CN114937769B - No-water-washing high-magnification hollow high-nickel cathode material and preparation method and application thereof - Google Patents
No-water-washing high-magnification hollow high-nickel cathode material and preparation method and application thereof Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 125
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 88
- 238000005406 washing Methods 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000010406 cathode material Substances 0.000 title abstract description 16
- 238000005245 sintering Methods 0.000 claims abstract description 49
- 239000000463 material Substances 0.000 claims abstract description 46
- UUCGKVQSSPTLOY-UHFFFAOYSA-J cobalt(2+);nickel(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Co+2].[Ni+2] UUCGKVQSSPTLOY-UHFFFAOYSA-J 0.000 claims abstract description 36
- YTBWYQYUOZHUKJ-UHFFFAOYSA-N oxocobalt;oxonickel Chemical compound [Co]=O.[Ni]=O YTBWYQYUOZHUKJ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000010438 heat treatment Methods 0.000 claims abstract description 27
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910001930 tungsten oxide Inorganic materials 0.000 claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 24
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 17
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 17
- 239000010405 anode material Substances 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 230000018044 dehydration Effects 0.000 claims abstract description 9
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 9
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 5
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 66
- 238000000034 method Methods 0.000 claims description 36
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 34
- 239000007774 positive electrode material Substances 0.000 claims description 33
- 239000002245 particle Substances 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 21
- 239000000839 emulsion Substances 0.000 claims description 19
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 14
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 13
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 13
- 239000010941 cobalt Substances 0.000 claims description 12
- 229910017052 cobalt Inorganic materials 0.000 claims description 12
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 10
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 9
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 9
- 229940011182 cobalt acetate Drugs 0.000 claims description 9
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 9
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 9
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 9
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 9
- 229940078494 nickel acetate Drugs 0.000 claims description 9
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 9
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 8
- 229910001416 lithium ion Inorganic materials 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 6
- QABDZOZJWHITAN-UHFFFAOYSA-F [Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[O-]P([O-])(F)=O.[O-]P([O-])(F)=O.[O-]P([O-])(F)=O.[O-]P([O-])(F)=O Chemical compound [Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[O-]P([O-])(F)=O.[O-]P([O-])(F)=O.[O-]P([O-])(F)=O.[O-]P([O-])(F)=O QABDZOZJWHITAN-UHFFFAOYSA-F 0.000 claims description 5
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 5
- 229940044175 cobalt sulfate Drugs 0.000 claims description 5
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 5
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 5
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 5
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 238000005054 agglomeration Methods 0.000 abstract description 12
- 230000002776 aggregation Effects 0.000 abstract description 12
- 239000011248 coating agent Substances 0.000 abstract description 11
- 239000011164 primary particle Substances 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 7
- 238000007670 refining Methods 0.000 abstract description 6
- 238000000576 coating method Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 15
- 239000003513 alkali Substances 0.000 description 6
- 230000009257 reactivity Effects 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 239000004202 carbamide Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- NWEKXBVHVALDOL-UHFFFAOYSA-N butylazanium;hydroxide Chemical compound [OH-].CCCC[NH3+] NWEKXBVHVALDOL-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 2
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009831 deintercalation 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
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000002427 irreversible effect Effects 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a water-washing-free high-magnification hollow high-nickel cathode material, and a preparation method and application thereof, wherein the preparation method comprises the following steps: mixing lithium salt, nickel cobalt oxide, aluminum oxide and tungsten oxide, and sintering to obtain a sintering material; mixing the sintering material with a coating agent, and carrying out heat treatment for coating to obtain the non-washing high-magnification hollow high-nickel anode material; the nickel cobalt oxide is obtained by heat treatment and dehydration of a nickel cobalt hydroxide precursor; and the mass percentage of Ni in the nickel cobalt hydroxide is more than or equal to 80 percent based on oxide. The preparation method provided by the invention does not need to wash when preparing the high-nickel material, and can relieve the agglomeration phenomenon among the sintering materials through the addition of the coating agent; the tungsten oxide can be distributed on the surface and the grain boundary of the primary particles during sintering, so that the growth of the primary particles is hindered, and the effect of refining the primary grains is achieved.
Description
Technical Field
The invention belongs to the technical field of batteries, relates to an electrode material, and in particular relates to a water-washing-free high-magnification hollow high-nickel positive electrode material, and a preparation method and application thereof.
