CN115458728A - Negative electrode material and preparation method and application thereof - Google Patents
Negative electrode material and preparation method and application thereof Download PDFInfo
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- CN115458728A CN115458728A CN202211288503.4A CN202211288503A CN115458728A CN 115458728 A CN115458728 A CN 115458728A CN 202211288503 A CN202211288503 A CN 202211288503A CN 115458728 A CN115458728 A CN 115458728A
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- titanium
- ruthenium
- niobium
- iridium
- negative electrode
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- 239000007773 negative electrode material Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- OBOYOXRQUWVUFU-UHFFFAOYSA-N [O-2].[Ti+4].[Nb+5] Chemical compound [O-2].[Ti+4].[Nb+5] OBOYOXRQUWVUFU-UHFFFAOYSA-N 0.000 claims abstract description 91
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 35
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 30
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002245 particle Substances 0.000 claims abstract description 19
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910000457 iridium oxide Inorganic materials 0.000 claims abstract description 16
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims abstract description 16
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001354 calcination Methods 0.000 claims description 83
- 239000000463 material Substances 0.000 claims description 70
- 239000011259 mixed solution Substances 0.000 claims description 65
- 238000000034 method Methods 0.000 claims description 51
- 230000008569 process Effects 0.000 claims description 38
- 239000010936 titanium Substances 0.000 claims description 35
- 239000010955 niobium Substances 0.000 claims description 31
- RJSRQTFBFAJJIL-UHFFFAOYSA-N niobium titanium Chemical compound [Ti].[Nb] RJSRQTFBFAJJIL-UHFFFAOYSA-N 0.000 claims description 31
- CJTCBBYSPFAVFL-UHFFFAOYSA-N iridium ruthenium Chemical compound [Ru].[Ir] CJTCBBYSPFAVFL-UHFFFAOYSA-N 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 24
- 239000012298 atmosphere Substances 0.000 claims description 23
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 20
- 229910052719 titanium Inorganic materials 0.000 claims description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 16
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 15
- 229910001416 lithium ion Inorganic materials 0.000 claims description 15
- 229910052758 niobium Inorganic materials 0.000 claims description 15
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 14
- 239000010405 anode material Substances 0.000 claims description 13
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 13
- -1 hexachloro ruthenium amine Chemical class 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 8
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 8
- 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 8
- 239000004408 titanium dioxide Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 6
- 239000012300 argon atmosphere Substances 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 4
- 238000000498 ball milling Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000003801 milling Methods 0.000 claims description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 2
- KQPASOPRFWJUAA-UHFFFAOYSA-K iridium(3+) trichlorate Chemical compound Cl(=O)(=O)[O-].[Ir+3].Cl(=O)(=O)[O-].Cl(=O)(=O)[O-] KQPASOPRFWJUAA-UHFFFAOYSA-K 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
- ZTILUDNICMILKJ-UHFFFAOYSA-N niobium(v) ethoxide Chemical compound CCO[Nb](OCC)(OCC)(OCC)OCC ZTILUDNICMILKJ-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
- DKNJHLHLMWHWOI-UHFFFAOYSA-L ruthenium(2+);sulfate Chemical compound [Ru+2].[O-]S([O-])(=O)=O DKNJHLHLMWHWOI-UHFFFAOYSA-L 0.000 claims description 2
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 abstract description 16
- 238000000576 coating method Methods 0.000 abstract description 16
- 239000011521 glass Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 12
- 229910052744 lithium Inorganic materials 0.000 description 12
- 239000013078 crystal Substances 0.000 description 11
- 239000010406 cathode material Substances 0.000 description 9
- 239000002131 composite material Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 7
- 210000004027 cell Anatomy 0.000 description 6
- 238000007600 charging Methods 0.000 description 6
- 239000011258 core-shell material Substances 0.000 description 6
- 239000002002 slurry Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- ZESXRMPHQZAUAI-UHFFFAOYSA-N [V].[Ti].[Nb].[Mo] Chemical compound [V].[Ti].[Nb].[Mo] ZESXRMPHQZAUAI-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 239000007770 graphite material Substances 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000006256 anode slurry Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
-
- 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
-
- 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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a negative electrode material and a preparation method and application thereof, wherein the negative electrode material comprises an inner core and a shell coated on the surface of the inner core, the inner core comprises titanium niobium oxide and ruthenium and iridium doped in the titanium niobium oxide, and the shell comprises ruthenium oxide and iridium oxide. According to the negative electrode material provided by the invention, the grain size of the titanium niobium oxide and the particle size of the negative electrode material are effectively reduced through internal doping of ruthenium and iridium and external coating of ruthenium oxide and iridium oxide, and the surface and internal structures of the titanium niobium oxide are changed, so that the electronic conductivity and ionic conductivity of the titanium niobium oxide are greatly improved, and the capacity performance, the quick charge performance and the cycle performance of a battery are further improved.
Description
Technical Field
The invention belongs to the technical field of battery production and manufacturing, and particularly relates to a negative electrode material and a preparation method and application thereof.
Background
With the wide application of lithium ion batteries in the fields of energy storage systems, electric vehicles and the like, people have higher and higher requirements on the quick charging performance and the endurance mileage of the lithium ion batteries. Common negative electrode materials of lithium ion batteries comprise a carbon material and a lithium titanate material (TLO), wherein the carbon material has an unstable structure in the process of rapidly embedding lithium ions, the lithium embedding potential of the carbon material is low, and lithium dendrites are easily formed by rapid charging and discharging, so that the cycle and stability of a battery cell are influenced. The lithium titanate material has a stable spinel structure, is stable in structure in the charge-discharge cycle process, and is called as a zero-tension material; meanwhile, the lithium titanate material has a high lithium intercalation potential, but the theoretical specific capacity is low (175 mAh/g), so that the application of the lithium titanate material is greatly limited.
