CN113233504A - Preparation method and application of high-conductivity titanium niobate negative electrode material - Google Patents
Preparation method and application of high-conductivity titanium niobate negative electrode material Download PDFInfo
- Publication number
- CN113233504A CN113233504A CN202110472322.6A CN202110472322A CN113233504A CN 113233504 A CN113233504 A CN 113233504A CN 202110472322 A CN202110472322 A CN 202110472322A CN 113233504 A CN113233504 A CN 113233504A
- Authority
- CN
- China
- Prior art keywords
- titanium niobate
- niobate
- titanium
- conductivity
- lithium ion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000010936 titanium Substances 0.000 title claims abstract description 230
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 225
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 225
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 99
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 76
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 72
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 32
- 238000000498 ball milling Methods 0.000 claims abstract description 25
- 239000000843 powder Substances 0.000 claims abstract description 19
- 239000002243 precursor Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000010405 anode material Substances 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000001694 spray drying Methods 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 claims abstract description 6
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- 229930195727 α-lactose Natural products 0.000 claims abstract description 5
- 239000011812 mixed powder Substances 0.000 claims abstract description 4
- 239000002131 composite material Substances 0.000 claims description 57
- 238000001354 calcination Methods 0.000 claims description 22
- 239000010955 niobium Substances 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 12
- 229910052758 niobium Inorganic materials 0.000 claims description 10
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 10
- 239000006258 conductive agent Substances 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 6
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 5
- 230000002572 peristaltic effect Effects 0.000 claims description 4
- 229910019804 NbCl5 Inorganic materials 0.000 claims description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- 239000006230 acetylene black Substances 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical group Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 17
- 229910052760 oxygen Inorganic materials 0.000 abstract description 17
- 239000001301 oxygen Substances 0.000 abstract description 17
- 239000011163 secondary particle Substances 0.000 abstract description 6
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 68
- 239000000463 material Substances 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 239000000725 suspension Substances 0.000 description 12
- 230000000630 rising effect Effects 0.000 description 11
- 230000009467 reduction Effects 0.000 description 10
- 238000007599 discharging Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 238000010926 purge Methods 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 239000011164 primary particle Substances 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000007833 carbon precursor Substances 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229910001290 LiPF6 Inorganic materials 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910002986 Li4Ti5O12 Inorganic materials 0.000 description 2
- -1 Polypropylene Polymers 0.000 description 2
- 229910010379 TiNb2O7 Inorganic materials 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000005486 organic electrolyte Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 description 1
- 229910019651 Nb(OC2H5)5 Inorganic materials 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 229910009866 Ti5O12 Inorganic materials 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- OBOYOXRQUWVUFU-UHFFFAOYSA-N [O-2].[Ti+4].[Nb+5] Chemical compound [O-2].[Ti+4].[Nb+5] OBOYOXRQUWVUFU-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000005678 chain carbonates Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 206010016766 flatulence Diseases 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000008101 lactose Substances 0.000 description 1
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G33/00—Compounds of niobium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method of a high-conductivity titanium niobate negative electrode material, which comprises the following steps: (1) adding water into carbon sources such as titanium niobate, alpha-lactose and the like, carrying out ball milling to obtain a mixed solution, and then carrying out spray drying to obtain precursor mixed powder; (2) mixing the precursor powder at high temperature H2And reducing in the atmosphere to obtain the high-conductivity titanium niobate negative electrode material. The high-conductivity titanium niobate anode material prepared by the spray drying method has the structure of secondary particles, and can be Li+Providing more directional transmission paths; second, by H2The titanium niobate is reduced to obtain a proper oxygen vacancy, and carbon is compounded to improve the conductivity of the titanium niobate synergistically, so that the obtained high-conductivity titanium niobate negative electrode material has the advantages of high cycle stability, high coulombic efficiency and high rate performance in a lithium ion battery.
Description
Technical Field
The invention belongs to the field of new energy lithium ion batteries, and particularly relates to a preparation method and application of a high-conductivity titanium niobate negative electrode material.
Background
Due to the fact that a great amount of fossil fuel is consumed at present, an increasingly serious energy crisis and environmental problems are caused, strong attention is paid to new green energy and related energy storage systems, among various energy storage devices, lithium ion batteries have high energy density and good cycle life, the lithium ion batteries are unprecedented since the 20 th century and the 90 th era, and the lithium ion batteries are widely applied to various fields such as smart grids, hybrid electric vehicles and portable devices at present.
At present, the negative electrode material of commercial lithium ion batteries is mainly graphite, and the intercalation/deintercalation lithium potential (0.1V vs Li)+Li) is very close to an electrode of metal lithium, which easily causes lithium dendrite to be formed and pierce a diaphragm in the lithium embedding process, causing short circuit and even explosion in the battery, and secondly, the graphite material has low lithium ion diffusion coefficient, and lithium ions can not be rapidly diffused during large-current charging and discharging, so that the high-rate performance is not satisfactory, which obviously cannot meet the requirements of high power and high safety of a power lithium ion battery. The main problems of the silicon-carbon negative electrode material are that the first turn of coulombic efficiency is low (generally lower than 80%) and the volume change is large (up to 300%) in the charging and discharging process. In recent years, of titanium-based oxide materials, Li has been mainly used commercially4Ti5O12Due to the presence of Li+During the insertion and extraction process, the crystal lattice is almost unchanged, called "zero strain" material, but the main problem is the low theoretical capacity (-175 mAh g)-1) And also the phenomenon of flatulence during the circulation. Niobium titanium oxide and Li4Ti5O12Similar in nature, with a relatively safe charge-discharge plateau (1.6V), and Li+The material structure is more stable in the charge and discharge process of the structure in the embedding and separating process, but the theoretical capacity of the titanium niobate negative electrode material is almost Li4Ti5O122 times of the capacity, reaches 387mAh g-1. Therefore, the titanium niobate anode material becomes a research hotspot of the fast-charging lithium ion anode material.
