CN105810894A - Multilayer coated structure lithium ion battery positive electrode material preparation method - Google Patents
Multilayer coated structure lithium ion battery positive electrode material preparation method Download PDFInfo
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- CN105810894A CN105810894A CN201410848430.9A CN201410848430A CN105810894A CN 105810894 A CN105810894 A CN 105810894A CN 201410848430 A CN201410848430 A CN 201410848430A CN 105810894 A CN105810894 A CN 105810894A
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000007774 positive electrode material Substances 0.000 title abstract 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 72
- 239000000463 material Substances 0.000 claims abstract description 44
- 239000011248 coating agent Substances 0.000 claims abstract description 31
- 238000000576 coating method Methods 0.000 claims abstract description 31
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 238000005245 sintering Methods 0.000 claims abstract description 9
- 239000007791 liquid phase Substances 0.000 claims abstract description 5
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 3
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 22
- 239000010405 anode material Substances 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 238000005253 cladding Methods 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- 230000006911 nucleation Effects 0.000 claims description 13
- 238000010899 nucleation Methods 0.000 claims description 13
- 229910021529 ammonia Inorganic materials 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 8
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000001099 ammonium carbonate Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 4
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 4
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 4
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 4
- 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
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 3
- 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 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 239000004254 Ammonium phosphate Substances 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
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 150000004703 alkoxides Chemical class 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 2
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- 239000011775 sodium fluoride Substances 0.000 claims description 2
- 235000013024 sodium fluoride Nutrition 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 abstract description 16
- 238000000034 method Methods 0.000 abstract description 14
- 239000000047 product Substances 0.000 abstract 2
- 239000002244 precipitate Substances 0.000 abstract 1
- 238000004062 sedimentation Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 45
- 238000003756 stirring Methods 0.000 description 17
- 239000012266 salt solution Substances 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000005406 washing Methods 0.000 description 8
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 238000010923 batch production Methods 0.000 description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 3
- 229940097267 cobaltous chloride Drugs 0.000 description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 description 3
- 239000011565 manganese chloride Substances 0.000 description 3
- 235000002867 manganese chloride Nutrition 0.000 description 3
- 229940099607 manganese chloride Drugs 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 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 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 229940071125 manganese acetate Drugs 0.000 description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 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 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 1
- 229910013172 LiNixCoy Inorganic materials 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 206010016766 flatulence Diseases 0.000 description 1
- 229940053652 fluorinse Drugs 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- -1 nickel salt Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a multilayer coated structure lithium ion battery positive electrode material preparation method. The preparation method comprises preparing a spherical core through a reaction through a liquid phase sedimentation method, adding reaction solutions with different formulas into the spherical core in a concurrent flow way so that precipitates grow on the spherical surface of the inner core, carrying out one or more layer coating through a spheroidization preparation device and method to obtain a multilayer-coated spherical precursor material and carrying out mixing sintering on the precursor material and a lithium salt to obtain the lithium ion battery positive electrode material. The preparation method simplifies equipment and operation processes, reduces a cost, has a smooth process, can easily control reaction system and product index stability and obviously improves product performances.
Description
Technical field
The preparation method that the present invention relates to the anode material for lithium-ion batteries of a kind of multilayer coating structure, in particular relates to the continuous preparation method of the spherical multicomponent material of a kind of lithium ion battery multilayer coating structure.
Background technology
Lithium ion battery multicomponent material is generally LiNixCoyMn1-x-yMO2Form, in its solid solution, the raising specific capacity along with Ni content increases to some extent, such as LiNi0.8Co0.1Mn0.1O2Reversible capacity is up to 190mAh/g, considerably beyond LiCoO2(the lithium electricity positive electrode that application is maximum at present, specific capacity is about 145mAh/g), but the cycle performance of material, security performance decline therewith, how when not sacrificing capacity, simultaneously improve its circulation and security performance, become problem demanding prompt solution.
