CN118054008A - Composite lithium ion battery positive electrode material with primary and secondary sphere morphology and preparation method thereof - Google Patents
Composite lithium ion battery positive electrode material with primary and secondary sphere morphology and preparation method thereof Download PDFInfo
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 85
- 239000002131 composite material Substances 0.000 title claims abstract description 66
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000010405 anode material Substances 0.000 claims abstract description 52
- 239000002994 raw material Substances 0.000 claims abstract description 47
- 238000002156 mixing Methods 0.000 claims abstract description 41
- 239000002245 particle Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000007787 solid Substances 0.000 claims abstract description 14
- 238000001694 spray drying Methods 0.000 claims abstract description 14
- 238000001238 wet grinding Methods 0.000 claims abstract description 8
- 239000002002 slurry Substances 0.000 claims description 19
- 238000005245 sintering Methods 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 16
- 238000005303 weighing Methods 0.000 claims description 16
- 239000008188 pellet Substances 0.000 claims description 14
- 239000002270 dispersing agent Substances 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 11
- 239000000654 additive Substances 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 34
- 238000005469 granulation Methods 0.000 abstract description 13
- 230000003179 granulation Effects 0.000 abstract description 13
- 230000007547 defect Effects 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 238000009792 diffusion process Methods 0.000 abstract description 3
- 239000003792 electrolyte Substances 0.000 abstract description 3
- 239000011572 manganese Substances 0.000 description 25
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 239000003570 air Substances 0.000 description 11
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 11
- 229910052808 lithium carbonate Inorganic materials 0.000 description 11
- 239000004576 sand Substances 0.000 description 11
- 239000012298 atmosphere Substances 0.000 description 10
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 10
- 239000002243 precursor Substances 0.000 description 10
- 102220043159 rs587780996 Human genes 0.000 description 10
- 238000004321 preservation Methods 0.000 description 9
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 4
- 229910009055 Li1.2Ni0.2Mn0.6O2 Inorganic materials 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910016087 LiMn0.5Ni0.5O2 Inorganic materials 0.000 description 2
- 229910014689 LiMnO Inorganic materials 0.000 description 2
- 229910011328 LiNi0.6Co0.2Mn0.2O2 Inorganic materials 0.000 description 2
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 2
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005056 compaction Methods 0.000 description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 2
- 229960001031 glucose Drugs 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- GBCAVSYHPPARHX-UHFFFAOYSA-M n'-cyclohexyl-n-[2-(4-methylmorpholin-4-ium-4-yl)ethyl]methanediimine;4-methylbenzenesulfonate Chemical compound CC1=CC=C(S([O-])(=O)=O)C=C1.C1CCCCC1N=C=NCC[N+]1(C)CCOCC1 GBCAVSYHPPARHX-UHFFFAOYSA-M 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- -1 oxides Chemical class 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000005955 Ferric phosphate Substances 0.000 description 1
- 229910008514 Li1.2Mn0.54Ni0.13Co0.13O2 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 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
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 229940071257 lithium acetate Drugs 0.000 description 1
- 229940008015 lithium carbonate Drugs 0.000 description 1
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 229940077478 manganese phosphate Drugs 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229940053662 nickel sulfate Drugs 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a composite lithium ion battery anode material with a primary-secondary sphere morphology and a preparation method thereof, wherein different raw materials are mixed by different mixing methods, and are calcined to generate 'secondary spheres'; and then wet grinding, wet mixing and centrifugal spray drying granulation are carried out to obtain the composite lithium ion battery anode material with the shape of 'primary and secondary spheres'. The particle size of the process of generating the 'sub-spheres' is controllable, the 'sub-spheres' are filled into the 'mother spheres', and the interval gaps between the solid 'sub-spheres' are beneficial to electrolyte permeation, so that as much space as possible is provided for lithium ion diffusion, and the rate performance and high-low temperature performance of the composite material are effectively improved. The method has simple process and low cost, and perfectly solves the defects of low initial coulomb efficiency, cycle capacity attenuation, fast voltage attenuation and the like of the positive electrode materials of the lithium ion batteries of different types. The lithium ion battery composite anode material prepared by the method has the advantages of the primary and secondary materials and has higher compatibility.
Description
Technical Field
The invention relates to the field of lithium ion battery anode materials, in particular to a composite lithium ion battery anode material with a primary-secondary morphology and a preparation method thereof.