CN 110137481A discloses carbon-coated oxygen defect titanium niobate negative electrode material, preparation method thereof and lithium batteryThe preparation process adopts secondary calcination, each calcination is carried out in a reducing atmosphere, and finally the titanium niobate anode material is wrapped by carbon, and the specific capacity of the titanium niobate anode material wrapped by carbon reaches 275.1mAh g-1The specific capacity of the titanium niobate anode material which is not wrapped by carbon is only 226.3mAh g-1The carbon coating is needed to achieve higher specific capacity, and the preparation process is complicated and is not suitable for industrial production.
CN 111740097A discloses a hexagonal prism-shaped titanium niobate negative electrode material and a preparation method thereof, and particularly discloses that the single crystal particles of the hexagonal prism-shaped titanium niobate negative electrode material are hexagonal prisms, and the chemical molecular formula of the material is TiNb1-xMxO7C (wherein 0)<x<0.1), the specific preparation method comprises the following steps: preparing a hexagonal prism-shaped titanium niobate precursor by a hydrothermal method by adopting a mixed suspension of a titanium source compound, a niobium source compound, a doping element M compound, a carbon source compound and a surfactant; and then roasting the precursor at high temperature under the protection of nitrogen atmosphere to obtain the hexagonal prism-shaped titanium niobate negative electrode material, wherein the prepared hexagonal prism-shaped titanium niobate negative electrode material is discharged at the rate of 20C, the capacity retention rate is 80%, the capacity retention rate is 100% after the material is circulated at the high temperature of 45 ℃ for 50 weeks, and the morphology of hexagonal prism-shaped single crystal particles enables the material to have higher compacted density (not less than 3.0 g/cm)3). However, the specific capacity and the first effect of the titanium niobate anode material prepared by the method are insufficient.
The prior titanium niobate negative electrode material has the following two defects. First, the band gap of titanium niobate is wide (-2.9 eV), and Ti therein4+And Nb5+All are in the highest valence state, and have no unpaired electrons, so that the material has poor conductivity and is almost insulating; second, Li of titanium niobate+The diffusion coefficient is also low, resulting in a large interface impedance between the titanium niobate negative electrode material and the electrolyte. Due to the defects of the two aspects, the electronic conductivity and the ionic conductivity of the titanium niobate negative electrode material are lower, so that the coulomb of the titanium niobate negative electrode material is seriously limitedEfficiency and rate capability. Moreover, the phase forming temperature of the titanium niobate is high (700-1100 ℃), which further influences the improvement of the rate capability of the titanium niobate cathode material. The defects limit the commercial application of the titanium niobate negative electrode material in the lithium ion battery.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a high-conductivity titanium niobate composite material, a composite electrode containing the same and application thereof aiming at the defects in the prior art, wherein H is utilized2Carbon and oxygen vacancies are introduced into the titanium niobate to synergistically improve the electronic conductivity and the ionic conductivity of the titanium niobate, so that the carbon and oxygen vacancies can obviously improve the specific capacity and the first effect of the lithium ion battery when being applied to the lithium ion battery.
The technical scheme adopted by the invention for solving the problems is as follows:
a preparation method of a high-conductivity titanium niobate negative electrode material comprises the following steps:
(1) adding a titanium source and a niobium source into a ball milling tank, adding deionized water, and carrying out ball milling to obtain a mixed solution A;
(2) spraying and drying the obtained mixed solution A by using a small spray dryer to obtain precursor powder A;
(3) calcining the precursor powder A in a muffle furnace to obtain titanium niobate;
(4) mixing the titanium niobate obtained in the step (3) with a carbon source, adding deionized water, and performing ball milling to obtain a mixed solution B;
(5) spraying and drying the obtained mixed solution B by using a small spray dryer to obtain titanium niobate/carbon precursor mixed powder B;
(6) mixing the titanium niobate/carbon precursor mixed powder B in H2And reducing in the atmosphere to obtain the high-conductivity titanium niobate negative electrode material.
Preferably, the titanium source is Ti (OC)4H9)4、TiO2、C12H28O4Ti, etc. As a most preferred scheme, the titanium source is TiO2。
As a preferred scheme, theThe niobium source is NbCl5、Nb2O5、Nb(OC2H5)5And the like. As a most preferred embodiment, the niobium source is Nb2O5。
Preferably, the molar ratio of the titanium source to the niobium source is 1: 0.5 to 2. As a most preferred embodiment, the molar ratio of the titanium source to the niobium source is 1: 1.
as a preferable scheme, in the step (2) and the step (5), the working conditions of the small spray dryer are as follows: air blowing rate: 50-80%, the speed of the feeding peristaltic pump is 1-10%, the feeding temperature is 100-200 ℃, and the air speed is 50-100%. As a most preferred option, the feed peristaltic pump rate is 10%, the feed temperature is 120 ℃ and the air velocity is 70%.
Preferably, in the step (3), the calcination temperature of the precursor powder A is 700-1100 ℃, and the calcination time is 2-48 h. As a most preferred embodiment, the calcination temperature of the precursor powder A is 1100 ℃ and the calcination time is 24 hours.
As a preferable scheme, in the step (4), the mass ratio of the titanium niobate to the carbon source is (90-98): (1-5).
In a preferable embodiment, in the step (4), the carbon source is one of sucrose, α -lactose, and the like. As a most preferred embodiment, the carbon source of the carbon-coated titanium niobate is α -lactose.
As a preferable scheme, in the step (6), the reduction temperature is 600-900 ℃ and the time is 1-6 h. As a most preferred scheme, the temperature of the reduction is 700 ℃ and the time is 2 h.
The inventors of the present invention have surprisingly found in extensive studies that in the prior art, the preparation parameters are controlled, and ball milling, spray drying, calcining and high temperature H are adopted under the premise of omitting preparation elements2The size of the titanium niobate negative electrode material is convenient to control through reduction, oxygen vacancies and a conductive carbon layer can be introduced, and the titanium niobate composite material with high electron/ion conductivity is obtained, so that the specific capacity and the first effect of the lithium ion battery can be obviously improved when the titanium niobate composite material is applied to the negative electrode of the lithium ion battery. It is composed ofIn the preparation process of the titanium niobate, spray drying is adopted, so that the slurry can be rapidly atomized and dried, and the size of titanium niobate particles is convenient to control; because the phase forming temperature of the titanium niobate is higher and is more than 1000 ℃, the invention optimally selects to process the titanium niobate precursor powder at 1100 ℃, simultaneously discovers that different calcining time can influence the capacity of the titanium niobate, obtains the first charging specific capacity of the titanium niobate by comparing different calcining time periods, discovers that the first charging specific capacity of the titanium niobate calcined for 24 hours is the highest, the calcining time is too short, the phase forming time of the titanium niobate is not enough, the calcining time is too long, and the crystal configuration of the titanium niobate is possibly damaged.
