CN114655984B - Lithium ion battery indium niobium oxide negative electrode material and preparation method thereof - Google Patents
Lithium ion battery indium niobium oxide negative electrode material and preparation method thereof Download PDFInfo
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- CN114655984B CN114655984B CN202210408840.6A CN202210408840A CN114655984B CN 114655984 B CN114655984 B CN 114655984B CN 202210408840 A CN202210408840 A CN 202210408840A CN 114655984 B CN114655984 B CN 114655984B
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- NJDGWMLMQLGHPA-UHFFFAOYSA-N [O--].[O--].[O--].[O--].[Nb+5].[In+3] Chemical compound [O--].[O--].[O--].[O--].[Nb+5].[In+3] NJDGWMLMQLGHPA-UHFFFAOYSA-N 0.000 title claims abstract description 22
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000007773 negative electrode material Substances 0.000 title description 20
- 239000010955 niobium Substances 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000010405 anode material Substances 0.000 claims abstract description 17
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 16
- 239000000654 additive Substances 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 229910052738 indium Inorganic materials 0.000 claims abstract description 11
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000004729 solvothermal method Methods 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000002243 precursor Substances 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims abstract 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 230000000996 additive effect Effects 0.000 claims description 10
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 claims description 9
- 229920000570 polyether Polymers 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 102000020897 Formins Human genes 0.000 claims description 5
- 108091022623 Formins Proteins 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- PDQICKRFOKDJCH-INIZCTEOSA-N (2s)-6-amino-2-(dodecanoylamino)hexanoic acid Chemical compound CCCCCCCCCCCC(=O)N[C@H](C(O)=O)CCCCN PDQICKRFOKDJCH-INIZCTEOSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 claims description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000003570 air Substances 0.000 claims description 2
- 150000001413 amino acids Chemical class 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 230000002950 deficient Effects 0.000 claims description 2
- VBXWCGWXDOBUQZ-UHFFFAOYSA-K diacetyloxyindiganyl acetate Chemical compound [In+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VBXWCGWXDOBUQZ-UHFFFAOYSA-K 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- LDPWMGUFXYRDRG-UHFFFAOYSA-I niobium(5+) pentaacetate Chemical compound [Nb+5].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O LDPWMGUFXYRDRG-UHFFFAOYSA-I 0.000 claims description 2
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 claims description 2
- WPCMRGJTLPITMF-UHFFFAOYSA-I niobium(5+);pentahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[Nb+5] WPCMRGJTLPITMF-UHFFFAOYSA-I 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 24
- 239000002244 precipitate Substances 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 6
- 230000001276 controlling effect Effects 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 229910001449 indium ion Inorganic materials 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G33/00—Compounds of niobium
-
- 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
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
Abstract
The invention belongs to the technical field of batteries, and discloses an indium niobium oxide anode material of a lithium ion battery and a preparation method thereof. The invention adopts a niobium source and an indium source as raw materials, and adds additives, and the raw materials are respectively dissolved in a proper solvent; mixing and stirring uniformly, placing the mixture in a high-temperature reaction kettle for solvothermal reaction, and washing and drying the precipitate for multiple times to obtain a precursor; transferring the obtained precursor material into a tube furnace, calcining under different atmospheres, and cooling along with the furnace to obtain the blocky indium-niobium oxide anode material, wherein the obtained material has excellent multiplying power performance and cycle stability.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery anode materials, and particularly relates to an indium niobium oxide anode material and a preparation method thereof.
Background
At present, most of commercial lithium ion battery cathode materials use graphite, however, the multiplying power performance of the graphite is not ideal, the lithium intercalation potential is low, lithium dendrites are easy to form in the rapid charge and discharge process, serious potential safety hazards are provided, and the increasingly developed energy storage field is difficult to meetIts requirements; li having spinel structure 4 Ti 5 O 12 The working voltage of the lithium ion battery is about 1.5V, no SEI film and lithium dendrite are generated in the charge and discharge process, so the cycle performance of the rate performance is very good, but the specific capacity (175 mAh g -1 ) Limiting its development.