On the basis of lithium titanate materials, titanium Niobium Oxide (TNO) has received much attention as a new negative electrode material for lithium batteries. The titanium niobium oxide material has high theoretical specific capacity (387 mAh/g) and a stable crystal structure, has extremely small volume change in the charge-discharge cycle process, and also has the characteristic of zero tension; the redox potential is high, the generation of an SEI film in the charge-discharge cycle process can be avoided, and the lithium ion battery anode material is excellent; however, the titanium niobium oxide material has a wide energy band gap and does not have unpaired electrons, so that the titanium niobium oxide material has poor conductivity and hinders diffusion of lithium ions, thereby severely limiting lithium storage performance and having serious capacity loss.
CN114420901A discloses a ruthenium-doped composite material, a preparation method and an application thereof, wherein the ruthenium-doped composite material is a ruthenium-doped titanium niobium oxide, and the structural formula of the titanium niobium oxide is TiNb 2 O 7 The ruthenium-doped composite material has the mass content of ruthenium of 2-5%, and the composite material improves the conductivity of the titanium niobium oxide to a certain extent through doping of ruthenium.
CN114388772A discloses a molybdenum vanadium titanium niobium composite oxide negative electrode material, a preparation method thereof, and a lithium ion battery, wherein the preparation method comprises: (1) Mixing and crushing a first solvent, a niobium source and a titanium source to form a first mixed material, and calcining the first mixed material for the first time to obtain a titanium niobium oxide; (2) Mixing and crushing a second solvent, a vanadium source, a molybdenum source and a titanium niobium oxide to form a second mixed material; and carrying out secondary calcination on the second mixed material to obtain the molybdenum vanadium titanium niobium composite oxide cathode material, and doping vanadium and molybdenum in the titanium niobium oxide to improve the electron mixed arrangement degree, so that the conductivity of the material is improved.
CN110380054A discloses a titanium niobium oxide electrode material and a preparation method thereof, and a lithium ion button cell, wherein the preparation method comprises the following steps: the titanium niobium oxide is doped with heterogeneous metal ions M, and the molecular formula of the titanium niobium oxide is Ti x Nb y O 2x+2.5y Wherein x = 0.1-1,y = 1-2, the electron conductivity of the titanium niobium oxide is improved by doping heterogeneous metal ions.
The above documents all adopt a doping method to improve the conductivity of the titanium niobium oxide, but all adopt a simple soaking doping method to obtain the titanium niobium oxide composite material, and the structure of the titanium niobium oxide composite material is not designed and optimized, so that the conductivity of the titanium niobium oxide composite material cannot be further improved, and further the capacity and cycle performance of the lithium ion battery cannot be further improved.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a negative electrode material and a preparation method and application thereof, and the internal doping of ruthenium and iridium and the external coating of ruthenium oxide and iridium oxide effectively reduce the grain size of the titanium niobium oxide and the particle size of the negative electrode material, and change the surface and internal structures of the titanium niobium oxide, so that the electronic conductivity and the ionic conductivity of the titanium niobium oxide are greatly improved, and the capacity performance, the quick charge performance and the cycle performance of a battery are further improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides an anode material, which includes an inner core and an outer shell coated on a surface of the inner core, wherein the inner core includes titanium niobium oxide and ruthenium and iridium doped in the titanium niobium oxide, and the outer shell includes ruthenium oxide and iridium oxide.
According to the invention, ruthenium oxide and iridium oxide are coated on the outer surface of the titanium niobium oxide through chemical bond acting force to form a core-shell structure, so that the particle size of the negative electrode material can be reduced, the transmission path of lithium ions and electrons is reduced, and the lithium ions and the electrons can be rapidly transmitted into the negative electrode material; and the external surface of the titanium niobium oxide is provided with a Ru-O-Ir bond, an Ir-O-Ti bond, a Ti-O-Ru bond and a Ti-O-Nb bond, because the combination energy of Ru, ir and O is larger, the Ti-O-Ru bond and the Ir-O-Ti bond deviate towards one ends of Ru and Ir, the position of a Ti element is moved, the surface structure of the titanium niobium oxide is changed, the energy band gap is narrowed, and the electron conductivity and the ion conductivity of the titanium niobium oxide are improved. In addition, ruthenium oxide and iridium oxide have good metal conductivity, high specific surface area, high catalytic activity, and excellent thermal stability.
Meanwhile, ruthenium and iridium are doped in the titanium niobium oxide, because ruthenium ions and iridium ions can be embedded into the titanium niobium oxide and replace partial titanium ions in the titanium niobium oxide in the three-time calcination process, the ionic radii of ruthenium and iridium are different from the radius of titanium ions, so that the lattice parameter and the unit cell volume of the titanium niobium oxide are changed, the average grain size is reduced, and the electronic conductivity of the titanium niobium oxide is further improved.
According to the negative electrode material provided by the invention, the grain size of the titanium niobium oxide and the particle size of the negative electrode material are effectively reduced through internal doping of ruthenium and iridium and external coating of ruthenium oxide and iridium oxide, and the surface and internal structures of the titanium niobium oxide are changed, so that the electronic conductivity and ionic conductivity of the titanium niobium oxide are greatly improved, and the capacity performance, the quick charge performance and the cycle performance of a battery are further improved.
As a preferable technical scheme of the invention, the chemical formula of the negative electrode material is Ti x Nb y Ru a Ir b O, wherein x is more than 3 and less than 6, y is more than 5 and less than 9, a is more than 0.1 and less than 0.9, and b is more than 0.1 and less than 0.9.