Background
Lithium ion batteries mainly rely on lithium ions to reciprocate between positive and negative electrodes, li during charge and discharge + To-and-fro intercalation and deintercalation between two electrodes: during charging, li + De-intercalation from the positive electrode, and embedding the negative electrode through electrolyte to enable the negative electrode to be in a lithium-rich state; the opposite is true when discharging. The lithium ion battery has the advantages of high energy density, good environmental compatibility, long cycle life and low self-discharge rate, and is widely applied to the fields of portable electronic equipment, electric automobiles, aerospace, power generation base stations and the like.
Currently, commercial lithium ion battery cathode materials include spinel lithium manganate (LiMn 2 O 4 ) Lithium iron phosphate (LiFePO) 4 ) Lithium cobalt oxide (LiCoO) 2 ) And ternary positive electrode materials (NCM), which are high nickel ternary positive electrode materials, are solutions to increase energy density and reduce production costs due to the current power cell requirements for energy density.
However, the high-nickel ternary positive electrode material has the defect of high content of residual alkali on the surface, is very sensitive to environmental humidity, is a relatively outstanding problem that the electrochemical performance of the material is affected in practical application, and is commonly used for removing the residual alkali on the surface by water washing.
CN 112186156a discloses a method for washing high nickel positive electrode material, its product and use of the product, the method comprises mixing high nickel positive electrode material with boric acid solution, reacting, sintering, obtaining washed high nickel positive electrode material; the washing method removes the residual alkali on the surface of the high-nickel cathode material at normal temperature, and the structural stability and the thermal stability of the high-nickel cathode material after washing are improved by utilizing the reaction of boric acid and the residual alkali which is not removed by washing on the surface of the high-nickel cathode material in the sintering process.
However, the water washing process is easy to destroy Li in the surface lattice of the material + The NiO inert layer without electrochemical activity is generated, the surface phase structure of the material is destroyed, and the electrochemical property of the material is also influencedThe chemical properties.
In addition, the high-nickel ternary positive electrode material is unstable Ni in the charge and discharge process 4+ In addition, the material structure is easy to change from a lamellar state to a spinel phase and finally to change into a rock salt phase. This gradual phase change transition from the surface to the inner layer of the material results in a reduction of the active material, which results in an irreversible capacity decay and thus an impact on the cycle performance. Moreover, since the nickel content is high and the Li removal of the high-nickel ternary positive electrode material is insufficient under high-rate charge and discharge, li in the Li layer + The content is higher, the vacancy is less, and the Ni element is prevented from being mixed and discharged into the Li layer.
CN 109167056a discloses a tungsten ion doped high nickel layered oxide lithium battery anode material and a preparation method thereof, the preparation method comprises the following steps: dissolving a nickel source, a cobalt source and a manganese source to obtain a mixed metal salt solution; adding inorganic strong base and ammonia water solution into the mixed metal salt solution to adjust the pH value to 10.6-11.5, stirring for reaction, filtering, washing and drying to obtain a high-nickel ternary precursor material containing nickel, cobalt and manganese; mixing a high-nickel ternary precursor material, a tungsten source and a lithium source to obtain a doped ternary precursor mixture; calcining the doped ternary precursor mixture, and grinding to obtain the tungsten ion doped high-nickel layered oxide lithium battery anode material. However, the initial discharge performance of the material is only 150mAh/g under the conditions that the voltage range is 2.7-4.3V, the test temperature is 25 ℃, the capacity retention rate of 100 circles is 95%, and the material has good cycle performance but poor rate performance.
Accordingly, it is required to provide a method capable of increasing Li + Diffusion speed in charge and discharge process, high-magnification hollow high-nickel anode material for reducing material structure phase transition, and preparation method and application thereof.
Disclosure of Invention
The invention aims to provide a water-free high-magnification hollow high-nickel cathode material, a preparation method and application thereof, wherein in the preparation process of the water-free high-magnification hollow high-nickel cathode material, the agglomeration phenomenon caused by the existence of residual alkali on the surface can be overcome, and primary grains can be refined, so that the finally obtained water-free high-magnification hollow high-nickel cathode material has excellent magnification performance.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the invention provides a preparation method of a non-washing high-magnification hollow high-nickel anode material, which comprises the following steps:
(1) Mixing lithium salt, nickel cobalt oxide, aluminum oxide and tungsten oxide, and sintering to obtain a sintering material;
(2) Mixing the sintering material and a coating agent, and performing heat treatment to coat to obtain the non-washing high-magnification hollow high-nickel anode material;
the nickel cobalt oxide is obtained by heat treatment and dehydration of a nickel cobalt hydroxide precursor;
the molar quantity of nickel in the nickel cobalt hydroxide accounts for more than 80 percent of the total molar quantity of nickel and cobalt.
