CN114655984A - Indium-niobium oxide cathode material of lithium ion battery and preparation method thereof - Google Patents
Indium-niobium oxide cathode material of lithium ion battery and preparation method thereof Download PDFInfo
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- CN114655984A CN114655984A CN202210408840.6A CN202210408840A CN114655984A CN 114655984 A CN114655984 A CN 114655984A CN 202210408840 A CN202210408840 A CN 202210408840A CN 114655984 A CN114655984 A CN 114655984A
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- indium
- niobium
- niobium oxide
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- lithium ion
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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 23
- 239000010406 cathode material Substances 0.000 title claims abstract description 16
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000010955 niobium Substances 0.000 claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 20
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000654 additive Substances 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 230000000996 additive effect Effects 0.000 claims abstract description 11
- 229910052738 indium Inorganic materials 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002243 precursor Substances 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000004729 solvothermal method Methods 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 3
- 239000007773 negative electrode material Substances 0.000 claims description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 15
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 12
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 11
- 229920000570 polyether Polymers 0.000 claims description 11
- 239000011259 mixed solution Substances 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
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 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
- 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
- 239000000243 solution Substances 0.000 claims description 5
- 239000003570 air Substances 0.000 claims description 4
- 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 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
- 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
- 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
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 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 29
- 239000002244 precipitate Substances 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 6
- 230000001351 cycling effect Effects 0.000 abstract description 3
- 239000010405 anode material Substances 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910001449 indium ion Inorganic materials 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910002785 ReO3 Inorganic materials 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910009866 Ti5O12 Inorganic materials 0.000 description 1
- 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 230000002687 intercalation Effects 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
- 238000007670 refining Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
Images
Classifications
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- 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 cathode material of a lithium ion battery and a preparation method thereof. The method adopts a niobium source and an indium source as raw materials, adds an additive, and respectively dissolves the raw materials in a proper solvent; mixing and stirring the materials uniformly, placing the mixture in a high-temperature reaction kettle for solvothermal reaction, and washing and drying precipitates for multiple times to obtain a precursor; and transferring the obtained precursor material into a tubular furnace, calcining the precursor material in different atmospheres, and cooling the calcined precursor material along with the furnace to obtain the blocky indium niobium oxide cathode material, wherein the obtained material has excellent rate capability and cycling stability.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery cathode materials, and particularly relates to an indium-niobium oxide cathode material and a preparation method thereof.
Background
Graphite is mostly used as the negative electrode material of the current commercial lithium ion battery, however, the rate performance of the graphite is not ideal, the lithium intercalation potential is low, lithium dendrite is easy to form in the rapid charging and discharging process, the potential safety hazard is serious, and the requirement of the increasingly developed energy storage field on the graphite is difficult to meet; li having spinel structure4Ti5O12The working voltage of the lithium ion battery is about 1.5V, and an SEI film and lithium dendrite are not generated in the charging and discharging processes, so the cycling performance of the rate capability of the lithium ion battery is very good, but the specific capacity (175mAh g) is lower-1) Limiting its development.
Niobium based oxides due to their higher theoretical specific capacity (-400 mAh g-1) And the high de-intercalation lithium potential (1-2V) of the lithium ion battery anode material becomes a candidate material with competitiveness for the lithium ion battery anode material. The huge niobium-based group provides a great deal of reference for the research of the energy storage performance of the niobium-based group, and the development of a new niobium-based group system has important significance for the further research of the niobium-based group system. Because the ionic radii of indium and niobium are not greatly different, the material structure cannot be greatly influenced after indium ions are introduced, and on the contrary, because the metal indium ions are introduced, a material structure layer can be migrated to form a stable shear phase structure, so that Li is very favorable+The fast 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 material structure and the electronic properties. 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 a certain soft template effect and can regulate and control the physicochemical properties (such as pH value and solution surface tension) of the solutionDispersion ability). Therefore, the invention provides the method for preparing the indium niobium oxide cathode material by adopting the solvothermal method, and no relevant report is found at present.
Disclosure of Invention
The invention aims to provide an indium niobium oxide anode material and a preparation method thereof, and further modify the indium niobium oxide anode material to obtain the indium niobium oxide anode material with excellent electrochemical performance.
The technical scheme of the invention is as follows:
a preparation method of an indium niobium oxide cathode material of a lithium ion battery comprises the following steps:
respectively dissolving a niobium source, an indium source and an additive in a solvent for dissolving, then uniformly mixing the solutions, continuously stirring the mixed solution for 2-24 hours, transferring the mixed solution into a high-temperature reaction kettle for solvent thermal reaction, filtering the obtained product, washing the product with deionized water and absolute ethyl alcohol for multiple times, and drying the product 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 blocky indium-niobium oxide cathode 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 solution and the indium source solution is 0.01-0.1 mol L-1(ii) a The mass ratio of the additive to the total amount of the solvent is (1-7) to (100).
The solvothermal reaction temperature is 160-240 ℃, and the reaction time is 6-48 h.
