時に反応器Ａに添加して反応させ、ここで、反応器Ａへ混合塩溶液を添加する流速は１６．６６Ｌ／ｈであり、この反応プロセスは図１に示されたとおりであり、窒素雰囲気の保護下で、反応のｐＨを１１．３、反応温度を５０℃、錯化剤のアンモニア水対総金属塩のモル比が１：１、反応時間は３０時間に制御しながら反応させることにより、前駆体沈殿物を得る。 To obtain the mixed salt solution, the second salt solution R2 is added to the first salt solution R1 with stirring at a flow rate of 6.67 L / h; then the mixed salt solution, the precipitating agent D and the complexing agent C are simultaneously added. The reaction is performed by adding to the reactor A, where the flow rate of adding the mixed salt solution to the reactor A is 16.66 L / h, and this reaction process is as shown in FIG. Under the protection, the reaction pH is 11.3, the reaction temperature is 50 ° C., the molar ratio of ammonia water of the complexing agent to the total metal salt is 1: 1, and the reaction time is controlled to 30 hours, A precursor precipitate is obtained.
前駆体沈殿物を濾過し、洗浄し、１２０℃で乾燥させることにより、多成分材料の前駆体を得る。前駆体を水酸化リチウムと１：１．０５のモル比で完全に混合し、空気雰囲気中、８９０℃で１０時間保持する。自然冷却、粉砕および篩い分けを行い、それによって傾斜構造を有する球状の多成分材料を得る。 The precursor precipitate is filtered, washed and dried at 120 ° C. to obtain a multi-component material precursor. The precursor is thoroughly mixed with lithium hydroxide at a molar ratio of 1: 1.05 and held at 890 ° C. for 10 hours in an air atmosphere. Natural cooling, grinding and sieving are performed, thereby obtaining a spherical multi-component material having an inclined structure.
本実施形態で調製した材料は、ＬｉＮｉ０．６Ｃｏ０．２Ｍｎ０．２Ｏ２の組成を有し、粒状材料の中心におけるＮｉ元素の含有量が１００ｍｏｌ％であり、Ｎｉ元素の含有量が内側から外側に連続的に減少し、粒状材料は球形であって；試験すると、メジアン径は１５．３μｍであり、タップ密度は２．５５ｇ／ｃｍ３である。 The material prepared in the present embodiment has a composition of LiNi 0.6 Co 0.2 Mn 0.2 O 2 , the content of Ni element at the center of the granular material is 100 mol%, and the content of Ni element Continuously decreasing from the inside to the outside, the granular material is spherical; when tested, the median diameter is 15.3 μm and the tap density is 2.55 g / cm 3 .
上記のリチウムイオン電池用の傾斜構造を有する多成分材料を、カーボンブラックとポリフッ化ビニリデン（ＰＶＤＦ）と重量比９４％：３％：３％でブレンドし、コーティングして電極板を形成し、このように作製したリチウムイオン電池の正極、負極として人造黒鉛を用いた電極、正極と負極の間のセパレータを、ロールしてから電解液を注入して、角形のアルミニウムシェル電池０５３０４８を形成した。これは、具体的には先行技術の作製方法を参照することができる。 The above multi-component material having an inclined structure for a lithium ion battery is blended with carbon black and polyvinylidene fluoride (PVDF) at a weight ratio of 94%: 3%: 3%, and coated to form an electrode plate. Thus, the positive electrode of the lithium ion battery produced, the electrode using artificial graphite as the negative electrode, the separator between the positive electrode and the negative electrode was rolled, and then the electrolyte solution was injected to form a square aluminum shell battery 053048. Specifically, reference can be made to a prior art manufacturing method.
リチウムイオンのための国家規格ＧＢ／Ｔ１８２８７−２０００に従って製造されたリチウムイオン電池の電気化学的性能と安全性能を試験する。試験は具体的には次のとおりである： Test the electrochemical and safety performance of lithium-ion batteries manufactured according to national standard GB / T18287-2000 for lithium-ion. The test is specifically as follows:
比放電容量 Specific discharge capacity
０．２Ｃ５Ａ充放電の間、放電状態で１ｇの正極材料によって放出される容量で、単位はｍＡｈ／ｇである。試験すると、本実施形態によって調製されたリチウムイオン電池用の傾斜構造を有する多成分材料は、１７１ｍＡｈ／ｇの比放電容量を有する。 The capacity discharged by 1 g of positive electrode material in the discharged state during 0.2 C 5 A charge / discharge, the unit is mAh / g. When tested, the multicomponent material having a graded structure for a lithium ion battery prepared according to this embodiment has a specific discharge capacity of 171 mAh / g.
１Ｃ５Ａ充放電サイクル 1C 5 A charge / discharge cycle
２０±５℃で１Ｃ５Ａで４．２Ｖまで充電を行い、充電電流≦０．０１Ｃ５Ａになるまで定電圧充電に切り替え、１Ｃ５Ａで２．７５Ｖまでで放電して１サイクルとした後、１Ｃ５Ａ充放電を繰り返す。試験すると、本実施形態により調製されたリチウムイオン電池用の傾斜構造を有する多成分材料は、１Ｃ５Ａかつ常温で充放電サイクルを１００回した後、容量維持率が９５％で、常温で良好なサイクル性能を有す。 Charge to 4.2V at 1C 5 A at 20 ± 5 ° C, switch to constant voltage charging until charging current ≤ 0.01C 5 A, and discharge to 2.75V at 1C 5 A to make one cycle Then, 1C 5 A charge / discharge is repeated. When tested, the multi-component material having a tilted structure for a lithium ion battery prepared according to this embodiment has a capacity retention rate of 95% and is good at room temperature after 1C 5 A and 100 times of charge / discharge cycles at room temperature. Cycle performance.
１Ｃ５Ａでの高温充放電サイクル High-temperature charge / discharge cycle at 1C 5 A
４５±２℃で、１Ｃ５Ａで４．２Ｖまで充電を行い、充電電流≦０．０１Ｃ５Ａになるまで定電圧充電に切り替え、１Ｃ５Ａで２．７５Ｖまで放電することを１サイクルした後、１Ｃ５Ａの充放電を繰り返す。試験すると、本実施形態によって調製されたリチウムイオン電池用の傾斜構造を有する多成分材料は、４５℃で１００サイクル後、容量維持率が９２％で、高温で良好なサイクル性能を有する。 In 45 ± 2 ° C., at 1C 5 A to 4.2V and charges, switching to the constant voltage until the charge current ≦ 0.01 C 5 A, and one cycle to discharge 1C 5 A to 2.75V Then, 1C 5 A charge / discharge is repeated. When tested, the multi-component material having a graded structure for a lithium ion battery prepared according to the present embodiment has a capacity retention rate of 92% after 100 cycles at 45 ° C. and has good cycle performance at high temperatures.
８５℃の高温保存後の電池厚みの変化率 Change rate of battery thickness after high temperature storage at 85 ℃
２０±５℃において、０．２Ｃ５Ａで４．２Ｖまで充電を行い、充電電流≦０．０１Ｃ５Ａになるまで定電圧充電に切り替え、１Ｃ５Ａで２．７５Ｖまで放電して１サイクルとした後、１Ｃ５Ａの充放電サイクルを行い、電池が３サイクル目の充電状態のとき、電池を取り出して初期の厚みを測定し；その後、８５±５℃で４時間放置してその厚さを測定し；電池の厚み変化率を算出する。試験すると、本実施形態により調製されたリチウムイオン電池用の傾斜構造を有する多成分材料は、８５℃の高温下で４時間保存した後の電池厚みの増加率が６．７％であり、高温時の電池膨れが小さい。 At 20 ± 5 ° C, charge up to 4.2V at 0.2C 5 A, switch to constant voltage charge until charge current ≤ 0.01C 5 A, discharge to 2.75V at 1C 5 A, 1 cycle 1C 5 A charge / discharge cycle was performed, and when the battery was charged in the third cycle, the battery was taken out and the initial thickness was measured; then, the thickness was left at 85 ± 5 ° C. for 4 hours. The thickness change rate of the battery is calculated. When tested, the multi-component material having a graded structure for a lithium ion battery prepared according to this embodiment has an increase rate of the battery thickness of 6.7% after being stored at a high temperature of 85 ° C. for 4 hours. Battery swelling is small.
ホットオーブン中の１５０℃における熱衝撃 Thermal shock at 150 ° C in a hot oven
２０±５℃で、０．２Ｃ５Ａで４．２Ｖまで充電を行い、充電電流≦０．０１Ｃ５Ａになるまで定電圧充電に切り替え、１Ｃ５Ａで２．７５Ｖまで放電して１サイクルとした後、１Ｃ５Ａの充放電サイクルを行い、電池が３サイクル目の充電状態のとき、電池を取り出してオーブンに入れ、５℃／分の昇温速度で１５０℃に加熱し、１５０℃で電池が破裂する時間を調べる。試験すると、本実施形態により調製されたリチウムイオン電池用の傾斜構造を有する多成分材料は、６０分以内に破裂または割れがなく、ホットオーブン中１５０℃での熱衝撃試験結果が示すように、安全性が良好である。 At 20 ± 5 ° C, charge to 4.2V at 0.2C 5 A, switch to constant voltage charging until charge current ≤ 0.01C 5 A, discharge to 2.75V at 1C 5 A, 1 cycle 1C 5 A charge / discharge cycle was performed, and when the battery was in the charge state of the third cycle, the battery was taken out and placed in an oven and heated to 150 ° C. at a rate of 5 ° C./min. Find out how long the battery will explode. When tested, the multi-component material having a graded structure for a lithium ion battery prepared according to the present embodiment has no rupture or cracking within 60 minutes, and the results of a thermal shock test at 150 ° C. in a hot oven show that Good safety.
