CN114275828B - Nickel-rich material, preparation method thereof, positive plate, battery and electric equipment - Google Patents
Nickel-rich material, preparation method thereof, positive plate, battery and electric equipment Download PDFInfo
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- CN114275828B CN114275828B CN202111569564.3A CN202111569564A CN114275828B CN 114275828 B CN114275828 B CN 114275828B CN 202111569564 A CN202111569564 A CN 202111569564A CN 114275828 B CN114275828 B CN 114275828B
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 328
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 156
- 239000000463 material Substances 0.000 title claims abstract description 100
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000002243 precursor Substances 0.000 claims abstract description 98
- 238000005245 sintering Methods 0.000 claims abstract description 48
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 31
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000002994 raw material Substances 0.000 claims abstract description 24
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 17
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 33
- 150000003839 salts Chemical class 0.000 claims description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 150000001868 cobalt Chemical class 0.000 claims description 6
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 6
- 150000002815 nickel Chemical class 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 5
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 5
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 5
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 5
- 238000001694 spray drying Methods 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 4
- 229940011182 cobalt acetate Drugs 0.000 claims description 4
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 4
- 229940044175 cobalt sulfate Drugs 0.000 claims description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 4
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229940078494 nickel acetate Drugs 0.000 claims description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 4
- 239000007790 solid phase Substances 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims description 3
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 3
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 3
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 3
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 38
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 38
- 239000007774 positive electrode material Substances 0.000 abstract description 25
- 230000002035 prolonged effect Effects 0.000 abstract description 5
- 150000002739 metals Chemical class 0.000 abstract description 3
- 230000000877 morphologic effect Effects 0.000 abstract 1
- 239000011572 manganese Substances 0.000 description 19
- 238000012360 testing method Methods 0.000 description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 15
- 239000000203 mixture Substances 0.000 description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 9
- 239000006258 conductive agent Substances 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 9
- 229910052744 lithium Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000005336 cracking Methods 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 8
- 239000002041 carbon nanotube Substances 0.000 description 6
- 239000010406 cathode material Substances 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- -1 polytetrafluoroethylene Polymers 0.000 description 6
- 239000006229 carbon black Substances 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000002134 carbon nanofiber Substances 0.000 description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 229910021389 graphene Inorganic materials 0.000 description 4
- 238000006138 lithiation reaction Methods 0.000 description 4
- 229940071125 manganese acetate Drugs 0.000 description 4
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910021383 artificial graphite Inorganic materials 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 229940053662 nickel sulfate Drugs 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000006245 Carbon black Super-P Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 229910013716 LiNi Inorganic materials 0.000 description 2
- 229910021314 NaFeO 2 Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000006183 anode active material Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000002121 nanofiber Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910001148 Al-Li alloy Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910008365 Li-Sn Inorganic materials 0.000 description 1
- 229910008410 Li-Sn-O Inorganic materials 0.000 description 1
- 229910006759 Li—Sn Inorganic materials 0.000 description 1
- 229910006763 Li—Sn—O Inorganic materials 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910010248 TiO2—Li4Ti5O12 Inorganic materials 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- INNSZZHSFSFSGS-UHFFFAOYSA-N acetic acid;titanium Chemical group [Ti].CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O INNSZZHSFSFSGS-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229940071257 lithium acetate Drugs 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical group [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 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
- 230000003446 memory effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 102220043159 rs587780996 Human genes 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000001291 vacuum drying 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 relates to a nickel-rich material, a preparation method thereof, a positive plate, a battery and electric equipment. In the preparation method of the nickel-rich material, a part of lithium salt and other metals in the preparation raw materials are used as precursor raw materials and are prepared into a precursor, so that the elements contained in the prepared precursor are the same as the types of elements contained in the finally prepared nickel-rich material, and the elements have similar macroscopic morphological structures; and mixing the precursor with the rest of lithium salt, sintering, and lithiating the precursor in the process, wherein the prepared nickel-rich material has a more stable structure, the Karman shape coefficient psi of the nickel-rich material can reach 0.8 or more, and the cycle service life of the lithium ion battery can be prolonged when the nickel-rich material is used as a positive electrode active material for preparing the lithium ion battery.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a nickel-rich material, a preparation method thereof, a positive plate, a battery and electric equipment.
Background
The lithium ion battery has the advantages of high energy density, high power density, high coulomb efficiency, environmental friendliness, no memory effect and the like, and is widely applied to the fields of electronic equipment, electric automobiles, medical electronic equipment, aerospace, power grids and the like, such as batteries of electric equipment such as automobiles, mobile phones, video cameras, digital cameras, notebook computers and the like. As a result, lithium ion batteries gradually occupy the major market of batteries, particularly in the field of electronic devices, which already has a very mature technical market. With the rapid development of technology, especially the development of electric automobile technology, higher requirements are also put on the cycle life of lithium ion batteries.