Multicomponent material presoma is generally spherical morphology, its performance directly influences multicomponent material and the performance of lithium ion battery made thereof, patent document CN101997113A provides a kind of technology in the process prepare presoma, material being coated with, to solve the performance issue of above-mentioned multicomponent material, its kernel adopts nickelic formula, prepares lithium ion battery and can play the height ratio capacity advantage of material；Clad adopts low nickel or without nickel formula, it is possible to increase the high temperature cyclic performance of battery and security performance.Adopting the capacity of lithium ion battery that this material is prepared high, battery tympanites is little, and high temperature circulation is stable, safety is high, and material preparation process is simple, relative inexpensiveness.
Sphere material generally can adopt the liquid phase deposition of interval to prepare, and is namely initially formed kernel precipitation and is collected, is subsequently adding in synthesis reactor as end liquid again at Surface Creation clad, and the reaction of interruption prepares the sphere material of multilayer coating structure.Patent document CN1635649 adopts batch process to be coated with one layer of cobalt hydroxide at ball shape nickel hydroxide surface, but batch process there is also the defect of self, preparation process and product index less stable, and technological process is smooth and easy not, and more difficult in control, processing cost is higher.Patent document CN1206072 discloses the continuous preparation method of a kind of spherical powder, at a certain temperature, respectively certain density nickel salt, sodium hydroxide, ammonia or the form with nickel salt+ammonia, sodium hydroxide+ammonia are continuously added in reactor, controlling the pH value of reaction system, reactant mean residence time and stirring condition, nickel hydroxide crystallizes out with spheroidal particle.Achieve the control of nickel hydroxide mean diameter and particle size distribution in this patent, but the method only achieves the preparation of ball material, prepared by the continuous way of unrealized multilayer coating structure sphere material.
Summary of the invention
The preparation method of the anode material for lithium-ion batteries of a kind of multilayer coating structure provided by the invention, this process simplify equipment and operation sequence, reduce cost, technological process ratio is smoothly, the stability of reaction system and product index can be controlled with comparalive ease, and properties of product obtain and are obviously improved.
Technical scheme is as follows:
The preparation method of the anode material for lithium-ion batteries of a kind of multilayer coating structure, comprises the steps:
(1) with liquid phase deposition, nucleation reaction solution is continued and in the nucleation reactor (0) that is injected into of stream, control reaction solution concentration 1 ~ 2mol/L, response time 5 ~ 30h, make reacted serosity naturally overflow in first order reaction still (1)；
(2) being continued by coating solution and stream is injected in first order reaction still (1), control the concentration 1 ~ 2mol/L of coating solution, response time 1 ~ 30h, reacted serosity overflows in secondary response still (2) naturally；
(3) serosity after ageing, by material filtering, washing, dries, obtains the spherical precursor material of spherical one layer cladding in secondary response still (2)；
When being coated with number of plies n > 1,
(4) n order reaction still serosity is constantly to n+1 order reaction still overflow, is continued by coating solution and stream is injected in n+1 order reaction still, controls response time 1 ~ 30h, and reacted serosity overflows in n+2 order reaction still naturally；Serosity after ageing, by material filtering, washing, dries, obtains the spherical precursor material of spherical n layer clad structure in n+2 order reaction still；
(5) by above-mentioned persursor material and lithium salts mix, under air or oxygen atmosphere, sintering prepares the anode material for lithium-ion batteries of multilayer coating structure.
In above-mentioned preparation method, the described cladding number of plies is generally 1-5.
Preferably, in above-mentioned preparation method, the reactor in each step is both preferably stirred autoclave.
In above-mentioned preparation method, in described step (1), nucleation reaction solution all includes metal mixed saline solution with coating solution in step (2), (4), and its metal consists of NixM1-x, wherein 0.5≤x≤1.0 in step (1), 0≤x≤0.5 in step (2), (4), one or more in Co, Mn, Fe, Mg, Ca, Sr, Ba, B, Al, Y, Sm, Ti, Zn, Zr, Nb, Mo or W of M.