The preparation method provided by the invention does not need to wash when preparing the high-nickel material, and can relieve the agglomeration phenomenon among the sintering materials through the addition of tungsten oxide; and tungsten oxide can be distributed on the surface and grain boundary of primary particles during sintering, so that the growth of the primary particles is hindered, the effect of refining the primary grains is achieved, and the finally obtained water-washing-free high-magnification hollow high-nickel positive electrode material has excellent magnification performance.
The term "high nickel" as used herein means that the molar amount of nickel in the nickel cobalt hydroxide is 80% or more of the total molar amount of nickel cobalt, and may be, for example, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 92%, 94% or 95%, but is not limited to the recited values, and other non-recited values within the numerical range are equally applicable.
Preferably, the temperature of the heat treatment dehydration is 450-650 ℃, for example, 450 ℃,500 ℃, 550 ℃,600 ℃ or 650 ℃, but not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
The nickel cobalt hydroxide is dehydrated through heat treatment, and the obtained nickel cobalt oxide has higher reactivity and larger specific surface area, and is convenient to combine with lithium salt. Although the high reactivity and the large specific surface area are easy to cause agglomeration after being combined with lithium salt, the agglomeration phenomenon can be relieved by matching with the subsequent operation of coating agent and heat treatment, and the rate capability of the material is improved.
Preferably, the nickel cobalt hydroxide is prepared by the following method: mixing a nickel source, a cobalt source, alcohol, a precipitator and water, and performing hydrothermal reaction on the obtained emulsion to obtain the nickel-cobalt hydroxide.
Preferably, the nickel source comprises any one or a combination of at least two of nickel nitrate, nickel chloride, nickel acetate or nickel sulfate, typically but not limited to a combination of nickel nitrate and nickel chloride, a combination of nickel chloride and nickel acetate, a combination of nickel acetate and nickel sulfate, a combination of nickel nitrate, nickel chloride and nickel acetate, a combination of nickel chloride, nickel acetate and nickel sulfate, or a combination of nickel nitrate, nickel chloride, nickel acetate and nickel sulfate.
Preferably, the cobalt source comprises any one or a combination of at least two of cobalt nitrate, cobalt chloride, cobalt acetate or cobalt sulfate; typical, but non-limiting, combinations include combinations of cobalt nitrate and cobalt chloride, cobalt chloride and cobalt acetate, cobalt acetate and cobalt sulfate, combinations of cobalt nitrate, cobalt chloride and cobalt acetate, combinations of cobalt chloride, cobalt acetate and cobalt sulfate, or combinations of cobalt nitrate, cobalt chloride, cobalt acetate and cobalt sulfate.
Preferably, the alcohol comprises t-butanol.
Preferably, the volume ratio of tertiary butanol to water is (8-10): 1, which may be, for example, 8:1, 8.5:1, 9:1, 9.5:1 or 10:1, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
According to the invention, the nickel cobalt hydroxide with uniform hollow structure can be obtained by controlling the volume ratio of tertiary butanol to water, which is beneficial to improving the multiplying power performance of the finally obtained water-free high-multiplying-power hollow high-nickel anode material.
Preferably, the precipitant comprises tetrabutylammonium hydroxide and/or urea.
According to the invention, through the use of tertiary butanol and a specific precipitant, nickel cobalt hydroxide with loose hollow morphology can be obtained, the hollow structure after heat treatment dehydration is beneficial to the infiltration of electrolyte, the diffusion path of lithium ions is shortened, the effect of refining primary grains by cooperating with tungsten oxide is achieved, the diffusion path of lithium ions is greatly shortened, and the rate capability is improved.
Preferably, the mass ratio of the precipitant to water is 1 (12-16), and can be, for example, 1:12, 1:13, 1:14, 1:15 or 1:16, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the molar concentration of the nickel source in the emulsion is 0.025 to 0.03mol/L, and may be, for example, 0.025mol/L, 0.026mol/L, 0.027mol/L, 0.028mol/L, 0.029mol/L, or 0.03mol/L, although not limited to the recited values, other non-recited values within the range of values are equally applicable.
Preferably, the molar concentration of the cobalt source in the emulsion is 0.001 to 0.006mol/L, for example, 0.001mol/L, 0.002mol/L, 0.003mol/L, 0.004mol/L, 0.005mol/L or 0.006mol/L, but is not limited to the recited values, as are other non-recited values within the range of values.
Preferably, the temperature of the hydrothermal reaction is 90-110 ℃ and the time is 20-26h.