上記の試験データから、本実施形態によって調製されたリチウムイオン電池用の傾斜構造を有する多成分材料は、ＬｉＣｏＯ２（約１４５ｍＡｈ／ｇ）の比放電容量をはるかに上回る１７０ｍＡｈ／ｇまでの高い比放電容量を有し；同時に、多成分材料は、優れた高温サイクル性能及び安全性能を有する。 From the above test data, the multi-component material having a graded structure for lithium ion batteries prepared according to this embodiment has a high ratio up to 170 mAh / g, far exceeding the specific discharge capacity of LiCoO 2 (about 145 mAh / g). Having a discharge capacity; at the same time, the multi-component material has excellent high temperature cycling and safety performance.
実施形態２
硫酸ニッケル、硫酸コバルトおよび硫酸マンガンを、０．８７：０．０６：０．０７の金属モル比で溶解して、２２５Ｌの１．５ｍｏｌ／Ｌの第１塩溶液Ｒ１を得、硫酸コバルトおよび硫酸マンガンを、１：１．３の金属モル比で溶解して、１．５ｍｏｌ／Ｌの第２塩溶液Ｒ２を３５Ｌ得、錯化剤Ｃとして５．０ｍｏｌ／Ｌのアンモニア水溶液を調製し、沈殿剤Ｄとして８ｍｏｌ／Ｌの水酸化ナトリウム溶液を調製し、第１塩溶液Ｒ１を、撹拌機を備えた容器に入れる。 Nickel sulfate, cobalt sulfate and manganese sulfate were dissolved at a metal molar ratio of 0.87: 0.06: 0.07 to obtain 225 L of a 1.5 mol / L first salt solution R1, cobalt sulfate and sulfuric acid Manganese is dissolved at a metal molar ratio of 1: 1.3 to obtain 35 L of a 1.5 mol / L second salt solution R2, and a 5.0 mol / L aqueous ammonia solution is prepared as a complexing agent C and precipitated. An 8 mol / L sodium hydroxide solution is prepared as the agent D, and the first salt solution R1 is put in a container equipped with a stirrer.
第１塩溶液Ｒ１に第２塩溶液Ｒ２を流速１．１６Ｌ／ｈで撹拌しながら添加して混合塩溶液を得；次いで、混合塩溶液、沈殿剤Ｄおよび錯化剤Ｃを反応器Ａに同時に添加して反応させ、ここで、反応器Ａに添加する混合塩溶液の流速は８．６７Ｌ／ｈであり、この反応プロセスは図１に示されたとおりであり、窒素雰囲気の保護下で、反応のｐＨを１１．３、反応温度を５０℃、アンモニア水対総金属塩のモル比を１：１、反応時間を３０時間に制御しながら反応させることにより、前駆体沈殿物を得る。 The second salt solution R2 is added to the first salt solution R1 at a flow rate of 1.16 L / h with stirring to obtain a mixed salt solution; the mixed salt solution, the precipitating agent D, and the complexing agent C are then added to the reactor A. The flow rate of the mixed salt solution added to the reactor A is 8.67 L / h, and the reaction process is as shown in FIG. 1 under the protection of a nitrogen atmosphere. The precursor precipitate is obtained by carrying out the reaction while controlling the reaction pH to 11.3, the reaction temperature to 50 ° C., the molar ratio of aqueous ammonia to the total metal salt to 1: 1, and the reaction time to 30 hours.
前駆体沈殿物を濾過し、洗浄し、１１０℃で乾燥させることにより、多成分材料の前駆体を得る。前駆体と水酸化リチウムとを１：１．０５のモル比で完全に混合し、酸素ガスの雰囲気中で８９０℃で１０時間保持する。自然冷却、粉砕および篩い分けを行うことによって、傾斜構造を有する球状の多成分材料を得る。 The precursor precipitate is filtered, washed and dried at 110 ° C. to obtain a multi-component material precursor. The precursor and lithium hydroxide are thoroughly mixed at a molar ratio of 1: 1.05 and kept at 890 ° C. for 10 hours in an oxygen gas atmosphere. By performing natural cooling, pulverization and sieving, a spherical multi-component material having an inclined structure is obtained.
実施形態１の方法を用いて、正極は、本実施形態で調製されたリチウムイオン電池用の傾斜構造を有する多成分材料から製造され、かつ、この正極を角形のアルミニウムシェル電池０５３０４８に加工する。
Using the method of
本実施形態により調製されたリチウムイオン電池用の傾斜構造を有する多成分材料は、ＬｉＮｉ０．７７Ｃｏ０．１０Ｍｎ０．１３Ｏ２の組成を有し、粒状材料の中心におけるＮｉ元素の含有量が８７ｍｏｌ％であり、Ｎｉ元素の含有量は内側から外側に向かって連続的に減少し、かつ、粒状材料は球形である。試験すると、メジアン径は１０．６μｍ、タップ密度は２．４３ｇ／ｃｍ３、比放電容量は１８３ｍＡｈ／ｇ、常温で１Ｃ５Ａで１００回の充放電サイクル後の容量維持率は９０％であり、４５℃で１００サイクル後の容量維持率は８８％であり、８５±２℃の高温で４時間保存後の電池厚みの増加率は７．９％であり、熱衝撃試験の結果は、１５０℃のホットオーブン中で６０分以内に、破裂または割れがおこらないことを示す。 The multi-component material having a graded structure for a lithium ion battery prepared according to this embodiment has a composition of LiNi 0.77 Co 0.10 Mn 0.13 O 2 and contains Ni element at the center of the granular material The amount is 87 mol%, the content of Ni element continuously decreases from the inside to the outside, and the granular material is spherical. When tested, the median diameter was 10.6 μm, the tap density was 2.43 g / cm 3 , the specific discharge capacity was 183 mAh / g, and the capacity retention rate after 100 charge / discharge cycles at 1C 5 A at room temperature was 90%. The capacity retention rate after 100 cycles at 45 ° C. is 88%, the rate of increase in battery thickness after 4 hours storage at a high temperature of 85 ± 2 ° C. is 7.9%, and the result of the thermal shock test is 150 Indicates that no bursting or cracking occurs within 60 minutes in a hot oven at 0 ° C.
図２は、実施形態２によって調製された多成分材料の走査電子顕微鏡画像である。図３は、図２の多成分材料粒子の断面の電子顕微鏡画像である。図４は、図３の断面の電子顕微鏡画像に示された多成分材料粒子の中心から周辺までのＮｉ、Ｃｏ及びＭｎ元素のエネルギースペクトル線走査像である。図２、図３、図４から、本実施形態で調製された多成分材料において、中心部から周辺部にかけてＮｉ含有量が連続的かつ単調に減少し、ＭｎおよびＣｏの含有量が中心部から周辺部にかけて連続的に増加することがわかる。
FIG. 2 is a scanning electron microscope image of the multi-component material prepared according to
実施形態３
塩化ニッケル、塩化コバルト及び塩化マンガンを０．８５：０．１：０．０５の金属モル比で溶解して、５００Ｌの２ｍｏｌ／Ｌの第１塩溶液Ｒ１を得；硝酸コバルト、硫酸マンガンおよび硝酸アルミニウムを０．５２：０．０５：０．４３の金属モル比で溶解して６６．５Ｌの２ｍｏｌ／Ｌの第２塩溶液Ｒ２を得；錯化剤Ｃとして２ｍｏｌ／Ｌの硫酸アンモニウム溶液を調製し、錯化剤Ｃ対総金属塩のモル比は０．７：１であり；沈殿剤Ｄとして５ｍｏｌ／Ｌの水酸化カリウム溶液を調製し、沈殿剤Ｄ対総金属塩のモル比を２：１に制御し；第１塩溶液Ｒ１を、撹拌器を備えた容器に入れる。 Nickel chloride, cobalt chloride and manganese chloride are dissolved in a metal molar ratio of 0.85: 0.1: 0.05 to obtain 500 L of a 2 mol / L first salt solution R1; cobalt nitrate, manganese sulfate and nitric acid Aluminum was dissolved at a metal molar ratio of 0.52: 0.05: 0.43 to obtain 66.5 L of a 2 mol / L second salt solution R2; 2 mol / L ammonium sulfate solution was prepared as complexing agent C The molar ratio of complexing agent C to total metal salt is 0.7: 1; 5 mol / L potassium hydroxide solution is prepared as precipitating agent D, and the molar ratio of precipitating agent D to total metal salt is 2 1; the first salt solution R1 is placed in a vessel equipped with a stirrer.
