CN114937769A - Washing-free high-rate hollow high-nickel cathode material and preparation method and application thereof - Google Patents
Washing-free high-rate hollow high-nickel cathode material and preparation method and application thereof Download PDFInfo
- Publication number
- CN114937769A CN114937769A CN202210676628.8A CN202210676628A CN114937769A CN 114937769 A CN114937769 A CN 114937769A CN 202210676628 A CN202210676628 A CN 202210676628A CN 114937769 A CN114937769 A CN 114937769A
- Authority
- CN
- China
- Prior art keywords
- nickel
- cobalt
- oxide
- sintering
- lithium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 89
- 239000010406 cathode material Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000005245 sintering Methods 0.000 claims abstract description 54
- 239000000463 material Substances 0.000 claims abstract description 51
- 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 40
- YTBWYQYUOZHUKJ-UHFFFAOYSA-N oxocobalt;oxonickel Chemical compound [Co]=O.[Ni]=O YTBWYQYUOZHUKJ-UHFFFAOYSA-N 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 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 29
- 229910001930 tungsten oxide Inorganic materials 0.000 claims abstract description 29
- 238000010438 heat treatment Methods 0.000 claims abstract description 28
- 238000002156 mixing Methods 0.000 claims abstract description 27
- 239000011248 coating agent Substances 0.000 claims abstract description 20
- 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 15
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002243 precursor Substances 0.000 claims abstract description 13
- 230000018044 dehydration Effects 0.000 claims abstract description 12
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 12
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 66
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 49
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 25
- 239000000839 emulsion Substances 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 19
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 17
- 239000007774 positive electrode material Substances 0.000 claims description 16
- 239000010941 cobalt Substances 0.000 claims description 14
- 229910017052 cobalt Inorganic materials 0.000 claims description 14
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 14
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 14
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 10
- 229910001416 lithium ion Inorganic materials 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
- 238000004519 manufacturing process Methods 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 238000007669 thermal treatment Methods 0.000 claims description 4
- 239000012716 precipitator Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 230000001376 precipitating effect Effects 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 13
- 238000005054 agglomeration Methods 0.000 abstract description 11
- 230000002776 aggregation Effects 0.000 abstract description 11
- 239000011164 primary particle Substances 0.000 abstract description 10
- 238000007670 refining Methods 0.000 abstract description 6
- 230000000052 comparative effect Effects 0.000 description 15
- 238000005406 washing Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000011056 performance test 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
- 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
- 230000007613 environmental effect Effects 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
- 239000000203 mixture 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
- 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
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 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
- 239000013543 active substance Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 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
- 230000002349 favourable effect Effects 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
- 238000009830 intercalation 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
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000010248 power generation Methods 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
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
Images
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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention relates to a waterless high-rate type 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 sintered material; mixing the sintering material with a coating agent, and carrying out heat treatment to coat to obtain the waterless high-rate hollow high-nickel anode material; the nickel-cobalt oxide is obtained by performing heat treatment dehydration on a nickel-cobalt hydroxide precursor; calculated by oxides, the mass percent of Ni in the nickel-cobalt hydroxide is more than or equal to 80%. The preparation method provided by the invention does not need to be washed with water when preparing the high-nickel material, and the agglomeration phenomenon among sintering materials can be relieved by adding the coating agent; and 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 particularly relates to a water-washing-free high-rate type hollow high-nickel positive electrode material, and a preparation method and application thereof.
Background
Lithium ion batteries operate by virtue of the reciprocating movement of lithium ions between a positive electrode and a negative electrode, and during the charging and discharging processes, Li + Intercalation and deintercalation to and from two electrodes: upon charging, Li + The lithium ion battery is separated from the positive electrode, and is inserted into the negative electrode through the electrolyte, so that the negative electrode is in a lithium-rich state; the opposite is true during discharge. 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 cobaltate (LiCoO) 2 ) And ternary positive electrode materials (NCM), which are solutions to increase energy density and reduce production costs due to the current power battery requirements for energy density.
However, the high-nickel ternary cathode material has the defect of high surface residual alkali content, is very sensitive to environmental humidity, and is a prominent problem that the electrochemical performance of the material is influenced in practical application.
CN 112186156A discloses a water washing method of a high-nickel anode material, a product thereof and the application of the product, wherein the water washing method comprises the steps of mixing the high-nickel anode material with a boric acid solution, reacting and sintering to obtain the water-washed high-nickel anode material; the water washing method removes the residual alkali on the surface of the high-nickel anode material at normal temperature, and improves the structural stability and the thermal stability of the high-nickel anode material after water washing by utilizing the reaction of boric acid and the residual alkali on the surface of the high-nickel anode material which is not removed by water washing in the sintering process.