The positive electrode active material is a decisive component of the performance of the lithium ion battery, the performance of the lithium ion battery is determined to a great extent by the properties of the positive electrode active material adopted in the lithium ion battery, and the positive electrode active materials which have been successfully commercialized comprise lithium cobaltate, lithium manganate, lithium iron phosphate and the like, but all the positive electrode materials have the defects and the defects of the positive electrode materials, and the ternary positive electrode material has the advantages of high discharge capacitance, excellent reaction reversibility, excellent high-current discharge capacity, wider charge-discharge voltage range, low toxicity and the like, so the ternary positive electrode material has become the main positive electrode active material for preparing the lithium ion battery. However, the lithium ion battery prepared by adopting the ternary positive electrode material is easy to burst in the repeated charge and discharge process, has lower cycle service life, and cannot meet the higher service life requirement of the modern technology on the lithium ion battery.
Thus, there is a need in the art for improvement.
Disclosure of Invention
Based on the nickel-rich material, the preparation method thereof, the positive plate, the battery and the electrical equipment, wherein the nickel-rich material can prolong the cycle life of the lithium ion battery.
In one aspect of the invention, a method for preparing a nickel-rich material is provided, comprising the following steps:
Providing a preparation raw material according to a stoichiometric ratio of a chemical formula shown in a formula (1), wherein the preparation raw material comprises lithium salt and other metal salts except the lithium salt;
Li(1+a1)NixCoyM(1-x-y)O2 (1)，
Wherein a1 is more than or equal to 0.03 and less than or equal to 0.1,0.6 and less than or equal to x is more than or equal to 0 and less than or equal to 0.1, y is more than or equal to 0 and less than or equal to 0.40, M is at least one of Mn, al, ti, ba, sr, mg, cr, zn, V, cu and Zr.
Taking the other metal salts and a part of the lithium salt as precursor raw materials to prepare a nickel-rich precursor;
and mixing the nickel-rich precursor with the rest of lithium salt, and sintering to obtain the nickel-rich material.
In some of these embodiments, the sintering step is performed in an oxygen-containing atmosphere at a sintering temperature of 600 ℃ to 700 ℃ for a sintering time of 5 hours to 10 hours.
In some of these embodiments, the nickel-rich precursor has a karman shape factor ψ of greater than 0.7 and a BET of less than 0.5 square meters per gram.
In some of these embodiments, the stoichiometry of each element in the precursor feedstock is as shown in formula (2):
LicNixCoyM(1-x-y)O2 (2)，
wherein c is more than 0 and less than 1;
The ratio of the number of moles of Li element in the remaining lithium salt to the total number of moles of Ni element, co element and M element in the other metal salt is (1+a1-c): 1.
In some embodiments, the nickel-rich material has a molecular formula of Li (1+a2)NixCoyM(1-x-y)O(2-b); -a2 is more than or equal to 0.10 and less than or equal to 0.20.
In some embodiments, the lithium salt is selected from at least one of lithium hydroxide, lithium nitrate, lithium carbonate, lithium sulfate, and lithium acetate.
In some of these embodiments, the other metal salts include nickel salts, cobalt salts, and M-containing salts; the nickel salt is at least one selected from nickel hydroxide, nickel carbonate, nickel sulfate and nickel acetate; and/or
The cobalt salt is at least one selected from cobalt hydroxide, cobalt carbonate, cobalt sulfate and cobalt acetate; and/or
The M-containing salt is selected from at least one of M-containing hydroxide, M-containing sulfate, M-containing carbonate and M-containing acetate.
In another aspect of the invention, a nickel-rich material is provided, and the nickel-rich material is prepared by the preparation method of the nickel-rich material.
In yet another aspect of the present invention, there is provided a positive electrode sheet comprising a current collector and an active layer formed on the current collector, the composition of the active layer comprising a nickel-rich material as described above.
In yet another aspect of the present invention, there is provided a battery including the positive electrode sheet as described above.
In yet another aspect of the present invention, a powered device is provided, the powered device comprising a battery as described above.
In the preparation method of the nickel-rich material, part of lithium salt and other metal salts in the preparation raw materials are used as precursor raw materials, and a nickel-rich precursor is prepared, so that elements contained in the prepared nickel-rich precursor are the same as the types of elements contained in the finally prepared nickel-rich material, and the nickel-rich precursor and the nickel-rich material have similar macroscopic morphology structures; and then mixing the nickel-rich precursor with the rest of lithium salt, sintering, and further lithiating the nickel-rich precursor in the process, wherein the prepared nickel-rich material has a more stable structure and a specific morphology, the shape coefficient psi of the Karman of the nickel-rich material can reach 0.8 or more, and the cycle service life of the lithium ion battery can be prolonged when the prepared nickel-rich material is used as an anode active material for preparing the lithium ion battery.
Further, in the preparation method, the sintering step is performed in an oxygen-containing atmosphere, the sintering temperature is 600-700 ℃, and the sintering time is 5-10 hours, because in the preparation method, the elements contained in the nickel-rich precursor prepared first and the elements contained in the nickel-rich material prepared finally have similar macroscopic morphology structures, the energy required by further lithiation of the nickel-rich precursor in the subsequent sintering process is lower, and the nickel-rich material with stable structure can be obtained at a relatively mild sintering temperature and a relatively short sintering time.
The nickel-rich material prepared by the preparation method of the nickel-rich material has stable structure, the shape factor psi of the Karman can reach 0.8 or more, and the cycle service life of the lithium ion battery can be prolonged.