混合塩溶液を得るために、第２塩溶液Ｒ２を第１塩溶液Ｒ１に３．３３Ｌ／ｈの流速で撹拌しながら添加し、次いで、混合塩溶液、沈殿剤Ｄおよび錯化剤Ｃを反応器Ａに同時に添加して反応させ、ここで、反応器Ａに添加される混合塩溶液の流速は２８．３２Ｌ／ｈであり、この反応プロセスは図１に示されたとおりであり、反応は窒素雰囲気の保護下で、反応ｐＨを１１．５、反応温度を６０℃、反応時間を２０時間に制御しながら行い、これにより前駆体沈殿物を得る。 To obtain the mixed salt solution, the second salt solution R2 is added to the first salt solution R1 with stirring at a flow rate of 3.33 L / h, and then the mixed salt solution, the precipitant D and the complexing agent C are reacted. The mixed salt solution added to the reactor A has a flow rate of 28.32 L / h, and the reaction process is as shown in FIG. Under the protection of nitrogen atmosphere, the reaction pH is controlled to 11.5, the reaction temperature is controlled to 60 ° C., and the reaction time is controlled to 20 hours, whereby a precursor precipitate is obtained.
前駆体沈殿物を濾過し、洗浄し、８０℃で乾燥させることにより、多成分材料の前駆体を得る。前駆体を炭酸リチウムと１：０．５２のモル比で完全に混合し、酸素ガス雰囲気中、８００℃で１５時間保持する。自然冷却、粉砕および篩い分けを行い、それによって傾斜構造を有する球状の多成分材料を得る。 The precursor precipitate is filtered, washed and dried at 80 ° C. to obtain a multi-component material precursor. The precursor is thoroughly mixed with lithium carbonate at a molar ratio of 1: 0.52, and held at 800 ° C. for 15 hours in an oxygen gas atmosphere. Natural cooling, grinding and sieving are performed, thereby obtaining a spherical multi-component material having an inclined structure.
実施形態１の方法を用いて、正極は、本実施形態で調製されたリチウムイオン電池用の傾斜構造を有する多成分材料から製造され、かつ、この正極を角形のアルミニウムシェル電池０５３０４８に加工する。
Using the method of
本実施形態により調製されたリチウムイオン電池用の傾斜構造を有する多成分材料は、ＬｉＮｉ０．７５Ｃｏ０．１５Ｍｎ０．０５Ａｌ０．０５Ｏ２の組成を有し、粒状材料の中心におけるＮｉ元素の含有量は８５ｍｏｌ％であり、Ｎｉ元素の含有量は連続的に内側から外側に向かって減少し、粒状材料は球形である。試験すると、メジアン径は１０．１μｍ、タップ密度は２．４５ｇ／ｃｍ３、比放電容量は１８０ｍＡｈ／ｇ、常温で、１Ｃ５Ａで１００回の充放電サイクル後の容量維持率は９２％であり、４５℃で１００回サイクル後の容量維持率は９０％であり、８５±２℃の高温で４時間保存後の電池厚みの増加率は７．７％であり、熱衝撃試験の結果は１５０℃のホットオーブン中で６０分以内に、破裂または割れがおこらないことを示す。 The multi-component material having a graded structure for a lithium ion battery prepared according to this embodiment has a composition of LiNi 0.75 Co 0.15 Mn 0.05 Al 0.05 O 2 and is in the center of the granular material. The content of Ni element is 85 mol%, the content of Ni element continuously decreases from the inside to the outside, and the granular material is spherical. When tested, the median diameter was 10.1 μm, the tap density was 2.45 g / cm 3 , the specific discharge capacity was 180 mAh / g, and the capacity retention rate after 100 charge / discharge cycles at 1C 5 A at 92 ° C. was 92%. Yes, the capacity retention rate after 100 cycles at 45 ° C. is 90%, and the increase rate of battery thickness after 4 hours storage at 85 ± 2 ° C. is 7.7%. Indicates that no rupture or cracking occurs within 60 minutes in a 150 ° C. hot oven.
実施形態４
硝酸ニッケル、硝酸コバルトおよび塩化マンガンを、０．８：０．１：０．１の金属モル比で溶解して、１１１１Ｌの１．８ｍｏｌ／Ｌの第１塩溶液Ｒ１を得、塩化コバルト、硫酸マンガン、硝酸アルミニウムおよび塩化マグネシウムを、０．５：０．３６６：０．１０７：０．０２７の金属モル比で溶解して、６６７Ｌの１．８ｍｏｌ／Ｌの第２塩溶液Ｒ２を得、錯化剤Ｃとして１０ｍｏｌ／Ｌのアンモニア水溶液を調製し、錯化剤Ｃ対総金属塩のモル比を０．８：１とし；沈殿剤Ｄとして８ｍｏｌ／Ｌの水酸化ナトリウム溶液を調製し、沈殿剤Ｄ対総金属塩のモル比を２．０５：１に制御し、第１塩溶液Ｒ１を撹拌機付き容器に入れる。 Nickel nitrate, cobalt nitrate and manganese chloride are dissolved at a metal molar ratio of 0.8: 0.1: 0.1 to obtain 1111 L of a 1.8 mol / L first salt solution R1, cobalt chloride, sulfuric acid Manganese, aluminum nitrate and magnesium chloride were dissolved in a metal molar ratio of 0.5: 0.366: 0.107: 0.027 to obtain 667 L of a 1.8 mol / L second salt solution R2, A 10 mol / L aqueous ammonia solution is prepared as the agent C, the molar ratio of the complexing agent C to the total metal salt is 0.8: 1; an 8 mol / L sodium hydroxide solution is prepared as the precipitant D and precipitated. The molar ratio of agent D to total metal salt is controlled to 2.05: 1 and the first salt solution R1 is placed in a vessel with a stirrer.
混合塩溶液を得るために、第２塩溶液Ｒ２を第１塩溶液Ｒ１に２６．７Ｌ／ｈの流速で撹拌しながら添加し；次いで、混合塩溶液、沈殿剤Ｄおよび錯化剤Ｃを同時に反応器Ａに添加して反応させ、ここで、反応器Ａに添加される混合塩溶液の流速は７１．１２Ｌ／ｈであり、この反応プロセスは図１に示されたとおりであり、反応のｐＨを１１．５、反応温度を５５℃、反応時間を２５時間に制御しながら、窒素雰囲気の保護下で反応させることにより、前駆体沈殿物を得る。 To obtain the mixed salt solution, the second salt solution R2 is added to the first salt solution R1 with stirring at a flow rate of 26.7 L / h; then the mixed salt solution, the precipitating agent D and the complexing agent C are simultaneously added. The reaction is performed by adding to the reactor A, where the flow rate of the mixed salt solution added to the reactor A is 71.12 L / h, and this reaction process is as shown in FIG. A precursor precipitate is obtained by reacting under the protection of a nitrogen atmosphere while controlling the pH at 11.5, the reaction temperature at 55 ° C., and the reaction time at 25 hours.
前駆体沈殿物を濾過し、洗浄し、１００℃で乾燥させることにより、多成分材料の前駆体を得る。前駆体を炭酸リチウムと１：０．５２５のモル比で完全に混合し、大気中、９５０℃で１６時間保持する。自然冷却、粉砕および篩い分けを行い、それによって傾斜構造を有する球状の多成分材料を得る。 The precursor precipitate is filtered, washed and dried at 100 ° C. to obtain a multi-component material precursor. The precursor is thoroughly mixed with lithium carbonate at a molar ratio of 1: 0.525 and held in air at 950 ° C. for 16 hours. Natural cooling, grinding and sieving are performed, thereby obtaining a spherical multi-component material having an inclined structure.
実施形態１の方法を用いて、正極は、本実施形態で調製されたリチウムイオン電池用の傾斜構造を有する多成分材料から製造され、かつ、この正極を角形のアルミニウムシェル電池０５３０４８に加工する。
Using the method of
本実施形態により調製されたリチウムイオン電池用の傾斜構造を有する多成分材料は、ＬｉＮｉ０．５０Ｃｏ０．２５Ｍｎ０．２０Ａｌ０．０４Ｍｇ０．０１Ｏ２の組成を有し、粒状材料の中心におけるＮｉ元素の含有量が８０ｍｏｌ％であり、Ｎｉ元素は内側から外側に向かって連続的に減少し、粒状材料は球形である。試験すると、メジアン径は９．９μｍ、タップ密度は２．４６ｇ／ｃｍ３、比放電容量は１５８ｍＡｈ／ｇ、常温で、１Ｃ５Ａで１００回の充放電サイクル後の容量維持率は９６％であり、４５℃で１００サイクル後の容量維持率は９３％であり、８５±２℃の高温で４時間保存後の電池厚みの増加率は５．９％であり、熱衝撃試験の結果は、１５０℃のホットオーブン中で６０分以内に、破裂または割れがおこらないことを示す。 The multi-component material having a graded structure for a lithium ion battery prepared according to this embodiment has a composition of LiNi 0.50 Co 0.25 Mn 0.20 Al 0.04 Mg 0.01 O 2 and is granular. The content of Ni element at the center of the material is 80 mol%, the Ni element continuously decreases from the inside to the outside, and the granular material is spherical. When tested, the median diameter was 9.9 μm, the tap density was 2.46 g / cm 3 , the specific discharge capacity was 158 mAh / g, and the capacity retention rate after 100 charge / discharge cycles at 1C 5 A was 96% at room temperature. Yes, the capacity retention rate after 100 cycles at 45 ° C. is 93%, the rate of increase in battery thickness after 4 hours storage at a high temperature of 85 ± 2 ° C. is 5.9%, and the result of the thermal shock test is Indicates that no rupture or cracking occurs within 60 minutes in a 150 ° C. hot oven.