However, the water washing process is easy to destroy Li in the crystal lattice on the surface of the material + And a NiO inert layer without electrochemical activity is generated, the surface phase structure of the material is damaged, and the electrochemical performance of the material is also influenced.
And the high-nickel ternary positive electrode material is unstable Ni in the charge-discharge process 4+ And the material structure is easy to be converted into a spinel phase from a lamellar state and finally into a rock salt phase. The phase transition process gradually occurring from the surface of the material to the inner layer leads to the reduction of active substances of the material, thereby leading to the irreversible capacity attenuation and further influencing the cycle performance. Furthermore, due to the high nickel content, Li removal from the high-nickel ternary positive electrode material is insufficient under high-rate charge and discharge, and therefore Li in the Li layer + The content is higher, the vacancy is less, and the mixed discharge of Ni element to the Li layer is prevented.
CN 109167056a discloses a tungsten ion doped high nickel layered oxide lithium battery positive electrode 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 an inorganic strong base and an 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 the high-nickel ternary precursor material, a tungsten source and a lithium source to obtain a doped ternary precursor mixture; and calcining the doped ternary precursor mixture, and grinding to obtain the tungsten ion doped high-nickel layered oxide lithium battery positive electrode material. But the initial discharge performance of the material at the 3C multiplying power is only 150mAh/g under the conditions that the voltage range is 2.7-4.3V, the test temperature is 25 ℃, and the capacity retention rate of the material is 95% after 100 cycles, although the cycle performance of the material is good, the multiplying power performance is poor.
Therefore, it is desirable to provide a lithium secondary battery capable of increasing Li + Under chargingThe high-rate type hollow high-nickel anode material has the advantages of reducing diffusion speed in the discharge process and reducing material structure phase transformation, and the preparation method and the application thereof.
Disclosure of Invention
The invention aims to provide a waterless high-rate hollow high-nickel cathode material and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a preparation method of a waterless high-rate hollow high-nickel cathode material, which comprises the following steps:
(1) mixing lithium salt, nickel-cobalt oxide, aluminum oxide and tungsten oxide, and sintering to obtain a sintered material;
(2) mixing the sintering material and a coating agent, and carrying out heat treatment to coat to obtain the waterless high-rate hollow high-nickel anode material;
the nickel-cobalt oxide in the step (1) is obtained by carrying out heat treatment dehydration on a nickel-cobalt hydroxide precursor;
the molar weight of nickel in the nickel cobalt hydroxide accounts for more than 80% of the total molar weight of nickel and cobalt.
The preparation method provided by the invention does not need water washing when preparing the high-nickel material, and can relieve the agglomeration phenomenon among sintering materials by adding tungsten oxide; and the tungsten oxide can be distributed on the surface and the crystal 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 waterless high-rate hollow high-nickel cathode material has excellent rate performance.
The term "high nickel" as used herein means that the nickel in the nickel cobalt hydroxide is greater than 80% by mole of the total 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 values not recited in the range of values are also applicable.
Preferably, the temperature for dehydration by heat treatment is 450 ℃ to 650 ℃, for example, 450 ℃, 500 ℃, 550 ℃, 600 ℃ or 650 ℃, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
The nickel cobalt hydroxide is dehydrated through heat treatment, and the obtained nickel cobalt oxide has high reaction activity and large specific surface area and is convenient to combine with lithium salt. Although agglomeration is easily caused after combination with lithium salt due to high reaction activity and large specific surface area, the agglomeration phenomenon can be relieved and the rate performance of the material can be improved by matching with subsequent coating agents and heat treatment operation.
Preferably, the nickel cobalt hydroxide is prepared by the following method: mixing a nickel source, a cobalt source, alcohol, a precipitator and water, and carrying out hydrothermal reaction on the obtained emulsion to obtain the nickel-cobalt hydroxide.
Preferably, the nickel source comprises any one of nickel nitrate, nickel chloride, nickel acetate or nickel sulfate or a combination of at least two of the foregoing, and typical but non-limiting combinations include 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 of cobalt nitrate, cobalt chloride, cobalt acetate or cobalt sulfate or a combination of at least two of the foregoing; typical but non-limiting combinations include a combination of cobalt nitrate and cobalt chloride, a combination of cobalt chloride and cobalt acetate, a combination of cobalt acetate and cobalt sulfate, a combination of cobalt nitrate, cobalt chloride and cobalt acetate, a combination of cobalt chloride, cobalt acetate and cobalt sulfate, or a combination of cobalt nitrate, cobalt chloride, cobalt acetate and cobalt sulfate.
Preferably, the alcohol comprises tert-butanol.