The temperature of the hydrothermal reaction according to the present invention is 90 to 110℃and may be, for example, 90℃95℃100℃105℃or 110℃but is not limited to the values recited, and other values not recited in the numerical range are equally applicable.
The hydrothermal reaction time of the present invention is 20-26h, for example, 20h, 21h, 22h, 23h, 24h, 25h or 26h, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the lithium salt of step (1) comprises any one or a combination of at least two of lithium hydroxide, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium difluorophosphate or lithium tetrafluorophosphate, typical but non-limiting combinations include combinations of lithium hexafluorophosphate and lithium tetrafluoroborate, combinations of lithium hexafluorophosphate and lithium difluorophosphate, combinations of lithium difluorophosphate and lithium tetrafluorophosphate, combinations of lithium hexafluorophosphate, lithium difluorophosphate and lithium tetrafluorophosphate, or combinations of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium difluorophosphate and lithium tetrafluorophosphate; preferably lithium hydroxide.
Preferably, the alumina in step (1) is 0.3-1% of the mass of nickel cobalt oxide, for example, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9% or 1%, but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
Preferably, the particle size D50 of the alumina in step (1) is 8-12nm, for example, 8nm, 9nm, 10nm, 11nm or 12nm, but not limited to the values recited, and other values not recited in the range are equally applicable.
Preferably, the tungsten oxide in the step (1) is 0.05-0.3% of the mass of nickel cobalt oxide, for example, 0.05%, 0.1%, 0.15%, 0.2%, 0.25% or 0.3%, but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
Preferably, the particle diameter D50 of the tungsten oxide in step (1) is 48-52nm, for example 48nm, 49nm, 50nm, 51nm or 52nm, but not limited to the values listed, and other values not listed in the range of values are equally applicable.
The invention utilizes the properties of large atomic mass and high chemical bond tendency of tungsten oxide to be distributed on the surface and grain boundary of primary particles, reduces the growth of the primary particles and achieves the effect of refining the primary grains.
Preferably, the molar ratio of the lithium salt to the nickel cobalt oxide in step (1) is (1.01-1.05): 1, and may be, for example, 1.01:1, 1.02:1, 1.03:1, 1.04:1 or 1.05:1, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
The invention can supplement the burning loss part of the lithium salt in the heat treatment process by adding excessive lithium salt.
Preferably, the sintering in step (1) is performed in an environment with an oxygen volume fraction of 80% or more, for example 80%, 85%, 90%, 95% or 100%, but not limited to the values recited, and other values not recited in the range are equally applicable.
Preferably, the sintering temperature in step (1) is 700-800 ℃, and may be 700 ℃, 720 ℃, 750 ℃, 760 ℃, 780 ℃, or 800 ℃, for example, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the sintering time in step (1) is 8-24h, for example, 8h, 10h, 12h, 15h, 16h, 18h, 20h, 21h or 24h, but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
Preferably, the sinter of step (1) has a particle size D50 of 2.5 to 5.5. Mu.m, for example, 2.5. Mu.m, 3. Mu.m, 3.5. Mu.m, 4. Mu.m, 4.5. Mu.m, 5. Mu.m, or 5.5. Mu.m, but is not limited to the values recited, and other values not recited in the numerical range are equally applicable.
The particle size of the sintering material is obtained by conventional crushing and sieving in the field after sintering, and the crushing and sieving are not repeated here.
Preferably, the coating agent of step (2) comprises nickel oxide.
The nickel oxide can react with lithium hydroxide and consume residual alkali on the surface, so that the adhesion agglomeration phenomenon among particles is relieved, and the rate performance of the obtained water-washing-free high-rate hollow high-nickel positive electrode material is improved.
Preferably, the particle size D50 of the coating agent in step (2) is 18-22nm, for example 18nm, 19nm, 20nm, 21nm or 22nm, but not limited to the values recited, and other values not recited in the range of values are equally applicable.
Preferably, the coating agent in step (2) is added in an amount of 0.2-0.8% by mass of the sinter, for example, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7% or 0.8%, but not limited to the values recited, and other values not recited in the numerical range are equally applicable.