In above-mentioned preparation method, the salt a kind of or wherein several mixture in sulfate, chlorate, nitrate, acetate or alkoxide in described metal mixed saline solution.
In above-mentioned preparation method, in described step (1), nucleation reaction solution all includes precipitant with coating solution in step (2), (4), the precipitant a kind of or wherein several mixture in ammonia, sodium hydroxide, potassium hydroxide, Lithium hydrate, sodium dihydrogen phosphate, disodium hydrogen phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, ammonium phosphate, ammonium hydrogen carbonate, ammonium carbonate, sodium bicarbonate, sodium carbonate, potassium carbonate, sodium fluoride, ammonium fluoride.
In above-mentioned preparation method, in described step (1), in nucleation reaction solution and step (2), (4), coating solution can also include reaction promoter, and reaction promoter is selected from a kind of in EDTA, ammonia, ammonium chloride, ammonium sulfate, ammonium nitrate, air, oxygen, ozone, hydrogen peroxide, sodium hypochlorite, sodium peroxydisulfate, nitrogen or wherein several nonreactive mixture.
In above-mentioned preparation method, the scope of the final anode material for lithium-ion batteries meso-position radius prepared is 3 ~ 25 μm.
Principles of the invention is: adopt liquid phase deposition, successive reaction prepares spherical inner core, simultaneously by the reaction solution of different formulations and flow addition, it is deposited in the spherical surface cladding growth of kernel, one layer of clad structure persursor material to multilamellar is realized by continuous way preparation facilities and method, again persursor material is mixed with lithium source, sinters, finally give the anode material for lithium-ion batteries of multilayer coating structure.
The present invention has an advantage that
1. adopt continuity method to prepare the ball-shaped lithium-ion battery anode material of multilayer coating structure, devise a set of reaction method and device, decrease unnecessary centrifugation apparatus compared with batch process, simplify operation sequence, reduce cost.
2. by reacting pH, temperature, the control of time, it is possible to realize continuously performing of reaction；Technological process ratio is smoothly, it is possible to be relatively easy to control the stability of reaction system and product index.
3. compared with batch process, more prominent, the anode material for lithium-ion batteries of multilayer coating structure prepared by employing continuity method, production efficiency is higher, and quality consistency is higher, and product is finer and close, and pattern and covered effect are better.
Embodiment 1
nullBy nickel sulfate、Cobaltous sulfate,The mixing salt solution (1) obtaining 2mol/L is dissolved according to the metal molar ratio than 0.80:0.20，By mixing salt solution (1)、10.5mol/L ammonia spirit，The sodium hydroxide solution of 10mol/L and flows in the nucleation reactor adding stirring simultaneously，The control response time is 30h，The pH value of reaction system solution is 12.3，It is 60 DEG C that heating in water bath controls temperature，Reacted serosity is made naturally to overflow in first order reaction still，By Nickel dichloride.、Cobaltous chloride、Manganese chloride、Magnesium chloride dissolves the mixing salt solution (2) obtaining 2mol/L according to the metal molar ratio than 0.33:0.33:0.33:0.01，By mixing salt solution (2)、10.5mol/L ammonia、The sodium hydroxide solution of 10mol/L and flows in the first order reaction still adding stirring simultaneously，Reaction is at N2Carrying out under atmosphere protection, the control response time is 29h, and the pH value of reaction system solution is 11.0, and it is 60 DEG C that heating in water bath controls temperature, in core surface cladding growth, by material filtering, washing, drying after reaction, obtains the spherical precursor material of one layer of cladding.By above-mentioned persursor material and Lithium hydrate mix, in air atmosphere, 880 DEG C of sintering 15h, prepare the anode material for lithium-ion batteries of one layer of clad structure, testing this positive electrode meso-position radius is 15.3mm.