Niobium-based oxides due to their relatively high theoretical specific capacities (-400 mAh g) -1 ) And the higher lithium intercalation potential (1-2V) becomes a candidate material with competitiveness of the lithium ion battery cathode material. The huge niobium group provides a great deal of reference for the research of the energy storage performance of the niobium group, and the development of a new niobium group system has important significance for the further research of the niobium group system. The ionic radii of indium and niobium are not greatly different, so that the material structure is not greatly influenced after indium ions are introduced, and on the contrary, the material structure layer is migrated to form a stable shear phase structure due to the introduction of metal indium ions, which is very beneficial to Li + The rapid de-intercalation of the niobium is realized, and the utilization rate of the niobium is greatly improved. Meanwhile, the self-doping and calcining conditions can further regulate and control the structure and the electronic properties of the material. The solvothermal method is a special form of a hydrothermal method, and has the advantages of high purity of the synthesized nano material, good grain development, low agglomeration degree, narrow particle size distribution and the like. The additives have the functions of soft template and regulating physical and chemical properties (such as pH value, solution surface tension and dispersing ability) of the solution to a certain extent. Therefore, the invention provides a method for preparing the indium niobium oxide anode material by adopting a solvothermal method, and no related report is yet found at present.
Disclosure of Invention
The invention aims to provide an indium-niobium oxide negative electrode material and a preparation method thereof, and the indium-niobium oxide negative electrode material is further modified, so that the indium-niobium oxide negative electrode material with excellent electrochemical performance is obtained.
The technical scheme of the invention is as follows:
the preparation method of the lithium ion battery indium niobium oxide anode material comprises the following steps:
respectively dissolving a niobium source, an indium source and an additive in a solvent for dissolution, uniformly mixing the solutions, continuously stirring the mixed solution for 2-24 hours, transferring the mixed solution into a high-temperature reaction kettle for solvothermal reaction, filtering the obtained product, respectively washing the obtained product with deionized water and absolute ethyl alcohol for multiple times, and drying to obtain a solid precursor; and then placing the solid precursor in a program temperature control tube furnace, calcining under different atmospheres, and cooling along with the furnace to obtain the bulk indium niobium oxide anode material.
The niobium source comprises at least one of niobium pentachloride, niobium oxalate and complex thereof, niobium hydroxide and niobium acetate;
the indium source comprises one or more of indium trichloride, indium nitrate and indium acetate.
The additive comprises one or more of sodium dodecyl sulfate, polyether F127, sodium dodecyl benzene sulfonate, N- (lauroyl) lysine, polyvinylpyrrolidone, triethanolamine, ammonia water, urea, sodium hydroxide, amino acid and salts thereof.
The solvent is at least one of deionized water and absolute ethyl alcohol.
In the mixed solution, the concentration of the niobium source and the indium source solution is 0.01 to 0.1mol L -1 The method comprises the steps of carrying out a first treatment on the surface of the The mass ratio of the additive to the total solvent is = (1-7): (100).
The solvothermal reaction temperature is 160-240 ℃ and the reaction time is 6-48 h.
The atmosphere comprises at least one of air, oxygen, argon, nitrogen and hydrogen-argon mixed gas; the temperature rising speed is 1-10 ℃ for min -1 The method comprises the steps of carrying out a first treatment on the surface of the The calcination temperature is 600-1300 ℃ and the calcination time is 2-24 h.
In the indium niobium oxide anode material, the stoichiometric ratio of In to Nb to O is x (2-x) to (5-x), wherein x is more than or equal to 0.01 and less than 1, and the excess coefficients of In and Nb are respectively 0-0.08 and 0-0.1.
When the atmosphere is argon, nitrogen or hydrogen-argon mixed gas, the indium-niobium oxide anode material is oxygen-deficient indium-niobium oxide.
The invention has the beneficial effects that:
the invention adopts a solvothermal method to prepare the indium niobium oxide electrode material. The obtained material has uniform block shape, so that the material has larger specific surface area;stable and open ReO 3 The crystal shearing structure ensures that the material has excellent cycle stability and rate capability; the introduction of indium ions enables more niobium in the niobium-based material to play an active role in oxidation-reduction reaction and promotes larger Nb 3+ /Nb 4+ The degree of reaction; at the same time, the stoichiometric ratio In can be realized by controlling the excess coefficient of In and Nb x Nb 2-x O 5-x The crystal structure of the material is further regulated and controlled, and the electrochemical performance of the material is improved; and calcination in inert atmosphere can lead the material to generate abundant anion vacancies, improve the electron conductivity and further improve the multiplying power performance. The indium-niobium oxide electrode material prepared by the invention has higher specific charge capacity, good cycle stability and excellent rate capability when being used as a lithium ion battery anode material.
Drawings
FIG. 1 is In example 1 0.5 Nb 24.5 O 62 XRD pattern of the negative electrode material.
FIG. 2 is In example 1 0.5 Nb 24.5 O 62 SEM image of the negative electrode material.
FIG. 3 is In example 1 0.5 Nb 24.5 O 62 Charge-discharge curve of the anode material.