Preferably, the volume ratio of tert-butanol to water is (8-10):1, and may be, for example, 8:1, 8.5:1, 9:1, 9.5:1 or 10:1, but is not limited to the values recited, and other values not recited within the range of values are equally applicable.
According to the invention, the nickel-cobalt hydroxide with a uniform hollow structure can be obtained by controlling the volume ratio of tert-butyl alcohol to water, and the rate capability of the finally obtained waterless high-rate hollow high-nickel anode material is favorably improved.
Preferably, the precipitant comprises tetrabutylammonium hydroxide and/or urea.
According to the invention, through the use of tert-butyl alcohol and a specific precipitator, the nickel-cobalt hydroxide with a loose hollow appearance can be obtained, the hollow structure after dehydration through heat treatment is favorable for the infiltration of electrolyte, the diffusion path of lithium ions is shortened, the effect of refining primary crystal 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 the water is 1 (12-16), and may be, for example, 1:12, 1:13, 1:14, 1:15 or 1:16, but is not limited to the enumerated values, and other unrecited values within the numerical range are also applicable.
Preferably, the molar concentration of the nickel source in the emulsion is in the range of 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, but is not limited to the values recited, and other values not recited in the numerical ranges are equally applicable.
Preferably, the molar concentration of the cobalt source in the emulsion is in the range of 0.001-0.006mol/L, and may be, 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, and other values not recited in the numerical ranges are equally applicable.
Preferably, the temperature of the hydrothermal reaction is 90-110 ℃ and the time is 20-26 h.
The hydrothermal reaction temperature in the present invention is 90 to 110 ℃, and may be, for example, 90 ℃, 95 ℃, 100 ℃, 105 ℃ or 110 ℃, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
The hydrothermal reaction time of the present invention is 20-26h, for example, 20h, 21h, 22h, 23h, 24h, 25h or 26h, but is not limited to the recited values, and other values not recited in the range of the values are also 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 a combination of lithium hexafluorophosphate and lithium tetrafluoroborate, a combination of lithium hexafluorophosphate and lithium difluorophosphate, a combination of lithium difluorophosphate and lithium tetrafluorophosphate, a combination of lithium hexafluorophosphate, lithium difluorophosphate and lithium tetrafluorophosphate, or a combination of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium difluorophosphate and lithium tetrafluorophosphate; lithium hydroxide is preferred.
Preferably, the alumina in step (1) is 0.3-1% of the nickel cobalt oxide, such as 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 values not recited in the range of values are also applicable.
Preferably, the particle size D50 of the alumina in step (1) is 8-12nm, such as 8nm, 9nm, 10nm, 11nm or 12nm, but is not limited to the recited values, and other values not recited in the numerical range are equally applicable.
Preferably, the tungsten oxide in step (1) is 0.05-0.3% of the nickel cobalt oxide, such as 0.05%, 0.1%, 0.15%, 0.2%, 0.25% or 0.3%, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the particle size D50 of the tungsten oxide in step (1) is 48-52nm, such as 48nm, 49nm, 50nm, 51nm or 52nm, but not limited to the values recited, and other values not recited in the range of values are equally applicable.
The invention utilizes the properties that tungsten oxide has large atomic mass and high chemical bond tendency to be distributed on the surface and the crystal boundary of the 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 values not recited in the numerical range are also applicable.
According to the invention, the loss of lithium salt due to burning in the heat treatment process can be supplemented by adding excessive lithium salt.
Preferably, the sintering in step (1) is carried out in an atmosphere with an oxygen volume fraction of 80% or more, for example 80%, 85%, 90%, 95% or 100%, but not limited to the recited values, and other values not recited within the range of values are also applicable.
Preferably, the sintering temperature in step (1) is 700-800 ℃, such as 700 ℃, 720 ℃, 750 ℃, 760 ℃, 780 ℃ or 800 ℃, but not limited to the recited values, and other unrecited values within the range of values are equally applicable.
Preferably, the sintering time in step (1) is 8-24h, such as 8h, 10h, 12h, 15h, 16h, 18h, 20h, 21h or 24h, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the particle size D50 of the sinter obtained in step (1) is 2.5-5.5. 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 not limited to the values listed, and other values not listed in the numerical ranges are equally applicable.
The particle size of the sintered material is obtained by conventional crushing and sieving in the field after sintering, and the crushing and sieving are not described in detail herein.
Preferably, the coating agent of step (2) comprises nickel oxide.
The nickel oxide can react with lithium hydroxide and can consume residual alkali on the surface, so that the phenomenon of adhesion and agglomeration among particles is relieved, and the rate capability of the obtained waterless high-rate hollow high-nickel cathode material is improved.