Embodiment 2
1.5mol/L nickel nitrate solution, the sodium hydroxide solution of 8mol/L, 5mol/L ammonia simultaneously and are flowed in the nucleation reactor adding stirring, the control response time is 30h, the pH value of reaction system solution is 12.6, and controlling temperature is 55 DEG C, and precipitation nature overflows in first order reaction still.
Nickel nitrate, manganese nitrate are dissolved the mixing salt solution (2) obtaining 1.8mol/L according to the metal molar ratio than 0.5:0.5, by mixing salt solution (2), the ammonium sulfate of 2mol/L, 5mol/L potassium hydroxide solution simultaneously and flow in the first order reaction still adding stirring, reaction is at N2Carrying out under atmosphere protection, the control response time is 20h, and the pH value of reaction system solution is 11.0, and it is 55 DEG C that heating in water bath controls temperature, and reacted one layer of serosity overflows in secondary response still naturally.
Cobaltous acetate, manganese acetate are dissolved the mixing salt solution (3) obtaining 1.5mol/L according to the metal molar ratio than 0.5:0.5, the disodium phosphate soln of mixing salt solution (3), 2mol/L simultaneously and is flowed in the secondary response still adding stirring, the control response time is 19h, the pH value of reaction system solution is 9.2, it is 55 DEG C that heating in water bath controls temperature, reacted two layers of cladding serosity, through precipitation, washing, dry, obtain the spherical precursor material of two layers of clad structure.By above-mentioned persursor material and lithium carbonate mix, in air atmosphere, 920 DEG C of sintering 12h, prepare the anode material for lithium-ion batteries of two layers of clad structure, testing this positive electrode meso-position radius is 23.1mm.
Embodiment 3
Nickel acetate, cobaltous acetate, manganese acetate are dissolved according to the metal molar ratio than 0.60:0.20:0.20 and obtains the mixing salt solution of 2.0mol/L, the sodium carbonate liquor of 2mol/L, 2mol/L ammonium carbonate and simultaneously and flow in the nucleation reactor adding stirring, the control response time is 5h, the pH value of the solution of reaction system is 8.5, controlling temperature is 45 DEG C, and reacted serosity nature overflow is discharged in first order reaction still.
The mixed liquor of 1.5mol/L that Nickel dichloride., cobaltous chloride, manganese chloride are obtained according to the metal molar ratio than 0.50:0.20:0.30, the ammonium chloride solution of 3mol/L, 8mol/L sodium hydroxide solution simultaneously and flow in the first order reaction still adding stirring, reaction is at N2Carrying out under atmosphere protection, the control response time is 3h, and the pH value of reaction system solution is 11.2, and water bath heating temperature is 50 DEG C, and in spheroidal particle superficial growth, reacted one layer of cladding serosity overflows in secondary response still naturally.
By manganese chloride, the mixing salt solution of 1.5mol/L that magnesium sulfate obtains according to the metal molar ratio than 0.9:0.1,3mol/L sal volatile simultaneously and flow in the secondary response still adding stirring, the control response time is 2h, the pH value of reaction system solution is 9.0, water bath heating temperature is 50 DEG C, in spheroidal particle superficial growth, reacted two layers of cladding serosity overflow in third-order reaction still naturally.
The mixing salt solution of 1.5mol/L that magnesium chloride, aluminum chloride, zirconyl chloride obtained according to the metal molar ratio than 0.4:0.4:0.2,2mol/L ammonium hydrogen carbonate, 3mol/L sodium bicarbonate solution simultaneously and flow in the third-order reaction still adding stirring, the control response time is 1h, the pH value of the solution of reaction system is 8.8, water bath heating temperature is 50 DEG C, in spheroidal particle superficial growth, reacted three layers cladding serosity overflows in fourth-order reaction still naturally, through precipitation, washing, dry, obtain the spherical precursor material of three layers clad structure.By above-mentioned persursor material and lithium nitrate mix, under oxygen atmosphere, 930 DEG C of sintering 20h, prepare the anode material for lithium-ion batteries of three layers clad structure, testing this positive electrode meso-position radius is 7.1mm.
Embodiment 4
Nickel sulfate, cobaltous sulfate are dissolved according to the metal molar ratio than 0.9:0.1 and obtains the mixing salt solution of 1.8mol/L, the sodium hydroxide solution of 5mol/L, 12mol/L ammonia and simultaneously and flow in the nucleation reactor adding stirring, the control response time is 13h, the pH value of reaction system solution is 12.5, controlling temperature is 55 DEG C, and precipitation nature overflows in first order reaction still.
By 3mol/L cobalt chloride solution, the hydrogen peroxide of 3mol/L, 5mol/L potassium hydroxide solution simultaneously and flow in the first order reaction still adding stirring, the control response time is 8h, the pH value of reaction system solution is 9.0, it is 60 DEG C that heating in water bath controls temperature, and reacted one layer of serosity overflows in secondary response still naturally.
The Fluorinse of 1.0mol/L aluminum sulfate solution, 1mol/L simultaneously and is flowed in the secondary response still adding stirring, the control response time is 7h, the pH value of reaction system solution is 7.8, it is 60 DEG C that heating in water bath controls temperature, reacted two layers of cladding serosity, through precipitation, washing, dry, obtain the spherical precursor material of two layers of clad structure.By above-mentioned persursor material and lithium carbonate mix, in air atmosphere, 990 DEG C of sintering 10h, prepare the anode material for lithium-ion batteries of two layers of clad structure, testing this positive electrode meso-position radius is 10.2mm.
Embodiment 5
nullBy nickel sulfate、Cobaltous sulfate、Aluminum sulfate dissolves the mixing salt solution obtaining 1.8mol/L according to the metal molar ratio than 0.8:0.17:0.03、The EDTA solution of 1mol/L、The ammonia of 5mol/L、5mol/L sodium hydroxide solution and flows in the nucleation reactor adding stirring simultaneously，The control response time is 25h，The pH value of reaction system solution is 11.5，It is 50 DEG C that heating in water bath controls temperature，Reacted serosity is made naturally to overflow in first order reaction still，The phosphoric acid ammonia solution of the aluminum nitrate solution of 1mol/L with 1mol/L and is flowed in the first order reaction still adding stirring simultaneously，The control response time is 18h，The pH value of reaction system solution is 9，It is 50 DEG C that heating in water bath controls temperature，In core surface cladding growth，By material filtering after reaction、Washing、Dry，Obtain the spherical precursor material of one layer of cladding.By above-mentioned persursor material and Lithium hydrate mix, under oxygen atmosphere, 850 DEG C of sintering 12h, prepare the anode material for lithium-ion batteries of one layer of clad structure, testing this positive electrode meso-position radius is 13.5mm.
Embodiment 6
The nickel sulfate solution of 1.5mol/L, the sodium hydroxide solution of 10mol/L, 2mol/L ammonium sulfate simultaneously and are flowed in the nucleation reactor adding stirring, the control response time is 16h, the pH value of the solution of reaction system is 12.9, controlling temperature is 65 DEG C, and reacted serosity nature overflow is discharged in first order reaction still.
Cobaltous chloride, magnesium chloride, aluminum chloride are dissolved the mixing salt solution obtaining 1.5mol/L according to the metal molar ratio than 0.9:0.05:0.05, by mixing salt solution, the sodium hypochlorite of 1mol/L, 5mol/L sodium hydroxide solution simultaneously and flow in the first order reaction still adding stirring, the control response time is 10h, the pH value of reaction system solution is 9.5, it is 65 DEG C that heating in water bath controls temperature, in core surface cladding growth, by material filtering, washing, drying after reaction, obtain the spherical precursor material of one layer of cladding.By above-mentioned persursor material and lithium carbonate mix, in air atmosphere, 980 DEG C of sintering 15h, prepare the anode material for lithium-ion batteries of one layer of clad structure, testing this positive electrode meso-position radius is 4.2mm.