FIG. 4 is In example 2 0.5 Nb 24.5 O 62 XRD pattern of the negative electrode material.
FIG. 5 is In example 3 0.5 Nb 24.99 O 63.225 XRD pattern of the negative electrode material.
FIG. 6 is In example 4 0.5 Nb 24.5 O 62-x And a rate performance graph of the anode material.
Detailed Description
Example 1
Stoichiometric ratio In 0.5 Nb 24.5 O 62 Preparation of a negative electrode material:
using niobium pentachloride and indium trichloride as raw materials, selecting polyether F127 as an additive, and controlling In x Nb 2-x O 5-x Wherein x=0.04, preparing the stoichiometric ratio In 0.5 Nb 24.5 O 62 A negative electrode material. Niobium pentachloride 0.004mol and polyether 0.2g are weighed, dissolved completely and mixed. And (3) loading the mixed solution into a high-temperature reaction kettle, and putting the high-temperature reaction kettle into a constant-temperature oven for reaction, wherein the reaction temperature is 200 ℃, and the reaction time is 24 hours. And after the reaction is finished, taking out the precipitate, washing the precipitate with water and absolute ethyl alcohol for multiple times, and then putting the precipitate into an oven for drying. Calcining the dried sample in a tubular furnace under the air atmosphere at 1000 deg.C for 6 hr at 4 deg.C for min -1 Cooling along with the furnace after heat preservation is completed to obtain In 0.5 Nb 24.5 O 62 A negative electrode material. The XRD pattern of the obtained material is shown in figure 1, the structure of the material is matched with that of PDF#72-1121, and the finishing result shows that the material has ReO 3 The crystal shearing structure is monoclinic system. SEM images are shown in fig. 2, and the resulting material is a bulk particle. The charge-discharge curve is shown in FIG. 3, and the initial charge specific capacity at 0.1C is 414.1mAh g -1 。
Example 2
Different crystal forms of In 0.5 Nb 24.5 O 62 Preparation of a negative electrode material:
using niobium pentachloride and indium trichloride as raw materials, selecting polyether F127 as an additive, and controlling In x Nb 2-x O 5-x Wherein x=0.04, preparing the stoichiometric ratio In 0.5 Nb 24.5 O 62 A negative electrode material. Niobium pentachloride 0.004mol and polyether 0.2g are weighed, dissolved completely and mixed. And (3) loading the mixed solution into a high-temperature reaction kettle, and putting the high-temperature reaction kettle into a constant-temperature oven for reaction, wherein the reaction temperature is 200 ℃, and the reaction time is 24 hours. And after the reaction is finished, taking out the precipitate, washing the precipitate with water and absolute ethyl alcohol for multiple times, and then putting the precipitate into an oven for drying. Calcining the dried sample in a tubular furnace under the air atmosphere at 900 deg.C for 6 hr at 4 deg.C for min -1 Cooling along with the furnace after heat preservation is completed to obtain In 0.5 Nb 24.5 O 62 A negative electrode material. The XRD pattern of the obtained material is shown in figure 4, and the structure of the material is matched with PDF#30-0873, and the material is in an orthorhombic system, which shows that the material is calcined under different temperature conditions to obtain samples with different crystal forms and different space groups.
Example 3
Cationic autodoping In 0.5 Nb 24.5 O 62 Preparation of a negative electrode material:
using niobium pentachloride and indium trichloride as raw materials, selecting polyether F127 as an additive, and controlling In x Nb 2-x O 5-x Wherein x=0.04, controlling the excess factor of Nb to be 0.02 based on example 1, nb was produced 5+ Doping In 0.5 Nb 24.5 O 62 Negative electrode material, i.e. In 0.5 Nb 24.99 O 63.225 . The remaining conditions remained the same. The material structure still remains matched with PDF#72-1121, being monoclinic as shown in FIG. 5; however, the cell parameters and the cell volume are changed, the cation local electronic structure is changed, and the multiplying power performance of the material is improved.