実施形態５ Embodiment 5
塩化ニッケル、硫酸コバルトおよび硫酸マンガンを０．７：０．１５：０．１５の金属モル比で溶解し、２５０Ｌの２ｍｏｌ／Ｌの第１塩溶液Ｒ１を得、硫酸アルミニウムと硫酸マグネシウムを０．５：０．５の金属モル比で溶解して、１０．５Ｌの２ｍｏｌ／Ｌの第２塩溶液Ｒ２を得、塩化アンモニウムとＥＤＴＡをモル比０．８：０．２で溶解させて２ｍｏｌ／Ｌの錯化剤Ｃを得、錯化剤Ｃ対総金属塩のモル比は０．２：１であり；沈殿剤Ｄとして７ｍｏｌ／Ｌ水酸化ナトリウム溶液を調製し、沈殿剤Ｄ対総金属塩のモル比を２．１：１に制御し、第１塩溶液Ｒ１を撹拌機付き容器に入れる。 Nickel chloride, cobalt sulfate and manganese sulfate were dissolved in a metal molar ratio of 0.7: 0.15: 0.15 to obtain 250 L of a 2 mol / L first salt solution R1, and aluminum sulfate and magnesium sulfate were added in an amount of 0.1. Dissolve at a metal molar ratio of 5: 0.5 to obtain 10.5 L of a 2 mol / L second salt solution R2, and dissolve ammonium chloride and EDTA at a molar ratio of 0.8: 0.2 to give 2 mol / L. L complexing agent C is obtained, the molar ratio of complexing agent C to total metal salt is 0.2: 1; 7 mol / L sodium hydroxide solution is prepared as precipitating agent D, precipitating agent D to total metal The salt molar ratio is controlled to 2.1: 1 and the first salt solution R1 is placed in a vessel with a stirrer.
混合塩溶液を得るために、０．７Ｌ／ｈの流速で第１塩溶液Ｒ１に第２塩溶液Ｒ２を撹拌しながら添加し；次いで、混合塩溶液、沈殿剤Ｄおよび錯化剤Ｃを同時に反応器Ａに添加して反応させ、ここで、反応器Ａに添加される混合塩溶液の流速は１７．３６Ｌ／ｈであり、この反応プロセスは図１に示されたとおりであり、反応のｐＨを１２．４、反応温度を６０℃、反応時間を１５時間に制御しながら、窒素雰囲気の保護下で反応させることにより、前駆体沈殿物を得る。 To obtain a mixed salt solution, the second salt solution R2 is added to the first salt solution R1 with stirring at a flow rate of 0.7 L / h; then the mixed salt solution, the precipitating agent D and the complexing agent C are simultaneously added. The reaction is performed by adding to the reactor A, where the flow rate of the mixed salt solution added to the reactor A is 17.36 L / h, and this reaction process is as shown in FIG. The precursor precipitate is obtained by reacting under the protection of nitrogen atmosphere while controlling the pH at 12.4, the reaction temperature at 60 ° C., and the reaction time at 15 hours.
前駆体沈殿物を濾過し、洗浄し、１４０℃で乾燥させることにより、多成分材料の前駆体を得る。前駆体を硝酸リチウムと１：１．０３のモル比で完全に混合し、酸素ガスの雰囲気中で、８２０℃で１２時間保持する。自然冷却、粉砕および篩い分けを行い、それによって傾斜構造を有する球状の多成分材料を得る。 The precursor precipitate is filtered, washed and dried at 140 ° C. to obtain a multi-component material precursor. The precursor is thoroughly mixed with lithium nitrate at a molar ratio of 1: 1.03 and held at 820 ° C. for 12 hours in an oxygen gas atmosphere. Natural cooling, grinding and sieving are performed, thereby obtaining a spherical multi-component material having an inclined structure.
実施形態１の方法を用いて、正極は、本実施形態で調製されたリチウムイオン電池用の傾斜構造を有する多成分材料から製造され、かつ、この正極を角形のアルミニウムシェル電池０５３０４８に加工する。
Using the method of
本実施形態で調製されたリチウムイオン電池用の傾斜構造を有する多成分材料は、ＬｉＮｉ０．６７２Ｃｏ０．１４４Ｍｎ０．１４４Ａｌ０．０２Ｍｇ０．０２Ｏ２の組成を有し、粒状材料の中心におけるＮｉ元素の含有量は７０ｍｏｌ％であり、Ｎｉ元素の含有量は内側から外側に向かって連続的に減少し、粒状材料は球形である。試験すると、材料のメジアン径は６．５μｍ、タップ密度は２．２１ｇ／ｃｍ３、比放電容量は１７５ｍＡｈ／ｇであり、常温において、１Ｃ５Ａで１００回の充放電サイクル後の容量維持率は９２％であり、４５℃で１００サイクル後の容量維持率は９０％であり、８５±２℃の高温で４時間保存後の電池厚みの増加率は８．６％であり、熱衝撃試験の結果は、１５０℃のホットオーブン中で６０分以内に破裂または割れがおこらないことを示す。 The multi-component material having a graded structure for a lithium ion battery prepared in this embodiment has a composition of LiNi 0.672 Co 0.144 Mn 0.144 Al 0.02 Mg 0.02 O 2 and is granular. The content of Ni element at the center of the material is 70 mol%, the content of Ni element continuously decreases from the inside to the outside, and the granular material is spherical. When tested, the median diameter of the material is 6.5 μm, the tap density is 2.21 g / cm 3 , the specific discharge capacity is 175 mAh / g, and the capacity retention rate after 100 charge / discharge cycles at 1 C 5 A at room temperature Is 92%, the capacity retention rate after 100 cycles at 45 ° C. is 90%, the increase rate of the battery thickness after storage for 4 hours at a high temperature of 85 ± 2 ° C. is 8.6%, and the thermal shock test The results show that no bursting or cracking occurs within 60 minutes in a hot oven at 150 ° C.
実施形態６ Embodiment 6
１．５ｍｏｌ／Ｌの硫酸ニッケル溶液６６７Ｌを第１塩溶液Ｒ１として調製し、硫酸コバルト、硫酸マンガン、硝酸アルミニウム、硫酸マグネシウムおよび硝酸イットリウムを、０．３７５：０．３７５：０．１：０．１：０．０５の金属モル比で溶解させて、１．５ｍｏｌ／Ｌの第２塩溶液Ｒ２を１６７Ｌ得、錯化剤Ｃとして１ｍｏｌ／Ｌのエチレンジアミン溶液を調製し、錯化剤Ｃ対総金属塩モル比は０．２：１であり；沈殿剤Ｄとして２ｍｏｌ／Ｌの炭酸ナトリウム溶液を調製し、沈殿剤Ｄ対総金属塩のモル比を１．１：１に制御し、撹拌機付き容器に第１塩溶液Ｒ１を入れる。 A 667 L of 1.5 mol / L nickel sulfate solution was prepared as the first salt solution R1, and cobalt sulfate, manganese sulfate, aluminum nitrate, magnesium sulfate and yttrium nitrate were added at 0.375: 0.375: 0.1: 0. 167 L of a 1.5 mol / L second salt solution R2 was obtained by dissolving at a metal molar ratio of 1: 0.05, and a 1 mol / L ethylenediamine solution was prepared as the complexing agent C. The metal salt molar ratio is 0.2: 1; a 2 mol / L sodium carbonate solution is prepared as the precipitant D, the molar ratio of the precipitant D to the total metal salt is controlled at 1.1: 1, and the stirrer Put the first salt solution R1 in the attached container.
混合塩溶液を得るために、第２塩溶液Ｒ２を第１塩溶液Ｒ１に流速４．１８Ｌ／ｈで撹拌しながら添加し；次いで、混合塩溶液、沈殿剤Ｄおよび錯化剤Ｃを同時に反応器Ａに添加して反応させ、ここで反応器Ａに添加される混合塩溶液の流速は２０．８５Ｌ／ｈであり、この反応プロセスは図１に示されたとおりであり、反応液のｐＨを９．０、反応温度を４５℃、反応時間を４０時間に制御しながら、窒素雰囲気の保護下で反応させ、前駆体沈殿物を得る。 To obtain the mixed salt solution, the second salt solution R2 is added to the first salt solution R1 with stirring at a flow rate of 4.18 L / h; then the mixed salt solution, the precipitating agent D and the complexing agent C are reacted simultaneously. The flow rate of the mixed salt solution added to the reactor A is 20.85 L / h, and this reaction process is as shown in FIG. Is controlled under a nitrogen atmosphere while controlling the reaction temperature at 9.0, the reaction temperature at 45 ° C., and the reaction time at 40 hours to obtain a precursor precipitate.