Drawings
FIG. 1 is an XRD pattern of the nickel-rich precursor and nickel-rich material prepared in example 1;
FIG. 2 is an electron microscope image of the nickel-rich precursor prepared in example 1;
FIG. 3 is an XRD pattern of the precursor and nickel-rich material prepared in comparative example 1;
FIG. 4 is an electron microscopic view of the precursor prepared in example 1;
FIG. 5 is a graph showing the cycle life test of the nickel-rich materials prepared in example 1 and comparative example 1;
FIG. 6 is an SEM image after cyclic testing of the nickel-rich materials prepared in example 1 (A) and comparative example 1 (B).
Detailed Description
In order that the invention may be understood more fully, a more particular description of the invention will be rendered by reference to preferred embodiments thereof. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
The traditional method for preparing the ternary cathode material comprises the following steps: and preparing a precursor containing the ternary main body material but not containing lithium, further sintering the precursor and a lithium source, and lithiating the precursor to obtain the ternary positive electrode material. In order to improve the stability of the ternary cathode material and further provide the recycling performance of the prepared lithium ion battery, technicians often adopt a precipitation method to prepare a precursor containing the ternary main body material with a coating layer but not containing lithium, so that the stability of the ternary cathode material is improved, but the higher service life requirement of the lithium ion battery by modern technology is still difficult to meet.
The skilled person in the present invention found in the study: the karman shape factor psi of the ternary cathode material has a great influence on the stability of the ternary cathode material, and after further research on the conventional technology, it is found that: when the Karman shape coefficient psi of the ternary positive electrode material prepared by the traditional technology is less than 0.8, cracks easily occur in the repeated charge and discharge process when the ternary positive electrode material is applied to a lithium ion battery, so that the battery is thermally out of control and is ignited and exploded.
Based on the above, after a great deal of experiments, the technical staff of the invention obtain the nickel-rich material capable of improving the cycle life of the lithium battery and the preparation method thereof. Specifically, the following is described.
An embodiment of the invention provides a preparation method of a nickel-rich material, which comprises the following steps S10-S30.
Step S10, providing preparation raw materials according to the stoichiometric ratio of the chemical formula shown in the formula (1), wherein the preparation raw materials comprise lithium salt and other metal salts except the lithium salt;
Li(1+a1)NixCoyM(1-x-y)O2 (1)，
Wherein a1 is more than or equal to 0.03 and less than or equal to 0.1,0.6 and less than or equal to x is more than or equal to 0 and less than or equal to 0.1, y is more than or equal to 0 and less than or equal to 0.40, M is at least one of Mn, al, ti, ba, sr, mg, cr, zn, V, cu and Zr.
And S20, taking other metal salts and a part of lithium salts as precursor raw materials to prepare a nickel-rich precursor.
And step S30, mixing the nickel-rich precursor with the rest of lithium salt, and sintering to obtain the nickel-rich material.
In the preparation method of the nickel-rich material, part of lithium salt and other metal salts in the preparation raw materials are used as precursor raw materials to prepare a nickel-rich precursor, so that elements contained in the prepared nickel-rich precursor are the same as the types of elements contained in the finally prepared nickel-rich material, and the nickel-rich precursor and the nickel-rich material have similar macroscopic morphology structures; and then mixing the nickel-rich precursor with the rest of lithium salt in the preparation raw materials, sintering, and carrying out further lithiation on the nickel-rich precursor in the process, wherein the prepared nickel-rich material has a more stable structure and a specific morphology, the Karman shape coefficient psi of the nickel-rich material can reach 0.8 or more, and the cycle service life of the lithium ion battery can be prolonged when the prepared nickel-rich material is used as an anode active material for preparing the lithium ion battery.
The technical personnel of the invention find that in the research of the traditional preparation method of the ternary positive electrode material: on the one hand, the karman shape factor psi of the precursor containing ternary main body material but not containing lithium, which is prepared by some technologies in the traditional preparation method, is more than 0.7, but because the structure of the precursor is far away from the architecture of the final ternary positive electrode material, higher energy is needed in the subsequent sintering lithiation process, namely higher sintering temperature and longer sintering time are needed to be controlled, and meanwhile, more lithium salt is needed to be added in order to avoid volatilization of lithium at high temperature for a long time, so that energy consumption is increased and raw material cost is increased; on the other hand, the karman shape factor ψ of the ternary main body material containing the precursor without lithium prepared by some technologies in the traditional preparation method is less than 0.7, but in order to ensure that lithium salt can quickly permeate into the precursor in the subsequent lithiation process, volatilization is reduced, the high porosity characteristic of a porous structure needs to be maintained, and the subsequent sintering needs to be carried out at a higher temperature. Thus, the finished product prepared by the traditional technology has low Karman coefficient, consumes more energy and has high cost.
In some of these embodiments, the nickel-rich precursor has a karman shape factor ψ of greater than 0.7 and a BET of less than 0.5 square meters per gram.
The Karman shape factor psi of the precursor is more than 0.7 and less than 8;0< BET <0.5.