Claims (6)
1. a preparation method for the anode material for lithium-ion batteries of multilayer coating structure, is made up of following steps:
(1) continue to be injected in nucleation reactor (0) by nucleation reaction solution with liquid phase deposition, control response time 5 ~ 30h, make reacted serosity naturally overflow in first order reaction still (1)；
(2) being continued by coating solution and stream is injected in first order reaction still (1), control coating response time 1 ~ 30h, reacted serosity overflows in secondary response still (2) naturally；
(3) serosity after ageing, by material filtering, dries, obtains the spherical precursor material of one layer of cladding in secondary response still (2)；
When being coated with number of plies n > 1,
(4) n order reaction still serosity is constantly to n+1 order reaction still overflow, is continued by coating solution and stream is injected in n+1 order reaction still, controls response time 1 ~ 30h, and reacted serosity overflows in n+2 order reaction still naturally；Serosity after ageing, by material filtering, dries, obtains the spherical precursor material of n layer clad structure in n+2 order reaction still;
(5) by above-mentioned persursor material and lithium salts mix, under air or oxygen atmosphere, sintering prepares the anode material for lithium-ion batteries of multilayer coating structure.
2. the preparation method of the anode material for lithium-ion batteries of multilayer coating structure according to claim 1, it is characterised in that the scope of described anode material for lithium-ion batteries meso-position radius is 3 ~ 25 μm.
3. the preparation method of the anode material for lithium-ion batteries of multilayer coating structure according to claim 1, it is characterised in that in described step (1), nucleating solution is metal mixed saline solution with coating solution in step (2), (4), and it consists of NixM1-x, wherein 0.5≤x≤1.0 in step (1), 0≤x≤0.5 in step (2), (4), one or more in Co, Mn, Fe, Mg, Ca, Sr, Ba, B, Al, Y, Sm, Ti, Zn, Zr, Nb, Mo or W of M.
4. the preparation method of the anode material for lithium-ion batteries of multilayer coating structure according to claim 3, it is characterised in that described metal mixed saline solution is a kind of or wherein several mixture in sulfate, chlorate, nitrate, acetate or alkoxide.
5. the preparation method of the anode material for lithium-ion batteries of multilayer coating structure according to claim 1, it is characterized in that in described step (1), nucleating solution also includes precipitant with coating solution in step (2), (4), precipitant is a kind of or wherein several mixture in sodium hydroxide, potassium hydroxide, Lithium hydrate, sodium dihydrogen phosphate, disodium hydrogen phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, ammonium phosphate, ammonium hydrogen carbonate, ammonium carbonate, sodium bicarbonate, sodium carbonate, potassium carbonate, sodium fluoride, ammonium fluoride.
6. the preparation method of the sphere material of multilayer coating structure according to claim 1, it is characterized in that in described step (1), in nucleating solution and step (2), (4), coating solution also includes reaction promoter solution, reaction promoter is a kind of in EDTA, ammonia, ammonium chloride, ammonium sulfate, ammonium nitrate, air, oxygen, ozone, hydrogen peroxide, sodium hypochlorite, sodium peroxydisulfate, nitrogen or wherein several nonreactive mixture.
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| CN112713263A (en) * | 2020-12-14 | 2021-04-27 | 宁波维科新能源科技有限公司 | Preparation method of metaphosphate coated lithium cobaltate material and lithium ion battery comprising metaphosphate coated lithium cobaltate material |
| CN112713263B (en) * | 2020-12-14 | 2021-12-28 | 宁波维科新能源科技有限公司 | Preparation method of metaphosphate coated lithium cobaltate material and lithium ion battery comprising metaphosphate coated lithium cobaltate material |
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