Preferably, the temperature of the heat treatment in step (2) is 500-700 ℃, for example 500 ℃, 550 ℃,600 ℃, 650 ℃, or 700 ℃, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the time of the heat treatment in step (2) is 6-10h, for example, 6h, 6.5h, 7h, 7.5h, 8h, 8.5h, 9h, 9.5h or 10h, but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
As a preferred technical scheme of the preparation method according to the first aspect of the present invention, the preparation method comprises the following steps:
(1) Mixing lithium salt, nickel cobalt oxide, aluminum oxide and tungsten oxide, and sintering in an environment with the oxygen volume fraction of more than or equal to 80% to obtain a sintered material; the alumina accounts for 0.3 to 1 percent of the mass of the nickel cobalt oxide, and the tungsten oxide accounts for 0.05 to 0.3 percent of the mass of the nickel cobalt oxide; the sintering temperature is 700-800 ℃ and the sintering time is 8-24 hours;
(2) Mixing the sintering material with nickel oxide with the particle size D50 of 18-22nm, and carrying out heat treatment at 500-700 ℃ for 6-10 hours to coat to obtain the non-water-washing high-magnification hollow high-nickel anode material; the addition amount of the nickel oxide is 0.2-0.8% of the mass of the sintering material;
the nickel cobalt oxide is obtained by dehydration of a nickel cobalt hydroxide precursor through heat treatment at 450-650 ℃; the molar quantity of nickel in the nickel cobalt hydroxide accounts for more than 80 percent of the total molar quantity of nickel and cobalt;
the nickel cobalt hydroxide is prepared by the following method: mixing a nickel source, a cobalt source, tertiary butyl alcohol, tetrabutylammonium hydroxide and water, and carrying out hydrothermal reaction on the obtained emulsion at 90-110 ℃ for 20-26 hours to obtain the nickel cobalt hydroxide.
In a second aspect, the invention provides a non-water-washing high-magnification hollow high-nickel cathode material, which is obtained by the preparation method in the first aspect.
In a third aspect, the invention provides a lithium ion battery, which comprises the non-washing high-rate hollow high-nickel positive electrode material in the second aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) The preparation method provided by the invention does not need to wash when preparing the high-nickel material, and can relieve the agglomeration phenomenon among the sintering materials through the addition of tungsten oxide; the tungsten oxide can be distributed on the surface and the grain boundary of the primary particles during sintering, so that the growth of the primary particles is hindered, the effect of refining the primary grains is achieved, and the finally obtained water-washing-free high-magnification hollow high-nickel positive electrode material has excellent magnification performance;
(2) The nickel cobalt hydroxide is dehydrated through heat treatment, and the obtained nickel cobalt oxide has higher reactivity and larger specific surface area, and is convenient to combine with lithium salt. Although the high reactivity and the large specific surface area are easy to cause agglomeration after being combined with lithium salt, the agglomeration phenomenon can be relieved by matching with the subsequent operation of coating agent and heat treatment, and the rate capability of the material is improved.
Drawings
FIG. 1 is a cross-sectional SEM image of the nickel cobalt oxide obtained in example 1;
FIG. 2 is an SEM image of a non-aqueous high magnification hollow high nickel positive electrode material obtained in example 1;
FIG. 3 is an SEM image of the high nickel cathode material obtained in comparative example 1;
fig. 4 is a graph of the rate performance test of example 1, comparative example 1 and comparative example 3.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a preparation method of a non-water-washing high-magnification hollow high-nickel anode material, which comprises the following steps:
(1) Mixing lithium hydroxide, nickel cobalt oxide, alumina with the particle size D50 of 10nm and tungsten oxide with the particle size D50 of 50nm, and sintering in an environment with the oxygen volume fraction of 80% to obtain a sintered material with the particle size D50 of 4 mu m; alumina is 0.6% of the mass of lithium hydroxide; tungsten oxide is 0.15% of the mass of lithium hydroxide; the sintering temperature is 750 ℃ and the sintering time is 16 hours; the molar ratio of the lithium hydroxide to the nickel cobalt oxide is 1.03:1;
(2) Mixing the sintering material with nickel oxide with the particle size D50 of 20nm, and carrying out heat treatment at 600 ℃ for 8 hours to coat to obtain the non-washing high-magnification hollow high-nickel positive electrode material; the addition amount of the nickel oxide is 0.5% of the mass of the sintering material;
the nickel cobalt oxide is obtained by dehydrating a nickel cobalt hydroxide precursor through heat treatment at 550 ℃ in the step (1) (see figure 1); the molar amount of nickel in the nickel cobalt hydroxide accounts for 80% of the total molar amount of nickel cobalt;
the nickel cobalt hydroxide is prepared by the following method:
(I) Mixing nickel nitrate, cobalt nitrate, tertiary butyl alcohol, tetrabutylammonium hydroxide and water to obtain emulsion; the molar concentration of nickel nitrate in the emulsion is 0.027mol/L, the molar concentration of cobalt nitrate is 0.004mol/L, the volume ratio of tertiary butanol to water is 9:1, and the mass ratio of tetrabutyl ammonium hydroxide to water is 1:15;
(II) carrying out hydrothermal reaction on the emulsion obtained in the step (I) at 100 ℃ for 24 hours to obtain the nickel cobalt hydroxide.