BET, i.e. specific surface area.
In some embodiments, the sintering step is performed in an oxygen-containing atmosphere at a sintering temperature of 600 ℃ to 700 ℃ for a sintering time of 5 hours to 10 hours.
In the preparation method, the elements contained in the nickel-rich precursor prepared first and the elements contained in the nickel-rich material prepared finally have the same types and similar macroscopic morphology structures, so that the nickel-rich precursor is further lithiated in the subsequent sintering process, the energy required in the process is lower, and the nickel-rich material with stable structure can be obtained at a relatively mild sintering temperature and a relatively short sintering time.
In some of these embodiments, the stoichiometry of each element in the precursor feedstock is as shown in formula (2):
LicNixCoyM(1-x-y)O2 (2)，
wherein c is more than 0 and less than 1;
The ratio of the number of moles of Li element in the remaining lithium salt to the total number of moles of Ni element, co element and M element in the other metal salt is (1+a1-c): 1.
Preferably, 0 < c < 0.65.
Further, the molecular formula of the nickel-rich precursor is Li c1NixCoyM(1-x-y)Od, c is more than 0 and less than 1, and d is more than 0 and less than or equal to 2.1.
It should be noted that, during the preparation of the nickel-rich precursor, the lithium salt may volatilize, so that the composition ratio of the prepared nickel-rich precursor and the ratio of the precursor raw materials may come in and go out, wherein c1 may be the same as or different from the value of c, and accordingly, the ratio of oxygen may also be different.
In some embodiments, the nickel-rich material has a molecular formula of Li (1+a2)NixCoyM(1-x-y)O(2-b); -a 2 is more than or equal to 0.10 and less than or equal to 0.20, -b is more than or equal to 0.05 and less than or equal to 0.10.
In addition, during the sintering process, a small amount of lithium salt volatilizes, so that the composition ratio of the prepared nickel-rich material is slightly different from that of the theory.
Further, the molecular formula of the nickel-rich material is Li 1NixCoyM(1-x-y)O2.
It is understood that the above lithium salts may be used as commonly used in the art, i.e., lithium salts containing no chlorine and no nitrogen.
In some embodiments, the lithium salt is selected from at least one of lithium hydroxide, lithium carbonate, lithium sulfate, and lithium acetate.
In some of these embodiments, the other metal salts described above include nickel salts, cobalt salts, and M-containing salts.
In some embodiments, the nickel salt is selected from at least one of nickel hydroxide, nickel carbonate, nickel sulfate, and nickel acetate.
In some embodiments, the cobalt salt is selected from at least one of cobalt hydroxide, cobalt carbonate, cobalt sulfate, and cobalt acetate.
In some embodiments, the M-containing salt is selected from at least one of an M-containing hydroxide, an M-containing sulfate, an M-containing carbonate, and an M-containing acetate.
When M is at least one of Mn, al, ti, ba, sr, mg, cr, zn, V, cu and Zr, and M is selected from a plurality of metals, the types of salts of different metals may be the same or different, and are independently selected from at least one of hydroxide, sulfate, carbonic acid and acetate.
In some of these embodiments, the step of preparing the nickel-rich precursor employs a spray drying process or a solid phase sintering process.
In some of these embodiments, the step of preparing the nickel-rich precursor employs a spray drying process comprising the steps of:
And mixing the precursor raw material with a solvent, and then performing spray drying in an oxidizing atmosphere at the temperature of 1000-1200 ℃ to obtain the nickel-rich precursor.
In some of these embodiments, the step of preparing the nickel-rich precursor employs a solid phase sintering process comprising the steps of:
The precursor raw material is mixed with a solvent, and then solid phase sintering is carried out for 6 to 8 hours at the temperature of 1000 to 1200 ℃ in an oxidizing atmosphere.
In some embodiments, the solvent is at least one of ethanol and water.
The invention further provides a nickel-rich material, which is prepared by the preparation method of the nickel-rich material.
The nickel-rich material has stable structure, the shape factor psi of the Karman can reach 0.8 or more, and the cycle service life of the lithium ion battery can be prolonged.
The invention further provides a positive plate, which comprises a current collector and an active layer formed on the current collector, wherein the component of the active layer comprises the nickel-rich material.
The nickel-rich material has a stable structure, the shape coefficient psi of the Karman can reach 0.8 or more, and the positive plate prepared by the nickel-rich material can improve the cycle service life of the lithium ion battery.
In some of these embodiments, the composition of the active layer of the positive electrode sheet further includes a binder and a conductive agent.
The binder and the conductive agent may be selected from binders and conductive agents for electrodes commonly used in the art.
In some embodiments, the conductive agent in the positive electrode sheet is at least one selected from the group consisting of graphite, carbon nanotubes, nanofibers, carbon black, and graphene.
Specifically, the carbon black composite conductive agent can be selected from at least one of SP, KS-6, graphite conductive carbon black Super-P Li, keqin black ECP with branched structure, SFG-6, vapor grown carbon fiber VGCF, carbon nanotube CNTs, graphene and composite conductive agent thereof.
In some embodiments, the binder includes at least one of polyvinyl alcohol, polytetrafluoroethylene, and polyvinylidene fluoride.