前駆体沈殿物を濾過し、洗浄し、５００℃で焼成することにより、多成分材料の前駆体を得る。前駆体を水酸化リチウムと１：１．０４のモル比で完全に混合し、酸素ガスの雰囲気中に、７５０℃で１５時間保持する。自然冷却、粉砕および篩い分けを行い、それによって傾斜構造を有するほぼ球形の多成分材料を得る。 The precursor precipitate is filtered, washed, and calcined at 500 ° C. to obtain a multi-component material precursor. The precursor is thoroughly mixed with lithium hydroxide at a molar ratio of 1: 1.04 and kept at 750 ° C. for 15 hours in an oxygen gas atmosphere. Natural cooling, pulverization and sieving are performed, thereby obtaining a substantially spherical multi-component material having an inclined structure.
実施形態１の方法を用いて、正極は、本実施形態で調製されたリチウムイオン電池用の傾斜構造を有する多成分材料から製造され、かつ、この正極を角形のアルミニウムシェル電池０５３０４８に加工する。
Using the method of
本実施形態により製造されたリチウムイオン電池用の傾斜構造を有する多成分材料は、ＬｉＮｉ０．８０Ｃｏ０．０７５Ｍｎ０．０７５Ａｌ０．０２Ｍｇ０．０２Ｙ０．０１Ｏ２の組成を有し、粒状材料の中心におけるＮｉ元素の含有量が１００ｍｏｌ％であり、Ｎｉ元素の含有量が内側から外側に向かって連続的に減少し、粒状材料は球形である。試験すると、メジアン径は２４．５μｍ、タップ密度は２．７３ｇ／ｃｍ３、比放電容量は１８４ｍＡｈ／ｇ、常温で、１Ｃ５Ａで１００回の充放電サイクル後の容量維持率は９１％、４５℃で１００サイクル後の容量維持率は８９％、８５±２℃の高温で４時間保存後の電池厚みの増加率は８．０％であり、熱衝撃試験の結果は、１５０℃のホットオーブン中で６０分以内に破裂または割れがおこらないことを示す。 The multi-component material having an inclined structure for a lithium ion battery manufactured according to the present embodiment has a composition of LiNi 0.80 Co 0.075 Mn 0.075 Al 0.02 Mg 0.02 Y 0.01 O 2 . And the content of Ni element at the center of the granular material is 100 mol%, the content of Ni element continuously decreases from the inside toward the outside, and the granular material is spherical. When tested, the median diameter was 24.5 μm, the tap density was 2.73 g / cm 3 , the specific discharge capacity was 184 mAh / g, and the capacity retention rate after 100 charge / discharge cycles at 1C 5 A at room temperature was 91%, The capacity retention rate after 100 cycles at 45 ° C. is 89%, the increase rate of the battery thickness after storage for 4 hours at a high temperature of 85 ± 2 ° C. is 8.0%, and the result of the thermal shock test is 150 ° C. hot Indicates no rupture or cracking within 60 minutes in oven.
実施形態７ Embodiment 7
塩化ニッケルと硫酸コバルトとを０．９：０．１の金属モル比で溶解し、金属モル比０．９：０．１で溶解して、１ｍｏｌ／Ｌの第１塩溶液Ｒ１を１０００Ｌ得、硫酸コバルト、硫酸マンガン、硫酸マグネシウムおよび塩化カルシウムを０．２：０．６：０．１：０．１の金属モル比で溶解して１．０ｍｏｌ／Ｌの第２塩溶液Ｒ２を２５０Ｌ得、錯化剤Ｃとして１ｍｏｌ／Ｌの硝酸アンモニウム溶液を調製し、錯化剤Ｃ対総金属塩のモル比を０．２：１であり；沈殿剤Ｄとして３ｍｏｌ／Ｌの重炭酸アンモニウム溶液を調製し、沈殿剤Ｄ対総金属塩のモル比を１：１に制御し、第１塩溶液Ｒ１を撹拌機付き容器に入れる。 Nickel chloride and cobalt sulfate were dissolved at a metal molar ratio of 0.9: 0.1, and dissolved at a metal molar ratio of 0.9: 0.1 to obtain 1000 L of a 1 mol / L first salt solution R1. Cobalt sulfate, manganese sulfate, magnesium sulfate and calcium chloride were dissolved at a metal molar ratio of 0.2: 0.6: 0.1: 0.1 to obtain 250 L of a 1.0 mol / L second salt solution R2, A 1 mol / L ammonium nitrate solution is prepared as complexing agent C, the molar ratio of complexing agent C to total metal salt is 0.2: 1; a 3 mol / L ammonium bicarbonate solution is prepared as precipitating agent D. The molar ratio of the precipitating agent D to the total metal salt is controlled to 1: 1, and the first salt solution R1 is placed in a vessel with a stirrer.
混合塩溶液を得るために、第２塩溶液Ｒ２を第１塩溶液Ｒ１に、２５Ｌ／ｈの流速で撹拌しながら添加し；次いで、混合塩溶液、沈殿剤Ｄおよび錯化剤Ｃを反応器Ａに同時に添加して反応させ、ここで反応器Ａに添加される混合塩溶液の流速は１２５Ｌ／ｈとであり、この反応プロセスは図１に示されたとおりであり、反応のｐＨを８．７、反応温度を４０℃、反応時間を１０時間に制御しながら、窒素雰囲気の保護下で反応させ、前駆体沈殿物を得る。 To obtain the mixed salt solution, the second salt solution R2 is added to the first salt solution R1 with stirring at a flow rate of 25 L / h; then the mixed salt solution, the precipitating agent D and the complexing agent C are added to the reactor. The mixed salt solution added to the reactor A is reacted at the same time, and the flow rate of the mixed salt solution is 125 L / h. The reaction process is as shown in FIG. .7, while controlling the reaction temperature to 40 ° C. and the reaction time to 10 hours, the reaction is performed under protection of a nitrogen atmosphere to obtain a precursor precipitate.
前駆体沈殿物を濾過し、洗浄し、６００℃で焼成することにより、多成分材料の前駆体を得る。前駆体を水酸化リチウムと１：１．０４のモル比で完全に混合し、酸素ガスの雰囲気中において温度８００℃で１６時間保持する。自然冷却、粉砕および篩い分けを行い、それによって傾斜構造を有する球状の多成分材料を得る。 The precursor precipitate is filtered, washed, and calcined at 600 ° C. to obtain a multi-component material precursor. The precursor is thoroughly mixed with lithium hydroxide at a molar ratio of 1: 1.04 and kept at a temperature of 800 ° C. for 16 hours in an oxygen gas atmosphere. Natural cooling, grinding and sieving are performed, thereby obtaining a spherical multi-component material having an inclined structure.
本実施形態により調製されたリチウムイオン電池用の傾斜構造を有する多成分材料は、ＬｉＮｉ０．７２Ｃｏ０．１２Ｍｎ０．１２Ｍｇ０．０２Ｃａ０．０２Ｏ２の組成を有し、粒状物質の中心におけるＮｉ元素の含有量が９０ｍｏｌ％であり、Ｎｉ元素は内側から外側に向かって連続的に減少し、粒状材料は球形である。試験すると、材料のメジアン径は７．３μｍ、タップ密度は２．３３ｇ／ｃｍ３、比放電容量は１７７ｍＡｈ／ｇ、常温で、１Ｃ５Ａで１００回の充放電サイクル後の容量維持率は９３％であり、４５℃で１００サイクル後の容量維持率は９１％であり、８５±２℃の高温で４時間保存後の電池厚みの増加率は７．４％であり、熱衝撃試験の結果は、１５０℃のホットオーブン中で６０分以内に破裂または割れが起こらないことを示す。 The multi-component material having a graded structure for a lithium ion battery prepared according to the present embodiment has a composition of LiNi 0.72 Co 0.12 Mn 0.12 Mg 0.02 Ca 0.02 O 2 and is granular. The content of Ni element at the center of the substance is 90 mol%, Ni element continuously decreases from the inside to the outside, and the granular material is spherical. When tested, the median diameter of the material was 7.3 μm, the tap density was 2.33 g / cm 3 , the specific discharge capacity was 177 mAh / g, and the capacity retention rate after 100 charge / discharge cycles at 1C 5 A at room temperature was 93. The capacity retention rate after 100 cycles at 45 ° C. is 91%, the increase rate of the battery thickness after storage for 4 hours at a high temperature of 85 ± 2 ° C. is 7.4%, and the result of the thermal shock test Indicates no rupture or cracking within 60 minutes in a 150 ° C. hot oven.
実施形態８ Embodiment 8
第１塩溶液Ｒ１として１．５ｍｏｌ／Ｌの硫酸ニッケル溶液６６７Ｌを調製し、硫酸コバルト、硫酸マンガン、硝酸アルミニウム、硫酸マグネシウムおよび硝酸イットリウムを金属モル比０．３７５：０．３７５：０．１：０．１：０．０５で溶解させて第２塩溶液Ｒ２を１６７Ｌ得、錯化剤Ｃとして５ｍｏｌ／Ｌのアンモニア水溶液を調製し、錯化剤Ｃ対総金属塩のモル比は０．９５：１であり；沈殿剤Ｄとして８ｍｏｌ／Ｌ水酸化ナトリウム溶液を調製し、沈殿剤Ｄ対総金属塩のモル比を２．０７：１に制御し、第１塩溶液Ｒ１を撹拌機付き容器に入れる。 A 667 L of a 1.5 mol / L nickel sulfate solution is prepared as the first salt solution R1, and the metal molar ratio of cobalt sulfate, manganese sulfate, aluminum nitrate, magnesium sulfate and yttrium nitrate is 0.375: 0.375: 0.1: 167 L of the second salt solution R2 was obtained by dissolving at 0.1: 0.05, and a 5 mol / L aqueous ammonia solution was prepared as the complexing agent C. The molar ratio of the complexing agent C to the total metal salt was 0.95. 1: 8 mol / L sodium hydroxide solution was prepared as the precipitating agent D, the molar ratio of the precipitating agent D to the total metal salt was controlled to 2.07: 1, and the first salt solution R1 was placed in a container equipped with a stirrer. Put in.