Where x may be 3.1, 3.2, 3.4, 3.6, 3.8, 4, 4.2, 4.4, 4.6, 4.8, 5, 5.2, 5.4, 5.6, 5.8 or 5.9, y may be 5.1, 5.3, 5.5, 5.8, 6, 6.2, 6.5, 6.7, 7, 7.3, 7.5, 7.8, 8, 8.2, 8.5, 8.8 or 8.9, a may be 0.11, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85 or 0.89, b may be 0.11, 0.15, 0.2, 0.25, 0.35, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85 or 0.89, b may be other values not specifically stated but are not limited to the stated values.
It should be noted that, in the present invention, x: y: a: b represents the molar ratio of the metal elements in the negative electrode material, that is, the molar ratio of titanium, niobium, ruthenium and iridium is (3-6) to (5-9) to (0.1-0.9), and the numerical range in the molar ratio does not include the end point, the reason why the molar ratio of titanium, niobium, ruthenium and iridium in the negative electrode material is limited to (3-6) to (5-9) to (0.1-0.9) is that the materials obtained from different molar ratios have different crystal structures, and the crystal structure is the root reason for restricting the de-intercalation behavior of lithium ions; within the molar ratio range defined by the invention, the obtained material is in a quasi-spherical structure, and the quasi-spherical structure exposes more active surfaces and is more beneficial to the combination of lithium ions and the material.
Preferably, the morphology of the negative electrode material is spherical or spheroidal.
Preferably, the particle size of the negative electrode material is 10 to 15 μm, and may be, for example, 10 μm, 10.5 μm, 11 μm, 11.5 μm, 12 μm, 12.5 μm, 13 μm, 13.5 μm, 14 μm, 14.5 μm or 15 μm, but is not limited to the values listed, and other values not listed in the numerical range are also applicable.
The invention limits the particle size of the negative electrode material to be 10-15 mu m, because the rate capability and the cycle performance of the negative electrode material with small particle size are better, and the effect and the compaction density of the negative electrode material with large particle size are higher, and the invention limits the particle size of the negative electrode material to be 10-15 mu m, thereby not only ensuring the first efficiency to be higher than 89%, but also meeting the requirement of 3C charging, namely meeting the requirement of a quick-charging battery.
In a second aspect, the present invention provides a method for preparing the anode material of the first aspect, the method comprising:
and dropwise adding the titanium-niobium mixed solution to the surface of a base material, carrying out primary calcination to generate a titanium-niobium oxide on the surface of the base material, then dropwise adding the ruthenium-iridium mixed solution, carrying out secondary calcination to generate an intermediate material on the surface of the base material, and then carrying out tertiary calcination to obtain the anode material.
Uniformly dropwise adding a titanium-niobium mixed solution to the surface of a base material, and attaching a spherical or sphere-like titanium-niobium oxide generated after primary calcination to the surface of the base material; then, dropping a ruthenium-iridium mixed solution for secondary calcination, and coating the titanium-niobium oxide on the surface of the base material, namely the intermediate material in the invention is also in a core-shell structure, wherein the core comprises the titanium-niobium oxide, and the shell comprises ruthenium oxide and iridium oxide; and finally, promoting ruthenium ions and iridium ions to enter the titanium niobium oxide core through three times of calcination to replace part of titanium ions, so that the core is formed to comprise the titanium niobium oxide and ruthenium and iridium doped in the titanium niobium oxide, and the shell comprises a core-shell structure negative electrode material of ruthenium oxide and iridium oxide. Further, the substrate in the present invention may be an inorganic glass plate.
As a preferred embodiment of the present invention, the process of forming the titanium niobium oxide on the surface of the substrate comprises:
and dropwise adding the titanium-niobium mixed solution to the surface of a base material, carrying out primary calcination, cooling, repeatedly dropwise adding the titanium-niobium mixed solution, carrying out the primary calcination process, and generating the titanium-niobium oxide on the surface of the base material.
The titanium niobium oxide is prepared by adopting a method of repeatedly coating and calcining for multiple times, so that a plurality of layers of titanium niobium oxides are loaded on the surface of the base material.
Preferably, the preparation process of the titanium-niobium mixed solution comprises the following steps: and mixing a titanium source, a niobium source and a first solvent to obtain the titanium-niobium mixed solution.
According to the invention, the adding amount of the titanium source and the niobium source is determined according to the molar ratio in the chemical formula of the obtained cathode material and the mass of the cathode material required to be prepared in the actual production process.
Preferably, the titanium source comprises any one or a combination of at least two of titanium dioxide, metatitanic acid, titanium ethoxide, tetrabutyl titanate, tetraethyl titanate, or tetraisopropyl titanate, and further preferably titanium dioxide.
Preferably, the niobium source comprises any one or a combination of at least two of niobium pentoxide, niobium ethoxide, niobium pentachloride, or niobium hydroxide, and further preferably niobium pentoxide.
Preferably, the solvent comprises deionized water.
Preferably, the titanium source, the niobium source, and the solvent are mixed under agitation.
The invention does not have specific requirements and special limitations on the stirring speed and time, and can ensure that the titanium source and the niobium source are fully dissolved in the first solvent.
In a preferred embodiment of the present invention, the temperature of the primary calcination is 1000 to 1400 ℃, and may be, for example, 1000 ℃,1200 ℃,1400 ℃, 1600 ℃, 1800 ℃, 2000 ℃, 2200 ℃, 2400 ℃, 2600 ℃, 2800 ℃, 3000 ℃, 3200 ℃, 3400 ℃, 3600 ℃, 3800 ℃ or 4000 ℃, but is not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable.
Preferably, the time of the primary calcination is 15min to 1h, and may be, for example, 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min or 60min, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
When the titanium niobium oxide is prepared by repeating the coating and calcining process for multiple times, the temperature and time for each calcining process are preferably the same.