In some embodiments, the current collector is made of metal foil; further, the current collector is made of gold foil or aluminum foil.
An embodiment of the present invention also provides a battery including the positive electrode sheet as described above.
The battery provided by the invention contains the positive plate, and the components of the positive plate comprise the nickel-rich material, so that the stability can be kept in the charge and discharge process of the battery, the cycle stability of the battery is improved, and the cycle service life of the battery is longer.
In some embodiments, the battery is a lithium ion battery.
In some embodiments, the battery further comprises a negative electrode sheet and an electrolyte. Further, if the electrolyte is a liquid electrolyte, the battery further includes a separator.
In particular, the separator is selected from Polyethylene (PE) separators or polypropylene (PP).
In some embodiments, the negative electrode active material in the negative electrode sheet includes at least one of graphite, mesophase micro carbon spheres, hard carbon, soft carbon, elemental silicon, a silicon oxygen compound, a Li-Sn alloy, a Li-Sn-O alloy, sn, snO, snO 2, a spinel-structured TiO 2-Li4Ti5O12, and a Li-Al alloy.
The graphite may be natural graphite or artificial graphite.
In some embodiments, the conductive agent in the negative electrode sheet is at least one selected from the group consisting of graphite, carbon nanotubes, nanofibers, carbon black, and graphene.
Specifically, the conductive agent in the negative electrode sheet can be selected from at least one of SP, KS-6, graphite conductive carbon black Super-P Li as a negative electrode, ketjen black ECP with a branched structure, SFG-6, vapor grown carbon fiber VGCF, carbon nanotube CNTs, graphene and a composite conductive agent thereof.
In some of these embodiments, the electrolyte is selected from the group consisting of lithium salts of electrolytes, such as lithium bistrifluoromethylsulfonate imide LiTFSI, lithium hexafluorophosphate.
An embodiment of the present invention further provides an electric device, where the electric device includes the battery as described above.
The electric equipment comprises the battery, and the service life is long.
The above-mentioned consumer is consumer, including but not limited to: automobiles, air conditioners, humidifiers, telephones, recorders, range hoods, microwave ovens, washing machines, cell phones, cell phone chargers, computers, fans, printers, and the like.
In some embodiments, the electrical device is an automobile.
The battery has high cycle stability and long service life, and can be used for preparing automobiles, further improve the cruising ability of the automobiles and promote the development of the field of electric automobiles.
The invention will be described in connection with specific embodiments, but the invention is not limited thereto, and it will be appreciated that the appended claims outline the scope of the invention, and those skilled in the art, guided by the inventive concept, will appreciate that certain changes made to the embodiments of the invention will be covered by the spirit and scope of the appended claims.
The following are specific examples.
Example 1
(1) Synthesizing a nickel-rich precursor: mixing nickel acetate, cobalt acetate, manganese acetate and lithium acetate according to a chemical formula Li 0.35Ni0.88Co0.05Mn0.07O2, dissolving in ethanol to obtain a mixed solution with a concentration of 2mol/L, adjusting the temperature of spray pyrolysis equipment to 1100 ℃, and spray drying the mixed solution by taking oxygen with a flow of 3mol/L as carrier gas to obtain a nickel-rich precursor. The nickel-rich precursor was tested to have a molecular formula of Li 0.33Ni0.88Co0.05Mn0.07O1.2, a karman shape factor ψ=0.76, bet=0.36 square meters/g.
XRD test is carried out on the prepared nickel-rich precursor, and the XRD test curve is shown in (a) of the attached figure 1, wherein the nickel-rich precursor has an alpha-NaFeO 2 layered structure; further, the prepared nickel-rich precursor is placed under an electron microscope, and an electron microscope diagram is shown in figure 2.
(2) Mixing the nickel-rich precursor with lithium hydroxide, wherein the ratio of the mole number of Li element in the lithium hydroxide to the sum of the mole numbers of Ni element, co element and Mn element in the nickel-rich precursor is 0.69:1, then placing the material into a sintering furnace to be sintered for 6 hours in pure oxygen atmosphere at 650 ℃ to obtain a nickel-rich material, and testing: the molecular formula of the nickel-rich material is as follows: liNi 0.88Co0.05Mn0.07O2, karman shape factor ψ=0.89.
Wherein, the raw materials used in the whole process of preparing the nickel-rich material accord with the chemical formula Li (1+0.04)Ni0.88Co0.05M0.07O2.
XRD test is carried out on the prepared nickel-enriched material, the XRD test curve is shown in (b) of figure 1, and the result shows that: the prepared nickel-rich material also has an alpha-NaFeO 2 type layered structure, and has a similar structure to the nickel-rich precursor prepared in the step (1).
(3) Mixing the nickel-rich anode material prepared in the step (2) with carbon black and polyvinylidene fluoride powder according to the following steps: 2:2, adding NMP solvent, stirring uniformly to obtain positive electrode slurry, and coating the slurry on aluminum foil with the thickness of 14 microns to obtain the positive electrode plate.