The inventors of the present invention have also surprisingly found in a number of studies that H can be converted into2The temperature of the reduced titanium niobate carbon precursor powder is accurately controlled at 600-900 ℃ and the time is controlled at 1-6 h, oxygen vacancies can be introduced into the titanium niobate, lactose can be carbonized under the condition, the electronic conductivity and the ionic conductivity of the titanium niobate can be synergistically improved with the help of the conductive carbon layer, and the specific capacity and the first effect of the lithium ion battery can be remarkably improved when the reduced titanium niobate carbon precursor powder is applied to the lithium ion battery. Meanwhile, the inventor further finds that when the reduction temperature is 700 ℃ and the time is 2 hours, the reduction temperature is probably suitable for forming oxygen vacancies, the electrochemical performance of the obtained titanium niobate/carbon composite material is more excellent, and the invention provides the application of the high-conductivity titanium niobate lithium ion battery cathode material as the cathode of the lithium ion button battery.
On the basis, the invention also provides a composite electrode, which comprises a conductive agent, a binder and the high-conductivity titanium niobate negative electrode material prepared by the method; the mass ratio of the high-conductivity titanium niobate negative electrode material to the conductive agent to the binder is (0.5-0.9): (0.3-0.05): (0.2-0.05).
As a preferable scheme, the conductive agent is one of acetylene black, carbon nanotubes, supper p, and the like.
On the basis, the invention also provides application of the composite electrode in a lithium ion battery, and the composite electrode is used as a negative electrode of the lithium ion battery.
The invention also provides a preparation method of the high-conductivity titanium niobate lithium ion battery composite electrode, which comprises the steps of uniformly mixing the high-conductivity titanium niobate negative electrode material, the conductive agent and the binder in proportion, adding 5-10 mL of solvent (deionized water and the like) into each 37mg of the obtained mixture, uniformly mixing the mixture, coating the mixture on a copper foil, drying the mixture in a vacuum drying oven at the temperature of 60-120 ℃ for 6-12 hours, cutting the mixture into pole pieces with the diameter of 8-18 mm by using a slicing machine, and finally placing the pole pieces in the air for storage for-20 days to obtain the high-conductivity titanium niobate lithium ion battery composite electrode. Wherein, the drying temperature is preferably 80 ℃, the drying time is preferably 12 hours, and the electrode plate is preferably 10mm in diameter.
The lithium ion battery provided by the invention comprises the high-conductivity titanium niobate lithium ion battery composite electrode, a diaphragm, organic electrolyte and metal lithium. The temperature of the lithium ion battery is 30 ℃.
In the lithium ion battery, the diaphragm is Preferably Polypropylene (PP) with the model of cellard 2400; the organic electrolyte is a carbonate electrolyte containing a solute, and the concentration of the solute is 0.1-4M, preferably 1M. Further, the carbonate electrolyte includes one or more selected from cyclic carbonate (PC, EC), chain carbonate (DEC, DMC, EMC), carboxylate (MF, MA, EA, MA, MP), and the like, preferably EC: DMC: EMC: 1:1:1, and a solute of the electrolyte is selected from LiPF6、LiClO4、LiBF4、、LiAsF6Etc., preferably LiPF6。
The invention aims to solve the problem that the application of the current titanium niobate material in a negative electrode of a lithium ion battery is limited due to poor electronic and ionic conductivity. Compared with the prior art, the invention has the following beneficial effects:
the invention is to spray dry the titanium source and the niobium source at high temperature H2The carbon/titanium niobate composite material prepared by the processes of reduction and the like has a secondary particle structure and can be Li+More azimuth transmission paths are provided, meanwhile, the preparation process of the invention is convenient to control the size of the titanium niobate cathode material, oxygen vacancies are possibly introduced, and the synergistic effect of the conductive carbon layer is added, so that the titanium niobate composite with high electronic conductivity and ionic conductivity is obtainedThe material has the advantages of high cycle stability, high coulombic efficiency and high rate performance, so that the specific capacity and the first effect of the lithium ion battery can be obviously improved when the material is applied to the lithium ion battery. Particularly, when the high-conductivity titanium niobate negative electrode material is used in a lithium ion battery, the specific capacity reaches 298.6mAh g-1The first charging efficiency reaches 95.84%. In addition, the method has the advantages of simple process, simple and convenient operation, low cost, low raw material price, low production cost and easy realization of industrial production.
Drawings
Fig. 1 is a graph showing a comparison of rate capability of the titanium niobate composite materials or the titanium niobate obtained in example 1, comparative example 2, and comparative example 10.
FIG. 2 is a TiNb scale prepared in example 12O7Scanning electron micrographs of titanium niobate of-1100-24.
Fig. 3 is a scanning electron micrograph of the high-conductivity titanium niobate composite material prepared in example 1.
Fig. 4 is a first charge-discharge curve of the titanium niobate composite materials or the titanium niobate obtained in example 1, comparative example 2, and comparative example 10.
Fig. 5 is a first charge-discharge curve of the titanium niobate obtained in comparative examples 2, 3, and 4.
Fig. 6 is a graph showing a comparison of cycle performance of the titanium niobate composite materials or titanium niobate of titanium niobate obtained in example 1, comparative example 2, and comparative example 10.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the content of the present invention, but the present invention is not limited to the following examples.
Example 1
Preparing titanium niobate (TiNb)2O7)
38.45g of Nb are weighed2O5And 11.55g TiO2Adding 50.0mL of deionized water into a 250mL PTFE ball milling tank, wherein the ball-to-material ratio is 4: 1, performing ball milling for 2 hours at a ball milling speed of 500rpm, and discharging; adding 400mL of deionized water into a ball milling tank for 5 times, and adding ballsGrinding and cleaning, and mixing all the washing liquid with the suspension; fully stirring and dispersing the suspension liquid of 500g for 2 hours; spray drying the suspension to obtain titanium niobate precursor powder; placing the obtained powder into a reactor, and reacting at 5 deg.C for min-1The temperature rising rate is increased to 1100 ℃, and the temperature is maintained for 24 hours to obtain the titanium niobate. Is named as TiNb2O7-1100-24. 1100-24 represent the titanium niobate obtained by calcining at 1100 ℃ for 24 hours.
As shown in fig. 2, the SEM image of the titanium niobate prepared by this method shows that the titanium niobate has a crystal structure with a size of about 1 μm, and the structure of the micrometer-sized titanium niobate is more stable during charge and discharge.
(II) preparation of titanium niobate/carbon composite
882.0g of TiNb are weighed2O7And 100.0g of alpha-lactose are added into a 3L PTFE ball milling tank, 1000.0mL of deionized water is added, ball milling is carried out for 6h, and discharging is carried out. And (3) adding 1000mL of deionized water into a ball milling tank for 3 times, carrying out ball milling and cleaning, and mixing all washing liquor with the suspension. The above-mentioned 9000g of suspension was thoroughly stirred and dispersed for 2 h. Spray drying the suspension to prepare precursor powder; the precursor powder obtained above is placed in a reactor, H2Purging the reactor for 2h, then keeping the temperature at 5 ℃ for min-1The temperature rise rate is increased to 700 ℃, and the temperature is kept for 2 hours to obtain the titanium niobate/carbon composite material, namely the high-conductivity titanium niobate cathode material. Is named as TiNb2O7@hC-H2-700-2。
As shown in fig. 3, the titanium niobate/carbon composite material obtained by the above method has characteristics of secondary particles, and is a secondary particle composed of primary particles of several tens to several hundreds nanometers, the size distribution of the primary particles is varied from several tens to several hundreds nanometers, the nanometer size can shorten the diffusion distance of lithium ions, and is beneficial to the diffusion of lithium ions, the secondary particles are in a micron-sized spherical shape (about 10 μm), and the micron-sized spherical shape can keep the structure of the composite material stable in the charging and discharging process.
(III) preparing the titanium niobate/carbon composite electrode
Mixing the prepared negative electrode material, a conductive agent Super P and a binder according to a mass ratio of 80: 10: 10, coating the mixture on a copper foil, vacuum drying the mixture for 12 hours at the temperature of 80 ℃, naturally cooling the mixture to obtain a composite electrode, and cutting the composite electrode into pole pieces with the diameter of 10 mm.
(IV) assembling the lithium ion battery
The prepared composite electrode and metal lithium are assembled into a CR2032 type lithium ion battery in a glove box filled with argon, and the electrolyte of the lithium ion battery is 1.0M LiPF6The EC/DEC/EMC carbonate electrolyte (EC: DEC: EMC mass ratio is 1:1:1) is adopted, and a polypropylene diaphragm is selected as the diaphragm.
And (3) carrying out constant-current charge and discharge test on the potassium ion battery in a 30 ℃ constant temperature box by using a Wuhan blue battery test system, wherein the test current density of the lithium ion battery is 0.1C, and the cycle test current density is 1C.
Comparative example 1
Preparing titanium niobate (TiNb)2O7)
The procedure was the same as in example 1.
(II) H2Reducing titanium niobate
2.0g of titanium niobate is weighed, placed in a reactor and firstly added with H2Purging the reactor for 2h, then at 5 ℃ for min-1The temperature rising rate is increased to 700 ℃, the temperature is kept for 2 hours, and finally the titanium niobate containing a certain oxygen vacancy is obtained after the titanium niobate is naturally cooled to the room temperature. Is named as TiNb2O7-H2-700-2。TiNb2O7-H2Is represented by the passage H2Reduced titanium niobate, 700-2 represents TiNb2O7At H2Keeping the temperature at 700 ℃ for 2h under the atmosphere. The following nomenclature is used in this context.
As shown in FIG. 1, H2The multiplying power comparison performance before and after reduction treatment is shown as H2The multiplying power performance of the treated titanium niobate is improved.
(III) preparing the titanium niobate composite electrode
The procedure was the same as in example 1.
(IV) assembling the lithium ion battery
The procedure was the same as in example 1.
Comparative example 2
Preparation ofTitanium niobate (TiNb)2O7)
The procedure was the same as in example 1.
(II) preparing titanium niobate composite electrode
The procedure was the same as in example 1.
(III) assembling the lithium ion battery
The procedure was the same as in example 1.
Comparative example 3
Preparing titanium niobate (TiNb)2O7)
38.45g of Nb are weighed2O5And 11.55g TiO2Adding 50.0mL of deionized water into a 250mL PTFE ball milling tank, wherein the ball-to-material ratio is 4: 1, performing ball milling for 2 hours at a ball milling speed of 500rpm, and discharging; adding 400mL of deionized water into a ball milling tank for 5 times, carrying out ball milling and cleaning, and mixing all washing liquor with the suspension; fully stirring and dispersing the suspension liquid of 500g for 2 hours; spray drying the suspension to obtain titanium niobate precursor powder; placing the obtained powder into a reactor, and reacting at 5 deg.C for min-1The temperature rising rate is increased to 1100 ℃, and the temperature is maintained for 4 hours to obtain the titanium niobate. Is named as TiNb2O7-1100-4. 1100-4 represents the titanium niobate obtained by calcining at 1100 ℃ for 4 hours.
(II) preparing titanium niobate composite electrode
The procedure was the same as in example 1.
(III) assembling the lithium ion battery
The procedure was the same as in example 1.
Comparative example 4
Preparing titanium niobate (TiNb)2O7)
38.45g of Nb are weighed2O5And 11.55g TiO2Adding 50.0mL of deionized water into a 250mL PTFE ball milling tank, wherein the ball-to-material ratio is 4: 1, performing ball milling for 2 hours at a ball milling speed of 500rpm, and discharging; adding 400mL of deionized water into a ball milling tank for 5 times, carrying out ball milling and cleaning, and mixing all washing liquor with the suspension; fully stirring and dispersing the suspension liquid of 500g for 2 hours; spraying the above suspensionDrying to obtain titanium niobate precursor powder; placing the obtained powder into a reactor, and reacting at 5 deg.C for min-1The temperature rising rate is increased to 1100 ℃, and the temperature is maintained for 48 hours to obtain the titanium niobate. Is named as TiNb2O7-1100-48. 1100-48 represent the titanium niobate obtained by calcining at 1100 ℃ for 48 hours.
(II) preparing titanium niobate composite electrode
The procedure was the same as in example 1.
(III) assembling the lithium ion battery
The procedure was the same as in example 1.
Comparative example 5
Preparing titanium niobate (TiNb)2O7)
1.20g F127 was dissolved in 50ml ethanol with vigorous stirring. Then, 0.54g of NbCl was added5And 0.341mL Ti (OC)4H9)4The mixed solution was stirred for 1 hour, and then the mixed solution was transferred to a 100mL Teflon stainless steel autoclave and subjected to hydrothermal treatment at 220 ℃ for 16 hours. The autoclave was then cooled to room temperature and the white precipitate was washed with deionized water and absolute ethanol and then dried under vacuum at 60 ℃ overnight. The product was incubated at 800 ℃ for 5 ℃ min-1Calcining for 5 hours at the temperature rising rate of (1) to obtain the titanium niobate.
(III) preparing the titanium niobate composite electrode
The procedure was the same as in example 1.
(IV) assembling the lithium ion battery
The procedure was the same as in example 1.
Comparative example 6
Preparing titanium niobate (TiNb)2O7)
The procedure was the same as in example 1.
(II) H2Reducing titanium niobate
2.0g of titanium niobate is weighed, placed in a reactor and firstly added with H2Purging the reactor for 2h, then at 5 ℃ for min-1The temperature rising rate is increased to 600 ℃, the temperature is kept for 2 hours, and finally the titanium niobate containing a certain oxygen vacancy is obtained after the titanium niobate is naturally cooled to the room temperature. Is named as TiNb2O7-H2-600-2。
(III) preparing the titanium niobate composite electrode
The procedure was the same as in example 1.
(IV) assembling the lithium ion battery
The procedure was the same as in example 1.
Comparative example 7
Preparing titanium niobate (TiNb)2O7)
The procedure was the same as in example 1.
(II) H2Reducing titanium niobate
2.0g of titanium niobate is weighed, placed in a reactor and firstly added with H2Purging the reactor for 2h, then at 5 ℃ for min-1The temperature rising rate is increased to 600 ℃, the temperature is kept for 4 hours, and finally the titanium niobate containing a certain oxygen vacancy is obtained after the titanium niobate is naturally cooled to the room temperature. Is named as TiNb2O7-H2-600-4。
(III) preparing the titanium niobate composite electrode
The procedure was the same as in example 1.
(IV) assembling the lithium ion battery
The procedure was the same as in example 1.
Comparative example 8
Preparing titanium niobate (TiNb)2O7)
The procedure was the same as in example 1.
(II) H2Reducing titanium niobate
2.0g of titanium niobate is weighed, placed in a reactor and firstly added with H2Purging the reactor for 2h, then at 5 ℃ for min-1The temperature rising rate is increased to 800 ℃, the temperature is kept for 2 hours, and finally the titanium niobate containing a certain oxygen vacancy is obtained after the titanium niobate is naturally cooled to the room temperature. Is named as TiNb2O7-H2-800-2。
(III) preparing the titanium niobate composite electrode
The procedure was the same as in example 1.
(IV) assembling the lithium ion battery
The procedure was the same as in example 1.
Comparative example 9
Preparing titanium niobate (TiNb)2O7)
The procedure was the same as in example 1.
(II) H2Reducing titanium niobate
2.0g of titanium niobate is weighed, placed in a reactor and firstly added with H2Purging the reactor for 2h, then at 5 ℃ for min-1The temperature rising rate is increased to 800 ℃, the temperature is kept for 4 hours, and finally the titanium niobate containing a certain oxygen vacancy is obtained after the titanium niobate is naturally cooled to the room temperature. Is named as TiNb2O7-H2-800-4。
(III) preparing the titanium niobate composite electrode
The procedure was the same as in example 1.
(IV) assembling the lithium ion battery
The procedure was the same as in example 1.
Comparative example 10
Preparing titanium niobate (TiNb)2O7)
The procedure was the same as in example 1.
(II) H2Reducing titanium niobate
2.0g of titanium niobate is weighed, placed in a reactor and firstly added with H2Purging the reactor for 2h, then at 5 ℃ for min-1The temperature rising rate is increased to 900 ℃, the temperature is kept for 2 hours, and finally the titanium niobate containing a certain oxygen vacancy is obtained after the titanium niobate is naturally cooled to the room temperature. Is named as TiNb2O7-H2-900-2。
(III) preparing the titanium niobate composite electrode
The procedure was the same as in example 1.
(IV) assembling the lithium ion battery
The procedure was the same as in example 1.
Comparative example 11
Preparing titanium niobate (TiNb)2O7)
The procedure was the same as in example 1.
(II) H2Reducing titanium niobate
2.0g of titanium niobate is weighed, placed in a reactor and firstly added with H2Purging the reactor for 2h, then at 5 ℃ for min-1The temperature rising rate is increased to 900 ℃, the temperature is kept for 4 hours, and finally the titanium niobate containing a certain oxygen vacancy is obtained after the titanium niobate is naturally cooled to the room temperature. Is named as TiNb2O7-H2-900-4。
(III) preparing the titanium niobate composite electrode
The procedure was the same as in example 1.
(IV) assembling the lithium ion battery
The procedure was the same as in example 1.
Comparative example 12
Preparing titanium niobate (TiNb)2O7)
The preparation procedure was the same as in comparative example 3.
(II) H2Reducing titanium niobate
The preparation procedure was the same as in comparative example 6.
(III) preparing the titanium niobate composite electrode
The procedure was the same as in example 1.
(IV) assembling the lithium ion battery
The procedure was the same as in example 1.
Comparative example 13
Preparing titanium niobate (TiNb)2O7)
The preparation procedure was the same as in comparative example 3.
(II) H2Reducing titanium niobate
The procedure was the same as in comparative example 7.
(III) preparing the titanium niobate composite electrode
The procedure was the same as in example 1.
(IV) assembling the lithium ion battery
The procedure was the same as in example 1.
Comparative example 14
Preparing titanium niobate (TiNb)2O7)
The preparation procedure was the same as in comparative example 3.
(II) H2Reducing titanium niobate
The procedure was the same as in comparative example 8.
(III) preparing the titanium niobate composite electrode
The procedure was the same as in example 1.
(IV) assembling the lithium ion battery
The procedure was the same as in example 1.
Comparative example 15
Preparing titanium niobate (TiNb)2O7)
The preparation procedure was the same as in comparative example 3.
(II) H2Reducing titanium niobate
The procedure was the same as in comparative example 9.
(III) preparing the titanium niobate composite electrode
The procedure was the same as in example 1.
(IV) assembling the lithium ion battery
The procedure was the same as in example 1.
Comparative example 16
Preparing titanium niobate (TiNb)2O7)
The preparation procedure was the same as in comparative example 3.
(II) H2Reducing titanium niobate
The procedure was the same as in comparative example 10.
(III) preparing the titanium niobate composite electrode
The procedure was the same as in example 1.
(IV) assembling the lithium ion battery
The procedure was the same as in example 1.
Comparative example 17
Preparing titanium niobate (TiNb)2O7)
The preparation procedure was the same as in comparative example 3.
(II) H2Reducing titanium niobate
The procedure was the same as in comparative example 11.
(III) preparing the titanium niobate composite electrode
The procedure was the same as in example 1.
(IV) assembling the lithium ion battery
The procedure was the same as in example 1.
Comparative example 18
Preparing titanium niobate (TiNb)2O7)
The preparation procedure was the same as in comparative example 4.
(II) H2Reducing titanium niobate
The preparation procedure was the same as in comparative example 6.
(III) preparing the titanium niobate composite electrode
The procedure was the same as in example 1.
(IV) assembling the lithium ion battery
The procedure was the same as in example 1.
Comparative example 19
Preparing titanium niobate (TiNb)2O7)
The preparation procedure was the same as in comparative example 4.
(II) H2Reducing titanium niobate
The procedure was the same as in comparative example 7.
(III) preparing the titanium niobate composite electrode
The procedure was the same as in example 1.
(IV) assembling the lithium ion battery
The procedure was the same as in example 1.
Comparative example 20
Preparing titanium niobate (TiNb)2O7)
The preparation procedure was the same as in comparative example 4.
(II) H2Reducing titanium niobate
The procedure was the same as in comparative example 8.
(III) preparing the titanium niobate composite electrode
The procedure was the same as in example 1.
(IV) assembling the lithium ion battery
The procedure was the same as in example 1.
Comparative example 21
Preparing titanium niobate (TiNb)2O7)
The preparation procedure was the same as in comparative example 4.
(II) H2Reducing titanium niobate
The procedure was the same as in comparative example 9.
(III) preparing the titanium niobate composite electrode
The procedure was the same as in example 1.
(IV) assembling the lithium ion battery
The procedure was the same as in example 1.
Comparative example 22
Preparing titanium niobate (TiNb)2O7)
The preparation procedure was the same as in comparative example 4.
(II) H2Reducing titanium niobate
The procedure was the same as in comparative example 10.
(III) preparing the titanium niobate composite electrode
The procedure was the same as in example 1.
(IV) assembling the lithium ion battery
The procedure was the same as in example 1.
Comparative example 23
Preparing titanium niobate (TiNb)2O7)
The preparation procedure was the same as in comparative example 4.
(II) H2Reducing titanium niobate
The procedure was the same as in comparative example 11.
(III) preparing the titanium niobate composite electrode
The procedure was the same as in example 1.
(IV) assembling the lithium ion battery
The procedure was the same as in example 1.
A statistical table of the capacities of the electrodes of the examples when assembled into a lithium ion battery is shown in table 1.
TABLE 1
As shown in fig. 1, in example 1, compared with comparative example 2, the rate performance of the lithium ion battery is significantly improved, and the specific charging capacities of 1C, 2C, 5C, 10C and 20C can reach 257mAh g respectively-1，236mAh g-1，197.3mAh g-1，125.8mAh g-1，100.4mAh g-1This may be due to H2The synergistic effect of oxygen vacancy and the carbon layer is introduced by reduction, so that the conductivity of the titanium niobate negative electrode material is improved. And, H2The reduction conditions also had an effect on the rate capability of the titanium niobate, in comparative example 1, H2Under the reducing condition, the rate performance of the titanium niobate is improved, and in the H of the comparative example 102Under the reducing condition, the rate performance of the titanium niobate is reduced.
FIG. 2 is a scanning electron microscope image of the titanium niobate obtained in example 1, the size is about 1 μm, and the micron size is beneficial to keeping the structural stability of the titanium niobate in the charging and discharging processes.
Fig. 3 is a scanning electron microscope image of the titanium niobate/carbon composite material of example 1, and as shown in the figure, the titanium niobate/carbon composite material is a secondary particle formed by agglomeration of primary particles, the size of the primary particles is distributed in tens to hundreds of nanometers, the primary particles at the nanometer level can shorten the diffusion distance of lithium ions, which is beneficial to the diffusion of lithium ions, and the primary particles are microspheres with the size of about 10 μm, which is beneficial to the structural stability of the material in the charging and discharging process.
FIG. 4 is a graph showing the first charge and discharge curves at 0.1C and the first cycle specific charge capacities of 298.6, 263.2, 276.3 and 242.6mAh g in this order for the lithium ion batteries of example 1, comparative example 2 and comparative example 10-1The first turn coulombic efficiencies were 95.84, 95.18, 90.67, and 89.26%, respectively, and the first turn charge capacity and efficiency were significantly highest for example 1.
Fig. 5 is a first-turn charge-discharge curve of the lithium ion batteries described in comparative example 2, comparative example 3, and comparative example 4 at a current density of 0.1C, and comparative example 2 shows higher specific charge capacity and coulombic efficiency, which illustrates that the calcination time has a certain influence on the realization of high-performance titanium niobate. The calcination time is too short, and the phase formation time of the titanium niobate is not enough; the crystal configuration of the titanium niobate may be damaged due to the excessively long calcination time.
As shown in fig. 6, which is a graph comparing the cycle performance of the lithium ion batteries of example 1, comparative example 2 and comparative example 10 at a current density of 1C, it can be seen that example 1 shows more excellent cycle stability, the specific capacity thereof is stable in the first 50 cycles, and is higher than those of comparative example 1, comparative example 2 and comparative example 10. The excellent electrochemical performance of the lithium ion battery described in example 1, probably due to H2The oxygen vacancy is introduced by reduction and the synergistic effect of the conductive carbon layer is realized, so that the conductivity of the titanium niobate negative electrode material is improved.
In conclusion, the lithium ion battery has higher charge-discharge specific capacity and high first coulombic efficiency, and has high first efficiency and good cycle performance in a normal battery working environment; the preparation method of the high-rate-performance titanium niobate composite negative electrode material is simple, the raw materials are wide in source, cheap and easy to obtain, the production period is short, and the product is convenient and safe to store and transport and has high practicability. Therefore, the lithium ion battery has good application prospect in the large-scale energy storage fields of renewable energy consumption, peak clipping and valley filling, distributed energy storage power stations and the like.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, many modifications and changes can be made without departing from the inventive concept of the present invention, and these modifications and changes are within the protection scope of the present invention.
Claims (10)
1. A preparation method of a high-conductivity titanium niobate negative electrode material is characterized by comprising the following steps:
(1) adding water into a titanium source and a niobium source, ball-milling to obtain a mixed solution, and then spray-drying to obtain precursor powder;
(2) calcining the precursor powder to obtain titanium niobate;
(3) adding water into titanium niobate and a carbon source, ball-milling to obtain a mixed solution, and then spray-drying to obtain precursor mixed powder of the titanium niobate/carbon;
(4) mixing the precursor powder at high temperature H2And reducing in the atmosphere to obtain the high-conductivity titanium niobate negative electrode material.
2. The method for preparing the high-conductivity titanium niobate anode material according to claim 1, wherein the titanium source is Ti (OC)4H9)4、TiO2One of (1); the niobium source is NbCl5、Nb2O5One of (1); the molar ratio of the titanium source to the niobium source is 1: 0.5 to 2.
3. The method for preparing the high-conductivity titanium niobate anode material according to claim 1, wherein the carbon source is one of sucrose and alpha-lactose.
4. The preparation method of the high-conductivity titanium niobate anode material according to claim 1, wherein in the step (1), the spray drying process conditions are as follows: the speed of the feeding peristaltic pump is 1-10%, and the feeding temperature is 100-200%oAnd C, the wind speed is 50-100%.
5. The method for preparing the high-conductivity titanium niobate anode material according to claim 1, wherein in the step (2), the calcining temperature is 700 to 1100%oAnd C, calcining for 2-48 h.
6. The preparation method of the high-conductivity titanium niobate anode material according to claim 1, wherein in the step (3), the mass ratio of the titanium niobate to the carbon source is (90-98): (1-5); the process conditions of the spray drying are as follows: the speed of the feeding peristaltic pump is 1-10%, and the feeding temperature is 100-200%oAnd C, the wind speed is 50-100%.
7. The preparation method of the high-conductivity titanium niobate anode material according to claim 1, wherein the temperature of the high temperature in the step (4) is 600-900%oC, the time of high-temperature treatment is 1-6 h; introduction of H2The rate of (c) is (60-100) mL/min.
8. A composite electrode, characterized in that the electrode comprises the high-conductivity titanium niobate composite material prepared by the preparation method of any one of claims 1 to 7, a conductive agent and a binder; the mass ratio of the high-conductivity titanium niobate composite material to the conductive agent to the binder is (0.5-0.9): (0.3-0.05): (0.2-0.05).
9. The composite electrode according to claim 8, wherein the conductive agent is one of acetylene black, carbon nanotubes, and SuperP.