Preferably, the particle size D50 of the coating agent in step (2) is 18-22nm, such as 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 recited values, and other values not recited in the numerical range are also 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 values not recited in the numerical range are also applicable.
Preferably, the heat treatment time 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 values not recited in the range of values are also applicable.
As a preferable technical solution of the preparation method of the first aspect of the present invention, the preparation method comprises the steps of:
(1) mixing lithium salt, nickel-cobalt oxide, aluminum oxide and tungsten oxide, and sintering in an environment with the volume fraction of oxygen being more than or equal to 80% to obtain a sintered material; the mass of the aluminum oxide is 0.3-1% of that of the nickel-cobalt oxide, and the mass of the tungsten oxide is 0.05-0.3% of that of the nickel-cobalt oxide; the sintering temperature is 700-800 ℃, and the time is 8-24 h;
(2) mixing the sintering material with nickel oxide with the particle size D50 of 18-22nm, and performing heat treatment at 500-700 ℃ for 6-10h for coating to obtain the waterless high-magnification type 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 in the step (1) is obtained by performing thermal treatment dehydration on a nickel cobalt hydroxide precursor at the temperature of 450 ℃ and 650 ℃; the molar weight of nickel in the nickel cobalt hydroxide accounts for more than 80% of the total molar weight of nickel and cobalt;
the nickel cobalt hydroxide is prepared by the following method: mixing a nickel source, a cobalt source, tert-butyl alcohol, tetrabutylammonium hydroxide and water, and carrying out hydrothermal reaction on the obtained emulsion at 90-110 ℃ for 20-26h to obtain the nickel-cobalt hydroxide.
In a second aspect, the invention provides a non-washing high-rate 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 waterless high-rate hollow high-nickel cathode material of 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 water washing when preparing the high-nickel material, and can relieve the agglomeration phenomenon among sintering materials by adding tungsten oxide; tungsten oxide can be distributed on the surface and the crystal 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 washing-free high-rate hollow high-nickel cathode material has excellent rate performance;
(2) the nickel cobalt hydroxide is dehydrated through heat treatment, and the obtained nickel cobalt oxide has high reaction activity and large specific surface area and is convenient to combine with lithium salt. Although agglomeration is easily caused after combination with lithium salt due to high reaction activity and large specific surface area, the agglomeration phenomenon can be relieved and the rate performance of the material can be improved by matching with subsequent coating agents and heat treatment operation.
Drawings
FIG. 1 is a SEM image of the nickel cobalt oxide obtained in example 1;
FIG. 2 is an SEM image of the non-washed high-magnification hollow high-nickel cathode 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 showing the rate performance test of example 1, comparative example 1 and comparative example 3.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a preparation method of a waterless high-rate hollow high-nickel cathode material, which comprises the following steps:
(1) mixing lithium hydroxide, nickel-cobalt oxide, aluminum oxide with the grain diameter D50 of 10nm and tungsten oxide with the grain diameter D50 of 50nm, and sintering in the environment with the volume fraction of oxygen of 80% to obtain a sintering material with the grain diameter D50 of 4 mu m; the mass of the aluminum oxide is 0.6 percent of that of the lithium hydroxide; tungsten oxide accounts for 0.15 percent of the mass of the lithium hydroxide; the sintering temperature is 750 ℃, and the sintering time is 16 h; the molar ratio of the lithium hydroxide to the nickel cobalt oxide is 1.03: 1;
(2) mixing the sintering material and nickel oxide with the particle size D50 of 20nm, and performing heat treatment at 600 ℃ for 8h for coating to obtain the waterless high-magnification hollow high-nickel anode material; the addition amount of the nickel oxide is 0.5 percent of the mass of the sintering material;
the nickel-cobalt oxide in the step (1) is obtained by performing heat treatment dehydration on a nickel-cobalt hydroxide precursor at 550 ℃ (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, tert-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 tert-butyl alcohol to water is 9:1, and the mass ratio of tetrabutylammonium hydroxide to water is 1: 15;
(II) carrying out hydrothermal reaction on the emulsion obtained in the step (I) at 100 ℃ for 24h to obtain the nickel cobalt hydroxide.
An SEM image of the water-washing-free high-magnification hollow high-nickel cathode material obtained in this example is shown in fig. 2.