Preferably, the primary calcination is carried out under an air atmosphere.
As a preferred technical solution of the present invention, the preparation process of the intermediate material comprises:
and dropwise adding the ruthenium-iridium mixed solution to the titanium-niobium oxide, carrying out secondary calcination, cooling, repeatedly dropwise adding the ruthenium-iridium mixed solution, carrying out the secondary calcination process, and generating the intermediate material on the surface of the base material.
The intermediate material is prepared by adopting the method of repeatedly coating and calcining for multiple times, the method for repeatedly coating for multiple times is simple to operate, the uniform and sufficient coating of the ruthenium oxide and the iridium oxide on the titanium niobium oxide is further promoted, and the structure of the intermediate material is more favorably controlled.
Preferably, the preparation process of the ruthenium-iridium mixed solution comprises the following steps: and mixing a ruthenium source, an iridium source and a second solvent to obtain the ruthenium-iridium mixed solution.
In the invention, the adding amount of the titanium source and the niobium source is determined according to the molar ratio in the chemical formula of the obtained anode material and the adding amount of the titanium source and the niobium source.
Preferably, the ruthenium source comprises any one of ruthenium trichloride, metallic ruthenium, ruthenium sulfate or hexachlororuthenamine or a combination of at least two of the two, and further preferably ruthenium trichloride.
Preferably, the iridium source comprises iridium chlorate.
Preferably, the second solvent comprises absolute ethanol.
Preferably, the ruthenium source, the iridium source and the second solvent are mixed under agitation.
The stirring speed and the stirring time are not particularly required or limited, and the ruthenium source and the iridium source can be fully dissolved in the second solvent.
In a preferred embodiment of the present invention, the temperature of the secondary calcination is 300 to 700 ℃, and may be, for example, 300, 320, 350, 380, 400, 430, 450, 480, 500, 520, 550, 580, 600, 620, 650, 680 or 700, but is not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable.
Preferably, the time of the second calcination is 5 to 20min, for example, 5min, 7min, 9min, 10min, 12min, 14min, 16min, 18min or 20min, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the secondary calcination is performed under an air atmosphere.
In a preferred embodiment of the present invention, the temperature of the third calcination is 400 to 600 ℃, and may be, for example, 400 ℃, 420 ℃, 440 ℃, 460 ℃, 480 ℃,500 ℃, 520 ℃, 540 ℃, 560 ℃, 580 ℃ or 600 ℃, but is not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable.
The temperature of the three times of calcination is limited to be 400-600 ℃, because the sintering temperature is crucial to the completeness of the crystal form, when the temperature of the three times of calcination is lower than 400 ℃, the generated crystal form has defects of incomplete growth and poor structural stability; when the temperature of the three times of calcination is higher than 600 ℃, although the crystal form is complete, the crystal grains are too large, and the active substance amount per unit volume is less.
Preferably, the time for the third calcination is 0.5 to 2 hours, and may be, for example, 0.5 hour, 0.7 hour, 0.9 hour, 1 hour, 1.2 hours, 1.4 hours, 1.6 hours, 1.8 hours or 2 hours, but is not limited to the enumerated values, and other values not enumerated within the numerical range are also applicable.
Preferably, the three calcinations are carried out under an inert atmosphere.
Preferably, the inert atmosphere comprises an argon atmosphere.
Preferably, after the three times of calcination, the negative electrode material is generated on the surface of the substrate, and then the negative electrode material is obtained by sequentially performing separation treatment and grinding treatment.
The separation treatment in the present invention means that the negative electrode material attached to the surface of the base material is separated and ground to obtain a negative electrode material having a particle diameter of 10 to 15 μm.
Preferably, the separation process comprises ultrasonic cleaning and drying.
Preferably, the milling process comprises ball milling.
The milling treatment in the present invention may be ball milling in a ball mill.
As a preferable technical solution of the present invention, the preparation method comprises:
s1: mixing a titanium source, a niobium source and a first solvent to obtain a titanium-niobium mixed solution, dropwise adding the titanium-niobium mixed solution to the surface of a base material, performing primary calcination at the temperature of 1000-1400 ℃ for 15 min-1 h in an air atmosphere, cooling, repeatedly dropwise adding the titanium-niobium mixed solution, performing the primary calcination process, and generating a titanium-niobium oxide on the surface of the base material;
s2: mixing a ruthenium source, an iridium source and a second solvent to obtain a ruthenium-iridium mixed solution, dropwise adding the ruthenium-iridium mixed solution to the titanium-niobium oxide, performing secondary calcination at the temperature of 300-700 ℃ for 5-20 min in an air atmosphere, repeatedly dropwise adding the ruthenium-iridium mixed solution after cooling, performing the secondary calcination process, and generating an intermediate material on the surface of the base material;
s3: after the intermediate material is generated on the surface of the base material, the intermediate material is calcined for three times for 0.5 to 2 hours at the temperature of 400 to 600 ℃ in an inert atmosphere, and a negative electrode material is generated on the surface of the base material, and then the negative electrode material is obtained by sequentially carrying out separation treatment and grinding treatment.
In a third aspect, the present invention provides a lithium ion battery, which includes the negative electrode material of the first aspect.
Compared with the prior art, the invention has the beneficial effects that:
according to the negative electrode material provided by the invention, the grain size of the titanium niobium oxide and the particle size of the negative electrode material are effectively reduced by internal doping of ruthenium and iridium and external coating of ruthenium oxide and iridium oxide, and the surface and internal structures of the titanium niobium oxide are changed, so that the electronic conductivity and the ionic conductivity of the titanium niobium oxide are greatly improved, and the capacity performance, the quick charging performance and the cycle performance of a battery are further improved.
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.