The atmosphere comprises air, oxygen, argon, nitrogen,At least one of hydrogen and argon mixed gas; the temperature rise speed is 1-10 ℃ min-1(ii) a The calcination temperature is 600-1300 ℃, and the calcination time is 2-24 h.
In the indium niobium oxide cathode 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 0-0.08 and 0-0.1 respectively.
When the atmosphere is argon, nitrogen or hydrogen-argon mixed gas, the indium niobium oxide cathode material is oxygen-deficient indium niobium oxide.
The invention has the beneficial effects that:
the indium niobium oxide electrode material is prepared by adopting a solvothermal method. The obtained material has uniform blocky appearance, so that the material has a large specific surface area; stable and open ReO3The material has excellent cycle stability and rate capability due to the crystal shear structure; the introduction of indium ions enables more niobium in the niobium-based material to play an active role in oxidation-reduction reaction, and promotes the larger Nb3+/Nb4+The degree of reaction; meanwhile, the stoichiometric ratio In can be realized by controlling the excess coefficients of In and NbxNb2-xO5-xThe cation self-doping is carried out, the crystal structure of the material is further regulated and controlled, and the electrochemical performance of the material is improved; and the calcination under the inert atmosphere can enable the material to generate abundant anion vacancies, improve the electronic conductivity of the material and further improve the rate capability of the material. The indium niobium oxide electrode material prepared by the invention has higher charge specific capacity, good cycling stability and excellent rate capability when being used as a lithium ion battery cathode material.
Drawings
FIG. 1 shows In example 10.5Nb24.5O62XRD pattern of the negative electrode material.
FIG. 2 shows In example 10.5Nb24.5O62SEM image of the negative electrode material.
FIG. 3 shows In example 10.5Nb24.5O62And (3) a charge-discharge curve diagram of the negative electrode material.
FIG. 4 shows In example 20.5Nb24.5O62XRD pattern of the negative electrode material.
FIG. 5 shows In example 30.5Nb24.99O63.225XRD pattern of the negative electrode material.
FIG. 6 shows In example 40.5Nb24.5O62-xAnd the rate performance graph of the negative electrode material.
Detailed Description
Example 1
Stoichiometric ratio In0.5Nb24.5O62Preparing a negative electrode material:
niobium pentachloride and indium trichloride are taken as raw materials, polyether F127 is selected as an additive, and In is controlledxNb2-xO5-xWhere x is 0.04, preparing the stoichiometric ratio In0.5Nb24.5O62And (3) a negative electrode material. 0.004mol of niobium pentachloride and 0.2g of polyether are weighed, respectively dissolved completely and then mixed. And putting the mixed solution into a high-temperature reaction kettle, and putting the high-temperature reaction kettle into a constant-temperature oven for reaction at the reaction temperature of 200 ℃ for 24 hours. And after the reaction is finished, taking out the precipitate, washing the precipitate for multiple times by using water and absolute ethyl alcohol, and then putting the precipitate into an oven for drying. Calcining the dried sample in a tubular furnace in the air atmosphere at 1000 ℃ for 6h at a heating rate of 4 ℃ for min-1And cooling with the furnace after heat preservation to obtain In0.5Nb24.5O62And (3) 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 refining result shows that the material has ReO3The crystal shear structure is monoclinic. The SEM image is shown in FIG. 2, and the obtained material is bulk particles. The charge-discharge curve is shown in FIG. 3, the first charge specific capacity at 0.1C is 414.1mAh g-1。
Example 2
In of different crystal forms0.5Nb24.5O62Preparing a negative electrode material:
niobium pentachloride and indium trichloride are taken as raw materials, polyether F127 is selected as an additive, and In is controlledxNb2-xO5-xWhere x is 0.04, preparing the stoichiometric ratio In0.5Nb24.5O62And (3) a negative electrode material. Niobium pentachloride0.004mol of polyether is taken, 0.2g of polyether is weighed, and the polyether is respectively dissolved completely and then mixed. And putting the mixed solution into a high-temperature reaction kettle, and putting the high-temperature reaction kettle into a constant-temperature oven for reaction at the reaction temperature of 200 ℃ for 24 hours. And after the reaction is finished, taking out the precipitate, washing the precipitate for multiple times by using water and absolute ethyl alcohol, and then putting the precipitate into an oven for drying. Calcining the dried sample in a tubular furnace in the air atmosphere at 900 ℃ for 6h at a heating rate of 4 ℃ for min-1And cooling with the furnace after heat preservation to obtain In0.5Nb24.5O62And (3) a negative electrode material. The XRD pattern of the obtained material is shown in figure 4, the structure of the material is matched with that of PDF #30-0873, and the material is an orthorhombic system, which indicates that the material is calcined under different temperature conditions to obtain samples with different crystal forms and different space groups.