Coating artificial graphite on an 8-micrometer copper foil to prepare a negative plate, taking a carbonate solution containing 1.5mol/L lithium hexafluorophosphate as an electrolyte, and then assembling the negative plate, the positive plate, the 12-micrometer PP diaphragm and the electrolyte to prepare the lithium ion battery. Tested: the initial ring capacity of the lithium ion battery is 1Ah when the lithium ion battery is charged and discharged at the rate of 0.33C within the voltage range of 3.0V-4.2V at the temperature of 30 ℃.
(4) And (3) placing the lithium ion battery in a constant temperature oven at 30 ℃, repeatedly charging and discharging 2000 times at 1C rate within a voltage range of 3.0-4.2V, discharging the battery to 2.8V at 0.33C rate, disassembling the battery, taking out the positive electrode plate, and observing the cracking condition of the positive electrode material.
The results show that: after repeated charge and discharge for 2000 times, the positive electrode material in the prepared lithium ion battery still keeps the structural integrity without cracking.
Example 2
(1) Synthesizing a nickel-rich precursor: mixing nickel hydroxide, cobalt hydroxide, manganese hydroxide and lithium acetate according to a chemical formula Li 0.42Ni0.88Co0.05Mn0.07O2, then placing the mixture in a pure alumina ceramic bowl, compacting the mixture to the thickness of 3cm by using the pressure of 100kg/cm 2, placing the mixture in a sintering furnace with the temperature of 1100 ℃, introducing oxygen into the sintering furnace at the flow of 5mol/L, and sintering for 6 hours to obtain a nickel-rich precursor. The nickel-rich precursor was tested to have a molecular formula of Li 0.4Ni0.88Co0.05Mn0.07O1.2, a karman shape factor ψ=0.74, bet=0.34 square meters/g.
(2) Mixing the nickel-rich precursor with lithium hydroxide, wherein the ratio of the mole number of Li element in the lithium hydroxide to the sum of the mole numbers of Ni element, co element and Mn element in the nickel-rich precursor is 0.64:1, then placing the material in a sintering furnace, introducing oxygen into the sintering furnace at a flow rate of 10mol/L, and sintering at 700 ℃ for 8 hours to obtain a nickel-rich material, and testing: the molecular formula of the nickel-rich material is as follows: liNi 0.88Co0.05Mn0.07O2, karman shape factor ψ=0.86.
Wherein, the raw materials used in the whole process of preparing the nickel-rich material accord with the chemical formula Li (1+0.06)Ni0.88Co0.05M0.07O2.
XRD tests are carried out on the prepared nickel-rich precursor and nickel-rich material respectively, and the results show that: the prepared nickel-rich precursor and nickel-rich material have similar structures.
(3) Mixing the nickel-rich cathode material prepared in the step (2) with carbon black and pdf powder according to a ratio of 96:2:2, adding NMP solvent, stirring uniformly to obtain positive electrode slurry, and coating the slurry on aluminum foil with the thickness of 14 microns to obtain the positive electrode plate.
Coating artificial graphite on an 8-micrometer copper foil to prepare a negative plate, taking a carbonate solution containing 1.5mol/L lithium hexafluorophosphate as an electrolyte, then assembling the negative plate, the positive plate, a 12-micrometer PP diaphragm and the electrolyte to prepare a lithium ion battery, and testing: the initial ring capacity of the lithium ion battery is 1Ah when the lithium ion battery is charged and discharged at the rate of 0.33C within the voltage range of 3.0V-4.2V at the temperature of 30 ℃.
(4) And (3) placing the lithium ion battery in a constant temperature oven at 30 ℃, repeatedly charging and discharging 2000 times at 1C rate within a voltage range of 3.0-4.2V, discharging the battery to 2.8V at 0.33C rate, disassembling the battery, taking out the positive electrode plate, and observing the cracking condition of the positive electrode material.
The results show that: after the charge and discharge are repeated 2000 times, the positive electrode material in the prepared lithium ion battery is placed under an electron microscope for observation, and as shown in (A) of fig. 6, the positive electrode material still keeps the structural integrity and has no cracking.
Example 3
(1) Synthesizing a nickel-rich precursor: mixing nickel hydroxide, cobalt hydroxide, manganese hydroxide and lithium acetate according to a chemical formula Li 0.64Ni0.88Co0.05Mn0.07O2, then placing the mixture in a pure alumina ceramic bowl, compacting the mixture to the thickness of 3cm by using the pressure of 100kg/cm 2, placing the mixture in a sintering furnace with the temperature of 1100 ℃, introducing oxygen into the sintering furnace at the flow of 5mol/L, and sintering for 6 hours to obtain a nickel-rich precursor. The nickel-rich precursor was tested to have a molecular formula of Li 0.62Ni0.88Co0.05Mn0.07O1.2, a karman shape factor ψ=0.79, bet=0.3 square meters/g.
(2) Mixing the nickel-rich precursor with lithium hydroxide, wherein the ratio of the mole number of Li element in the lithium hydroxide to the sum of mole numbers of Ni element, co element and Mn element in the nickel-rich precursor is 0.41:1:1, then placing the material in a sintering furnace, introducing oxygen into the sintering furnace at a flow rate of 10mol/L, and sintering at 700 ℃ for 8 hours to obtain a nickel-rich material, and testing: the molecular formula of the nickel-rich material is as follows: liNi 0.88Co0.05Mn0.07O2, karman shape factor ψ=0.85.
Wherein, the raw materials used in the whole process of preparing the nickel-rich material accord with the chemical formula Li (1+0.05)Ni0.88Co0.05M0.07O2.
XRD tests are carried out on the prepared nickel-rich precursor and nickel-rich material respectively, and the results show that: the prepared nickel-rich precursor and nickel-rich material have similar structures.
Subsequent steps (3) to (4): steps (3) to (4) are the same as in example 1.
The results show that: after repeated charge and discharge for 2000 times, the positive electrode material in the prepared lithium ion battery still keeps the structural integrity without cracking.
Example 4
Example 4 is substantially the same as example 1, except that: in the step (1), manganese acetate is replaced by copper acetate with the same mole number.
The remaining steps were the same as in example 1.
The results show that: the molecular formula of the prepared nickel-rich material is as follows: liNi 0.88Co0.05Cu0.07O2, the karman shape factor ψ=0.86, and the prepared nickel-rich material has a similar structure to the prepared nickel-rich precursor, and the positive electrode material of the prepared lithium ion battery still keeps complete structure and has no cracking after repeated charge and discharge for 2000 times.
Example 5
Example 5 is substantially the same as example 1, except that: in the step (1), manganese acetate is replaced with titanium acetate with the same mole number.
The remaining steps were the same as in example 1.
The results show that: the molecular formula of the prepared nickel-rich material is as follows: and the shape coefficient phi of the LiNi 0.88Co0.05Ti0.07O2 is=0.84, the prepared nickel-rich material and the prepared nickel-rich precursor have similar structures, and the positive electrode material of the prepared lithium ion battery still keeps complete structure and has no cracking after being repeatedly charged and discharged for 2000 times.
Example 6
Example 6 is substantially the same as example 1, except that: in the step (1), manganese acetate is replaced with magnesium acetate with the same mole number.
The remaining steps were the same as in example 1.
The results show that: the molecular formula of the prepared nickel-rich material is as follows: and the shape coefficient phi of the LiNi 0.88Co0.05Mg 0.07O2 is=0.87, the prepared nickel-rich material and the prepared nickel-rich precursor have similar structures, and the positive plate of the prepared lithium ion battery still keeps complete structure and has no cracking after being repeatedly charged and discharged for 2000 times.
Comparative example 1
(1) Synthesizing a nickel-rich precursor: mixing nickel sulfate, cobalt sulfate and manganese sulfate according to a chemical formula Ni 0.88Co0.05Mn0.07(OH)2 in proportion, dissolving in deionized water to obtain a mixed solution with the concentration of 2mol/L, adding the mixed solution and an aqueous solution of 2mol/L of NaOH and an aqueous solution of 5mol/L of ammonia into a reaction kettle with a stirring device at the same time, carrying out precipitation reaction at 60 ℃ under the protection of nitrogen, stopping the reaction when the particle size D50=5 mu m of the precursor is obtained, filtering, and vacuum drying a filter cake at 100 ℃ to obtain the precursor. The molecular formula of the precursor is tested to be Ni 0.88Co0.05Mn0.07(OH)2, the Karman shape factor psi=0.45 and BET=11.03 square meters per gram.
(2) Mixing the precursor with lithium hydroxide, wherein the ratio of the mole number of Li element in the lithium hydroxide to the sum of mole numbers of Ni element, co element and Mn element in the nickel-rich precursor is 1.04:1, then placing the material into a sintering furnace, sintering for 18 hours in pure oxygen atmosphere at 750 ℃ to obtain a nickel-rich material, and testing: the molecular formula of the nickel-rich material is as follows: liNi 0.88Co0.05Mn0.07O2, karman shape factor ψ=0.6.
XRD tests are respectively carried out on the prepared precursor and the nickel-rich material, the XRD test curve of the precursor is shown in (a) of figure 3, the XRD test curve of the nickel-rich material is shown in (b) of figure 3, and the result shows that: the structure of the nickel-rich material is far from that of the precursor prepared in the step (1). Further, the prepared precursor is placed under an electron microscope, and an electron microscope image is shown as a figure (4).
Comparing FIG. 2 with FIG. 4, it can be seen that the morphology of the nickel-rich precursor prepared in example 1 is far different from that of the precursor prepared in comparative example 1.
The subsequent steps (3) to (4) are the same as those of the steps (3) to (4) of example 1.
The results show that: during the cycle test, the capacity retention rate of the battery prepared using the nickel-rich material prepared in comparative example 1 was greatly attenuated with the increase of the cycle life, while the capacity retention rate of the battery prepared using the nickel-rich material prepared in example 1 was significantly reduced with the increase of the cycle life by a much smaller extent than that of comparative example 1.
