CN114975987A - Nickel niobate negative electrode material and preparation method and application thereof - Google Patents
Nickel niobate negative electrode material and preparation method and application thereof Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 140
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000007773 negative electrode material Substances 0.000 title claims description 26
- 239000000203 mixture Substances 0.000 claims abstract description 26
- 238000002156 mixing Methods 0.000 claims abstract description 25
- 238000001035 drying Methods 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- 150000002816 nickel compounds Chemical class 0.000 claims abstract description 9
- 150000002822 niobium compounds Chemical class 0.000 claims abstract description 9
- 238000000227 grinding Methods 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 239000010406 cathode material Substances 0.000 claims abstract description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 34
- 229910001416 lithium ion Inorganic materials 0.000 claims description 33
- 239000010955 niobium Substances 0.000 claims description 12
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 6
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 6
- 239000010405 anode material Substances 0.000 claims description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- WYGQZDSIRBBVTA-UHFFFAOYSA-D [Nb+5].[Nb+5].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O Chemical compound [Nb+5].[Nb+5].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O WYGQZDSIRBBVTA-UHFFFAOYSA-D 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229910001514 alkali metal chloride Inorganic materials 0.000 claims description 2
- 229910001515 alkali metal fluoride Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 2
- KUJRRRAEVBRSIW-UHFFFAOYSA-N niobium(5+) pentanitrate Chemical compound [Nb+5].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUJRRRAEVBRSIW-UHFFFAOYSA-N 0.000 claims description 2
- IIDYTZRUUWUVQF-UHFFFAOYSA-D niobium(5+) pentasulfate Chemical compound [Nb+5].[Nb+5].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IIDYTZRUUWUVQF-UHFFFAOYSA-D 0.000 claims description 2
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 2
- WPCMRGJTLPITMF-UHFFFAOYSA-I niobium(5+);pentahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[Nb+5] WPCMRGJTLPITMF-UHFFFAOYSA-I 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 claims description 2
- 229910005805 NiNb Inorganic materials 0.000 claims 1
- 150000003839 salts Chemical class 0.000 abstract description 10
- 238000012360 testing method Methods 0.000 description 14
- 239000000463 material Substances 0.000 description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- 239000011889 copper foil Substances 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 210000004027 cell Anatomy 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 229910052593 corundum Inorganic materials 0.000 description 8
- 239000010431 corundum Substances 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
- 239000002033 PVDF binder Substances 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 5
- 239000006229 carbon black Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000006258 conductive agent Substances 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 4
- 239000011149 active material Substances 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 4
- 239000011324 bead Substances 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- -1 polypropylene Polymers 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 239000012429 reaction media Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000002051 biphasic effect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 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
- H01M4/48—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
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a nickel niobate cathode material and a preparation method and application thereof. The preparation method comprises the following steps: mixing a niobium compound and a nickel compound, and adding an inorganic salt to obtain a mixture; adding a proper amount of ethanol solution into the mixture to completely soak the mixture, wet mixing the mixture, and drying the mixture; grinding the dried product into powder, putting the powder into a muffle furnace, heating to 600-1200 ℃, preserving heat for 0.5-20 h, and then cooling; and washing, filtering and drying the cooled product to obtain the nickel niobate cathode material. The invention adopts a molten salt method to prepare nickel niobate, the method can successfully prepare the nickel niobate below 1000 ℃, and the prepared nickel niobate has higher capacity, excellent rate performance and cycle performance.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a nickel niobate negative electrode material and a preparation method and application thereof.
Background
Lithium Ion (LIBs) batteries are one of the most attractive energy storage technologies due to their light weight, small size, high operating voltage, low self-discharge rate, and long cycle life. As electric vehicles, portable consumer electronics, and energy storage systems are increasingly used, the demand for LIBs is also increasing. Rapid charge/discharge capability has received increasing attention and interest worldwide as one of the key properties of the new generation of lithium ion batteries. The rapid charge and discharge performance of a lithium ion battery depends on the kinetics of electrochemical reactions and the electron ion transport characteristics inside the battery. The electrode active material and its properties as the core of the energy storage determine the overall performance of the lithium ion battery. The traditional graphite-based negative electrode material has poor bulk lithium intercalation kinetics, lithium dendrites are easily formed in the charging and discharging process, and a series of safety problems exist under high current density. Therefore, the development of a novel cathode material with high charge-discharge rate, high energy density, high cycle stability and high safety is a key point for further improving the performance of the lithium ion battery, and has important significance for promoting the development of power automobiles, hybrid power automobiles and high-power energy storage equipment.
Disclosure of Invention
The invention provides a nickel niobate negative electrode material and a preparation method and application thereof for solving the technical problems. The invention adopts a molten salt method to prepare nickel niobate, the method can successfully prepare the nickel niobate below 1000 ℃, and the prepared nickel niobate has higher capacity, excellent rate performance and cycle performance.
In order to realize the purpose, the invention adopts the technical scheme that:
a preparation method of a nickel niobate anode material comprises the following steps:
mixing a niobium compound and a nickel compound, and adding an inorganic salt to obtain a mixture;
adding a proper amount of ethanol solution into the mixture to completely soak the mixture, wet-mixing the mixture and drying the mixture;
grinding the dried product into powder, putting the powder into a muffle furnace, heating to 600-1200 ℃, preserving heat for 0.5-20 h, and then cooling;
and washing, filtering and drying the cooled product to obtain the nickel niobate cathode material.
Preferably, the drying temperature is 60-150 ℃. And drying for 12-24 hours after wet mixing.
Preferably, the heating rate to 600-1200 ℃ is 0.5-20 ℃/min.
Preferably, the niobium compound is one or a mixture of two or more of niobium oxide, niobium carbonate, niobium hydroxide, niobium chloride, niobium nitrate and niobium sulfate; the nickel compound is one or more of nickel oxide, nickel carbonate, nickel hydroxide, nickel chloride, nickel nitrate and nickel sulfate.
Preferably, the niobium compound and the nickel compound are mixed in a molar ratio of 0.5 to 18.
Preferably, the inorganic salt is a mixture of nickel chloride and two or more of alkali metal chloride or fluoride, and the nickel chloride accounts for 3-15 mol% of the total amount of the inorganic salt.
Preferably, the mass ratio of the inorganic salt to the total amount of both the niobium compound and the nickel compound is 5:1 to 1: 20.
Preferably, the wet mixing time is 2-24 h.
Preferably, the heating rate is 0.5-20 ℃/min.
The nickel niobate negative electrode material obtained by the preparation method.
Preferably, the nickel niobate is Ni 2 Nb 34 O 67 、NiNb 2 O 6 、Ni 2 Nb 2 O 7 、Ni 4 Nb 2 O 9 Single phase or mixed phase.
The nickel niobate cathode material is applied to a lithium ion battery.
The invention also provides a preparation method of the lithium electronic battery cathode, which comprises the following steps: the mass percentages are (70-85): (5-10): and (10-20) mixing and grinding the nickel niobate, the carbon black (conductive agent) and the polyvinylidene fluoride (PVDF, binder), adding NMP to prepare uniform slurry, and uniformly coating the slurry on a copper foil to obtain the lithium ion battery cathode.
Compared with the prior art, the invention has the beneficial effects that: the invention adopts a molten salt method to select various niobium and nickel raw materials, has simple preparation process and is convenient for large-scale application. Compared with a solid phase method, the method can effectively reduce the reaction temperature, improve the reaction uniformity, and reduce the particle size of the product, thereby being beneficial to shortening the diffusion path of the lithium ions and improving the diffusion rate of the lithium ions.
Drawings
Fig. 1 is an XRD pattern of nickel niobate, a negative electrode material of a lithium ion battery, prepared in example 1.
Fig. 2 is an SEM image of nickel niobate, a negative electrode material of a lithium ion battery, prepared in example 1.
Fig. 3 is an XRD pattern of nickel niobate, a negative electrode material of a lithium ion battery, prepared in example 2.
Fig. 4 is an SEM image of nickel niobate, a negative electrode material of a lithium ion battery, prepared in example 2.
Fig. 5 is the rate capability of nickel niobate, a negative electrode material for lithium ion batteries, prepared in example 1.
Fig. 6 shows the cycle performance of nickel niobate, which is a negative electrode material of the lithium ion battery prepared in example 1, at 1C.
Fig. 7 is an XRD pattern of nickel niobate, which is a negative electrode material of a lithium ion battery prepared in example 3.
Fig. 8 is the rate capability of nickel niobate, a negative electrode material for lithium ion batteries, prepared in example 3.
Fig. 9 shows the cycle performance of nickel niobate, which is a negative electrode material for a lithium ion battery prepared in example 3, at 1C.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
Preparation of nickel niobate (NiNb) 2 O 6 ) Materials:
mixing Nb with 2 O 5 And Ni (OH) 2 According to the Nb/Ni molar ratio of 2: 1 mixing and adding inorganic salts KCl, NaCl and NiCl 2 (the mol percentage content is 45%, 45% and 10% respectively) as a molten salt reaction medium, and the mass ratio of the metal oxide to the inorganic salt is 1: 5, mixing; adding appropriate amount of ethanol solution into the mixture to completely soak the mixture, wet-mixing for 4h, and drying in an oven at 80 ℃ for 24 h. Grinding the dried product into powder, placing the powder in a corundum crucible, placing the corundum crucible in a muffle furnace, heating to 750 ℃ at the heating rate of 10 ℃/min, preserving the heat for 5 hours, and then cooling to room temperature. Then washing and filtering the product in the crucible for many times by using deionized water, and drying at 80 ℃ to obtain the nickel niobate (NiNb) 2 O 6 Single phase) material. FIG. 1 is the XRD pattern of nickel niobate as the negative electrode material of the lithium ion battery prepared in example 1, and it can be seen from FIG. 1 that pure-phase NiNb can be prepared according to the scheme of example 1 2 O 6 。
For comparison, the molten salt medium without adding NiCl was also performed 2 The reaction of (3), i.e. KCl and NaCl as medium (50% mol% respectively), other reaction raw materials, reaction conditions and treatment process are not changed. It can also be seen from FIG. 1 that, under the same conditions, no NiCl is added to the molten salt medium of the reaction 2 This results in incomplete reaction, with significant Nb in the figure 2 O 5 The diffraction peak of (2) appears. Indicating a small amount of NiCl 2 Can promote the reaction of nickel in the niobium acid production and avoid Nb 2 O 5 Formation of residues and other niobate impurities.
Fig. 2 is an SEM image of nickel niobate, a negative electrode material of a lithium ion battery, prepared in example 1. As can be seen from FIG. 2, NiNb was prepared according to the scheme of example 1 2 O 6 The particles of (A) are flaky and have small sizes, and the sizes are basically within 500 nm.
Assembling the battery by adopting the prepared nickel niobate:
the synthesized sample (active material), carbon black (conductive agent) and PVDF (binder) were mixed in a mass ratio of 7: 2: 1, adding zirconium beads, carrying out ball milling, adjusting the viscosity by using NMP, then uniformly coating on a copper foil, and placing in a vacuum drying oven to be dried for 12 hours at 40 ℃. Then, the copper foil was cut into an electrode disk having a diameter of 12mm, and the electrode disk was used as a negative electrode. A metal lithium sheet is used as a counter electrode, a Celgard2325 type polypropylene porous membrane is used as a diaphragm, and the CR2016 type button lithium ion battery is assembled in a glove box protected by high-purity argon. The assembled cell was allowed to stand at room temperature for 24 hours before testing for electrochemical performance. Battery test parameters: the multiplying power performance of the material is tested in a voltage window of 0.005-3V: during the charge-discharge circulation, according to different current densities of 0.5, 1, 2, 5, 10, 20 and 50C (1C is 236mAh g) -1 ) The batteries were cycled 10 times, and finally returned to a rate of 1C. The cycle performance test was performed by cycling the cell at a fixed current density (1C, 10C). The charge and discharge test temperatures of all the batteries were carried out in a 25 ℃ incubator.
Fig. 5 is the rate capability of nickel niobate, a negative electrode material for lithium ion batteries, prepared in example 1. As can be seen from FIG. 5, the nickel niobate prepared according to the scheme of example 1 exhibits excellent rate capability with 300mAh g at 1C -1 Above specific capacity, the specific capacity at 5C is more than 200mAh g -1 And after different multiplying power tests, the product is recovered to 1C, and the specific capacity of the product is kept at a level equivalent to the initial capacity.
Fig. 6 shows the cycle performance of nickel niobate, which is a negative electrode material of the lithium ion battery prepared in example 1, at 1C. As can be seen from FIG. 6, the prepared nickel niobate exhibits excellent cycle stability according to the scheme of example 1, which can maintain 330mAh g after 250 cycles of 1C cycle -1 The specific capacity of (A).
Example 2
Preparation of nickel niobate (NiNb) 2 O 6 ) Materials:
mixing Nb with 2 O 5 And NiO in a Nb/Ni molar ratio of 2: 1 mixing andadding KCl, NaCl and NiCl 2 (the mol percentage content is 46%, 46% and 8% respectively) as molten salt reaction medium, the metal oxide and the inorganic salt are mixed according to the mass ratio of 1: 3, mixing; adding appropriate amount of ethanol solution into the mixture to completely soak the mixture, wet-mixing for 4h, and drying in an oven at 80 ℃ for 24 h. Grinding the dried product into powder, placing the powder in a corundum crucible, placing the corundum crucible in a muffle furnace, heating to 950 ℃ at the heating rate of 10 ℃/min, preserving the heat for 5 hours, and then cooling to room temperature. Then washing and filtering the product in the crucible for many times by deionized water, and drying at 80 ℃ to obtain the nickel niobate (NiNb) 2 O 6 Single phase) material.
Fig. 3 is an XRD pattern of nickel niobate, a negative electrode material of a lithium ion battery, prepared in example 2. As can be seen from FIG. 3, according to the scheme of example 2, NiNb with pure phase can be prepared 2 O 6 。
Fig. 4 is an SEM image of nickel niobate, a negative electrode material of a lithium ion battery, prepared in example 2. As can be seen from FIG. 4, NiNb was prepared according to the scheme of example 2 2 O 6 The particles of (A) are in the shape of flakes and have small sizes, and the sizes are basically within 1 mu m.
The prepared nickel niobate (NiNb) is adopted 2 O 6 ) Assembling the battery:
the synthesized sample (active material), carbon black (conductive agent) and PVDF (binder) were mixed in a mass ratio of 8: 1: 1, adding zirconium beads, carrying out ball milling, adjusting the viscosity by using NMP, then uniformly coating on a copper foil, and placing in a vacuum drying oven to be dried for 12 hours at 40 ℃. Then, the copper foil was cut into an electrode disk having a diameter of 12mm, and the electrode disk was used as a negative electrode. A metal lithium sheet is used as a counter electrode, a Celgard2325 type polypropylene porous membrane is used as a diaphragm, and the CR2016 type button lithium ion battery is assembled in a glove box protected by high-purity argon. The assembled cell was allowed to stand at room temperature for 24 hours before testing for electrochemical performance.
Battery test parameters: the multiplying power performance of the material is tested in a voltage window of 0.005-3V: during the charge-discharge circulation, according to different current densities of 0.5, 1, 2, 5, 10, 20 and 50C (1C is 236mAh g) -1 ) The batteries were respectively cycled for 10 times, and finally the batteries were recovered to 1C timesAnd (4) rate. The cycle performance test was performed by cycling the cell at a fixed current density (1C, 10C). The charge and discharge test temperatures of all the batteries were carried out in a 25 ℃ incubator.
Example 3
Preparation of nickel niobate (Ni) 4 Nb 2 O 9 And NiNb 2 O 6 Miscible) material:
mixing Nb with 2 O 5 And Ni (OH) 2 According to the Nb/Ni molar ratio of 3: 1 mixing and adding KCl, NaCl and NiCl 2 (the mol percentage content is 45%, 45% and 10% respectively) as a molten salt reaction medium, and the mass ratio of the metal oxide to the inorganic salt is 1: 5, mixing; adding appropriate amount of ethanol solution into the above mixture to completely soak, wet-mixing for 4 hr, and drying in 80 deg.C oven for 24 hr. Grinding the dried product into powder, placing the powder in a corundum crucible, placing the corundum crucible in a muffle furnace, heating to 950 ℃ at the heating rate of 10 ℃/min, preserving the heat for 8 hours, and then cooling to room temperature. Then washing and filtering the product in the crucible for many times by deionized water, and drying at 80 ℃ to obtain the nickel niobate (Ni) 4 Nb 2 O 9 And NiNb 2 O 6 Miscible) material.
Fig. 7 is an XRD pattern of nickel niobate, a negative electrode material of a lithium ion battery, prepared in example 3. As can be seen from FIG. 7, NiNb can be prepared according to the protocol of example 3 2 O 6 And Ni 4 N 2 O 9 The biphasic nickel niobate of (4).
Assembling the battery by adopting the prepared nickel niobate:
the synthesized sample (active material), carbon black (conductive agent) and PVDF (binder) were mixed in a mass ratio of 7: 2: 1, adding zirconium beads, carrying out ball milling, adjusting the viscosity by using NMP, then uniformly coating on a copper foil, and placing in a vacuum drying oven to be dried for 12 hours at 40 ℃. Then, the copper foil was cut into an electrode disk having a diameter of 12mm, and the electrode disk was used as a negative electrode. A metal lithium sheet is used as a counter electrode, a Celgard2325 type polypropylene porous membrane is used as a diaphragm, and the CR2016 type button lithium ion battery is assembled in a glove box protected by high-purity argon. The assembled cell was allowed to stand at room temperature for 24 hours before testing for electrochemical performance.
Battery test parameters: the multiplying power performance of the material is tested under a voltage window of 0.005-3V: during the charge-discharge circulation, according to different current densities of 0.5, 1, 2, 5, 10, 20 and 50C (1C is 236mAh g) -1 ) The batteries were cycled 10 times, and finally returned to a rate of 1C. The cycle performance test was performed by cycling the cell at a fixed current density (1C, 10C). The charge and discharge test temperatures of all the batteries were carried out in a 25 ℃ incubator.
Fig. 8 is the rate capability of nickel niobate, a negative electrode material for lithium ion batteries, prepared in example 3. As can be seen from FIG. 8, according to the scheme of example 3, the prepared nickel niobate shows excellent rate capability, which has 300mAh g at 1C -1 Above specific capacity, the specific capacity at 5C is more than 200mAh g -1 And after different multiplying power tests, the product is recovered to 1C, and the specific capacity of the product is kept at a level equivalent to the initial capacity.
Fig. 9 shows the cycle performance of nickel niobate, which is a negative electrode material for a lithium ion battery prepared in example 3, at 1C. As can be seen from FIG. 9, according to the scheme of example 3, the prepared nickel niobate shows excellent cycle stability, which can still maintain 360mAh g after 250 cycles of 1C cycle -1 The specific capacity of (A).
Example 4
Preparation of nickel niobate (Ni) 2 Nb 2 O 7 ) Materials:
reacting NbCl 5 And NiO in a Nb/Ni molar ratio of 1: 1 mixing and adding KF, NaF and NiCl 2 (the mol percentage content is 44%, 44% and 12% respectively) as molten salt reaction medium, the metal oxide and the inorganic salt are mixed according to the mass ratio of 1: 3, mixing; adding appropriate amount of ethanol solution into the mixture to completely soak the mixture, wet-mixing for 8h, and drying in an oven at 80 ℃ for 24 h. Grinding the dried product into powder, placing the powder in a corundum crucible, placing the corundum crucible in a muffle furnace, heating to 850 ℃ at the heating rate of 5 ℃/min, preserving heat for 6 hours, and then cooling to room temperature. Then washing and filtering the product in the crucible for many times by deionized water, and drying at 80 ℃ to obtain the nickel niobate (Ni) 2 Nb 2 O 7 ) A material.
Using the prepared nickel (Ni) niobate 2 Nb 2 O 7 ) Assembling the battery:
the synthesized sample (active material), carbon black (conductive agent) and PVDF (binder) were mixed in a mass ratio of 7: 2: 1, adding zirconium beads, carrying out ball milling, adjusting the viscosity by using NMP, then uniformly coating on a copper foil, and placing in a vacuum drying oven to be dried for 12 hours at 40 ℃. Then, the copper foil was cut into an electrode disk having a diameter of 12mm, and the electrode disk was used as a negative electrode. A metal lithium sheet is used as a counter electrode, a Celgard2325 type polypropylene porous membrane is used as a diaphragm, and the CR2016 type button lithium ion battery is assembled in a glove box protected by high-purity argon. The assembled cell was allowed to stand at room temperature for 24 hours before testing for electrochemical performance.
Battery test parameters: the multiplying power performance of the material is tested in a voltage window of 0.005-3V: during the charge-discharge circulation, according to different current densities of 0.5, 1, 2, 5, 10, 20 and 50C (1C is 236mAh g) -1 ) The batteries were cycled 10 times, and finally returned to a rate of 1C. The cycle performance test was performed by cycling the cell at a fixed current density (1C, 10C). The charge and discharge test temperatures of all the batteries were carried out in a 25 ℃ incubator.
The above embodiments are merely examples for clearly illustrating the present invention and do not limit the present invention. Other variants and modifications of the invention, which are obvious to those skilled in the art and can be made on the basis of the above description, are not necessary or exhaustive for all embodiments, and are therefore within the scope of the invention.
Claims (10)
1. A preparation method of a nickel niobate anode material is characterized by comprising the following steps:
mixing a niobium compound and a nickel compound, and adding an inorganic salt to obtain a mixture;
adding a proper amount of ethanol solution into the mixture to completely soak the mixture, wet-mixing the mixture and drying the mixture;
grinding the dried product into powder, putting the powder into a muffle furnace, heating to 600-1200 ℃, preserving heat for 0.5-20 h, and then cooling;
and washing, filtering and drying the cooled product to obtain the nickel niobate cathode material.
2. The method according to claim 1, wherein the niobium compound is one or a mixture of two or more of niobium oxide, niobium carbonate, niobium hydroxide, niobium chloride, niobium nitrate, and niobium sulfate; the nickel compound is one or more of nickel oxide, nickel carbonate, nickel hydroxide, nickel chloride, nickel nitrate and nickel sulfate.
3. The method according to claim 1, wherein the niobium compound and the nickel compound are mixed in a molar ratio of 0.5 to 18.
4. The method according to claim 1, wherein the inorganic salt is a mixture of two or more of alkali metal chloride or fluoride and nickel chloride, and the nickel chloride is present in an amount of 3 to 15 mol% based on the total amount of the inorganic salt.
5. The production method according to claim 1, wherein the mass ratio of the inorganic salt to the total amount of the niobium compound and the nickel compound is 5:1 to 1: 20.
6. The method of claim 1, wherein the wet mixing is carried out for a period of 2 to 24 hours.
7. The method according to claim 1, wherein the temperature rise rate is 0.5 to 20 ℃/min.
8. The nickel niobate negative electrode material obtained by the preparation method according to claim 1.
9. The nickel niobate anode material of claim 8, wherein the niobiumThe nickel acid is Ni 2 Nb 34 O 67 、NiNb 2 O 6 、Ni 2 Nb 2 O 7 、Ni 4 Nb 2 O 9 Single phase or mixed phase.
10. Use of the nickel niobate negative electrode material of claim 8 or 9 in a lithium ion battery.
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Non-Patent Citations (2)
| Title |
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| JIANG CHENGZHI 等: "熔盐法制备NiNb2O6 纳米粉末", 《MCGM2009》, pages 336 - 338 * |
| RUI XIA 等: "Nickel Niobate Anodes for High Rate Lithium-Ion Batteries", 《ADVANCED ENERGY MATERIALS》, pages 1 - 11 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117254019A (en) * | 2023-10-11 | 2023-12-19 | 深圳市谷口科技有限公司 | Nickel niobate negative electrode material, nickel lithium niobate battery and application thereof |
| CN117254019B (en) * | 2023-10-11 | 2024-05-31 | 深圳市谷口科技有限公司 | Nickel niobate negative electrode material, nickel lithium niobate battery and application thereof |
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