Example 3
Cation self-doping In0.5Nb24.5O62Preparing a negative electrode material:
niobium pentachloride and indium trichloride are taken as raw materials, polyether F127 is selected as an additive, and In is controlledxNb2-xO5-xWherein x is 0.04, and the excess coefficient of Nb is controlled to be 0.02 on the basis of example 1, Nb is prepared5+Doping with In0.5Nb24.5O62Anode material, i.e. In0.5Nb24.99O63.225. The remaining conditions remained consistent. The material structure still remained matched with PDF #72-1121, and was monoclinic, as shown in FIG. 5; however, the unit cell parameters and the unit cell volume are changed, the cation local electron structure is changed, and the multiplying power performance of the material is improved.
Example 4
Oxygen vacancy-regulated In0.5Nb24.5O62Preparing a negative electrode material:
niobium pentachloride and indium trichloride are taken as raw materials, polyether F127 is selected as an additive, and In is controlledxNb2-xO5-xWhere x is 0.04, preparing the stoichiometric ratio In0.5Nb24.5O62And (3) a negative electrode material. 0.004mol of niobium pentachloride and 0.2g of polyether are weighed, and are respectively dissolved completely and then mixed. Putting the mixed solution into a high-temperature reaction kettle, putting the high-temperature reaction kettle into a constant-temperature oven for reaction,the reaction temperature is 200 ℃, and the reaction time is 24 h. And after the reaction is finished, taking out the precipitate, washing the precipitate for multiple times by using water and absolute ethyl alcohol, and then putting the precipitate into an oven for drying. Calcining the dried sample in a tubular furnace in an argon atmosphere at 1000 ℃ for 6h at a heating rate of 4 ℃ for min-1Cooling the heat-insulating material along with the furnace to obtain anoxic In0.5Nb24.5O62And (3) a negative electrode material. The electronic conductivity of the material is enhanced, and the rate capability is improved, as shown in fig. 6.
Claims (9)
1. A preparation method of an indium niobium oxide cathode material of a lithium ion battery is characterized by comprising the following specific steps:
(1) respectively dissolving a niobium source, an indium source and an additive in a solvent for dissolving, then uniformly mixing all the solutions, continuously stirring the mixed solution, transferring the mixed solution into a high-temperature reaction kettle for solvent thermal reaction, filtering the obtained product, washing the product with deionized water and absolute ethyl alcohol for multiple times, and drying the product to obtain a solid precursor;
(2) and (2) placing the precursor obtained in the step (1) in a program temperature control tube furnace, calcining under different atmospheres, and cooling along with the furnace to obtain the blocky indium-niobium oxide cathode material.
2. The method according to 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 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 acids 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 ethyl alcohol.
5. The method according to claim 1, wherein in the step (1), the mixed solution contains the niobium source and the indium source in concentrations of 0.01 to 0.1mol L-1(ii) a The mass ratio of the additive to the solvent is (1-7) to (100), and the stirring is continued for 2-24 hours.
6. The preparation method according to claim 1, wherein in the step (1), the solvothermal reaction temperature is 160-240 ℃ and the reaction time is 6-48 h.
7. The method according to claim 1, wherein in the step (2), the atmosphere comprises at least one of air, oxygen, argon, nitrogen, and a mixture of hydrogen and argon; the temperature rise speed is 1-10 ℃ min-1(ii) a The calcination temperature is 600-1300 ℃, and the calcination time is 2-24 h.
8. An indium niobium oxide cathode material of a lithium ion battery is characterized by being prepared by the preparation method according to any one of claims 1 to 7, wherein the stoichiometric ratio of In to Nb to O In the indium niobium oxide cathode material 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 0-0.08 and 0-0.1 respectively.
9. The indium niobium oxide negative electrode material of the lithium ion battery as claimed in claim 8, wherein when the atmosphere in step (2) is argon, nitrogen or a mixture of hydrogen and argon, the obtained indium niobium oxide negative electrode material is oxygen-deficient indium niobium oxide.
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| CN202210408840.6A CN114655984B (en) | 2022-04-19 | 2022-04-19 | Lithium ion battery indium niobium oxide negative electrode material and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114890475A (en) * | 2022-06-30 | 2022-08-12 | 江苏大学 | Preparation method of niobium-based oxide negative electrode material |
| CN116282168A (en) * | 2023-03-16 | 2023-06-23 | 广州大学 | Lithium ion battery negative electrode material, and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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- 2022-04-19 CN CN202210408840.6A patent/CN114655984B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
|---|
| JIE ZHAO等: "Solvothermal synthesis of InNbO4 cubes for efficient degradation of pefloxacin", 《SPECTROCHIMICA ACTA PART A: MOLECULAR AND BIOMOLECULAR SPECTROSCOPY》, pages 118247 * |
| LIZHI ZHANG等: "Nonaqueous Sol–Gel Synthesis of a Nanocrystalline InNbO4 Visible-Light Photocatalyst", 《ADV. MATER.》, pages 2083 - 2086 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114890475A (en) * | 2022-06-30 | 2022-08-12 | 江苏大学 | Preparation method of niobium-based oxide negative electrode material |
| CN116282168A (en) * | 2023-03-16 | 2023-06-23 | 广州大学 | Lithium ion battery negative electrode material, and preparation method and application thereof |
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