CN115744986A - Preparation of titanium niobium oxide lithium ion battery cathode material based on high oxidation state ion doping - Google Patents
Preparation of titanium niobium oxide lithium ion battery cathode material based on high oxidation state ion doping Download PDFInfo
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- 150000002500 ions Chemical class 0.000 title claims abstract description 18
- 230000003647 oxidation Effects 0.000 title claims abstract description 18
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 18
- 239000010406 cathode material Substances 0.000 title claims abstract description 12
- MHODFDJXZDYLNT-UHFFFAOYSA-N lithium niobium(5+) oxygen(2-) titanium(4+) Chemical compound [O-2].[Nb+5].[Ti+4].[Li+].[O-2].[O-2].[O-2].[O-2] MHODFDJXZDYLNT-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 22
- -1 cerium ions Chemical class 0.000 claims abstract description 7
- 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 abstract description 4
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 238000001354 calcination Methods 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 7
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000010405 anode material Substances 0.000 claims 2
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- 230000035484 reaction time Effects 0.000 claims 1
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 16
- OBOYOXRQUWVUFU-UHFFFAOYSA-N [O-2].[Ti+4].[Nb+5] Chemical compound [O-2].[Ti+4].[Nb+5] OBOYOXRQUWVUFU-UHFFFAOYSA-N 0.000 abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 abstract description 9
- 239000001301 oxygen Substances 0.000 abstract description 9
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- 239000002994 raw material Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 24
- 239000004005 microsphere Substances 0.000 description 11
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- 239000010936 titanium Substances 0.000 description 9
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
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- 229910000484 niobium oxide Inorganic materials 0.000 description 2
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
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- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
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- 229910052758 niobium Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
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- 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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Abstract
The invention relates to preparation of a high oxidation state ion doped titanium niobium oxide lithium ion battery cathode material in a lithium ion battery energy storage system. The invention provides a titanium niobium oxide negative electrode material which is introduced with high oxidation state ions, and the titanium niobium oxide negative electrode material is adjusted by expanding the volume of unit crystals, generating oxygen vacancies and accelerating charge transfer, so that the inherent poor ionic and electronic conductivity of the conventional titanium niobium oxide negative electrode material is improved. According to the invention, tetrabutyl titanate and niobium pentachloride are used as raw materials, and the titanium niobium oxide doped with cerium ions in a high oxidation state is prepared by a hydrothermal method, and the titanium niobium oxide doped with cerium ions in a high oxidation state has the advantages of high ionic and electronic conductivity, excellent rate capability, cycle stability and the like.
Description
Technical Field
The invention belongs to the technical field of lithium ion quick-charging batteries, and particularly relates to a preparation method of a titanium niobium oxide lithium ion battery cathode material based on high oxidation state ion doping.
Background
Lithium ion batteries are becoming one of the most important chemical power sources due to their excellent performance, and their market share is now surpassing the rest of secondary batteries. One of the main advantages of the lithium ion battery is that the lithium ion battery has ideal energy density, which makes the lithium ion battery hopeful to become an energy storage tool for various new energy sources, power grids and the like, and in future development, the lithium ion battery is also hopeful to be used as a power battery, so the future energy field development will not leave the contribution of the lithium ion battery. While the lithium ion battery is composed of a plurality of parts, in which a negative electrode material is one of the components directly related to battery performance, a carbon material is used as a negative electrode material widely used in the current commercial lithium ion battery, and is relatively inexpensive and has a high energy density. However, with the gradual development of electric equipment, the rapid charging capability of energy storage equipment draws people's attention, people urgently need the next generation of extremely rapid charging lithium ion batteries, carbon materials cannot meet the rapid charging and discharging requirements needed by people, and meanwhile, the problem of low safety coefficient of the carbon materials is not well solved at present. At present, negative electrode materials widely concerned by researchers in various countries mainly include carbon materials, silicon materials, lithium titanate, titanium niobate and the like.