In one embodiment, the invention provides an anode material, which comprises an inner core and a shell coated on the surface of the inner core, wherein the inner core comprises titanium niobium oxide and ruthenium and iridium doped in the titanium niobium oxide, and the shell comprises ruthenium oxide and iridium oxide; the shape of the negative electrode material is spherical or sphere-like.
Example 1
The embodiment provides a preparation method of an anode material, which comprises the following steps:
s1: mixing titanium dioxide, niobium pentoxide and deionized water to obtain a titanium-niobium mixed solution, dropwise adding the titanium-niobium mixed solution to the surface of an inorganic glass plate, performing primary calcination at the temperature of 1200 ℃ for 30min in an air atmosphere, cooling, repeatedly dropwise adding the titanium-niobium mixed solution, performing the primary calcination process, and generating a titanium-niobium oxide on the surface of the inorganic glass plate;
s2: mixing ruthenium trichloride, chloroiridic acid and absolute ethyl alcohol to obtain a ruthenium-iridium mixed solution, dropwise adding the ruthenium-iridium mixed solution to the titanium-niobium oxide, carrying out secondary calcination at the temperature of 500 ℃ for 10min in an air atmosphere, repeatedly dropwise adding the ruthenium-iridium mixed solution after cooling, carrying out the secondary calcination process, and generating an intermediate material on the surface of the inorganic glass plate;
s3: after the intermediate material is generated on the surface of the inorganic glass plate, carrying out three times of calcination for 1h at the temperature of 500 ℃ in an argon atmosphere, generating a negative electrode material on the surface of the inorganic glass plate, and then sequentially carrying out separation treatment and grinding treatment to obtain the negative electrode material; the chemical formula of the cathode material is Ti 5 Nb 7 Ru 0.5 Ir 0.5 O, average particle size 12 μm.
Example 2
The embodiment provides a preparation method of an anode material, which comprises the following steps:
s1: mixing titanium dioxide, niobium pentoxide and deionized water to obtain a titanium-niobium mixed solution, dropwise adding the titanium-niobium mixed solution to the surface of an inorganic glass plate, carrying out primary calcination at the temperature of 1000 ℃ for 1h in an air atmosphere, cooling, repeatedly dropwise adding the titanium-niobium mixed solution, carrying out the primary calcination process, and generating a titanium-niobium oxide on the surface of the inorganic glass plate;
s2: mixing ruthenium trichloride, chloroiridic acid and absolute ethyl alcohol to obtain a ruthenium-iridium mixed solution, dropwise adding the ruthenium-iridium mixed solution to the titanium-niobium oxide, performing secondary calcination at the temperature of 700 ℃ for 5min in an air atmosphere, repeatedly dropwise adding the ruthenium-iridium mixed solution after cooling, performing the secondary calcination process, and generating an intermediate material on the surface of the inorganic glass plate;
s3: after the intermediate material is generated on the surface of the inorganic glass plate, carrying out three times of calcination for 2 hours at the temperature of 400 ℃ in an argon atmosphere, generating a negative electrode material on the surface of the inorganic glass plate, and then sequentially carrying out separation treatment and grinding treatment to obtain the negative electrode material; the chemical formula of the negative electrode material is Ti 3.2 Nb 5.1 Ru 0.15 Ir 0.13 O, average particle size 10 μm.
Example 3
The embodiment provides a preparation method of an anode material, which comprises the following steps:
s1: mixing titanium dioxide, niobium pentoxide and deionized water to obtain a titanium-niobium mixed solution, dropwise adding the titanium-niobium mixed solution to the surface of an inorganic glass plate, performing primary calcination at 1400 ℃ for 15min in an air atmosphere, cooling, repeatedly dropwise adding the titanium-niobium mixed solution, performing the primary calcination process, and generating a titanium-niobium oxide on the surface of the inorganic glass plate;
s2: mixing ruthenium trichloride, chloroiridic acid and absolute ethyl alcohol to obtain a ruthenium-iridium mixed solution, dropwise adding the ruthenium-iridium mixed solution to the titanium-niobium oxide, performing secondary calcination at the temperature of 300 ℃ for 20min in an air atmosphere, repeatedly dropwise adding the ruthenium-iridium mixed solution after cooling, performing the secondary calcination process, and generating an intermediate material on the surface of the inorganic glass plate;
s3: after the intermediate material is generated on the surface of the inorganic glass plate, carrying out three times of calcination for 0.5h at the temperature of 600 ℃ in an argon atmosphere, generating a negative electrode material on the surface of the inorganic glass plate, and then sequentially carrying out separation treatment and grinding treatment to obtain the negative electrode material; the chemical formula of the negative electrode material is Ti 5.8 Nb 8.6 Ru 0.86 Ir 0.88 O, average particle diameter 15 μm.
Example 4
This example differs from example 1 in that the amount of added ruthenium trichloride was increased in step S2, and the chemical formula Ti was obtained in step S3 5 Nb 7 Ru 1.2 Ir 0.5 O, the remaining process parameters and operating conditions were the same as in example 1.
Example 5
This example differs from example 1 in that the amount of ruthenium trichloride added is reduced in step S2 and a chemical formula of Ti is obtained in step S3 5 Nb 7 Ru 0.05 Ir 0.5 O, the remaining process parameters and operating conditions were the same as in example 1.
Example 6
This example differs from example 1 in that the amount of chloroiridic acid added is increased in step S2 and a chemical formula of Ti is obtained in step S3 5 Nb 7 Ru 0.5 Ir 1.2 O, the remaining process parameters and operating conditions were the same as in example 1.
Example 7
This example differs from example 1 in that the amount of chloroiridic acid added is reduced in step S2 and a chemical formula of Ti is obtained in step S3 5 Nb 7 Ru 0.5 Ir 0.05 O, the remaining process parameters and operating conditions were the same as in example 1.