After the cycle test was performed 2000 times, the positive electrode material in the lithium ion battery prepared in comparative example 1 was observed under an electron microscope, and as shown in (B) of fig. 6, the positive electrode material was cracked, and significant cracks were generated.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (11)
1. The preparation method of the nickel-rich material is characterized by comprising the following steps of:
Providing a preparation raw material according to a stoichiometric ratio of a chemical formula shown in a formula (1), wherein the preparation raw material comprises lithium salt and other metal salts except the lithium salt;
Li(1+a1)NixCoyM(1-x-y)O2（1），
Wherein a1 is more than or equal to 0.03 and less than or equal to 0.1,0.6 and less than or equal to x is more than or equal to 0 and less than or equal to 0.1, y is more than or equal to 0 and less than or equal to 1-x-y is more than or equal to 0.40, and M is at least one of Mn, al, ti, ba, sr, mg, cr, zn, V, cu and Zr; taking the other metal salts and a part of the lithium salt as precursor raw materials to prepare a nickel-rich precursor;
Mixing the nickel-rich precursor with the rest of lithium salt, and sintering to obtain a nickel-rich material;
the stoichiometry of each element in the precursor raw material is shown as a formula (2):
LicNixCoyM(1-x-y)O2（2），
wherein c is more than 0 and less than 0.65;
The ratio of the number of moles of Li element in the remaining lithium salt to the total number of moles of Ni element, co element and M element in the other metal salt is (1+a1-c): 1, a step of; the nickel-rich precursor has a karman shape factor ψ of greater than 0.7 and a BET of less than 0.5 square meters per gram.
2. The method for preparing a nickel-rich material according to claim 1, wherein the sintering step is performed in an oxygen-containing atmosphere at a sintering temperature of 600 ℃ to 700 ℃ for 5h to 10h.
3. The method of claim 1, wherein the step of preparing the nickel-rich precursor is performed by a spray drying method or a solid phase sintering method.
4. The method for preparing a nickel-rich material according to any one of claims 1 to 3, wherein the molecular formula of the nickel-rich material is Li (1+a2)NixCoyM(1-x-y)O(2-b); -a 2 is more than or equal to 0.10 and less than or equal to 0.20, -b is more than or equal to 0.05 and less than or equal to 0.10.
5. The method for producing a nickel-rich material according to any one of claims 1 to 3, wherein the lithium salt is at least one selected from the group consisting of lithium hydroxide, lithium carbonate, lithium sulfate and lithium acetate.
6. The method for preparing a nickel-rich material according to any one of claims 1 to 3, wherein the other metal salts include nickel salts, cobalt salts and salts containing M; the nickel salt is at least one selected from nickel hydroxide, nickel carbonate, nickel sulfate and nickel acetate.
7. The method of producing a nickel-rich material according to claim 6, wherein the cobalt salt is at least one selected from the group consisting of cobalt hydroxide, cobalt carbonate, cobalt sulfate and cobalt acetate; and/or
The M-containing salt is selected from at least one of M-containing hydroxide, M-containing sulfate, M-containing carbonate and M-containing acetate.
8. A nickel-rich material prepared by the method for preparing a nickel-rich material according to any one of claims 1 to 7.
9. A positive electrode sheet comprising a current collector and an active layer formed on the current collector, the active layer comprising the nickel-rich material of claim 8.
10. A battery comprising the positive electrode sheet according to claim 9.
11. A powered device comprising the battery of claim 10.
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| CN101070191A (en) * | 2006-05-08 | 2007-11-14 | 上海川那电池制造有限公司 | Process for preparing lithium ion cell positive pole material |
| CN104538618A (en) * | 2014-12-22 | 2015-04-22 | 东北大学 | Method for synthesizing monocrystalline-like spinel lithium manganese with high-temperature cyclic stability for lithium battery |
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| CN111170369A (en) * | 2020-01-08 | 2020-05-19 | 济南大学 | Lithium manganate or lithium nickel manganese material and preparation method and application thereof |
| CN112133890A (en) * | 2019-06-24 | 2020-12-25 | 比亚迪股份有限公司 | Lithium-containing ternary precursor and preparation method thereof, ternary cathode material and preparation method thereof, and lithium ion battery |
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| CN101070191A (en) * | 2006-05-08 | 2007-11-14 | 上海川那电池制造有限公司 | Process for preparing lithium ion cell positive pole material |
| CN104538618A (en) * | 2014-12-22 | 2015-04-22 | 东北大学 | Method for synthesizing monocrystalline-like spinel lithium manganese with high-temperature cyclic stability for lithium battery |
| CN107359323A (en) * | 2017-06-22 | 2017-11-17 | 芜湖浙鑫新能源有限公司 | A kind of lithium-rich manganese-based anode material being prepared based on full element Direct precipitation and preparation method thereof |
| CN108682844A (en) * | 2018-05-04 | 2018-10-19 | 贵州大龙汇成新材料有限公司 | A kind of preparation method of lithium ion battery mangaic acid lithium anode material |
| CN112133890A (en) * | 2019-06-24 | 2020-12-25 | 比亚迪股份有限公司 | Lithium-containing ternary precursor and preparation method thereof, ternary cathode material and preparation method thereof, and lithium ion battery |
| CN111170369A (en) * | 2020-01-08 | 2020-05-19 | 济南大学 | Lithium manganate or lithium nickel manganese material and preparation method and application thereof |
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