Background
The lithium ion battery has the advantages of high specific energy, no memory effect, long cycle life and the like, is praised as the most potential secondary power supply, and becomes the main current power supply of portable electronic products such as mobile phones, notebook computers and the like. Meanwhile, in the field of power batteries, high energy density and rapid charge and discharge capability are particularly important indicators. The current power lithium ion battery cannot meet the rapidly-growing market demand. The energy density of the battery is mainly the energy density of an electrode material, and the positive electrode materials which are commercially applied at present are lithium cobaltate, lithium manganate, ternary materials, lithium iron phosphate and the like, and the materials have respective problems in terms of energy density, cycle performance, safety and cost. And thus developed.
Because the existing lithium ion battery anode material has the defects of low initial coulomb efficiency, poor multiplying power performance, quick cycle attenuation and the like, people generally use means such as cladding, doping, compounding new materials and the like to improve the electrochemical performance of the material.
Disclosure of Invention
Aiming at the defects that the existing lithium ion battery positive electrode material is insufficient and direct mixing is not suitable among different positive electrode materials, the invention provides a preparation method of a composite lithium ion battery positive electrode material with a primary-secondary sphere morphology and a product thereof, and aims to prepare the lithium ion battery positive electrode material with a special primary-secondary sphere morphology, adjustable internal primary-secondary sphere particle size and complete external primary-secondary sphere morphology. The method has simple process and low cost, and perfectly solves the defects of low initial coulomb efficiency, cycle capacity attenuation, fast voltage attenuation and the like of the positive electrode materials of the lithium ion batteries of different types. The lithium ion battery composite anode material prepared by the method has the advantages of the primary and secondary materials and has higher compatibility.
The invention provides a composite lithium ion battery positive electrode material with a primary-secondary sphere morphology, which is characterized by comprising a primary sphere and a secondary sphere, wherein the primary sphere is filled in the secondary sphere, the internal primary sphere is tightly combined with an outer-layer secondary sphere, and gaps are reserved among the multiple primary spheres; the son balls are solid small particles, and the mother balls are hollow large particles; the particle size of the internal son spheres of the positive electrode material can be regulated and controlled, and the appearance of the external mother spheres is complete; the ball is one or more lithium ion battery anode materials, and the mother ball is one lithium ion battery anode material.
The lithium ion battery anode materials used for the pellets and the mother pellets include, but are not limited to, lithium cobaltate, lithium nickelate, lithium manganate, lithium ion battery binary materials, lithium ion battery ternary materials, lithium ion battery multi-element materials, lithium ion battery lithium-rich manganese-based anode materials, lithium iron phosphate, lithium manganese iron phosphate and the like.
Further, the particle size D50 of the son spheres is less than or equal to 10 mu m, and the particle size D50 of the mother spheres is more than or equal to 15 mu m.
Further, the son balls account for 20-80% of the composite lithium ion battery anode material in the morphology of the son-mother balls.
The invention also provides a preparation method of the composite lithium ion battery anode material with the shape of the primary and secondary spheres, which comprises the following steps:
(1) Preparing a ball: weighing various raw materials in stoichiometric ratio according to the pellet chemical formula of the composite lithium ion battery anode material with the morphology of the primary and secondary pellets, mixing the various raw materials by a certain method under the action of a proper amount of additives, and sintering to obtain pellets;
The raw materials for preparing the nanospheres can be one or more of salts, oxides, hydroxides and the like containing metal elements; the mixing method of the raw materials is one or more of wet coprecipitation, a solid phase method, wet grinding, a spray granulation method, a sol-gel method, a hydrothermal method and the like; wherein, the wet grinding can be a planetary ball milling method or a sand milling method; the additive used in the preparation of the pellets can be one or more of ammonia water, sodium hydroxide, potassium hydroxide, sodium carbonate, citric acid, PEG, PAM, PAN, CMC, cetyltrimethylammonium bromide, sodium dodecyl benzene sulfonate, sodium dodecyl sulfonate and polyvinylpyrrolidone; one or more of oxygen, air, argon, nitrogen and hydrogen can be introduced into the sintering process according to different materials.
(2) Preparing a primary-secondary ball: weighing raw materials with stoichiometric ratio according to the chemical formula of the mother balls of the composite lithium ion battery anode material with the morphology of the mother balls, mixing various raw materials by a wet method, adding a certain amount of dispersing agent, carrying out wet grinding after the dispersing is completed, adding the son balls prepared in the first step into slurry after the grinding is completed, uniformly mixing, and carrying out centrifugal spray drying and sintering to obtain the composite lithium ion battery anode material with the morphology of the mother balls.