Example 8
This example differs from example 1 in that the temperature of the tertiary calcination in step S3 is 350 ℃ and the remaining process parameters and operating conditions are the same as in example 1.
Example 9
This example is different from example 1 in that the temperature of the tertiary calcination in step S3 is 650 deg.C, and the remaining process parameters and operating conditions are the same as in example 1.
Example 10
This example is different from example 1 in that the required titanium-niobium mixed solution is added dropwise to the surface of the inorganic glass plate in step S1 at one time, and the remaining process parameters and operating conditions are the same as in example 1.
Example 11
This example is different from example 1 in that the desired ruthenium iridium mixed solution is added dropwise to the titanium niobium oxide in one step in step S2, and the remaining process parameters and operating conditions are the same as in example 1.
Example 12
This example differs from example 1 in that in step S3, three times of calcination were carried out in an air atmosphere, and the remaining process parameters and operating conditions were the same as in example 1.
Comparative example 1
The present comparative example is different from example 1 in that the step of three times of calcination, that is, the intermediate material obtained in step S2 is used as the anode material, is omitted in step S3, and the rest of the process parameters and the operating conditions are the same as those in example 1.
Comparative example 2
The comparative example provides a preparation method of a negative electrode material with a non-core-shell structure, and the preparation method comprises the following steps:
s1: mixing titanium dioxide, niobium pentoxide and deionized water to obtain a titanium-niobium mixed solution, mixing ruthenium trichloride, chloroiridic acid and absolute ethyl alcohol to obtain a ruthenium-iridium mixed solution, and then mixing the titanium-niobium mixed solution, the ruthenium-iridium mixed solution and an SBA-15 template agent to obtain a raw material mixed solution;
s2: dropwise adding the raw material mixed solution obtained in the step S1 to the surface of an inorganic glass plate, and calcining at 1000 ℃ for 40min in an air atmosphere to generate a negative electrode material on the surface of the inorganic glass plate; then, sequentially carrying out separation treatment and grinding treatment to obtain the cathode material; the chemical formula of the negative electrode material is Ti 5 Nb 7 Ru 0.5 Ir 0.5 O, average particle diameter of12μm。
Comparative example 3
The comparative example is different from example 1 in that step S2 and three calcination steps in S3 are omitted, that is, the titanium niobium oxide obtained in step S1 is directly used as a negative electrode material, and the rest of the process parameters and operating conditions are the same as those in example 1.
Comparative example 4
The comparative example takes a graphite material (material source: shanghai fir QC8 graphite) as a negative electrode material.
The negative electrode materials in examples 1 to 12 and comparative examples 1 to 4 were prepared into negative electrode sheets, and the negative electrode sheets were assembled into batteries, and the specific processes and test parameters were as follows:
(1) The preparation process of the negative pole piece comprises the following steps: mixing CMC serving as a binder with water in advance to obtain a CMC solution with the solid content of 1.5%, and then mixing the negative electrode material, SP and CMC in a mass ratio of 96.7:0.8:1.5 adding into a stirring tank for mixing (adding CMC according to the powder mass/the CMC glue solution solid content) to obtain uniformly dispersed negative electrode slurry, uniformly coating the negative electrode slurry on the surface of copper foil, baking the slurry, removing the water in the slurry to obtain a negative electrode plate, rolling the electrode plate under a certain pressure, reducing the distance between particles, and cutting the rolled electrode plate into a required shape.
(2) The preparation process of the positive pole piece comprises the following steps: LFP, SP, CNT and PVDF were mixed in 97.4%:0.5%:0.4%: uniformly mixing 1.7% of the slurry in a stirring tank, and adding an NMP solution (the required added NMP amount is obtained by calculating according to the solid content of the final slurry to be 62%) to obtain positive slurry; and coating the uniformly dispersed anode slurry on the surface of an aluminum foil for drying, rolling, and slitting the rolled anode sheet to obtain the required size.
(3) The assembling process of the battery comprises the following steps: assembling a layer of positive pole piece, a layer of diaphragm and a layer of negative pole piece in sequence, and then carrying out the processes of liquid injection, formation and grading. Wherein the diaphragm is a conventional double-sided gluing diaphragm, the thickness of the base film is 12 mu m, the thickness of the double-sided coating is 4 mu m, and the overall thickness of the diaphragm is 16 mu m.
(4) 3C specific charge-discharge capacity test parameters: and (3) assembling the rolled negative plate and the lithium plate into a button cell in a glove box, clamping the button cell on a test channel, and starting a test program of the Land cell. The testing process comprises the following steps: (1) 3C constant current discharge to 5mv, (2) standing for 10min, (3) 0.5C constant current discharge to 5mv, (4) standing for 10min, (5) 0.05C constant current discharge to 5mv, (6) standing for 10min, (7) 0.1C constant current charge to 2V, and (8) circulation for 3 weeks. The average of (1) + (3) + (5) was taken 3 times as the 3C discharge gram capacity (C =350mAh/g negative plate weight/g 96.7%).
The results of electrochemical performance tests performed on the batteries manufactured using the negative electrode materials in examples 1 to 12 and comparative examples 1 to 4 are shown in table 1.
TABLE 1
From the data of table 1, one can see:
(1) The batteries assembled by the negative electrode materials of examples 1 to 3 show excellent quick charge performance and cycle performance, which shows that the negative electrode material provided by the invention effectively reduces the grain size of the titanium niobium oxide and the particle size of the negative electrode material through internal doping of ruthenium and iridium and external coating of ruthenium oxide and iridium oxide, and changes the surface and internal structures of the titanium niobium oxide, thereby greatly improving the electronic conductivity and ionic conductivity of the titanium niobium oxide and further improving the capacity performance, quick charge performance and cycle performance of the batteries.
(2) The difference between the quick charge performance and the cycle performance of the battery assembled by the cathode material in the embodiment 4 and the embodiment 1 is small, which shows that the electrochemical performance of the battery cannot be further improved even if the addition amount of ruthenium trichloride is increased, and the cost is increased; the battery assembled by the negative electrode material in the embodiment 5 has lower quick charge performance and cycle performance than those of the battery in the embodiment 1, because the addition amount of the ruthenium trichloride in the embodiment 5 is too low, the fact that the doping amount of the ruthenium is regulated to be in a proper range is proved, and the quick charge performance and the cycle performance of the battery are further improved.
(3) The battery assembled by the negative electrode material in the embodiment 6 has the quick charge performance and the cycle performance which are not greatly different from those of the battery in the embodiment 1, and the fact that the electrochemical performance of the battery cannot be further improved even if the addition amount of the chloroiridic acid is increased is shown, and the cost is increased; the battery assembled by the negative electrode material in the embodiment 7 has lower quick charge performance and cycle root seeking than those of the battery in the embodiment 1, and the reason is that the addition amount of the chloroiridic acid in the embodiment 7 is too low, which indicates that the doping amount of iridium is regulated to be in a proper range, and the quick charge performance and the cycle performance of the battery are further improved.
(4) The battery assembled by the negative electrode material in the example 8 has lower quick charge performance and cycle performance than those of the battery assembled by the negative electrode material in the example 1, and the battery assembled by the negative electrode material in the example 9 has lower cycle performance than that of the battery assembled in the example 1, because the temperature of the three times of calcination in the example 8 is too low, the temperature of the three times of calcination in the example 9 is too high, and when the temperature of the three times of calcination is too low, the generated crystal form has incomplete growth and defects, and the structural stability is poor; when the temperature of the three times of calcination is too high, although the crystal form is complete, the crystal grains are too large, and the active material amount per unit volume is less.
(5) The fast charge performance and the cycle performance of the battery assembled by the cathode materials in the embodiments 10 to 12 are lower than those of the battery assembled in the embodiment 1, which is because the titanium-niobium mixed solution is dropwise added to the surface of the inorganic glass plate at one time in the embodiment 10, the titanium-niobium mixed solution cannot be fully calcined, the controllability of the titanium-niobium oxide is low, and the crystal integrity is poor; in the embodiment 11, the ruthenium iridium mixed solution is dripped on the titanium niobium oxide at one time, and the ruthenium oxide and the iridium oxide have poor coating uniformity on the titanium niobium oxide, which is not beneficial to controlling the structure of an intermediate material; in example 12, the three times of calcination are carried out in an air atmosphere, which is not favorable for ruthenium ions and iridium ions to enter the titanium niobium oxide core to replace part of titanium ions.
(6) The batteries assembled by the negative electrode materials of comparative examples 1 to 3 have lower quick charge performance and cycle performance than those of example 1, because the process of three times of calcination is omitted in comparative example 1, and ruthenium and iridium cannot be doped in the titanium niobium oxide; comparative example 2 mixing and calcining a Ti-Nb mixed solution, a Ru-Ir mixed solution and a template to obtain irregular Ti 5 Nb 7 Ru 0.5 Ir 0.5 O negative electrode material, rather than forming a core-shell structure; in the comparative example 3, titanium niobium oxide was directly used as the anode material; according to the preparation method, the negative electrode material with the core-shell structure is formed by doping ruthenium and iridium and coating ruthenium oxide and iridium oxide outside, so that the grain size of the titanium niobium oxide and the particle size of the negative electrode material can be effectively reduced, and the surface and internal structures of the titanium niobium oxide are changed, so that the electronic conductivity and ionic conductivity of the titanium niobium oxide are greatly improved, and the capacity performance, the quick charge performance and the cycle performance of the battery are further improved.
(7) The battery of comparative example 4, in which the graphite material was directly assembled as the negative electrode material, had a 3C first cycle discharge specific capacity that was high, but had a 3C constant current charging of 80% soc for lithium deposition, the cycle stability was much lower than that of example 1; ti provided by the present application x Nb y Ru a Ir b The dynamic performance of the battery 3C assembled by the O cathode material is improved by 10 percent compared with that of graphite, the normal-temperature and high-temperature circulating capacity retention rate is about 5 percent, the dynamic performance is obviously superior to that of the graphite, and the Ti-based lithium iron bismuth oxide (NXTYRuaIrbO) battery provided by the application is proved x Nb y Ru a Ir b The O cathode material is more suitable for a quick charging system than graphite.
The above-mentioned embodiments, objects, technical solutions and advantages of the present invention are further described in detail, it should be understood that the above-mentioned embodiments are only examples of the present invention, and should not be construed as limiting the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The anode material is characterized by comprising an inner core and an outer shell, wherein the surface of the inner core is coated with the outer shell, the inner core comprises titanium niobium oxide, ruthenium and iridium doped in the titanium niobium oxide, and the outer shell comprises ruthenium oxide and iridium oxide.
2. The negative electrode material according to claim 1, wherein the negative electrode is characterized in thatThe chemical formula of the material is Ti x Nb y Ru a Ir b O, wherein x is more than 3 and less than 6, y is more than 5 and less than 9, a is more than 0.1 and less than 0.9, and b is more than 0.1 and less than 0.9;
preferably, the morphology of the negative electrode material is spherical or spheroidal;
preferably, the particle size of the negative electrode material is 10 to 15 μm.
3. A method for preparing the anode material according to claim 1 or 2, characterized by comprising:
and dropwise adding the titanium-niobium mixed solution to the surface of a base material, carrying out primary calcination, generating a titanium-niobium oxide on the surface of the base material, dropwise adding the ruthenium-iridium mixed solution, carrying out secondary calcination, generating an intermediate material on the surface of the base material, and then carrying out tertiary calcination to obtain the negative electrode material.
4. The method according to claim 3, wherein the step of forming the titanium niobium oxide on the surface of the substrate comprises:
dropwise adding the titanium-niobium mixed solution to the surface of a base material, calcining for the first time, cooling, repeatedly dropwise adding the titanium-niobium mixed solution, and calcining for the first time to generate the titanium-niobium oxide on the surface of the base material;
preferably, the preparation process of the titanium-niobium mixed solution comprises the following steps: mixing a titanium source, a niobium source and a first solvent to obtain the titanium-niobium mixed solution;
preferably, the titanium source comprises any one or a combination of at least two of titanium dioxide, metatitanic acid, titanium ethoxide, tetrabutyl titanate, tetraethyl titanate, or tetraisopropyl titanate, further preferably titanium dioxide;
preferably, the niobium source comprises any one or combination of at least two of niobium pentoxide, niobium ethoxide, niobium pentachloride or niobium hydroxide, and further preferably niobium pentoxide;
preferably, the solvent comprises deionized water;
preferably, the titanium source, the niobium source, and the solvent are mixed under agitation.
5. The method according to claim 3 or 4, wherein the temperature of the primary calcination is 1000 to 1400 ℃;
preferably, the time of the primary calcination is 15 min-1 h;
preferably, the primary calcination is carried out under an air atmosphere.
6. The method of any one of claims 3-5, wherein the intermediate material is prepared by a process comprising:
dropwise adding the ruthenium-iridium mixed solution to the titanium-niobium oxide, carrying out secondary calcination, cooling, repeatedly dropwise adding the ruthenium-iridium mixed solution, carrying out the secondary calcination process, and generating the intermediate material on the surface of the base material;
preferably, the preparation process of the ruthenium iridium mixed solution comprises the following steps: mixing a ruthenium source, an iridium source and a second solvent to obtain a ruthenium-iridium mixed solution;
preferably, the ruthenium source comprises any one of ruthenium trichloride, metallic ruthenium, ruthenium sulfate or hexachloro ruthenium amine or a combination of at least two of the ruthenium trichloride, and further preferably ruthenium trichloride;
preferably, the iridium source comprises iridium chlorate;
preferably, the second solvent comprises absolute ethanol;
preferably, the ruthenium source, the iridium source and the second solvent are mixed under agitation.
7. The method according to any one of claims 3 to 6, wherein the temperature of the secondary calcination is 300 to 700 ℃;
preferably, the time of the secondary calcination is 5-20 min;
preferably, the secondary calcination is carried out under an air atmosphere.
8. The method according to any one of claims 3 to 7, wherein the temperature of the tertiary calcination is 400 to 600 ℃;
preferably, the time of the third calcination is 0.5-2 h;
preferably, the tertiary calcination is carried out under an inert atmosphere;
preferably, the inert atmosphere comprises an argon atmosphere;
preferably, after the three times of calcination, the negative electrode material is generated on the surface of the base material, and then the negative electrode material is obtained by sequentially performing separation treatment and grinding treatment;
preferably, the separation process comprises ultrasonic cleaning and drying;
preferably, the milling process comprises ball milling.
9. The production method according to any one of claims 3 to 8, characterized by comprising:
s1: mixing a titanium source, a niobium source and a first solvent to obtain a titanium-niobium mixed solution, dropwise adding the titanium-niobium mixed solution to the surface of a base material, performing primary calcination at the temperature of 1000-1400 ℃ for 15 min-1 h in an air atmosphere, cooling, repeatedly dropwise adding the titanium-niobium mixed solution, performing the primary calcination process, and generating a titanium-niobium oxide on the surface of the base material;
s2: mixing a ruthenium source, an iridium source and a second solvent to obtain a ruthenium-iridium mixed solution, dropwise adding the ruthenium-iridium mixed solution to the titanium-niobium oxide, performing secondary calcination at the temperature of 300-700 ℃ for 5-20 min in an air atmosphere, cooling, repeatedly dropwise adding the ruthenium-iridium mixed solution, performing the secondary calcination process, and generating an intermediate material on the surface of the base material;
s3: after the intermediate material is generated on the surface of the base material, the intermediate material is calcined for three times for 0.5 to 2 hours at the temperature of 400 to 600 ℃ in an inert atmosphere, and a negative electrode material is generated on the surface of the base material, and then the negative electrode material is obtained by sequentially carrying out separation treatment and grinding treatment.
10. A lithium ion battery, characterized in that it comprises the negative electrode material of claim 1 or 2.
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| JP2006134613A (en) * | 2004-11-02 | 2006-05-25 | Canon Inc | Electrode catalyst for solid polymer electrolyte fuel cell and fuel cell using it |
| CN105322143A (en) * | 2014-07-04 | 2016-02-10 | 中信国安盟固利动力科技有限公司 | Nano microsphere niobium-based composite oxide and preparation method thereof |
| CN110620215A (en) * | 2018-06-20 | 2019-12-27 | 深圳市贝特瑞纳米科技有限公司 | Cathode material, preparation method thereof and lithium ion battery containing cathode material |
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| JP2006134613A (en) * | 2004-11-02 | 2006-05-25 | Canon Inc | Electrode catalyst for solid polymer electrolyte fuel cell and fuel cell using it |
| CN105322143A (en) * | 2014-07-04 | 2016-02-10 | 中信国安盟固利动力科技有限公司 | Nano microsphere niobium-based composite oxide and preparation method thereof |
| CN110620215A (en) * | 2018-06-20 | 2019-12-27 | 深圳市贝特瑞纳米科技有限公司 | Cathode material, preparation method thereof and lithium ion battery containing cathode material |
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