混合塩溶液を得るために、第２塩溶液Ｒ２を第１塩溶液Ｒ１に流速４．１８Ｌ／ｈで撹拌しながら添加し；次いで、混合塩溶液、沈殿剤Ｄおよび錯化剤Ｃを同時に反応器Ａに添加して反応させ、ここで、反応器Ａに添加される混合塩溶液の流速は２０．８５Ｌ／ｈであり、この反応プロセスは図１に示されたとおりであり、反応のｐＨを１２．１、反応温度を５０℃、反応時間を４０時間に制御しながら、窒素雰囲気の保護下で反応させて前駆体沈殿物を得る。 To obtain the mixed salt solution, the second salt solution R2 is added to the first salt solution R1 with stirring at a flow rate of 4.18 L / h; then the mixed salt solution, the precipitating agent D and the complexing agent C are reacted simultaneously. The mixed salt solution added to the reactor A is reacted at a flow rate of 20.85 L / h, and the reaction process is as shown in FIG. The precursor precipitate is obtained by reacting under the protection of nitrogen atmosphere while controlling the reaction temperature at 12.1, the reaction temperature at 50 ° C., and the reaction time at 40 hours.
前駆体沈殿物を濾過し、洗浄し、１３０℃で乾燥させることにより、多成分材料の前駆体を得る。前駆体を水酸化リチウムと１：１．０４のモル比で完全に混合し、酸素ガスの雰囲気中で温度７６０℃で１５時間保持する。自然冷却、粉砕および篩い分けを行い、それによって傾斜構造を有する球状の多成分材料を得る。 The precursor precipitate is filtered, washed and dried at 130 ° C. to obtain a multi-component material precursor. The precursor is thoroughly mixed with lithium hydroxide at a molar ratio of 1: 1.04 and held at a temperature of 760 ° C. for 15 hours in an oxygen gas atmosphere. Natural cooling, grinding and sieving are performed, thereby obtaining a spherical multi-component material having an inclined structure.
本実施形態により調製されたリチウムイオン電池用の傾斜構造を有する多成分材料は、ＬｉＮｉ０．８Ｃｏ０．０７５Ｍｎ０．０７５Ａｌ０．０２Ｍｇ０．０２Ｙ０．０１Ｏ２の組成を有し、粒状材料の中心におけるＮｉ元素の含有量が１００％であり、Ｎｉ元素の含有量が内側から外側に向かって連続的に減少し、粒状材料は球形である。試験すると、材料のメジアン径は１２．２μｍ、タップ密度は２．６０ｇ／ｃｍ３、比放電容量は１８７ｍＡｈ／ｇ、常温で、１Ｃ５Ａで１００回の充放電サイクル後の容量維持率は９０％であり、４５℃で１００サイクル後の容量維持率は８８％であり、８５±２℃の高温で４時間保存後の電池厚みの増加率は８．４％であり、熱衝撃試験の結果は、１５０℃のホットオーブン中で６０分以内に破裂または割れがおこらなかったことを示す。 The multi-component material having an inclined structure for a lithium ion battery prepared according to the present embodiment has a composition of LiNi 0.8 Co 0.075 Mn 0.075 Al 0.02 Mg 0.02 Y 0.01 O 2 . And the content of Ni element at the center of the granular material is 100%, the content of Ni element continuously decreases from the inside to the outside, and the granular material is spherical. When tested, the median diameter of the material was 12.2 μm, the tap density was 2.60 g / cm 3 , the specific discharge capacity was 187 mAh / g, and the capacity retention rate after 100 charge / discharge cycles at 1C 5 A at 90 ° C. was 90 The capacity retention rate after 100 cycles at 45 ° C. is 88%, and the increase rate of the battery thickness after storage for 4 hours at a high temperature of 85 ± 2 ° C. is 8.4%. Indicates that no rupture or cracking occurred within 60 minutes in a 150 ° C. hot oven.
比較例 Comparative example
硫酸ニッケル、硫酸コバルトおよび硫酸マンガンを０．６：０．２：０．２の金属モル比で溶解し、１．５ｍｏｌ／Ｌの混合塩溶液５００Ｌを得、錯化剤Ｃとして５．０ｍｏｌ／Ｌのアンモニア水溶液と、沈殿剤Ｄとしての８ｍｏｌ／Ｌの水酸化ナトリウム溶液を調製し、次いで、混合塩溶液、沈殿剤Ｄおよび錯化剤Ｃとを同時に反応器Ａに添加して反応させ、ここで、添加される混合塩溶液の反応器Ａへの流速は１６．６７Ｌ／ｈであり、反応は、反応のｐＨを１１．３、反応温度を５０℃、錯化剤アンモニア水対総金属塩のモル比を１：１、反応時間を３０時間に制御しながら、窒素雰囲気の保護下で行われ、これにより前駆体沈殿物を得る。 Nickel sulfate, cobalt sulfate and manganese sulfate are dissolved at a metal molar ratio of 0.6: 0.2: 0.2 to obtain 500 L of a 1.5 mol / L mixed salt solution, and 5.0 mol / L as complexing agent C. An aqueous ammonia solution of L and an 8 mol / L sodium hydroxide solution as a precipitating agent D are prepared, and then the mixed salt solution, the precipitating agent D and the complexing agent C are simultaneously added to the reactor A and reacted. Here, the flow rate of the mixed salt solution to be added to the reactor A is 16.67 L / h, and the reaction is performed at a pH of 11.3, a reaction temperature of 50 ° C., a complexing agent ammonia water versus total metal. It is carried out under the protection of a nitrogen atmosphere while controlling the molar ratio of salt to 1: 1 and the reaction time to 30 hours, thereby obtaining a precursor precipitate.
前駆体沈殿物を濾過し、洗浄し、１２０℃で乾燥することにより、多成分材料の前駆体を得る。前駆体を水酸化リチウムと１：１．０５のモル比で完全に混合し、空気雰囲気中、温度８９０℃で１０時間保持する。自然冷却、粉砕および篩い分けを行い、それによって傾斜構造を有する球状の多成分材料を得る。 The precursor precipitate is filtered, washed, and dried at 120 ° C. to obtain a multi-component material precursor. The precursor is thoroughly mixed with lithium hydroxide at a molar ratio of 1: 1.05 and held in an air atmosphere at a temperature of 890 ° C. for 10 hours. Natural cooling, grinding and sieving are performed, thereby obtaining a spherical multi-component material having an inclined structure.
実施形態１の方法を用いて、正極は、本実施形態で調製されたリチウムイオン電池用の傾斜構造を有する多成分材料から製造され、かつ、この正極を角形のアルミニウムシェル電池０５３０４８に加工する。
Using the method of
本実施形態によって調製されたリチウムイオン電池用の傾斜構造を有する多成分材料は、ＬｉＮｉ０．６Ｃｏ０．２Ｍｎ０．２Ｏ２の組成を有し、粒状物質は球形である。試験すると、メジアン径は１５．６μｍ、タップ密度は２．５６ｇ／ｃｍ３、比放電容量は１７０ｍＡｈ／ｇ、常温で、１Ｃ５Ａでの１００回の充放電サイクル後の容量維持率は８５％、４５℃で１００サイクル後の容量維持率が７０％であり、８５±２℃の高温で４時間保存後の電池厚みの増加率は１４．５％であり、熱衝撃試験の結果は、１５０℃のホットオーブン中で６０分以内に破裂または割れを示さない。 The multi-component material having a graded structure for a lithium ion battery prepared according to the present embodiment has a composition of LiNi 0.6 Co 0.2 Mn 0.2 O 2 and the granular material is spherical. When tested, the median diameter is 15.6 μm, the tap density is 2.56 g / cm 3 , the specific discharge capacity is 170 mAh / g, and the capacity retention rate after 100 charge / discharge cycles at 1 C 5 A is 85% at room temperature. The capacity retention rate after 100 cycles at 45 ° C. is 70%, the rate of increase in battery thickness after storage for 4 hours at a high temperature of 85 ± 2 ° C. is 14.5%, and the result of the thermal shock test is 150 No bursting or cracking within 60 minutes in a hot oven at 0 ° C.
上記の試験データから、比較例により製造されたリチウムイオン電池用の傾斜構造を有する多成分材料は、明らかに低い比放電容量であり、常温での１００回の充放電サイクル後の容量維持率は８５％に達したに過ぎず、４５℃での１００サイクル後の容量維持率は７０％であり、したがって、比較例の多成分材料の常温サイクル性能と高温サイクル性能は、いずれも、本願発明の実施形態により調製された材料より劣っていて、また、高温での貯蔵性能及び安全性能も劣っている。 From the above test data, the multi-component material having an inclined structure for a lithium ion battery manufactured according to the comparative example has a clearly low specific discharge capacity, and the capacity retention rate after 100 charge / discharge cycles at room temperature is The capacity retention rate after 100 cycles at 45 ° C. was only 70%. Therefore, the normal temperature cycle performance and the high temperature cycle performance of the multi-component material of the comparative example are both of the present invention. It is inferior to the material prepared according to the embodiment and also has poor storage and safety performance at high temperatures.