The raw material can be one or more of salts, oxides, hydroxides and the like containing metal elements when the mother ball is prepared; the solvent in the wet mixing process is one or more of ethanol, deionized water and the like; the mixing mode is one or more of mechanical stirring, ultrasonic dispersing, magnetic stirring and the like; the wet grinding is one or more of a planetary ball mill and a sand mill;
The dispersing agent in the wet mixing process is one or more of PEG, PAM, PAN, CMC, hexadecyl trimethyl ammonium bromide, sodium dodecyl benzene sulfonate, sodium dodecyl sulfonate and polyvinylpyrrolidone; the solid content of the slurry in the wet mixing process is 20% -60%; the D50 of the granularity of the final slurry after wet grinding is below 500 nm; the spray drying granulation particle diameter D50 is more than 15 mu m; one or more of oxygen, air, argon, nitrogen and hydrogen can be introduced into the sintering process according to different materials.
Compared with the prior art, the invention has the beneficial effects that:
(1) The preparation process of the composite lithium ion battery anode material with the shape of the 'primary and secondary spheres' is divided into two parts: the composite lithium ion battery anode material with the shape of the 'primary and secondary spheres' and the 'primary and secondary spheres'. Firstly, mixing different raw materials by different mixing methods, and calcining to generate 'balls'; and then wet grinding, wet mixing and centrifugal spray drying granulation are carried out to obtain the composite lithium ion battery anode material with the shape of 'primary and secondary spheres'. The particle size of the process of generating the 'sub-spheres' is controllable, the 'sub-spheres' are filled into the 'mother spheres', and the interval gaps between the solid 'sub-spheres' are beneficial to electrolyte permeation, so that as much space as possible is provided for lithium ion diffusion, and the rate performance and high-low temperature performance of the composite material are effectively improved. And the 'mother balls' are hollow large particles, so that the lithium ion deintercalation path is shortened, the lithium ions are more beneficial to being intercalated and deintercalated, the cycle efficiency of the material is improved, and the 'son balls' in the composite lithium ion battery anode material with the 'son-mother balls' shape are tightly combined with the hollow 'mother balls' on the outer layer, so that the composite lithium ion battery anode material is not easy to crush and has high tap density, and the structural strain in the charging and discharging processes can be buffered, and the compaction density and the energy density are effectively improved.
(2) The composite lithium ion battery anode material with the shape of the composite 'primary and secondary spheres' synthesized by the invention has high compatibility, can be used for compositing different types of anode materials, perfectly solves the problem that the different types of anode materials are difficult to composite, can fully exert the advantages of the respective materials, inhibit the defects, reach the balance point of performance and cost, and has market application prospect.
(3) The preparation method of the composite lithium ion battery anode material with the shape of the 'primary and secondary spheres' is simple to operate, has clear process and low cost, and is suitable for large-scale industrial production.
Drawings
Fig. 1 is a scanning electron microscope image of a composite lithium ion battery positive electrode material with a morphology of a 'primary and secondary sphere' prepared in example 1.
Fig. 2 shows the first charge-discharge curves at 0.1C of the positive electrode materials prepared in example 1, comparative example 1, and comparative example 2.
Fig. 3 shows the rate performance graphs of the positive electrode materials prepared in example 1, comparative example 1, and comparative example 2.
Fig. 4 is a graph showing the cycle performance of the positive electrode materials prepared in example 1, comparative example 1, and comparative example 2, which were cycled at 1C for 100 weeks.
Detailed Description
The present invention will be described in detail with reference to the following examples.
Example 1
① "Ball": weighing manganese dioxide and nickel hydroxide raw materials according to a stoichiometric ratio Mn: ni=3:1, mixing the manganese dioxide and nickel hydroxide raw materials with deionized water, adding a sodium dodecyl benzene sulfonate dispersing agent with the mass of 3 per mill of the raw materials, transferring into a sand mill to start grinding after the dispersing is completed, and carrying out airflow spray drying granulation after the granularity D50 of the slurry is reduced to below 500nm to obtain a precursor material with the granularity D50=5 mu m. Uniformly mixing the dried material with lithium carbonate according to a stoichiometric ratio, and sintering in an air atmosphere: and (3) carrying out heat preservation at 450 ℃ for 6 hours and at 900 ℃ for 12 hours to obtain the 'sub-spheres' in the composite lithium ion battery anode material with the chemical formula of Li 1.2Ni0.2Mn0.6O2 'sub-mother spheres'.