Example 4
Oxygen vacancy control In 0.5 Nb 24.5 O 62 Preparation of a negative electrode material:
using niobium pentachloride and indium trichloride as raw materials, selecting polyether F127 as an additive, and controlling In x Nb 2-x O 5-x Wherein x=0.04, preparing the stoichiometric ratio In 0.5 Nb 24.5 O 62 A negative electrode material. Niobium pentachloride 0.004mol and polyether 0.2g are weighed, dissolved completely and mixed. And (3) loading the mixed solution into a high-temperature reaction kettle, and putting the high-temperature reaction kettle into a constant-temperature oven for reaction, wherein the reaction temperature is 200 ℃, and the reaction time is 24 hours. And after the reaction is finished, taking out the precipitate, washing the precipitate with water and absolute ethyl alcohol for multiple times, and then putting the precipitate into an oven for drying. Calcining the dried sample in a tubular furnace under argon atmosphere at 1000 ℃ for 6h at a heating rate of 4 ℃ for min -1 Cooling along with the furnace after heat preservation is completed to obtain anoxic In 0.5 Nb 24.5 O 62 A negative electrode material. The electron conductivity of the material is enhanced, and the rate performance is improved, as shown in fig. 6.
Claims (8)
1. The preparation method of the lithium ion battery indium niobium oxide anode material is characterized by comprising the following specific steps:
(1) Respectively dissolving a niobium source, an indium source and an additive in a solvent for dissolution, uniformly mixing the solutions, continuously stirring the mixed solution, transferring the mixed solution into a high-temperature reaction kettle for solvothermal reaction, filtering the obtained product, respectively washing the obtained product with deionized water and absolute ethyl alcohol for multiple times, and drying to obtain a solid precursor;
(2) Placing the precursor obtained in the step (1) in a program temperature-controlled tubular furnace, calcining under different atmospheres, and cooling along with the furnace to obtain a blocky indium-niobium oxide anode material;
the atmosphere comprises at least one of air, oxygen, argon, nitrogen and hydrogen-argon mixed gas; the temperature rising speed is 1-10 ℃ for min -1 The method comprises the steps of carrying out a first treatment on the surface of the The calcination temperature is 600-1300 ℃ and the calcination time is 2-24 h.
2. The method of claim 1, wherein in step (1), the niobium source comprises at least one of niobium pentachloride, niobium oxalate and its complex, niobium hydroxide, and niobium acetate; the indium source comprises one or more of indium trichloride, indium nitrate and indium acetate.
3. The method according to claim 1, wherein in the step (1), the additive comprises one or more of sodium dodecyl sulfate, polyether F127, sodium dodecyl benzene sulfonate, N- (lauroyl) lysine, polyvinylpyrrolidone, triethanolamine, ammonia water, urea, sodium hydroxide, amino acid and salts thereof.
4. The method according to claim 1, wherein in the step (1), the solvent is at least one of deionized water and absolute ethanol.
5. The method according to claim 1, wherein in the step (1), the concentration of the solutions of the niobium source and the indium source in the mixed solution is 0.01 to 0.1mol L -1 The method comprises the steps of carrying out a first treatment on the surface of the The mass ratio of the additive to the total solvent is = (1-7): (100), and the stirring time is 2-24 h.
6. The process of claim 1, wherein in step (1), the solvothermal reaction temperature is 160-240 ℃ and the reaction time is 6-48 hours.
7. The lithium ion battery indium niobium oxide anode material is characterized In that the preparation method is according to any one of claims 1-6, the stoichiometric ratio of In to Nb to O is x (2-x): 5-x, wherein x is more than or equal to 0.01 and less than 1, and the excess coefficients of In and Nb are respectively 0-0.08 and 0-0.1.
8. The lithium ion battery indium niobium oxide anode material according to claim 7, wherein when the atmosphere in the step (2) is argon, nitrogen or hydrogen-argon mixture, the obtained indium niobium oxide anode material is oxygen-deficient indium niobium oxide.
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| CN111969199A (en) * | 2020-08-24 | 2020-11-20 | 福州大学 | Potassium calcium niobate composite salt negative electrode material for potassium ion battery and preparation process thereof |
| CN112103493A (en) * | 2020-08-13 | 2020-12-18 | 华北电力大学 | Preparation method of lithium battery negative electrode material titanium-niobium composite oxide |
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| CN112103493A (en) * | 2020-08-13 | 2020-12-18 | 华北电力大学 | Preparation method of lithium battery negative electrode material titanium-niobium composite oxide |
| CN111969199A (en) * | 2020-08-24 | 2020-11-20 | 福州大学 | Potassium calcium niobate composite salt negative electrode material for potassium ion battery and preparation process thereof |
Non-Patent Citations (2)
| Title |
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| Nonaqueous Sol–Gel Synthesis of a Nanocrystalline InNbO4 Visible-Light Photocatalyst;Lizhi Zhang等;《Adv. Mater.》;2083-2086 * |
| Solvothermal synthesis of InNbO4 cubes for efficient degradation of pefloxacin;Jie Zhao等;《Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy》;118247 * |
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