最後に、上記の実施形態は、本発明の技術的解決策を限定するのではなく、単に例示することを意図するものであり；本発明は上述の実施形態を参照して具体的に説明されたが、当業者であれば、前述の実施形態に記載された技術的解決策を依然として変更することができ、またはその中の技術的特徴の一部または全部を均等なものに置換でき；これらの変更およびこれらの置換は、対応する技術的解決策の本質を本発明の上記の実施形態における技術的解決策の範囲から逸脱するものではない。 Finally, the above embodiments are not intended to limit the technical solutions of the present invention, but are intended to be exemplary only; the present invention is specifically described with reference to the above embodiments. However, those skilled in the art can still change the technical solutions described in the above embodiments, or can replace some or all of the technical features therein with equivalents; These changes and their substitutions do not depart from the scope of the technical solutions in the above embodiments of the present invention from the essence of the corresponding technical solutions.
（式中、０．４≦ｘ≦０．９，０≦ｙ＋ｚ≦０．６，０≦ｄ≦０．１，ｘ＋ｙ＋ｚ＋ｄ＝１，Ｇは、Ｌｉ、Ｃｒ、Ｆｅ、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｂ、Ａｌ、Ｙ、Ｓｍ、Ｔｉ、Ｚｎ、Ｚｒ、Ｖ、Ｎｂ、Ｔａ、Ｍｏ、Ｗ元素の１種以上である。）で示される平均組成を有し、多成分材料は粒子状であり、リチウムイオン電池用の傾斜構造を有する多成分材料において、Ｎｉ元素の含有量が粒子の中心から表面に向かって連続的に減少する。 (In the formula, 0.4 ≦ x ≦ 0.9, 0 ≦ y + z ≦ 0.6, 0 ≦ d ≦ 0.1, x + y + z + d = 1, G is Li, Cr, Fe, Mg, Ca, Sr, Ba , B, Al, Y, Sm, Ti, Zn, Zr, V, Nb, Ta, Mo, and W elements)), and the multi-component material is in the form of particles in multi-component material having a gradient structure for lithium ion batteries, continuously decreases toward the surface from the center of the content of Ni element particles.
本発明により提供されるリチウムイオン電池用の傾斜構造を有する多成分材料は、Ｎｉ、Ｃｏ、ＭｎおよびＧ元素の１種以上を含む金属塩をＮｉ含有金属塩溶液に徐々に添加して、沈殿剤および錯化剤と沈殿反応させ、その後酸素ガスを含む雰囲気中で、沈殿反応の沈殿生成物とリチウム源とを焼結する。 The multi-component material having an inclined structure for a lithium ion battery provided by the present invention is obtained by gradually adding a metal salt containing one or more of Ni, Co, Mn and G elements to a Ni-containing metal salt solution, agent and precipitated reacts with the complexing agent and after that in an atmosphere containing oxygen gas, the precipitation buttocks product of the precipitation reaction and the lithium source for sintering.
（３）傾斜構造を有する多成分材料の前駆体とリチウム源とを均一に混合して混合物を得、空気または酸素ガスの反応雰囲気中で、５００〜１１００℃で４〜３０時間該混合物を焼結し、好ましくは７００〜１０００℃で７〜２０時間該混合物を焼結し、焼結体を得、該焼結体の粉砕を行い、リチウム電池用の傾斜構造を有する多成分材料を得る工程
を含む。
(3) the precursor of the multi-component material having an inclined structure and the lithium source were uniformly mixed to obtain a mixture, in a reaction atmosphere of air or oxygen gas, from 4 to 30 o'clock Ma該mixture at 500 to 1100 ° C. sintering, preferably sintering the 7-20 o'clock Ma該mixture at 700 to 1000 ° C., to obtain a sintered body performs pulverizng of sintered bodies, multi-component material having a gradient structure for a lithium battery The process of obtaining.
また、本発明は、リチウムイオン電池用の傾斜構造を有する上記多成分材料から調製されたリチウムイオン電池の正極を提供する。調製方法は、従来技術の方法を参照してよい。例えば、上記リチウムイオン電池用の傾斜構造を有する多成分材料を、カーボンブラックとポリフッ化ビニリデン（ＰＶＤＦ）と重量比９４％：３％：３％でブレンドして、得られた混合物をコーティングして電極板を形成することで、リチウムイオン電池の正極を作製してもよい。 Moreover, this invention provides the positive electrode of the lithium ion battery prepared from the said multi-component material which has the inclination structure for lithium ion batteries. The preparation method may refer to a prior art method. For example, the multi-component material having a gradient structure for the lithium-ion battery, the weight ratio of 94% carbon black and polyvinylidene fluoride (PVDF): 3%: a blend with 3%, the resulting mixture was co Computing Then, the positive electrode of the lithium ion battery may be produced by forming an electrode plate.
前駆体沈殿物を濾過し、洗浄し、１２０℃で乾燥させることにより、多成分材料の前駆体を得る。前駆体を水酸化リチウムと１：１．０５のモル比で完全に混合して混合物を得、該混合物を、空気雰囲気中、８９０℃で１０時間保持し、焼結体を得る。該焼結体の自然冷却、粉砕および篩い分けを行い、それによって傾斜構造を有する球状の多成分材料を得る。 The precursor precipitate is filtered, washed and dried at 120 ° C. to obtain a multi-component material precursor. The precursor and lithium hydroxide were mixed thoroughly in a molar ratio of 1.05 to obtain a mixture, the mixture in air atmosphere, for 10 hours retained at 890 ° C., to obtain a sintered body. Natural cooling of the sintered body, and milling and sieving, thereby obtaining a multi-component material of spherical shape having an inclined structure.
上記のリチウムイオン電池用の傾斜構造を有する多成分材料を、カーボンブラックとポリフッ化ビニリデン（ＰＶＤＦ）と重量比９４％：３％：３％でブレンドし、得られた混合物をコーティングして電極板を形成し、このように作製したリチウムイオン電池の正極、負極として人造黒鉛を用いた電極、正極と負極の間のセパレータを、ロールしてから電解液を注入して、角形のアルミニウムシェル電池０５３０４８を形成した。これは、具体的には先行技術の作製方法を参照することができる。 The multi-component material having a gradient structure for a lithium ion battery above, the weight ratio of 94% carbon black and polyvinylidene fluoride (PVDF): 3%: a blend with 3%, the resulting mixture was co computing electrodes A rectangular aluminum shell battery in which a plate is formed and a positive electrode of the lithium ion battery thus produced, an electrode using artificial graphite as a negative electrode, a separator between the positive electrode and the negative electrode is rolled, and then an electrolyte is injected. 053048 was formed. Specifically, reference can be made to a prior art manufacturing method.
前駆体沈殿物を濾過し、洗浄し、１１０℃で乾燥させることにより、多成分材料の前駆体を得る。前駆体と水酸化リチウムとを１：１．０５のモル比で完全に混合して混合物を得、該混合物を、酸素ガスの雰囲気中で８９０℃で１０時間保持し、焼結体を得る。該焼結体の自然冷却、粉砕および篩い分けを行うことによって、傾斜構造を有する球状の多成分材料を得る。
The precursor precipitate is filtered, washed and dried at 110 ° C. to obtain a multi-component material precursor.
前駆体沈殿物を濾過し、洗浄し、８０℃で乾燥させることにより、多成分材料の前駆体を得る。前駆体を炭酸リチウムと１：０．５２のモル比で完全に混合して混合物を得、該混合物を、酸素ガス雰囲気中、８００℃で１５時間保持し、焼結体を得る。該焼結体の自然冷却、粉砕および篩い分けを行い、それによって傾斜構造を有する球状の多成分材料を得る。 The precursor precipitate is filtered, washed and dried at 80 ° C. to obtain a multi-component material precursor. The precursor and lithium carbonate were mixed 1: thoroughly in a molar ratio of 0.52 to obtain a mixture, the mixture, in oxygen atmosphere, for 15 hours retained at 800 ° C., to obtain a sintered body. Natural cooling of the sintered body, and milling and sieving, thereby obtaining a multi-component material of spherical shape having an inclined structure.
前駆体沈殿物を濾過し、洗浄し、１００℃で乾燥させることにより、多成分材料の前駆体を得る。前駆体を炭酸リチウムと１：０．５２５のモル比で完全に混合して混合物を得、該混合物を、空気中、９５０℃で１６時間保持し、焼結体を得る。該焼結体の自然冷却、粉砕および篩い分けを行い、それによって傾斜構造を有する球状の多成分材料を得る。 The precursor precipitate is filtered, washed and dried at 100 ° C. to obtain a multi-component material precursor. The precursor and lithium carbonate 1: thoroughly mixed in a molar ratio of 0.525 to obtain a mixture, the mixture in air for 16 hours retained at 950 ° C., to obtain a sintered body. Natural cooling of the sintered body, and milling and sieving, thereby obtaining a multi-component material of spherical shape having an inclined structure.