Example 2
The embodiment provides a preparation method of a waterless high-rate hollow high-nickel cathode 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 volume fraction of oxygen of 90% to obtain a sintering material with the particle size D50 of 2.5 microns; the mass of the aluminum oxide is 0.3 percent of that of the lithium hydroxide; tungsten oxide accounts for 0.05 percent of the mass of the 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 and nickel oxide with the particle size D50 of 18nm, and performing heat treatment at 500 ℃ for 10h for coating to obtain the waterless high-magnification hollow high-nickel cathode material; the addition amount of the nickel oxide is 0.2 percent of the mass of the sintering material;
the nickel-cobalt oxide in the step (1) is obtained by carrying out thermal treatment dehydration on a nickel-cobalt hydroxide precursor 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, tert-butyl alcohol, tetrabutyl ammonium 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 tert-butyl alcohol to water is 8:1, and the mass ratio of tetrabutylammonium hydroxide to water is 1: 12;
(II) carrying out hydrothermal reaction on the emulsion obtained in the step (I) at 90 ℃ for 26h to obtain the nickel cobalt hydroxide.
Example 3
The embodiment provides a preparation method of a waterless high-rate hollow high-nickel cathode material, which comprises the following steps:
(1) mixing lithium hydroxide, nickel cobalt oxide, aluminum oxide with the grain diameter D50 of 12nm and tungsten oxide with the grain diameter D50 of 52nm, and sintering in an environment with the oxygen volume fraction of 100% to obtain a sintered material with the grain diameter D50 of 5.5 microns; the mass of the aluminum oxide is 1 percent of that of the lithium hydroxide; tungsten oxide accounts for 0.3 percent of the mass of the lithium hydroxide; the sintering temperature is 800 ℃, and the sintering time is 8 h; the molar ratio of the lithium hydroxide to the nickel cobalt oxide is 1.05: 1;
(2) mixing the sintering material and nickel oxide with the particle size D50 of 22nm, and performing heat treatment at 700 ℃ for 6h for coating to obtain the waterless high-magnification hollow high-nickel cathode material; the addition amount of the nickel oxide is 0.8 percent of the mass of the sintering material;
the nickel-cobalt oxide in the step (1) is obtained by performing thermal treatment dehydration on a nickel-cobalt hydroxide precursor 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, tert-butyl alcohol, tetrabutyl ammonium 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 tert-butyl alcohol to water is 10:1, and the mass ratio of tetrabutylammonium 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
This example provides a method for producing a waterless high-rate hollow high-nickel positive electrode material, which is the same as that of example 1 except that tetrabutylammonium hydroxide and the like are replaced by urea.
Example 5
This example provides a method for producing a waterless high-rate hollow high-nickel positive electrode material, which was the same as in example 1, except that tetrabutylammonium hydroxide or the like was replaced by a combination of tetrabutylammonium hydroxide and urea in a mass ratio of 1: 1.
Example 6
This example provides a method for preparing a waterless high-rate hollow high-nickel cathode material, which is the same as that of example 1 except that the mass ratio of butylammonium hydroxide to water is 1: 10.
Example 7
This example provides a method for preparing a waterless high-rate hollow high-nickel cathode material, which is the same as that of example 1 except that the mass ratio of butyl ammonium hydroxide to water is 1: 18.
Example 8
This example provides a method for producing a water-washable high-rate hollow high-nickel positive electrode material, which is the same as in example 1, except that an equimolar amount of lithium hydroxide is replaced with lithium hexafluorophosphate.
Example 9
This example provides a method for producing a water-free high rate hollow high nickel positive electrode material, which is the same as that of example 1 except that an equimolar amount of lithium hydroxide is replaced with lithium tetrafluoroborate.
Example 10
This example provides a method for preparing a waterless high-rate hollow high-nickel cathode material, which is the same as that of example 1 except that the volume ratio of tert-butyl alcohol to water is 7: 1.
Example 11
This example provides a method for preparing a non-aqueous-washing high-rate hollow high-nickel cathode material, which is the same as that of example 1 except that the volume ratio of tert-butyl alcohol to water is 11:1
Comparative example 1
This comparative example provides a method of preparing a high nickel positive electrode material, which is the same as example 1 except that tungsten oxide, etc. are replaced by alumina having a particle size D50 of 10 nm.
The 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, which includes the steps of:
(1) mixing lithium hydroxide, nickel-cobalt oxide, aluminum oxide with the grain diameter D50 of 10nm and tungsten oxide with the grain diameter D50 of 50nm, and sintering in the environment with the volume fraction of oxygen of 80% to obtain a sintering material with the grain diameter D50 of 4 mu m; the aluminum oxide accounts for …% of the mass of the lithium hydroxide; tungsten oxide accounts for 0.15 percent of the mass of lithium hexafluorophosphate; the sintering temperature is 750 ℃, and the sintering time is 16 h; the molar ratio of the lithium hydroxide to the nickel cobalt oxide is 1.03: 1;
(2) carrying out heat treatment on the sintered material in the step (1) at 600 ℃ for 8h to obtain the high-nickel anode material;
the nickel-cobalt oxide in the step (1) is obtained by performing heat treatment dehydration on a nickel-cobalt hydroxide precursor 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, tert-butyl alcohol, tetrabutyl ammonium 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 tert-butyl alcohol to water is 9:1, and the mass ratio of tetrabutylammonium hydroxide to water is 1: 15;
(II) carrying out hydrothermal reaction on the emulsion obtained in the step (I) at 100 ℃ for 24h to obtain the nickel cobalt hydroxide.