An SEM image of the non-aqueous high-magnification hollow high-nickel positive electrode material obtained in this example is shown in fig. 2.
Example 2
The embodiment provides a preparation method of a non-water-washing high-magnification hollow high-nickel anode material, which comprises the following steps:
(1) Mixing lithium hydroxide, nickel cobalt oxide, aluminum oxide with the particle size D50 of 8nm and tungsten oxide with the particle size D50 of 48nm, and sintering in an environment with the oxygen volume fraction of 90% to obtain a sintered material with the particle size D50 of 2.5 mu m; alumina is 0.3% of the mass of lithium hydroxide; tungsten oxide is 0.05% of the mass of lithium hydroxide; the sintering temperature is 700 ℃ and the sintering time is 24 hours; the molar ratio of the lithium hydroxide to the nickel cobalt oxide is 1.01:1;
(2) Mixing the sintering material with nickel oxide with the particle size D50 of 18nm, and carrying out heat treatment at 500 ℃ for 10 hours to coat to obtain the non-washing high-magnification hollow high-nickel positive electrode material; the addition amount of the nickel oxide is 0.2% of the mass of the sintering material;
the nickel cobalt oxide is obtained by dehydration of a nickel cobalt hydroxide precursor through heat treatment at 450 ℃; the molar amount of nickel in the nickel cobalt hydroxide accounts for 80% of the total molar amount of nickel cobalt;
the nickel cobalt hydroxide is prepared by the following method:
(I) Mixing nickel acetate, cobalt acetate, tertiary butanol, tetrabutylammonium hydroxide and water to obtain emulsion; the molar concentration of nickel acetate in the emulsion is 0.025mol/L, the molar concentration of cobalt acetate is 0.001mol/L, the volume ratio of tertiary butanol to water is 8:1, and the mass ratio of tetrabutyl ammonium hydroxide to water is 1:12;
(II) carrying out hydrothermal reaction on the emulsion obtained in the step (I) at 90 ℃ for 26 hours to obtain the nickel cobalt hydroxide.
Example 3
The embodiment provides a preparation method of a non-water-washing high-magnification hollow high-nickel anode material, which comprises the following steps:
(1) Mixing lithium hydroxide, nickel cobalt oxide, alumina with the particle size D50 of 12nm and tungsten oxide with the particle size D50 of 52nm, and sintering in an environment with the oxygen volume fraction of 100% to obtain a sintered material with the particle size D50 of 5.5 mu m; alumina is 1% of the mass of lithium hydroxide; tungsten oxide is 0.3% of the mass of lithium hydroxide; the sintering temperature is 800 ℃ and the sintering time is 8 hours; the molar ratio of the lithium hydroxide to the nickel cobalt oxide is 1.05:1;
(2) Mixing the sintering material with nickel oxide with the particle size D50 of 22nm, and carrying out heat treatment at 700 ℃ for 6 hours to coat to obtain the non-washing high-magnification hollow high-nickel positive electrode material; the addition amount of the nickel oxide is 0.8% of the mass of the sintering material;
the nickel cobalt oxide is obtained by dehydration of a nickel cobalt hydroxide precursor through heat treatment at 650 ℃; the molar amount of nickel in the nickel cobalt hydroxide accounts for 80% of the total molar amount of nickel cobalt;
the nickel cobalt hydroxide is prepared by the following method:
(I) Mixing nickel chloride, cobalt chloride, tertiary butyl alcohol, tetrabutylammonium hydroxide and water to obtain emulsion; the molar concentration of nickel chloride in the emulsion is 0.03mol/L, the molar concentration of cobalt chloride is 0.006mol/L, the volume ratio of tertiary butanol to water is 10:1, and the mass ratio of tetrabutyl ammonium hydroxide to water is 1:16;
(II) carrying out hydrothermal reaction on the emulsion obtained in the step (I) to obtain the nickel cobalt hydroxide; the volume ratio of tetrabutylammonium hydroxide to water is 4.5:1.
Example 4
The present example provides a method for preparing a non-aqueous high-magnification hollow high-nickel positive electrode material, which is the same as example 1 except that the same mass as tetrabutylammonium hydroxide is replaced with urea.
Example 5
The present example provides a method for preparing a non-aqueous high-magnification hollow high-nickel positive electrode material, which is the same as example 1 except that the same mass as tetrabutylammonium hydroxide is replaced by a combination of tetrabutylammonium hydroxide and urea, and the mass ratio of tetrabutylammonium hydroxide to urea is 1:1.
Example 6
The present example provides a method for preparing a non-aqueous high-magnification hollow high-nickel positive electrode material, which is the same as example 1 except that the mass ratio of butylammonium hydroxide to water is 1:10.
Example 7
The present example provides a method for preparing a non-aqueous high-magnification hollow high-nickel positive electrode material, which is the same as example 1 except that the mass ratio of butylammonium hydroxide to water is 1:18.
Example 8
This example provides a method for preparing a non-aqueous high-rate hollow high-nickel positive electrode material, which is the same as example 1 except that the equimolar amount of lithium hydroxide is replaced with lithium hexafluorophosphate.
Example 9
This example provides a method for preparing a non-aqueous high-rate hollow high-nickel positive electrode material, which is the same as example 1 except that the equimolar amount of lithium hydroxide is replaced with lithium tetrafluoroborate.
Example 10
The present example provided a method for preparing a non-aqueous high-magnification hollow high-nickel positive electrode material, which was the same as example 1 except that the volume ratio of t-butanol to water was 7:1.
Example 11
The present example provides a method for preparing a non-aqueous high-magnification hollow high-nickel positive electrode material, which is the same as example 1 except that the volume ratio of t-butanol to water is 11:1
Comparative example 1
This comparative example provides a method for preparing a high nickel cathode material, which is the same as example 1 except that the mass of tungsten oxide or the like is replaced with alumina having a particle diameter D50 of 10 nm.
An SEM image of the high nickel cathode material obtained in this comparative example is shown in fig. 3.
Comparative example 2
The comparative example provides a preparation method of a high nickel cathode material, comprising the following steps:
(1) Mixing lithium hydroxide, nickel cobalt oxide, alumina with the particle size D50 of 10nm and tungsten oxide with the particle size D50 of 50nm, and sintering in an environment with the oxygen volume fraction of 80% to obtain a sintered material with the particle size D50 of 4 mu m; alumina is …% of the mass of lithium hydroxide; tungsten oxide is 0.15% of the mass of lithium hexafluorophosphate; the sintering temperature is 750 ℃ and the sintering time is 16 hours; the molar ratio of the lithium hydroxide to the nickel cobalt oxide is 1.03:1;
(2) The sintered material is subjected to heat treatment at 600 ℃ for 8 hours to obtain the high-nickel anode material;
the nickel cobalt oxide is obtained by dehydration of a nickel cobalt hydroxide precursor through heat treatment at 550 ℃; the molar amount of nickel in the nickel cobalt hydroxide accounts for 80% of the total molar amount of nickel cobalt;
the nickel cobalt hydroxide is prepared by the following method:
(I) Mixing nickel nitrate, cobalt nitrate, tertiary butyl alcohol, tetrabutylammonium hydroxide and water to obtain emulsion; the molar concentration of nickel nitrate in the emulsion is 0.027mol/L, the molar concentration of cobalt nitrate is 0.004mol/L, the volume ratio of tertiary butanol to water is 9:1, and the mass ratio of tetrabutyl ammonium hydroxide to water is 1:15;
(II) carrying out hydrothermal reaction on the emulsion obtained in the step (I) at 100 ℃ for 24 hours to obtain the nickel cobalt hydroxide.
In this comparative example, no nickel oxide was added to coat the sintered material as compared with example 1.
Comparative example 3
This comparative example provides a method for preparing a high nickel cathode material, which is the same as comparative example 2 except that the mass of tungsten oxide or the like is replaced with alumina having a particle diameter D50 of 10 nm.
Performance testing
The non-aqueous high-magnification hollow high-nickel positive electrode materials provided in examples 1 to 11 and the high-nickel positive electrode materials provided in comparative examples 1 to 3 were combined into a CR2025 type button cell with a positive electrode sheet obtained by positive electrode material, binder (PVDF), conductive agent (acetylene black) =90:5:5, and metallic lithium as a counter electrode in a glove box filled with argon gas, and LiPF with an electrolyte of 1M 6 DMC: FEC (the volume ratio of EC, DMC and FEC is 1:1:1), the diaphragm is Celgard2400 microporous diaphragm, and the test method is as follows:
the initial discharge specific capacity was tested under the conditions of the voltage ranges of 3 to 4.3V, 0.2C/0.2C, the rate capability of 0.5C/0.2C, 1C/0.2C, 2C/0.2C, 4C/0.2C and 8C/0.2C was examined, and the capacity retention rate at 50 cycles was tested under the conditions of 1.2C/1C, and the results obtained are shown in Table 1, wherein the rate capability test results of example 1, comparative example 1 and comparative example 3 are shown in FIG. 4.