前駆体沈殿物を濾過し、洗浄し、１４０℃で乾燥させることにより、多成分材料の前駆体を得る。前駆体を硝酸リチウムと１：１．０３のモル比で完全に混合して混合物を得、該混合物を、酸素ガスの雰囲気中で、８２０℃で１２時間保持し、焼結体を得る。該焼結体の自然冷却、粉砕および篩い分けを行い、それによって傾斜構造を有する球状の多成分材料を得る。 The precursor precipitate is filtered, washed and dried at 140 ° C. to obtain a multi-component material precursor. The precursor and lithium nitrate were mixed 1: thoroughly in a molar ratio of 1.03 to obtain a mixture, the mixture, in an atmosphere of oxygen gas, and 12 hours hold at 820 ° C., to obtain a sintered body . Natural cooling of the sintered body, and milling and sieving, thereby obtaining a multi-component material of spherical shape having an inclined structure.
前駆体沈殿物を濾過し、洗浄し、５００℃で焼成することにより、多成分材料の前駆体を得る。前駆体を水酸化リチウムと１：１．０４のモル比で完全に混合して混合物を得、該混合物を、酸素ガスの雰囲気中に、７５０℃で１５時間保持し、焼結体を得る。該焼結体の自然冷却、粉砕および篩い分けを行い、それによって傾斜構造を有するほぼ球形の多成分材料を得る。 The precursor precipitate is filtered, washed, and calcined at 500 ° C. to obtain a multi-component material precursor. The precursor and lithium hydroxide were mixed thoroughly in a molar ratio of 1.04 to obtain a mixture, the mixture, in an atmosphere of oxygen gas, and 15 hours hold at 750 ° C., the sintered body obtain. Natural cooling of the sintered body, and milling and sieving, thereby obtaining a substantially spherical multi-component material having a gradient structure.
前駆体沈殿物を濾過し、洗浄し、６００℃で焼成することにより、多成分材料の前駆体を得る。前駆体を水酸化リチウムと１：１．０４のモル比で完全に混合して混合物を得、該混合物を、酸素ガスの雰囲気中において温度８００℃で１６時間保持し、焼結体を得る。該焼結体の自然冷却、粉砕および篩い分けを行い、それによって傾斜構造を有する球状の多成分材料を得る。 The precursor precipitate is filtered, washed, and calcined at 600 ° C. to obtain a multi-component material precursor. The precursor and lithium hydroxide were mixed thoroughly in a molar ratio of 1.04 to obtain a mixture, the mixture was 16 hours hold at temperature 800 ° C. in an atmosphere of oxygen gas, the sintered body obtain. Natural cooling of the sintered body, and milling and sieving, thereby obtaining a multi-component material of spherical shape having an inclined structure.
前駆体沈殿物を濾過し、洗浄し、１３０℃で乾燥させることにより、多成分材料の前駆体を得る。前駆体を水酸化リチウムと１：１．０４のモル比で完全に混合して混合物を得、該混合物を、酸素ガスの雰囲気中で温度７６０℃で１５時間保持し、焼結体を得る。該焼結体の自然冷却、粉砕および篩い分けを行い、それによって傾斜構造を有する球状の多成分材料を得る。 The precursor precipitate is filtered, washed and dried at 130 ° C. to obtain a multi-component material precursor. The precursor and lithium hydroxide were mixed thoroughly in a molar ratio of 1.04 to obtain a mixture, the mixture for 15 hours retained at a temperature 760 ° C. in an atmosphere of oxygen gas, the sintered body obtain. Natural cooling of the sintered body, and milling and sieving, thereby obtaining a multi-component material of spherical shape having an inclined structure.
前駆体沈殿物を濾過し、洗浄し、１２０℃で乾燥することにより、多成分材料の前駆体を得る。前駆体を水酸化リチウムと１：１．０５のモル比で完全に混合して混合物を得、該混合物を、空気雰囲気中、温度８９０℃で１０時間保持し、焼結体を得る。該焼結体の自然冷却、粉砕および篩い分けを行い、それによって傾斜構造を有する球状の多成分材料を得る。 The precursor precipitate is filtered, washed, and dried at 120 ° C. to obtain a multi-component material precursor. The precursor and lithium hydroxide were mixed thoroughly in a molar ratio of 1.05 to obtain a mixture, the mixture in air atmosphere, for 10 hours retained at a temperature 890 ° C., to obtain a sintered body. Natural cooling of the sintered body, and milling and sieving, thereby obtaining a multi-component material of spherical shape having an inclined structure.
Claims (12)
ＬｉＮｉｘＣｏｙＭｎｚＧｄＯ２ 式（Ｉ）
（式中、０．４≦ｘ≦０．９，０≦ｙ＋ｚ≦０．６，０≦ｄ≦０．１，ｘ＋ｙ＋ｚ＋ｄ＝１、ＧはＬｉ、Ｃｒ、Ｆｅ、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｂ、Ａｌ、Ｙ、Ｓｍ、Ｔｉ、Ｚｎ、Ｚｒ、Ｖ、Ｎｂ、Ｔａ、Ｍｏ及びＷ元素の１種以上である。）
で示される平均組成を有し、
リチウムイオン電池用の傾斜構造を有する多成分材料中、Ｎｉ元素の含有量は粒子の中心から表面に向かって連続的に減少する、リチウムイオン電池用の傾斜構造を有する多成分材料。 A multicomponent material having an inclined structure for a lithium ion battery, wherein the multicomponent material is represented by the formula (I):
LiNi x Co y Mn z G d O 2 Formula (I)
(Wherein 0.4 ≦ x ≦ 0.9, 0 ≦ y + z ≦ 0.6, 0 ≦ d ≦ 0.1, x + y + z + d = 1, G is Li, Cr, Fe, Mg, Ca, Sr, Ba, B, Al, Y, Sm, Ti, Zn, Zr, V, Nb, Ta, Mo and one or more of W elements.)
Having an average composition represented by
A multi-component material having an inclined structure for a lithium-ion battery, wherein the content of Ni element continuously decreases from the center of the particle toward the surface in the multi-component material having an inclined structure for a lithium-ion battery.
（１）Ｎｉ含有金属塩を水に溶解して第１塩溶液を調製し、Ｎｉ、Ｃｏ、ＭｎおよびＧ元素の１種以上を含む金属塩を水に溶解して第２塩溶液を調製する工程；
（２）撹拌しながら第２塩溶液を第１塩溶液に徐々に添加して混合塩溶液を得、次いで、混合塩溶液、錯化剤および沈殿剤を反応器に同時に注入し、ｐＨ値を８〜１３、反応温度を４０〜８０℃、反応時間を５〜５０時間に制御することにより前駆体沈殿物を得、前駆体沈殿物を濾過、洗浄、熱処理した後、傾斜構造を有する多成分材料の前駆体を得る工程；
（３）傾斜構造を有する多成分材料の前駆体と、リチウム源とを均一に混合し、空気または酸素ガスの反応雰囲気中で５００〜１１００℃で４〜３０時間焼成し、粉砕してリチウムイオン電池用の傾斜構造を有する多成分材料を得る工程
を含む、請求項１〜３のいずれか一項に記載のリチウムイオン電池用の傾斜構造を有する多成分材料の調製方法。 The following steps:
(1) A first salt solution is prepared by dissolving a Ni-containing metal salt in water, and a second salt solution is prepared by dissolving a metal salt containing one or more of Ni, Co, Mn and G elements in water. Process;
(2) The second salt solution is gradually added to the first salt solution with stirring to obtain a mixed salt solution, and then the mixed salt solution, complexing agent and precipitating agent are simultaneously injected into the reactor to adjust the pH value. 8-13, a precursor precipitate is obtained by controlling the reaction temperature to 40 to 80 ° C. and the reaction time to 5 to 50 hours, and after the precursor precipitate is filtered, washed and heat-treated, it has a multi-component having a gradient structure Obtaining a precursor of the material;
(3) A precursor of a multi-component material having an inclined structure and a lithium source are uniformly mixed, calcined at 500 to 1100 ° C. for 4 to 30 hours in a reaction atmosphere of air or oxygen gas, pulverized and lithium ions The preparation method of the multicomponent material which has the inclination structure for lithium ion batteries as described in any one of Claims 1-3 including the process of obtaining the multicomponent material which has the inclination structure for batteries.
A lithium ion battery comprising the positive electrode of the lithium ion battery according to claim 10.
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| CN110224123A (en) * | 2019-06-13 | 2019-09-10 | 广东邦普循环科技有限公司 | A kind of high voltage lithium cobalt oxide anode and its preparation method and application |
| JP2021520052A (en) * | 2018-05-21 | 2021-08-12 | エルジー・ケム・リミテッド | Positive electrode for secondary battery and secondary battery including this |
| JP2022529760A (en) * | 2020-03-27 | 2022-06-24 | 深▲セン▼市貝特瑞納米科技有限公司 | Positive electrode material, its manufacturing method and lithium secondary battery |
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|---|---|
| KR20170102293A (en) | 2017-09-08 |
| JP6612356B2 (en) | 2019-11-27 |
| CN107004851A (en) | 2017-08-01 |
| WO2016107237A1 (en) | 2016-07-07 |
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