Compared with example 1, the coating of the sintered material is carried out without adding nickel oxide in the comparative example.
Comparative example 3
The comparative example provides a method for preparing a high nickel positive electrode material, which is the same as that of comparative example 2 except that tungsten oxide and the like are replaced by alumina having a particle size D50 of 10 nm.
Performance test
The nonaqueous-washing high-rate 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 in a glove box filled with argon gas to form a CR2025 type button cell using metal lithium as a counter electrode according to the ratio of the positive electrode material to binder (PVDF) to conductive agent (acetylene black) being 90:5:5 to obtain a positive electrode sheet, and the electrolyte was 1M LiPF 6 DMC: FEC (EC, DMC to FEC volume ratio 1:1:1), diaphragm Celgard2400 microporous diaphragm, test method:
the initial discharge specific capacity is tested under the conditions of voltage ranges of 3-4.3V and 0.2C/0.2C, the rate performance of 0.5C/0.2C, 1C/0.2C, 2C/0.2C, 4C/0.2C and 8C/0.2C is considered, the capacity retention rate of 50 cycles is tested under the condition of 1.2C/1C, and the obtained results are shown in table 1, wherein the rate performance test results of example 1, comparative example 1 and comparative example 3 are shown in fig. 4.
TABLE 1
In conclusion, the preparation method provided by the invention does not need to be washed with water when preparing the high-nickel material, and the agglomeration phenomenon among sintering materials can be relieved by adding the coating agent; tungsten oxide can be distributed on the surface and the crystal 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 washing-free high-rate hollow high-nickel cathode material has excellent rate performance; the nickel cobalt hydroxide is dehydrated through heat treatment, and the obtained nickel cobalt oxide has high reaction activity and large specific surface area, and is convenient to combine with lithium salt. Although agglomeration is easily caused after combination with lithium salt due to high reaction activity and large specific surface area, the agglomeration phenomenon can be relieved and the rate performance of the material can be improved by matching with subsequent coating agents and heat treatment operation.
The above description is only for the specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the protection scope and the disclosure of the present invention.
Claims (10)
1. A preparation method of a waterless high-rate hollow high-nickel cathode material is characterized by comprising the following steps:
(1) mixing lithium salt, nickel cobalt oxide, aluminum oxide and tungsten oxide, and sintering to obtain a sintered material;
(2) mixing the sintering material and a coating agent, and performing heat treatment to coat to obtain the waterless high-rate hollow high-nickel anode material;
the nickel-cobalt oxide in the step (1) is obtained by carrying out heat treatment dehydration on a nickel-cobalt hydroxide precursor;
the molar weight of nickel in the nickel cobalt hydroxide accounts for more than 80% of the total molar weight of nickel and cobalt.
2. The method as claimed in claim 1, wherein the temperature for dehydration by heat treatment is 450-650 ℃.
3. The method of claim 1 or 2, wherein the nickel cobalt hydroxide is prepared by: mixing a nickel source, a cobalt source, alcohol, a precipitator and water, and carrying out hydrothermal reaction on the obtained emulsion to obtain the nickel-cobalt hydroxide;
preferably, the nickel source comprises any one of nickel nitrate, nickel chloride, nickel acetate or nickel sulfate or a combination of at least two of the same;
preferably, the cobalt source comprises any one of cobalt nitrate, cobalt chloride, cobalt acetate or cobalt sulfate or a combination of at least two of the foregoing;
preferably, the alcohol comprises tert-butanol;
preferably, the volume ratio of the tertiary butanol to the water is (8-10) to 1;
preferably, the precipitating agent comprises tetrabutylammonium hydroxide and/or urea;
preferably, the mass ratio of the precipitant to the water is 1 (12-16).
4. The method according to claim 3, wherein the molar concentration of the nickel source in the emulsion is 0.025 to 0.03 mol/L;
preferably, the molar concentration of the cobalt source in the emulsion is 0.001-0.006 mol/L;
preferably, the temperature of the hydrothermal reaction is 90-110 ℃ and the time is 20-26 h.