The titanium niobium oxide has a unique crystal structure, and is beneficial to the insertion and extraction of Li +. And the TiNb is found by in situ characterization 2 O 7 The crystal structure is stable in the charging and discharging process, and the cycle process is highly reversible. In the process of lithium deintercalation, ti-based intercalation and deintercalation can occur 4+ And Ti 3+ Single electron reaction of Nb 5+ And Nb 3+ The theoretical specific capacity of the 5 electron transfer of the two-electron reaction corresponds to the oxidation-reduction reaction of 5 electron pairs, and reaches 387.6 mAh g -1 . Meanwhile, the high-voltage power supply also has a high voltage platform (-1.6V vs. Li) + /Li) can effectively avoid the formation of an SEI film. Thus, tiNb 2 O 7 The material becomes a research hotspot of the fast-charging type lithium ion battery cathode material. However, titanium niobium oxide materials provide poor electrochemical performance due to their low ionic and electronic conductivity.
Disclosure of Invention
The invention aims to solve the problem that the existing titanium niobium oxide material has poor electrochemical performance due to low ionic conductivity and electronic conductivity, and provides a thought of a titanium niobium oxide lithium ion battery cathode material based on high oxidation state ion doping.
In order to solve the defects of the titanium niobium oxide, high-oxidation-state cerium ions are introduced and doped by ions with larger radius, so that the volume of a doped unit cell is increased, and the diffusion of lithium ions in the titanium niobium oxide crystal is facilitated, so that the rate capability of the material can be improved. In addition, oxygen vacancies generated by cerium ion doping make the material have a lower lithium ion diffusion barrier. The wider the diffusion path of lithium ions in the crystal, the more favorable the electrochemical reaction. The fermi level caused by the doping of cerium ions enters the conduction band resulting in a significant reduction in the band gap, thereby greatly improving the conductivity. At the same time, high conductivity may lead to faster kinetics of the electrochemical reaction. Thus, the bandgap shortening caused by doping promotes the formation of free electrons and holes, resulting in higher conductivity. The doping engineering also enhances the structural stability of the titanium niobium oxide. Therefore, the invention designs the titanium niobium oxide doped with high oxidation state ions by utilizing a hydrothermal method from the crystal structure engineering. Corresponding physical and electrochemical characterization means prove that the cathode material has higher ionic and electronic conductivity, high specific capacity, excellent rate performance and long cycle life.
Drawings
FIG. 1 and FIG. 1 show Ce doped TiNb prepared by the present invention 2 O 7 SEM of microspheres under a scanning electron microscope, scale bar, 1 μm;
FIG. 2 shows the 1% Ce doped TiNb prepared by the present invention 2 O 7 EDS picture of microspheres under scanning electron microscope;
FIG. 3 shows the 1% Ce doped TiNb prepared by the present invention 2 O 7 TEM images under a transmission electron microscope;
FIG. 4 is a graph of TiNb with different Ce doping ratios 2 O 7 XRD pattern of the material;
FIG. 5 shows TiNb with different Ce doping ratios 2 O 7 A locally magnified XRD image of the material; (ii) a
FIG. 6 shows 1% Ce doped TiNb prepared in example 1 of the present invention 2 O 7 The high resolution XPS spectrum of Ti 2 p;
FIG. 7 shows the present inventionExample 1 prepared 1% Ce doped TiNb 2 O 7 The high resolution XPS spectrum of Nb 3d of (1);
FIG. 8 is a graph of 1% Ce doped TiNb prepared in example 1 of the present invention 2 O 7 The high resolution XPS spectrum of Ce 3d of (1);
FIG. 9 shows 1% Ce doped TiNb prepared in example 1 of the present invention 2 O 7 High resolution XPS spectra of O1 s of (a);
FIG. 10 shows TiNb prepared in example 1 of the present invention 2 O 7 TiNb doped with Ce 2 O 7 (ii) a raman spectral image of;
FIG. 11 is a 1% Ce doped TiNb prepared in example 1 of the present invention 2 O 7 Cyclic voltammetry curve images;
FIG. 12 is a graph of pure TiNb prepared in example 1 of the present invention 2 O 7 Carrying out GCD curve images on the material at different scanning speeds;
FIG. 13 is a 0.5% Ce doped TiNb prepared in example 1 of the present invention 2 O 7 Carrying out GCD curve images on the material at different scanning speeds;
FIG. 14 shows 1% Ce doped TiNb prepared in example 1 of the present invention 2 O 7 Carrying out GCD curve images on the material at different scanning speeds;
FIG. 15 shows 1.5% Ce doped TiNb prepared in example 1 of the present invention 2 O 7 Carrying out GCD curve images on the material at different scanning speeds;
FIG. 16 is a graph of pure TiNb prepared in example 1 of the present invention 2 O 7 And 1% Ce doped TiNb 2 O 7 Alternating impedance image contrast of (1);
FIG. 17 shows pure TiNb prepared in example 1 of the present invention 2 O 7 And 1% Ce doped TiNb 2 O 7 A cyclic stability curve image for 1000 cycles at a current density of 20C;
FIG. 18 shows pure TiNb prepared in example 1 of the present invention 2 O 7 And 1% Ce doped TiNb 2 O 7 Magnification performance curve images at different scan speeds.
Detailed Description
The first specific implementation way is as follows: the preparation method of the high oxidation state ion doped titanium niobium oxide lithium ion battery cathode material is based on the preparation of the high oxidation state ion doped titanium niobium oxide lithium ion battery cathode material.
The second embodiment is as follows: the preparation method of the high oxidation state ion doping-based titanium niobium oxide lithium ion battery cathode material comprises the following steps:
1. TiNb 2 O 7 Synthesis of a precursor: first, 1.02 g tetrabutyl titanate, 1.62 g niobium pentachloride, and cerium chloride were dissolved in an ethanol solution, and stirred for 30 min to obtain a uniform mixed solution. The resulting solution was then transferred to a 100 mL teflon-lined stainless steel autoclave and held at 180 ℃ for 24 h. After the autoclave was cooled to room temperature, the precipitate was collected by centrifugation, washed several times with ethanol, deionized water, and dried at 60 ℃ for 24 h;
in the first step, the cerium chloride corresponds to 0.0056 g, 0.0112 g and 0.0168 g according to different doping amounts (0.5%, 1% and 1.5%);
the volume of the ethanol in the first step is 50 mL;
2. TiNb 2 O 7 And (3) synthesis of microspheres: putting the obtained precursor sample into a tube furnace, calcining the precursor sample in the air atmosphere for 5 days, and cooling the precursor sample to room temperature to form TiNb 2 O 7 And (3) microspheres.
In the second step, the calcining temperature of the tubular furnace is 800 ℃;
in the second step, the calcining time of the tube furnace is 5 h;
in the second step, the heating rate of the tubular furnace is 5 ℃/min;
3. weighing 1 g, the titanium-doped niobium oxide material of example 1, 0.0125 g acetylene black and 0.0125 g polyvinylidene fluoride (dissolved in N-methyl pyrrolidone), mixing, grinding into slurry, uniformly coating on copper foil, drying in a vacuum drying oven at 80 ℃ to obtain a pole piece, and assembling the pole piece into a button cell in a glove box by using metal lithium as a counter electrode. And carrying out charge-discharge and cycle test on the blue test system.
The following experiments and characterization were performed to verify the effects of the present invention
The first test is that the preparation method of the high oxidation state ion doping-based titanium niobium oxide lithium ion battery cathode material is carried out according to the following steps:
1. TiNb 2 O 7 Synthesis of a precursor: first, 1.02 g tetrabutyl titanate, 1.62 g niobium pentachloride, and cerium chloride (0%, 0.5%, 1%, 1.5%) were dissolved in an ethanol solution, and stirred for 30 min to obtain a uniform mixed solution. The resulting solution was then transferred to a 100 mL teflon-lined stainless steel autoclave and held at 180 ℃ for 24 h. After the autoclave was cooled to room temperature, the precipitate was collected by centrifugation, washed several times with ethanol, deionized water, and dried at 60 ℃ for 24 h;
in the first step, the cerium chloride corresponds to 0 g, 0.0056 g, 0.0112 g and 0.0168 g according to different doping amounts (0%, 0.5%, 1% and 1.5%);
the volume of the ethanol in the first step is 50 mL;
2. TiNb 2 O 7 And (3) synthesis of microspheres: the obtained precursor sample is put into a tube furnace to be calcined in the air atmosphere and cooled to the room temperature to form pure TiNb 2 O 7 Microspheres and Ce-doped TiNb 2 O 7 And (3) microspheres.
In the second step, the calcining temperature of the tube furnace is 800 ℃;
in the second step, the calcining time of the tube furnace is 5 h;
in the second step, the heating rate of the tubular furnace is 5 ℃/min;
3. weighing 1 g, the titanium-doped niobium oxide material of example 1, 0.0125 g acetylene black and 0.0125 g polyvinylidene fluoride (dissolved in N-methyl pyrrolidone), mixing, grinding into slurry, uniformly coating on copper foil, drying in a vacuum drying oven at 80 ℃ to obtain a pole piece, and assembling the pole piece into a button cell in a glove box by using metal lithium as a counter electrode. And carrying out charge-discharge and cycle test on the blue test system.
Characterization test
The morphology of the synthesized materials with different components is characterized by using a Scanning Electron Microscope (SEM):
FIG. 1 shows Ce doped TiNb prepared by the present invention 2 O 7 SEM image of microspheres under scanning electron microscope; FIG. 2 shows Ce doped TiNb prepared by the present invention 2 O 7 EDS picture of microspheres under scanning electron microscope; from FIG. 1, it can be observed that Ce is doped TiNb 2 O 7 The surface of the microsphere material is relatively rough and consists of a plurality of small particles. From FIG. 2, it can be observed that Ce is doped TiNb 2 O 7 The surface element composition of the microsphere material proves that the Ce element is successfully doped into the TiNb 2 O 7 In the material.
(II) doping TiNb to Ce by using Transmission Electron Microscope (TEM) 2 O 7 The material is subjected to morphology characterization:
FIG. 3 is a Ce-doped TiNb 2 O 7 TEM images under transmission electron microscopy. From FIG. 3, it can be observed that Ce is doped TiNb 2 O 7 The spherical form of (2).
And (III) the synthesized materials with different components are characterized by X-ray diffraction (XRD):
TiNb with different Ce doping ratios can be observed as shown in FIG. 4 2 O 7 The corresponding characteristic peak is in good agreement with the PDF #70-2009 standard card lattice interface, and the reduction of the peak intensity is related to the introduced oxygen defect due to the lattice structure damage caused by the oxygen defect in the sample. Proves that the Ce is doped with the TiNb 2 O 7 The successful synthesis of the compound. As shown in fig. 5, it can be observed that as the Ce doping amount increases from 0 to 1.5%, the positions of the diffraction peaks gradually move toward a small angle direction, indicating that the in-plane distance increases as the doping concentration increases.
And (IV) the synthesized materials with different components are characterized by X-ray electron spectroscopy (XPS):
the XPS measurement spectra shown in fig. 6 to 9 confirmed the coexistence of the elements titanium, niobium, cerium, and oxygen. It is confirmed in FIGS. 6 to 8 that TiNb is doped in Ce 2 O 7 In the presence of Ti 3+ /Ti 4+ 、Nb 4+ /Nb 5+ And Ce 3+ /Ce 4+ Peak of (2) demonstrates TiNb 2 O 7 Successful synthesis of Ce element and successful doping of Ce element. The increase in the peak area of oxygen defects as shown in fig. 9 is attributed to the increase in oxygen defects caused by doping.
(V) characterizing different materials by using a Raman test:
in the Raman spectrum, at 269, 540 and 642, 894 and 1000 cm, as shown in FIG. 10 -1 The nearby peaks are respectively assigned to Nb (Ti) -O bond, nb (Ti) -O-Nb (Ti), tiO 6 Octahedron and NbO 6 Octahedron. Compared with the original material, the peak intensity of the Raman spectrum after Ce doping is obviously reduced, namely the grain size is increased.
And (VI) performing half-cell electrochemical test characterization by using cyclic voltammetry:
the distinct redox peaks demonstrate the abundance of reversible faradaic reactions and rate capability as the scan rate increases as shown in figure 11.
Seventhly, performing half-cell discharge capacity performance characterization by using a constant current charge-discharge method:
for TiNb as shown in FIGS. 12 to 15 2 O 7 And TiNb with different Ce doping amount 2 O 7 The material was tested for specific capacitance at different sweep rates, ce doped TiNb due to faster charge/ion transfer 2 O 7 Specific capacitance of (2) exceeds that of the original TiNb 2 O 7 . And the doped amount of 1 percent Ce of TiNb can be known by comparison 2 O 7 With the maximum discharge capacity.
(eighthly) characterizing the reaction kinetics under a three-electrode system by using an Electrochemical Impedance Spectroscopy (EIS) test:
the charge transfer resistance (Rct) was obtained by evaluating the diameter of a semicircular scaffold representing the kinetics of the redox reaction as shown in fig. 16. And TiNb 2 O 7 Compared with the TiNb with the doping amount of 1 percent Ce 2 O 7 Is smaller, indicating a faster charge transfer process due to oxygen defects.
(nine) testing the cycling stability and the rate capability by using a constant current charging and discharging method:
TiNb with 1% Ce doping amount as shown in FIG. 17 2 O 7 The best stability was demonstrated, maintaining 84.7% of the initial capacitance after 1000 cycles at a current density of 20C. The reason is that the expansion of the lithium ion transport channel in the crystal structure after Ce doping can alleviate the volume contraction/expansion effect during cycling. In addition, oxygen defects may better excite ion/electron transport. FIG. 18 shows TiNb 2 O 7 And TiNb with different Ce doping amounts 2 O 7 The multiplying power test of the material under different current densities shows that the TiNb with the doping amount of 1 percent Ce 2 O 7 Providing the best rate performance of these four samples. When the current density returns to 0.2C, 312.9 mAh g can still be maintained -1 This value is close to the initial capacity, indicating good reversibility.
Claims (3)
1. The preparation method of the high oxidation state ion doped titanium niobium oxide lithium ion battery cathode material comprises the following steps:
(1) Firstly, dissolving tetrabutyl titanate, niobium pentachloride and cerium chloride in an ethanol solution and stirring; then, the resulting solution was transferred to a teflon-lined stainless steel autoclave and held at a certain temperature for 24 hours; cooling the autoclave to room temperature, washing with ethanol and deionized water, centrifuging, collecting precipitate, and drying;
(2) And putting the obtained precursor sample into a tube furnace, calcining for 5 hours at a certain temperature in the air, and cooling to room temperature.
2. The preparation method of the high oxidation state ion doped titanium niobium oxide lithium ion battery anode material according to claim 1, is characterized in that: in the step (1), the cerium ions in a high oxidation state are added, the doping amount of the cerium ions is 0.5-1.5%, the volume of the absolute ethyl alcohol is 50-70 mL, the reaction temperature is 180 ℃, and the reaction time is 24 hours.
3. The preparation method of the high oxidation state ion doped titanium niobium oxide lithium ion battery anode material according to claim 1, is characterized in that: the temperature of the tubular furnace in the step (2) is 800 ℃, the calcining time is 5 hours, and high oxidation state ions are added.
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Citations (4)
| 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 negative electrode and battery containing composite material |
| CN112357960A (en) * | 2020-11-09 | 2021-02-12 | 哈尔滨工业大学 | Preparation method and application of rare earth element neodymium-doped titanium niobate material |
| CN114388772A (en) * | 2021-12-09 | 2022-04-22 | 格力钛新能源股份有限公司 | Molybdenum vanadium titanium niobium composite oxide negative electrode material, preparation method thereof and lithium ion battery |
| US20220315442A1 (en) * | 2019-12-26 | 2022-10-06 | Kubota Corporation | Titanium-niobium oxides, and electrodes and lithium-ion secondary cells including titanium-niobium oxides |
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| 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 negative electrode and battery containing composite material |
| US20220315442A1 (en) * | 2019-12-26 | 2022-10-06 | Kubota Corporation | Titanium-niobium oxides, and electrodes and lithium-ion secondary cells including titanium-niobium oxides |
| CN112357960A (en) * | 2020-11-09 | 2021-02-12 | 哈尔滨工业大学 | Preparation method and application of rare earth element neodymium-doped titanium niobate material |
| CN114388772A (en) * | 2021-12-09 | 2022-04-22 | 格力钛新能源股份有限公司 | Molybdenum vanadium titanium niobium composite oxide negative electrode material, preparation method thereof and lithium ion battery |
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