TABLE 1
In conclusion, the high nickel material is prepared by the preparation method provided by the invention without washing, and the agglomeration phenomenon among the sintering materials can be relieved by adding the coating agent; the tungsten oxide can be distributed on the surface and the grain boundary of the primary particles during sintering, so that the growth of the primary particles is hindered, the effect of refining the primary grains is achieved, and the finally obtained water-washing-free high-magnification hollow high-nickel positive electrode material has excellent magnification performance; the nickel cobalt hydroxide is dehydrated through heat treatment, and the obtained nickel cobalt oxide has higher reactivity and larger specific surface area, and is convenient to combine with lithium salt. Although the high reactivity and the large specific surface area are easy to cause agglomeration after being combined with lithium salt, the agglomeration phenomenon can be relieved by matching with the subsequent operation of coating agent and heat treatment, and the rate capability of the material is improved.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that fall within the technical scope of the present invention disclosed herein are within the scope of the present invention.
Claims (15)
1. The preparation method of the non-water-washing high-magnification hollow high-nickel anode material is characterized by comprising the following steps of:
(1) Mixing lithium salt, nickel cobalt oxide, aluminum oxide and tungsten oxide, and sintering in an environment with the oxygen volume fraction of more than or equal to 80% to obtain a sintered material; the alumina accounts for 0.3 to 1 percent of the mass of the nickel cobalt oxide, and the tungsten oxide accounts for 0.05 to 0.3 percent of the mass of the nickel cobalt oxide; the sintering temperature is 700-800 ℃ and the sintering time is 8-24 hours;
(2) Mixing the sintering material with nickel oxide with the particle size D50 of 18-22nm, and carrying out heat treatment at 500-700 ℃ for 6-10 hours to coat to obtain the non-water-washing high-magnification hollow high-nickel anode material; the addition amount of the nickel oxide is 0.2-0.8% of the mass of the sintering material;
the nickel cobalt oxide is obtained by dehydration of a nickel cobalt hydroxide precursor through heat treatment at 450-650 ℃; the molar quantity of nickel in the nickel cobalt hydroxide accounts for more than 80 percent of the total molar quantity of nickel and cobalt;
the nickel cobalt hydroxide is prepared by the following method: mixing a nickel source, a cobalt source, tertiary butyl alcohol, tetrabutylammonium hydroxide and water, and carrying out hydrothermal reaction on the obtained emulsion at 90-110 ℃ for 20-26 hours to obtain the nickel cobalt hydroxide.
2. The method of claim 1, wherein the nickel source comprises any one or a combination of at least two of nickel nitrate, nickel chloride, nickel acetate, or nickel sulfate.
3. The method of claim 1, wherein the cobalt source comprises any one or a combination of at least two of cobalt nitrate, cobalt chloride, cobalt acetate, or cobalt sulfate.
4. The method according to claim 1, wherein the volume ratio of t-butanol to water is (8-10): 1.
5. The preparation method according to claim 1, wherein the mass ratio of tetrabutylammonium hydroxide to water is 1 (12-16).
6. The method of claim 1, wherein the emulsion has a molar concentration of nickel source of 0.025-0.03mol/L.
7. The method of claim 1, wherein the molar concentration of cobalt source in the emulsion is 0.001-0.006mol/L.
8. The method of claim 1, wherein the lithium salt of step (1) comprises any one or a combination of at least two of lithium hydroxide, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium difluorophosphate, or lithium tetrafluorophosphate.
9. The method of claim 8, wherein the lithium salt in step (1) is lithium hydroxide.
10. The method according to claim 1, wherein the alumina in step (1) has a particle diameter D50 of 8 to 12nm.
11. The method according to claim 1, wherein the tungsten oxide in the step (1) has a particle diameter D50 of 48 to 52nm.
12. The method according to claim 1, wherein the molar ratio of the lithium salt to the nickel cobalt oxide in the step (1) is 1.01 to 1.05.
13. The process according to claim 1, wherein the sintered material obtained in the step (1) has a particle diameter D50 of 2.5 to 5.5. Mu.m.
14. The non-water-washing high-magnification hollow high-nickel positive electrode material is characterized in that the non-water-washing high-magnification hollow high-nickel positive electrode material is obtained by the preparation method of any one of claims 1-13.
15. A lithium ion battery comprising the non-aqueous high-rate hollow high-nickel positive electrode material of claim 14.
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