5. The production method according to any one of claims 1 to 4, wherein the lithium salt in step (1) comprises any one or a combination of at least two of lithium hydroxide, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium difluorophosphate, or lithium tetrafluorophosphate, preferably lithium hydroxide;
preferably, the alumina in the step (1) accounts for 0.3-1% of the mass of the nickel cobalt oxide;
preferably, the particle size D50 of the alumina in the step (1) is 8-12 nm;
preferably, the tungsten oxide in the step (1) accounts for 0.05-0.3% of the mass of the nickel cobalt oxide;
preferably, the particle size D50 of the tungsten oxide in the step (1) is 48-52 nm;
preferably, the molar ratio of the lithium salt to the nickel cobalt oxide in the step (1) is (1.01-1.05): 1.
6. The production method according to any one of claims 1 to 5, wherein the sintering in step (1) is performed in an atmosphere having an oxygen volume fraction of 80% or more;
preferably, the sintering temperature in the step (1) is 700-800 ℃;
preferably, the sintering time in the step (1) is 8-24 h;
preferably, the grain diameter D50 of the sintering material obtained in the step (1) is 2.5-5.5 μm.
7. The production method according to any one of claims 1 to 6, wherein the coating agent of step (2) comprises nickel oxide;
preferably, the particle size D50 of the coating agent in the step (2) is 18-22 nm;
preferably, the addition amount of the coating agent in the step (2) is 0.2-0.8% of the mass of the sintering material;
preferably, the temperature of the heat treatment in the step (2) is 500-700 ℃;
preferably, the time of the heat treatment in the step (2) is 6-10 h.
8. The production method according to any one of claims 1 to 7, characterized by comprising the steps of:
(1) mixing lithium salt, nickel cobalt oxide, aluminum oxide and tungsten oxide, and sintering in an environment with oxygen volume fraction of more than or equal to 80% to obtain a sintered material; the mass of the aluminum oxide is 0.3-1% of that of the nickel-cobalt oxide, and the mass of the tungsten oxide is 0.05-0.3% of that of the nickel-cobalt oxide; the sintering temperature is 700-800 ℃, and the time is 8-24 h;
(2) mixing the sintering material with nickel oxide with the particle size D50 of 18-22nm, and performing heat treatment at 500-700 ℃ for 6-10h for coating to obtain the waterless high-magnification type 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 in the step (1) is obtained by performing thermal treatment dehydration on a nickel cobalt hydroxide precursor at the temperature of 450 ℃ and 650 ℃; the molar weight of nickel in the nickel cobalt hydroxide accounts for more than 80% of the total molar weight of nickel and cobalt;
the nickel cobalt hydroxide is prepared by the following method: mixing a nickel source, a cobalt source, tert-butyl alcohol, tetrabutylammonium hydroxide and water, and carrying out hydrothermal reaction on the obtained emulsion at 90-110 ℃ for 20-26h to obtain the nickel-cobalt hydroxide.
9. The washing-free high-rate hollow high-nickel cathode material is characterized by being obtained by the preparation method of any one of claims 1 to 8.
10. A lithium ion battery, characterized in that the lithium ion battery comprises the waterless high-rate hollow high-nickel positive electrode material according to claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210676628.8A CN114937769B (en) | 2022-06-15 | 2022-06-15 | No-water-washing high-magnification hollow high-nickel cathode material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210676628.8A CN114937769B (en) | 2022-06-15 | 2022-06-15 | No-water-washing high-magnification hollow high-nickel cathode material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114937769A true CN114937769A (en) | 2022-08-23 |
| CN114937769B CN114937769B (en) | 2023-12-05 |
Family
ID=82867764
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210676628.8A Active CN114937769B (en) | 2022-06-15 | 2022-06-15 | No-water-washing high-magnification hollow high-nickel cathode material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114937769B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024217022A1 (en) * | 2023-04-21 | 2024-10-24 | 宁德时代新能源科技股份有限公司 | Positive electrode active material and preparation method therefor, positive electrode sheet, secondary battery and electrical device |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109273688A (en) * | 2018-09-17 | 2019-01-25 | 国联汽车动力电池研究院有限责任公司 | A kind of nickelic positive electrode and its preparation method and application of surface richness rock salt phase |
| CN111899988A (en) * | 2020-08-06 | 2020-11-06 | 合肥工业大学 | Macro preparation method and application of nickel-cobalt double-metal hydroxide electrode material |
| CN112018341A (en) * | 2019-05-28 | 2020-12-01 | 天津国安盟固利新材料科技股份有限公司 | High-capacity high-nickel cathode material and preparation method thereof |