10. The use of the composite electrode of any one of claims 8 to 9 in a lithium ion battery, wherein the composite electrode is used as a negative electrode of the lithium ion battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110472322.6A CN113233504A (en) | 2021-04-29 | 2021-04-29 | Preparation method and application of high-conductivity titanium niobate negative electrode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110472322.6A CN113233504A (en) | 2021-04-29 | 2021-04-29 | Preparation method and application of high-conductivity titanium niobate negative electrode material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113233504A true CN113233504A (en) | 2021-08-10 |
Family
ID=77131523
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110472322.6A Pending CN113233504A (en) | 2021-04-29 | 2021-04-29 | Preparation method and application of high-conductivity titanium niobate negative electrode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113233504A (en) |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102479950A (en) * | 2010-11-23 | 2012-05-30 | 中国科学院物理研究所 | Titanium niobate composite material, preparation method thereof, and cathode and battery containing the same |
| CN104466150A (en) * | 2013-09-20 | 2015-03-25 | 株式会社东芝 | Active substance, nonaqueous electrolyte battery, and battery pack |
| CN105449185A (en) * | 2014-09-18 | 2016-03-30 | 株式会社东芝 | Active material for batteries, nonaqueous electrolyte battery, and battery pack |
| JP2016066600A (en) * | 2014-09-18 | 2016-04-28 | 株式会社東芝 | Active material for battery, nonaqueous electrolyte battery and battery pack |
| JP6030708B1 (en) * | 2015-05-26 | 2016-11-24 | 太平洋セメント株式会社 | Method for producing titanium niobium oxide negative electrode active material |
| JP6126192B1 (en) * | 2015-12-10 | 2017-05-10 | 太平洋セメント株式会社 | Oxide-based negative electrode active material for secondary battery and method for producing the same |
| CN106784773A (en) * | 2016-11-14 | 2017-05-31 | 华中科技大学 | A kind of preparation method of electrode material |
| JP2017182888A (en) * | 2016-03-28 | 2017-10-05 | 太平洋セメント株式会社 | Active material-containing particle mixture for nonaqueous electrolyte secondary battery, and method for manufacturing the same |
| JP2018160432A (en) * | 2017-03-24 | 2018-10-11 | 太平洋セメント株式会社 | Negative electrode active material composite for lithium ion secondary battery and method of manufacturing the same |
| CN109859957A (en) * | 2017-11-30 | 2019-06-07 | 中国科学院大连化学物理研究所 | A kind of carbon and titanium niobium oxide composite negative pole material and its preparation and application |
| CN112551583A (en) * | 2020-12-10 | 2021-03-26 | 哈尔滨工业大学 | Preparation method and application of carbon-coated oxygen-less titanium niobate negative electrode material |
-
2021
- 2021-04-29 CN CN202110472322.6A patent/CN113233504A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102479950A (en) * | 2010-11-23 | 2012-05-30 | 中国科学院物理研究所 | Titanium niobate composite material, preparation method thereof, and cathode and battery containing the same |
| CN104466150A (en) * | 2013-09-20 | 2015-03-25 | 株式会社东芝 | Active substance, nonaqueous electrolyte battery, and battery pack |
| CN105449185A (en) * | 2014-09-18 | 2016-03-30 | 株式会社东芝 | Active material for batteries, nonaqueous electrolyte battery, and battery pack |
| JP2016066600A (en) * | 2014-09-18 | 2016-04-28 | 株式会社東芝 | Active material for battery, nonaqueous electrolyte battery and battery pack |
| JP6030708B1 (en) * | 2015-05-26 | 2016-11-24 | 太平洋セメント株式会社 | Method for producing titanium niobium oxide negative electrode active material |
| JP6126192B1 (en) * | 2015-12-10 | 2017-05-10 | 太平洋セメント株式会社 | Oxide-based negative electrode active material for secondary battery and method for producing the same |
| JP2017182888A (en) * | 2016-03-28 | 2017-10-05 | 太平洋セメント株式会社 | Active material-containing particle mixture for nonaqueous electrolyte secondary battery, and method for manufacturing the same |
| CN106784773A (en) * | 2016-11-14 | 2017-05-31 | 华中科技大学 | A kind of preparation method of electrode material |
| JP2018160432A (en) * | 2017-03-24 | 2018-10-11 | 太平洋セメント株式会社 | Negative electrode active material composite for lithium ion secondary battery and method of manufacturing the same |
| CN109859957A (en) * | 2017-11-30 | 2019-06-07 | 中国科学院大连化学物理研究所 | A kind of carbon and titanium niobium oxide composite negative pole material and its preparation and application |
| CN112551583A (en) * | 2020-12-10 | 2021-03-26 | 哈尔滨工业大学 | Preparation method and application of carbon-coated oxygen-less titanium niobate negative electrode material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111244448B (en) | In-situ carbon-coated high-rate large-size Prussian blue type sodium ion positive electrode material and preparation method thereof | |
| CN108598390A (en) | A kind of preparation method and lithium-sulfur cell of positive material for lithium-sulfur battery | |
| CN108598444B (en) | Vanadium trioxide/graphene composite negative electrode material of lithium ion battery and preparation method | |
| CN111952547A (en) | Surface-coated modified lithium ion battery positive electrode material and preparation method thereof | |
| CN105655582A (en) | Method for coating and modifying lithium vanadium phosphate positive pole material with novel carbon source | |
| CN115224254B (en) | Cu, zn and Mg co-doped layered oxide sodium ion battery positive electrode material, and preparation method and application thereof | |
| CN101800304A (en) | Different-orientation spherical natural graphite negative electrode material and preparation method thereof | |
| CN104577123A (en) | Preparation method of cathode material for lithium ion cell | |
| GB2620047A (en) | Lithium ion battery pre-lithiation agent, preparation method therefore, and application | |
| CN112110448A (en) | Nitrogen-doped carbon and nano-silicon composite anode material and preparation method thereof | |
| CN108400296B (en) | Heterogeneous element doped ferroferric oxide/graphene negative electrode material | |
| CN110790248B (en) | Iron-doped cobalt phosphide microsphere electrode material with flower-shaped structure and preparation method and application thereof | |
| CN111777065A (en) | Graphite modified material for lithium ion battery and preparation method thereof | |
| CN113690420B (en) | Nitrogen-sulfur doped silicon-carbon composite material and preparation method and application thereof | |
| CN114620702A (en) | Preparation method of positive electrode material, positive plate and sodium ion battery | |
| CN113066988B (en) | Negative pole piece and preparation method and application thereof | |
| CN112018355B (en) | Preparation method of three-dimensional rod-shaped potassium titanate material | |
| CN116936771A (en) | Hollow spherical shell structure ferric sodium sulfate composite positive electrode material, preparation method and sodium ion battery | |
| CN115050944B (en) | Composite material with three-dimensional nano flower structure and preparation method and application thereof | |
| CN116344763A (en) | Metal/carbon coated lithium oxide composite positive electrode material, preparation method thereof, positive electrode plate containing positive electrode material and battery | |
| CN110190277A (en) | A kind of anode material for lithium-ion batteries LiMnO2@C and preparation method thereof | |
| CN115763719A (en) | Titanium lanthanum lithium phosphate coated magnesium-doped lithium cobaltate cathode material and preparation method thereof | |
| CN115101738A (en) | Carbon-coated iron-vanadium bimetallic sodium pyrophosphate phosphate composite material and preparation method and application thereof | |
| CN114538523A (en) | Iron vanadate material and preparation method and application thereof | |
| CN111261866B (en) | Preparation method of ZnO/C nano composite microsphere material with capsule structure |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210810 |
|
| RJ01 | Rejection of invention patent application after publication |