② "Primary and secondary ball": the 'mother balls' are prepared according to the quantity that 'son balls' of the composite lithium ion battery positive electrode material account for 50 percent of the molar percentage of the composite lithium ion battery positive electrode material. Weighing manganese dioxide, nickel hydroxide and cobaltosic oxide raw materials according to the stoichiometric ratio Mn: ni: co=0.54:0.13:0.13, mixing with deionized water, adding CMC dispersing agent with the mass of 3 per mill of the raw materials, transferring into a sand mill to start grinding after the dispersion is completed, adding the 'pellet' composite lithium ion battery anode material Li 1.2Ni0.2Mn0.6O2 into the slurry after the slurry granularity D50 is reduced to below 500nm, uniformly mixing, and carrying out centrifugal spray drying granulation to obtain the precursor material with the particle size D50=30 mu m. Uniformly mixing the dried material with lithium carbonate according to a stoichiometric ratio, and sintering in an air atmosphere: and (3) carrying out heat preservation at 450 ℃ for 6 hours and at 900 ℃ for 12 hours to obtain the composite lithium ion battery anode material with the chemical formula of 0.5Li1.2Ni0.2Mn0.6O2·0.5Li1.2Mn0.54Ni0.13Co0.13O2" 'primary and secondary balls' morphology.
Example 2
① "Ball": and (3) weighing nickel sulfate, manganese sulfate and cobalt sulfate raw materials according to a stoichiometric ratio of Ni to Mn to Co=3 to 1, uniformly mixing the raw materials with deionized water, adding ammonia water and sodium hydroxide solution into a reaction kettle at the same time, continuously stirring during the reaction, continuously aging for 8 hours after the addition, and carrying out suction filtration, washing and drying on the slurry to obtain a precursor material with the particle size of D50=8 mu m. Uniformly mixing the dried material with lithium carbonate according to a stoichiometric ratio, and sintering in an air atmosphere: and (3) preserving heat for 5h at 450 ℃ and preserving heat for 10h at 750 ℃ to obtain the 'sub-spheres' in the composite lithium ion battery anode material with the chemical formula of LiNi 0.6Co0.2Mn0.2O2 'sub-mother spheres'.
② "Primary and secondary ball": the method comprises the steps of preparing a 'mother ball' according to the amount that 'son ball' of the composite lithium ion battery positive electrode material accounts for 20% of the molar percentage of the composite lithium ion battery positive electrode material. Weighing iron phosphate, lithium carbonate and anhydrous glucose raw materials according to a stoichiometric ratio of Fe to Li to C=1 to 1.05 to 0.8, mixing with deionized water according to a solid content of 50%, adding polyvinylpyrrolidone dispersing agent with a mass of 2 per mill of the raw materials, transferring into a sand mill to start grinding after the dispersion is completed, adding a 'pellet' composite lithium ion battery anode material LiNi 0.6Co0.2Mn0.2O2 into the slurry after the slurry granularity D50 is reduced to below 300nm, uniformly mixing, and performing centrifugal spray drying granulation to obtain a precursor material with a particle size D50=25 mu m. Sintering the dried material in nitrogen atmosphere: and (3) preserving heat for 2h at 350 ℃ and preserving heat for 12h at 650 ℃ to obtain the composite lithium ion battery anode material with the chemical formula of 0.2LiNi 0.6Co0.2Mn0.2O2·0.8LiFePO4 'primary and secondary sphere' morphology.
Example 3
① "Ball": weighing lithium carbonate, manganese dioxide and nickel hydroxide raw materials according to the stoichiometric ratio of Li to Mn to Ni=2 to 1, uniformly mixing the raw materials by a planetary ball mill, and sintering the raw materials in an air atmosphere: and (3) carrying out heat preservation at 450 ℃ for 6 hours and at 720 ℃ for 12 hours to obtain the 'sub-spheres' in the composite lithium ion battery anode material with the chemical formula of LiMn 0.5Ni0.5O2 'sub-mother spheres'.
② "Primary and secondary ball": the method comprises the steps of preparing a 'mother ball' according to the amount that 'son ball' of the composite lithium ion battery positive electrode material accounts for 70% of the molar percentage of the composite lithium ion battery positive electrode material. Weighing manganese dioxide, nickel hydroxide and cobaltosic oxide raw materials according to the stoichiometric ratio Mn: ni: co=1:1:1, mixing the raw materials with deionized water according to the solid content of 30%, adding a PAM dispersing agent with the mass of 1.5 per mill of the raw materials, completely dispersing, transferring into a sand mill, starting grinding, adding LiMn 0.5Ni0.5O2 serving as a 'pellet' composite lithium ion battery anode material into the slurry after the slurry granularity D50 is reduced to below 350nm, uniformly mixing, and performing centrifugal spray drying granulation to obtain a precursor material with the particle size D50=35 mu m. Uniformly mixing the dried material with lithium carbonate according to a stoichiometric ratio, and sintering in an air atmosphere: and (3) carrying out heat preservation at 450 ℃ for 6 hours and at 750 ℃ for 12 hours to obtain the composite lithium ion battery anode material with the chemical formula of 0.7LiMn 0.5Ni0.5O2·0.3LiMn0.33Ni0.33Co0.33O2 'primary and secondary sphere' morphology.
Example 4
① "Ball": weighing lithium acetate, manganese acetate, nickel acetate and cobalt acetate raw materials according to the stoichiometric ratio of Li to Ni to Co=1.05 to 0.8 to 0.1, dissolving the raw materials in deionized water to form a solution, and continuously stirring under the water bath condition of 70 ℃, wherein citric acid and sodium dodecyl benzene sulfonate are added as complexing agents and template agents until gel is formed; the gel obtained was dried in vacuo at 120 ℃ for 10h and then sintered in an oxygen atmosphere: and (3) carrying out heat preservation at 450 ℃ for 6 hours and at 750 ℃ for 12 hours to obtain the 'sub-spheres' in the composite lithium ion battery anode material with the chemical formula of LiNi 0.8Co0.1Mn0.1O2 'sub-mother spheres'.
② "Primary and secondary ball": the 'mother balls' are prepared according to the quantity that 'son balls' of the composite lithium ion battery positive electrode material account for 40% of the molar percentage of the composite lithium ion battery positive electrode material. Weighing manganese phosphate, ferric phosphate, lithium carbonate and anhydrous glucose raw materials according to the stoichiometric ratio Mn: fe: li: C=0.6:0.4:1.05:0.8, mixing the raw materials with deionized water according to the solid content of 40%, adding a PAN dispersing agent with the mass of 2 per mill of the raw materials, transferring the raw materials into a sand mill to start grinding after the raw materials are completely dispersed, adding a 'pellet' composite lithium ion battery anode material LiNi 0.8Co0.1Mn0.1O2 into the slurry after the granularity D50 of the slurry is reduced below 250nm, uniformly mixing, and performing centrifugal spray drying granulation to obtain a precursor material with the granularity D50=20 mu m. Sintering the dried material in nitrogen atmosphere: and (3) preserving heat for 2h at 350 ℃ and preserving heat for 10h at 750 ℃ to obtain the composite lithium ion battery anode material with the chemical formula of 0.4LiNi 0.8Co0.1Mn0.1O2·0.6LiMn0.6Fe0.4PO4 'primary and secondary sphere' morphology.
Example 5
① "Ball": weighing manganese dioxide and nickel hydroxide raw materials according to a stoichiometric ratio Mn: ni=1:1, firstly mixing manganese dioxide with deionized water according to a solid content of 40%, adding PEG dispersing agent with a raw material mass of 1 per mill, after the dispersing is completed, transferring into a sand mill to start grinding, and carrying out airflow spray drying granulation after the slurry granularity D50 is reduced to below 400nm to obtain a precursor material with a particle size D50=6 mu m. Uniformly mixing the dried material with lithium carbonate according to a stoichiometric ratio, and sintering in an air atmosphere: and (3) carrying out heat preservation at 450 ℃ for 6 hours and at 700 ℃ for 12 hours to obtain the 'sub-sphere a' in the composite lithium ion battery anode material with the chemical formula of LiMnO 2 'sub-sphere' morphology. And then the nickel hydroxide is processed according to the same steps to obtain the 'sub-sphere b' in the composite lithium ion battery anode material with the chemical formula of LiNiO 2 'sub-sphere' morphology.
② "Primary and secondary ball": the 'mother balls' are prepared according to the quantity that 'son balls' of the composite lithium ion battery positive electrode material account for 80 percent of the molar percentage of the composite lithium ion battery positive electrode material. Weighing manganese dioxide, nickel hydroxide and cobaltosic oxide raw materials according to the stoichiometric ratio Mn: ni: co=1:1:1, mixing the raw materials with deionized water according to the solid content of 30%, adding a PAM dispersing agent with the mass of 1.5 per mill of the raw materials, completely dispersing, transferring into a sand mill, starting grinding, adding the slurry particle size D50 to below 350nm, adding LiMnO 2 and LiNiO 2 serving as 'pellet' composite lithium ion battery anode materials into the slurry, uniformly mixing, and performing centrifugal spray drying granulation to obtain a precursor material with the particle size D50=35 mu m. Uniformly mixing the dried material with lithium carbonate according to a stoichiometric ratio, and sintering in an air atmosphere: and (3) carrying out heat preservation at 450 ℃ for 6 hours and at 750 ℃ for 12 hours to obtain the composite lithium ion battery anode material with the chemical formula of [0.1LiMnO 2·0.1LiNiO2]·0.8LiMn0.33Ni0.33Co0.33O2 'primary and secondary spheres'.
Comparative example 1
Weighing manganese dioxide and nickel hydroxide raw materials according to a stoichiometric ratio Mn: ni=0.6:0.2, mixing the raw materials with deionized water according to a solid content of 25%, adding a PAM dispersing agent with a mass of 3 per mill of the raw materials, transferring the raw materials into a sand mill to start grinding after the raw materials are completely dispersed, and carrying out airflow spray drying granulation after the slurry granularity D50 is reduced to below 500nm to obtain a precursor material with a particle size D50=5 mu m. Uniformly mixing the dried material with lithium carbonate according to a stoichiometric ratio, and sintering in an air atmosphere: and (3) heat preservation is carried out for 6 hours at 450 ℃ and 12 hours at 900 ℃ to obtain the lithium ion battery anode material with the chemical formula of Li 1.2Ni0.2Mn0.6O2.
Comparative example 2
Weighing manganese dioxide, nickel hydroxide and cobaltosic oxide raw materials according to the stoichiometric ratio Mn: ni: co=0.54:0.13:0.13, mixing with deionized water according to the solid content of 25%, adding PAM dispersing agent with the mass of 2 per mill of the raw materials, transferring into a sand mill to start grinding after the dispersion is completed, and performing centrifugal spray drying granulation after the slurry granularity D50 is reduced to below 300nm to obtain a precursor material with the particle size D50=30 mu m. Uniformly mixing the dried material with lithium carbonate according to a stoichiometric ratio, and sintering in an air atmosphere: heat preservation is carried out for 6h at 450 ℃ and 12h at 900 ℃, and the positive electrode material of the Li 1.2Mn0.54Ni0.13Co0.13O2 lithium ion battery is prepared.
Fig. 1 is a scanning electron microscope image of a composite lithium ion battery positive electrode material 0.5Li1.2Ni0.2Mn0.6O2·0.5Li1.2Mn0.54Ni0.13Co0.13O2 with a morphology of a "primary and secondary sphere" prepared in example 1. The figure shows that the particles are smooth in surface, the inside is of a hollow structure, the particles are solid small particles, the particles are tightly combined with the outer hollow mother balls, and the compaction density and the volume energy density of the material are improved. Gaps exist among the solid 'sub-spheres', so that electrolyte permeation is facilitated, space is provided for lithium ion diffusion, and the rate capability of the composite material is effectively improved.
Fig. 2 shows the first charge-discharge curves at 0.1C of the positive electrode materials prepared in example 1, comparative example 1, and comparative example 2. The figure shows that the composite lithium ion battery anode material 0.5Li1.2Ni0.2Mn0.6O2·0.5Li1.2Mn0.54Ni0.13Co0.13O2 with the shape of the 'primary and secondary spheres' has higher initial discharge specific capacity.
Fig. 3 is a graph showing the cycle performance of the positive electrode materials prepared in example 1, comparative example 1, and comparative example 2, which were cycled at 1C for 100 weeks. From the figure, it can be seen that the composite lithium ion battery cathode material 0.5Li1.2Ni0.2Mn0.6O2·0.5Li1.2Mn0.54Ni0.13Co0.13O2 prepared in example 1 and having the morphology of "primary and secondary spheres" has the best cycle performance.
Fig. 4 shows the rate performance graphs of the positive electrode materials prepared in example 1, comparative example 1, and comparative example 2. From the figure, it can be seen that the composite lithium ion battery cathode material 0.5Li1.2Ni0.2Mn0.6O2·0.5Li1.2Mn0.54Ni0.13Co0.13O2 with the morphology of the "primary and secondary spheres" prepared in example 1 still exhibits better electrochemical performance at high magnification.
Table 1 shows the tap density, the 0.1C first coulombic efficiency, and the 1C cycle 100 weeks voltage decay of the example 1, comparative example 2 prepared cathode materials. As can be seen from the table, the composite lithium ion battery anode material 0.5Li1.2Ni0.2Mn0.6O2·0.5Li1.2Mn0.54Ni0.13Co0.13O2 with the shape of the primary and secondary spheres has high tap density, excellent electrochemical performance and very high market application prospect.
Claims (4)
1. The composite lithium ion battery positive electrode material with the shape of the primary and secondary spheres is characterized by comprising the primary spheres and the secondary spheres, wherein the primary spheres are filled in the secondary spheres, the internal primary spheres are tightly combined with the outer-layer secondary spheres, and gaps are reserved among the multiple primary spheres; the son balls are solid small particles, and the mother balls are hollow large particles; the particle size of the internal son spheres of the positive electrode material can be regulated and controlled, and the appearance of the external mother spheres is complete; the ball is one or more lithium ion battery anode materials, and the mother ball is one lithium ion battery anode material.
2. The composite lithium ion battery positive electrode material with the morphology of the primary and secondary spheres, as claimed in claim 1, wherein the particle size D50 of the primary spheres is less than or equal to 10 mu m, and the particle size D50 of the secondary spheres is more than or equal to 15 mu m.
3. The composite lithium ion battery anode material with the morphology of the primary and secondary spheres, as claimed in claim 1, wherein the primary spheres account for 20-80% of the composite lithium ion battery anode material with the morphology of the primary and secondary spheres.
4. The method for preparing the composite lithium ion battery anode material with the morphology of the primary and secondary spheres according to any one of claims 1 to 3, which is characterized by comprising the following steps:
(1) Preparing a ball: weighing various raw materials in stoichiometric ratio according to the pellet chemical formula of the composite lithium ion battery anode material with the morphology of the primary and secondary pellets, mixing the various raw materials by a certain method under the action of a proper amount of additives, and sintering to obtain pellets;
(2) Preparing a primary-secondary ball: weighing raw materials with stoichiometric ratio according to the chemical formula of the mother balls of the composite lithium ion battery anode material with the morphology of the mother balls, mixing various raw materials by a wet method, adding a certain amount of dispersing agent, carrying out wet grinding after the dispersing is completed, adding the son balls prepared in the first step into slurry after the grinding is completed, uniformly mixing, and carrying out centrifugal spray drying and sintering to obtain the composite lithium ion battery anode material with the morphology of the mother balls.
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Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20070049810A (en) * | 2005-11-09 | 2007-05-14 | 한양대학교 산학협력단 | Core-shell cathode active materials with high safety and high capacity for lithium secondary batteries, method of preparing thereof and the product thereby |
| JP2009032647A (en) * | 2007-06-25 | 2009-02-12 | Mitsubishi Chemicals Corp | Material for positive electrode active material for lithium secondary battery, positive electrode for lithium secondary battery using it, and lithium secondary battery |
| JP2009117241A (en) * | 2007-11-08 | 2009-05-28 | Mitsubishi Chemicals Corp | Positive-electrode active material for lithium secondary battery and its manufacturing method, and positive electrode for lithium secondary battery active material and lithium secondary battery using positive electrode |
| CN103066282A (en) * | 2013-01-10 | 2013-04-24 | 东莞新能源科技有限公司 | High-voltage anode material for lithium ion battery and lithium ion battery comprising same |
| KR20140034606A (en) * | 2012-09-12 | 2014-03-20 | 삼성에스디아이 주식회사 | Composite cathode active material, cathode and lithium battery containing the material and preparation method thereof |
| US20160036042A1 (en) * | 2013-03-15 | 2016-02-04 | Johnson Matthey Public Limited Company | Lithium transition metal phosphate secondary agglomerates and process for its manufacture |
| CN105633365A (en) * | 2015-12-30 | 2016-06-01 | 北京鼎能开源电池科技股份有限公司 | Composite cathode material for lithium-ion battery and preparation method of composite cathode material |
| CN107331853A (en) * | 2017-08-18 | 2017-11-07 | 郑州大学 | A kind of graphene composite multi-layer spherical manganic acid lithium electrode material with holes and its lithium ion battery of preparation |
| CN109713357A (en) * | 2017-10-26 | 2019-05-03 | 银隆新能源股份有限公司 | The preparation method of ferrotianium lithium battery |
| CN111244459A (en) * | 2020-01-21 | 2020-06-05 | 华东理工大学 | High-nickel positive electrode material, nickel-cobalt precursor material, preparation method and lithium ion battery |
| CN116154174A (en) * | 2023-04-12 | 2023-05-23 | 河南电池研究院有限公司 | Multiphase composite layered manganese-based positive electrode material and preparation method thereof |
| WO2023207248A1 (en) * | 2022-04-25 | 2023-11-02 | 广东邦普循环科技有限公司 | Nca positive electrode material precursor having core-shell structure, method for preparing same, and use thereof |
| CN117276503A (en) * | 2023-09-21 | 2023-12-22 | 赣州立探新能源科技有限公司 | Polyanion material with core-shell structure and preparation method and application thereof |
-
2024
- 2024-04-15 CN CN202410444924.4A patent/CN118054008A/en active Pending
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20070049810A (en) * | 2005-11-09 | 2007-05-14 | 한양대학교 산학협력단 | Core-shell cathode active materials with high safety and high capacity for lithium secondary batteries, method of preparing thereof and the product thereby |
| JP2009032647A (en) * | 2007-06-25 | 2009-02-12 | Mitsubishi Chemicals Corp | Material for positive electrode active material for lithium secondary battery, positive electrode for lithium secondary battery using it, and lithium secondary battery |
| JP2009117241A (en) * | 2007-11-08 | 2009-05-28 | Mitsubishi Chemicals Corp | Positive-electrode active material for lithium secondary battery and its manufacturing method, and positive electrode for lithium secondary battery active material and lithium secondary battery using positive electrode |
| KR20140034606A (en) * | 2012-09-12 | 2014-03-20 | 삼성에스디아이 주식회사 | Composite cathode active material, cathode and lithium battery containing the material and preparation method thereof |
| CN103066282A (en) * | 2013-01-10 | 2013-04-24 | 东莞新能源科技有限公司 | High-voltage anode material for lithium ion battery and lithium ion battery comprising same |
| US20160036042A1 (en) * | 2013-03-15 | 2016-02-04 | Johnson Matthey Public Limited Company | Lithium transition metal phosphate secondary agglomerates and process for its manufacture |
| CN105633365A (en) * | 2015-12-30 | 2016-06-01 | 北京鼎能开源电池科技股份有限公司 | Composite cathode material for lithium-ion battery and preparation method of composite cathode material |
| CN107331853A (en) * | 2017-08-18 | 2017-11-07 | 郑州大学 | A kind of graphene composite multi-layer spherical manganic acid lithium electrode material with holes and its lithium ion battery of preparation |
| CN109713357A (en) * | 2017-10-26 | 2019-05-03 | 银隆新能源股份有限公司 | The preparation method of ferrotianium lithium battery |
| CN111244459A (en) * | 2020-01-21 | 2020-06-05 | 华东理工大学 | High-nickel positive electrode material, nickel-cobalt precursor material, preparation method and lithium ion battery |
| WO2023207248A1 (en) * | 2022-04-25 | 2023-11-02 | 广东邦普循环科技有限公司 | Nca positive electrode material precursor having core-shell structure, method for preparing same, and use thereof |
| CN116154174A (en) * | 2023-04-12 | 2023-05-23 | 河南电池研究院有限公司 | Multiphase composite layered manganese-based positive electrode material and preparation method thereof |
| CN117276503A (en) * | 2023-09-21 | 2023-12-22 | 赣州立探新能源科技有限公司 | Polyanion material with core-shell structure and preparation method and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| MUHARREM KUNDURACI等: "Spherical and core–shell-structured LiMn1.5Ni0.5O4 lithium-ion battery cathode with enhanced cyclability", 《JOURNAL OF APPLIED ELECTROCHEMISTRY》, vol. 52, no. 3, 6 January 2022 (2022-01-06), pages 477, XP037683107, DOI: 10.1007/s10800-021-01653-y * |
| ZHAOFENG YANG等: "Pomegranate-like Ti-doped LiNi0.4Mn1.6O4 5 V-class cathode with superior high-voltage cycle and rate performance for Li-ion batteries", 《CHEMICAL ENGINEERING SCIENCE》, vol. 231, 12 November 2020 (2020-11-12), pages 116297, XP086441806, DOI: 10.1016/j.ces.2020.116297 * |
| 路中培: "锂离子电池Li-Mn-O系正极材料的制备和改性研究", 《中国优秀硕士学位论文全文数据库 (工程科技Ⅱ辑)》, no. 1, 15 January 2018 (2018-01-15), pages 042 - 1149 * |
| 郝冠男: "锂离子电池正极用磷酸系铁基材料的研究", 《中国优秀硕士学位论文全文数据库 (工程科技Ⅱ辑)》, no. 5, 15 May 2012 (2012-05-15), pages 042 - 760 * |
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