| WO2021114746A1 (en) * | 2019-12-11 | 2021-06-17 | 深圳市贝特瑞纳米科技有限公司 | Method for repairing surface structure of high-nickel positive electrode material, high-nickel positive electrode material obtained therefrom, and lithium ion battery |
-
2022
- 2022-06-15 CN CN202210676628.8A patent/CN114937769B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109273688A (en) * | 2018-09-17 | 2019-01-25 | 国联汽车动力电池研究院有限责任公司 | A kind of nickelic positive electrode and its preparation method and application of surface richness rock salt phase |
| CN112018341A (en) * | 2019-05-28 | 2020-12-01 | 天津国安盟固利新材料科技股份有限公司 | High-capacity high-nickel cathode material and preparation method thereof |
| WO2021114746A1 (en) * | 2019-12-11 | 2021-06-17 | 深圳市贝特瑞纳米科技有限公司 | Method for repairing surface structure of high-nickel positive electrode material, high-nickel positive electrode material obtained therefrom, and lithium ion battery |
| CN111899988A (en) * | 2020-08-06 | 2020-11-06 | 合肥工业大学 | Macro preparation method and application of nickel-cobalt double-metal hydroxide electrode material |
Non-Patent Citations (3)
| Title |
|---|
| ZAHRA AHALIABADEH,ET AL.: "Extensive comparison of doping and coating strategies for Ni-rich positive electrode materials", 《JOURNAL OF POWER SOURCES》, vol. 540, pages 231633 * |
| 王鑫等: "锂离子电池富镍正极材料基础科学问题：表面残锂及其去除", 《复合材料学报》, vol. 39, no. 1, pages 97 - 110 * |
| 赵段等: "锂离子电池高镍三元材料的包覆改性研究进展", 《无机盐工业》, vol. 53, no. 8, pages 1 - 7 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024217022A1 (en) * | 2023-04-21 | 2024-10-24 | 宁德时代新能源科技股份有限公司 | Positive electrode active material and preparation method therefor, positive electrode sheet, secondary battery and electrical device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114937769B (en) | 2023-12-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112750999B (en) | Cathode material, preparation method thereof and lithium ion battery | |
| JP4973825B2 (en) | Method for producing positive electrode active material for non-aqueous electrolyte secondary battery, non-aqueous electrolyte secondary battery | |
| CN111785960B (en) | Vanadium pentoxide/rGO coated nickel cobalt lithium manganate positive electrode material and preparation method thereof | |
| JP5656012B2 (en) | Positive electrode active material powder for non-aqueous electrolyte secondary battery, method for producing the same, and non-aqueous electrolyte secondary battery | |
| CN107068995B (en) | In-situ precipitated oxide coated lithium ion battery positive electrode material and preparation method and application thereof | |
| CN108448109B (en) | Layered lithium-rich manganese-based positive electrode material and preparation method thereof | |
| CN106784790B (en) | A kind of preparation method of nickle cobalt lithium manganate tertiary cathode material | |
| CN110429268A (en) | A kind of modified boron doping lithium-rich manganese-based anode material and the preparation method and application thereof | |
| CN113363476B (en) | Ternary cathode material of lithium ion battery and preparation method thereof | |
| CN112645390B (en) | Lithium cobaltate precursor with coating structure, preparation method and application thereof | |
| CN111422919A (en) | Quaternary positive electrode material, preparation method thereof, positive electrode and battery | |
| CN109841822A (en) | A kind of preparation method of the modified monocrystalline tertiary cathode material of lithium ion battery | |
| CN112635735A (en) | Nickel-cobalt lithium manganate precursor with coating structure, preparation method and application thereof | |
| CN112670475A (en) | Lithium iron phosphate composite material, preparation method thereof, lithium battery using composite material and battery power vehicle | |
| CN115064670A (en) | Preparation method of doped coated modified sodium nickel manganese oxide cathode material | |
| CN114937769B (en) | No-water-washing high-magnification hollow high-nickel cathode material and preparation method and application thereof | |
| CN112531154B (en) | Preparation method of tungsten trioxide micro-nano particle gradient doped ternary material, prepared ternary material and application | |
| CN112186166B (en) | Molybdenum/cobalt oxide-carbon composite material and preparation method thereof, lithium ion battery negative electrode piece and lithium ion battery | |
| CN111900473B (en) | Lithium ion battery electrolyte for improving performance of anode material and lithium ion battery | |
| CN109755486A (en) | The nickle cobalt lithium manganate and preparation method thereof of LiFePO4 cladding | |
| CN115340134B (en) | Preparation method of nickel cobalt lithium manganate precursor with coating structure and lithium ion battery containing precursor | |
| CN115196683B (en) | Positive electrode material, secondary battery and electric equipment | |
| CN114005977B (en) | High-energy-density superconducting lithium ion battery positive electrode material and preparation method thereof | |
| CN113328077B (en) | Cathode material, preparation method and application thereof | |
| CN112436135B (en) | Cathode material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |