CN110759378A - Preparation method of fibrous lithium titanate and fibrous lithium titanate - Google Patents
Preparation method of fibrous lithium titanate and fibrous lithium titanate Download PDFInfo
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- CN110759378A CN110759378A CN201911009917.7A CN201911009917A CN110759378A CN 110759378 A CN110759378 A CN 110759378A CN 201911009917 A CN201911009917 A CN 201911009917A CN 110759378 A CN110759378 A CN 110759378A
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- lithium titanate
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- lithium
- titanium
- collagen fiber
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- GLUCAHCCJMJHGV-UHFFFAOYSA-N dilithium;dioxido(oxo)titanium Chemical compound [Li+].[Li+].[O-][Ti]([O-])=O GLUCAHCCJMJHGV-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 102000008186 Collagen Human genes 0.000 claims abstract description 62
- 108010035532 Collagen Proteins 0.000 claims abstract description 62
- 229960005188 collagen Drugs 0.000 claims abstract description 62
- 229920001436 collagen Polymers 0.000 claims abstract description 62
- 239000000835 fiber Substances 0.000 claims abstract description 60
- 239000010936 titanium Substances 0.000 claims abstract description 45
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 44
- RTAQQCXQSZGOHL-UHFFFAOYSA-N titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000001354 calcination Methods 0.000 claims abstract description 27
- WHXSMMKQMYFTQS-UHFFFAOYSA-N lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 25
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 8
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 50
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 44
- 238000003756 stirring Methods 0.000 claims description 26
- 239000000463 material Substances 0.000 claims description 15
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 14
- BDAGIHXWWSANSR-UHFFFAOYSA-N formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 12
- 239000007853 buffer solution Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 10
- HDUMBHAAKGUHAR-UHFFFAOYSA-J titanium(4+);disulfate Chemical group [Ti+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O HDUMBHAAKGUHAR-UHFFFAOYSA-J 0.000 claims description 10
- XIXADJRWDQXREU-UHFFFAOYSA-M Lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 9
- 229940071257 Lithium acetate Drugs 0.000 claims description 9
- UIIMBOGNXHQVGW-UHFFFAOYSA-M NaHCO3 Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000011780 sodium chloride Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- XPFJYKARVSSRHE-UHFFFAOYSA-K trisodium;2-hydroxypropane-1,2,3-tricarboxylate;2-hydroxypropane-1,2,3-tricarboxylic acid Chemical compound [Na+].[Na+].[Na+].OC(=O)CC(O)(C(O)=O)CC(O)=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O XPFJYKARVSSRHE-UHFFFAOYSA-K 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 230000000717 retained Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 21
- 235000019441 ethanol Nutrition 0.000 description 16
- 239000002244 precipitate Substances 0.000 description 16
- 229910001416 lithium ion Inorganic materials 0.000 description 14
- 238000002441 X-ray diffraction Methods 0.000 description 13
- 238000001878 scanning electron micrograph Methods 0.000 description 13
- -1 magnesium-lithium Chemical compound 0.000 description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 10
- 238000005303 weighing Methods 0.000 description 9
- 239000012153 distilled water Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 229910010252 TiO3 Inorganic materials 0.000 description 5
- 239000004408 titanium dioxide Substances 0.000 description 5
- LLZRNZOLAXHGLL-UHFFFAOYSA-J Titanic acid Chemical group O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 4
- 239000012267 brine Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium Ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 229910007848 Li2TiO3 Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000011068 load Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N AI2O3 Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 102000012422 Collagen Type I Human genes 0.000 description 1
- 108010022452 Collagen Type I Proteins 0.000 description 1
- 229910002986 Li4Ti5O12 Inorganic materials 0.000 description 1
- 229920001410 Microfiber Polymers 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K Trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000003592 biomimetic Effects 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 1
- 229960002303 citric acid monohydrate Drugs 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000003658 microfiber Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- 239000002831 pharmacologic agent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 230000001502 supplementation Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- LCKIEQZJEYYRIY-UHFFFAOYSA-N titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 1
- 230000001131 transforming Effects 0.000 description 1
- 239000011778 trisodium citrate Substances 0.000 description 1
- 229940038773 trisodium citrate Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
- C01G23/005—Alkali titanates
-
- H—ELECTRICITY
- H01—BASIC 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—BASIC 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- 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
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
-
- 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 fibrous lithium titanate and fibrous lithium titanate, and solves the problem that the fibrous lithium titanate prepared by using collagen fibers as a template does not exist in the prior art. The invention relates to a preparation method of fibrous lithium titanate, which adopts collagen fiber as a template, an inorganic titanium source as a titanium tanning agent, lithium salt as a lithium source, collagen fiber as a template, an inorganic titanium source as a titanium tanning agent and lithium salt as a lithium source, wherein the titanium source is firstly loaded on the collagen fiber, and then the lithium source is combined with the titanium source, so that the preparation of the fibrous lithium titanate is realized. The method is simple, is simple and convenient to operate, creatively adopts the collagen fiber as a template, loads metal ions on the collagen fiber, and removes the collagen fiber template through calcination, so that the structural information in the collagen fiber supermolecular structure is copied and retained on the lithium titanate, and the fibrous lithium titanate is prepared.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and particularly relates to a preparation method of fibrous lithium titanate and the fibrous lithium titanate.
Background
The lithium resource supply in China is mainly based on extraction of lithium from ores, but with the massive development of lithium resources, the reserve of lithium ores in China cannot meet the requirements of people on the lithium resources in the future, so that extraction of lithium from liquid lithium resources such as salt lake brine with large lithium reserve and seawater becomes an important direction and an inevitable choice for obtaining the lithium resources. However, lithium resources in the brine mainly coexist with a large amount of alkali metal and alkaline earth metal ions in an ion form, most of the brine has low lithium content, and the salt lake brine in China has the characteristic of high magnesium-lithium ratio, so that the development technical difficulty is high. The titanium lithium ion sieve can selectively adsorb and enrich lithium ions, and is considered to be an effective method for solving the problems. The preparation of the titanium lithium ion sieve is generally obtained by proper treatment of lithium titanate with an eluent, and the lithium titanate mainly has two structures, namely spinel type Li4Ti5O12One is metatitanic acid type Li2TiO3. Spinel type lithium titanate is commonly used as an electrode material of a lithium ion battery, and metatitanic acid type lithium titanate is commonly used for preparing a titanium lithium ion sieve due to the advantages of stable structure, large theoretical exchange adsorption capacity and the like. Metatitanic acid type Li2TiO3The preparation method comprises a solid phase method, a hydrothermal method, a sol-gel method, a precipitation peptization method and the like. Li prepared at present2TiO3The titanium lithium ion sieve is mainly in a common powder shape, and the titanium lithium ion sieve obtained by the method is also in a common powder shape. The powder titanium lithium ion sieve has repeated solid-liquid separation (the filtration resistance is very high)Large), difficult washing, leaching, regeneration and enrichment, low production efficiency and the like, and is difficult to realize engineering. The special shape, especially fibrous or tubular shape, has excellent geometric flexibility, and the fibrous lithium ion sieve overcomes the problems of poor permeability and flowability of the powdery lithium ion sieve, and is easier to realize industrial application.
The template method is one of the most effective methods for constructing a material with a special shape. The templating method was initially established from a biomimetic point of view, when the organism is in the mineralization mode, the organic molecules are first pre-assembled, where the inorganic species nucleate and grow. The template method has the advantages of simple experimental device, controllable form, wide application range and the like. The template method can be divided into two major categories, namely a hard template and a soft template: the hard template comprises porous alumina, silicon dioxide, carbon nanotubes and the like; the soft template includes surfactant, polymer, biological template (biological molecule) and so on. The biological template technology is a new technology for preparing a material with a special structure by taking biomolecules as a template, has the advantages of high efficiency, convenience and the like, and is developed rapidly in recent years. When a biological template method is adopted to prepare a material with a special morphology structure, the selection of a template agent is very important.
The collagen fiber is a supermolecular structure formed by self-assembly of type I collagen molecules and has a regular fiber shape, in the collagen fiber, the collagen molecules are arranged in a quarter staggered mode to form a gap, the collagen molecules are rod-shaped molecules with the diameter of 1.5nm and the length of 300nm, and are formed into a spiral structure formed by 3 α -peptide chains, and 4-8 collagen molecules form microfibers and are further assembled into collagen fibers and collagen fiber bundles.
The collagen fiber has special multi-level structure and chemical reaction characteristics, and contains-OH, -COOH and-NH in the molecule according to the principle of tanning chemistry2The active groups can be combined with water molecules by hydrogen bonds, so that the collagen fibers have particularly strong hydrophilic capacity. In addition, the collagen fibers can be coordinated with Cr (III), Al (III), Zr (IV), Ti (IV), Fe (III), La (III), etcCombine to form a stable complex. Therefore, the collagen fiber is taken as a template, a plurality of metal ions are loaded on the collagen fiber, and after the template is removed by calcination, the structural information in the supermolecular structure of the collagen fiber can be expected to be copied and retained, so that the material with a specific morphology can be prepared. However, preparation of lithium titanate (Li) having a fibrous structure using collagen fibers as a template2TiO3) Further, the preparation of a metatitanic acid type titanium lithium ion sieve has not been reported. Thus, a fibrous lithium titanate (Li)2TiO3) The preparation of (A) is necessary.
Disclosure of Invention
The invention discloses a preparation method of fibrous lithium titanate and fibrous lithium titanate prepared by the preparation method.
The inventor of the invention discovers that by using the leather collagen fiber as a template, the economical and practical inorganic titanium source titanium sulfate as a titanium tanning agent and the lithium acetate as a lithium source, the lithium titanate (Li) with the fiber structure is synthesized by a method of direct reaction of the collagen fiber and inorganic metal ions2TiO3) The permeability and the fluidity of the composite material are improved, and the industrial application is easier to realize.
The technical scheme adopted by the invention is as follows:
the preparation method of the fibrous lithium titanate provided by the invention adopts collagen fibers as a template, an inorganic titanium source as a titanium tanning agent and a lithium salt as a lithium source, firstly loads the titanium source on the collagen fibers, and then combines the lithium source and the titanium source, thereby realizing the preparation of the fibrous lithium titanate.
Further, the collagen fibers are collagen fibers;
the inorganic titanium source is selected from titanium sulfate;
the lithium source is one or two of lithium acetate and lithium carbonate.
Further, the molar ratio of titanium to lithium in the inorganic titanium source and the lithium salt is 1: 2-4.
Further, the amount of the collagen fiber is equal to or greater than the mass of the fibrous lithium titanate produced.
Further, the method specifically comprises the following steps:
step 1, preparing a collagen fiber solution: adding water and sodium chloride into collagen fiber raw material, mixing, adding acid to adjust pH value to 1.0-4.0, and stirring;
step 2, preparing an inorganic titanium solution: adding buffer solution into inorganic titanium for dissolving, and then adding alkali solution to adjust the pH value to 1.0-4.0;
step 3, adding the inorganic titanium solution prepared in the step 2 into the collagen fiber solution prepared in the step 1, continuously stirring, adding an alkali solution to adjust the pH value to 3.0-5.0, reacting for a period of time, centrifuging, washing, and soaking in ethanol;
step 4, adding lithium salt into the ethanol obtained in the step 3, stirring, then carrying out ultrasonic treatment, centrifuging and drying;
and 5, calcining the dried material obtained in the step 4, and cooling the calcined material to room temperature along with the furnace to obtain the fibrous lithium titanate.
Specifically, the collagen fiber raw material is hide powder, and water is added to prepare a solution with the concentration of 0.02-0.08 g/mL; sodium chloride is added to make the concentration of the sodium chloride in water be 0.01-0.03 g/mL.
More specifically, in the step 2, the inorganic titanium is added into the buffer solution to prepare the titanium ion content of 0.2 × 10-3-0.6×10-3mol/mL solution.
Further, the acid solution in the step 1 is prepared from dilute sulfuric acid and formic acid with the mass fraction of 25% according to the mass ratio of 3: 1;
as an embodiment of the invention, the pH value is adjusted to 2.0 by adding acid in the step 1.
The buffer solution in the step 2 is a citric acid-trisodium citrate buffer solution;
and the alkali solutions in the step 2 and the step 3 are both saturated sodium bicarbonate solutions.
Further, the stirring in the step 1 is stirring for 2-6 hours at normal temperature;
the stirring in the step 3 is stirring for 6 to 10 hours at normal temperature;
and the stirring in the step 4 is carried out for 2 to 6 hours at normal temperature.
Further, in the step 3, after adding an alkali solution to adjust the pH value to 3.0-5.0, reacting for 1-4 hours at 35-40 ℃;
in the step 4, the ultrasonic treatment time is 15-25 min; drying at 50-80 deg.C.
In step 3, a base solution is added to adjust the pH to 4.0.
Further, the calcination in the step 5 is to calcine the lithium titanate by a muffle furnace at the temperature of 600-800 ℃ for 6-10h, the heating rate is 5 ℃/min, and the fibrous lithium titanate is obtained after the calcination is finished and cooled to room temperature along with the furnace.
The fibrous lithium titanate prepared by the preparation method is provided by the invention.
Compared with the prior art, the invention has the beneficial effects that:
the method is simple, is simple and convenient to operate, creatively adopts the collagen fiber as a template, loads metal ions on the collagen fiber, and removes the collagen fiber template through calcination, so that the structural information in the collagen fiber supermolecular structure is copied and retained on the lithium titanate, and the fibrous lithium titanate is prepared. The XRD pattern shows that the product prepared by the process of the present invention has lithium titanate (Li)2TiO3) The crystal phase composition of (a); the SEM images show that the product produced by the process of the invention has a fibrous structure; the method can overcome the problem of poor permeability and flowability of powdery lithium titanate (titanium lithium ion sieve), and is easier to realize industrial application.
The method creatively combines titanium ions with sites on the collagen fiber, loads a titanium source on the collagen fiber, combines a lithium source with the titanium source, and loads the titanium source on the collagen fiber, thereby realizing the preparation of fibrous lithium titanate; effectively overcomes the problem that no site suitable for being combined with lithium ions exists on the collagen fiber, and the lithium ions can not be directly loaded on the collagen fiber.
The invention adopts inorganic titanium source such as titanium sulfate as raw material, which is more economical and practical than other titanium sources; the invention adopts the collagen fiber as the raw material, and realizes high-value utilization of the collagen.
Drawings
Fig. 1 is an XRD pattern of the fibrous lithium titanate prepared in example 1.
Fig. 2 is an SEM image of the fibrous lithium titanate obtained in example 1.
Fig. 3 is an XRD pattern of the fibrous lithium titanate prepared in example 2.
Fig. 4 is an SEM image of the fibrous lithium titanate obtained in example 2.
Fig. 5 is an XRD pattern of the fibrous lithium titanate prepared in example 3.
Fig. 6 is an SEM image of the fibrous lithium titanate obtained in example 3.
FIG. 7 is an XRD pattern of sample D1 obtained in comparative example 1.
FIG. 8 is an SEM image of sample D1 obtained in comparative example 1.
FIG. 9 is an XRD pattern of sample D2 obtained in comparative example 2.
FIG. 10 is an SEM image of sample D2 obtained in comparative example 2.
FIG. 11 is an XRD pattern of sample D3 obtained in comparative example 3.
FIG. 12 is an SEM image of sample D3 obtained in comparative example 3.
Detailed Description
The present invention will be further described with reference to the following description and examples, which include but are not limited to the following examples.
The preparation method of the citric acid-trisodium citrate buffer solution used in the embodiment of the invention comprises the following steps: 10.5g of citric acid monohydrate and 0.025g of trisodium citrate are weighed, dissolved in a 50mL beaker, transferred to a 500mL volumetric flask, the beaker is rinsed several times and the rinse is transferred to the volumetric flask, the volume is fixed and shaken up.
The preparation method of the mixed acid used in the embodiment of the invention comprises the following steps: dilute sulphuric acid and formic acid with the mass fraction of 25 percent are prepared according to the mass concentration ratio of 3:1, for example, concentrated H is prepared2SO427mL, 15mL formic acid and 129mL distilled water are mixed evenly to obtain the product.
The ultrasonic equipment used in the embodiment of the invention is an ultrasonic cleaner produced by Repu electronic instruments of Tianjin, and the model is as follows: the QT series.
Example 1
The embodiment provides a preparation method of fibrous lithium titanate, which specifically comprises the following steps:
step 1: preparing a collagen fiber solution: weighing 1.5g of hide powder in a 250mL beaker, adding 30mL of distilled water, adding 0.6g of NaCl, adjusting the pH value to 2.0 by using mixed acid, and stirring for 4 hours at normal temperature by using a magnetic stirrer;
step 2: preparing an inorganic titanium solution: weighing 2.4g (0.01mol) of titanium sulfate into a 250mL beaker, adding 30mL of citric acid-trisodium citrate buffer solution, and adjusting the pH value to 2.0 by using a saturated sodium bicarbonate solution after the titanium sulfate is completely dissolved;
and step 3: adding the inorganic titanium solution prepared in the step 2 into the collagen fiber solution prepared in the step 1, continuously stirring for 8 hours by using a magnetic stirrer at normal temperature, then adjusting the pH value of the solution to 4.0 by using a saturated sodium bicarbonate solution, then carrying out water bath for 2 hours at 38 ℃, centrifuging for 5 minutes under the condition of 4000r/min, washing the precipitate for four times by using distilled water, then washing the precipitate for two times by using ethanol, then soaking the precipitate for 4 hours in absolute ethyl alcohol, wherein the using amount of the ethanol is required to completely soak the precipitate;
and 4, step 4: weighing 2.04g of lithium acetate in the ethanol obtained in the step 3, then adding absolute ethanol, stirring for 4 hours at normal temperature by using a magnetic stirrer, then carrying out ultrasonic treatment for 20 minutes, centrifuging once, and drying the centrifugal precipitate at the temperature of 60 ℃. Wherein, the amount of the added absolute ethyl alcohol is 20-30mL, so that the magnetic stirring can be normally carried out.
And 5: and (4) calcining the dried material in the step (4) at 700 ℃ for 8h by using a muffle furnace, wherein the heating rate is about 5 ℃/min, and cooling to room temperature along with the furnace after calcining to obtain the fibrous lithium titanate.
The XRD pattern of the fibrous lithium titanate obtained in this example is shown in fig. 1, and the result shows that the lithium titanate obtained in this example has the crystal phase composition of lithium titanate.
The SEM image of the fibrous lithium titanate obtained in this example is shown in fig. 2, and the result shows that the lithium titanate obtained in this example has a fibrous structure.
Example 2
This example provides a method for preparing fibrous lithium titanate according to the present invention, wherein the calcination temperature in step 5 is different, the calcination temperature in step 650 ℃ is adopted, and the rest conditions are the same as those in example 1.
The XRD pattern of the fibrous lithium titanate obtained in this example is shown in fig. 3, which shows that the lithium titanate obtained in this example has the crystal phase composition of lithium titanate.
The SEM image of the fibrous lithium titanate obtained in this example is shown in fig. 4, and the result shows that the lithium titanate obtained in this example has a fibrous structure.
Example 3
This example provides a method for preparing fibrous lithium titanate according to the present invention, wherein the calcination temperature in step 5 is different, the calcination temperature in step 750 ℃ is adopted, and the rest conditions are the same as those in example 1.
The XRD pattern of the fibrous lithium titanate obtained in this example is shown in fig. 5, which shows that the lithium titanate obtained in this example has the crystal phase composition of lithium titanate.
The SEM image of the fibrous lithium titanate obtained in this example is shown in fig. 6, and the result shows that the lithium titanate obtained in this example has a fibrous structure.
Example 4
The embodiment provides a preparation method of fibrous lithium titanate, which specifically comprises the following steps:
step 1: preparing a collagen fiber solution: weighing 0.66g of hide powder in a 250mL beaker, adding 30mL of distilled water, adding 0.3g of NaCl, adjusting the pH value to 4.0 by using mixed acid, and stirring for 6h at normal temperature by using a magnetic stirrer;
step 2: preparing an inorganic titanium solution: weighing 1.44g (0.006mol) of titanium sulfate in a 250mL beaker, adding 30mL of citric acid-trisodium citrate buffer solution, and adjusting the pH value to 4.0 by using a saturated sodium bicarbonate solution after the titanium sulfate is completely dissolved;
and step 3: adding the inorganic titanium solution prepared in the step 2 into the collagen fiber solution prepared in the step 1, continuously stirring for 6 hours by using a magnetic stirrer at normal temperature, then adjusting the pH of the solution to 3.0 by using a saturated sodium bicarbonate solution, then carrying out water bath for 1 hour at 35 ℃, centrifuging for 5 minutes under the condition of 4000r/min, washing the precipitate for four times by using distilled water, then washing the precipitate for two times by using ethanol, and then soaking the precipitate for 4 hours in the ethanol, wherein the dosage of the ethanol needs to be completely soaked and precipitated;
and 4, step 4: weighing 0.792g (0.012mol) of lithium acetate in the ethanol obtained in the step 3, then adding a certain amount of absolute ethanol, stirring for 2 hours at normal temperature by adopting a magnetic stirrer, then carrying out ultrasonic treatment for 15 minutes, centrifuging once, and drying at 50 ℃. Wherein, the amount of the added absolute ethyl alcohol is 20-30mL, so that the magnetic stirring can be normally carried out.
And 5: and (4) calcining the dried material in the step (4) at 700 ℃ for 10h by using a muffle furnace, wherein the heating rate is about 5 ℃/min, and cooling to room temperature along with the furnace after calcining to obtain the fibrous lithium titanate.
Example 5
The embodiment provides a preparation method of fibrous lithium titanate, which specifically comprises the following steps:
step 1: preparing a collagen fiber solution: weighing 2.2g of hide powder in a 250mL beaker, adding 30mL of distilled water, adding 0.9g of NaCl, adjusting the pH value to 1.0 by using mixed acid, and stirring for 2 hours at normal temperature by using a magnetic stirrer;
step 2: preparing an inorganic titanium solution: weighing 4.32g (0.018mol) of titanium sulfate into a 250mL beaker, adding 30mL of citric acid-trisodium citrate buffer solution, and adjusting the pH value to 1.0 by using a saturated sodium bicarbonate solution after the titanium sulfate is completely dissolved;
and step 3: adding the inorganic titanium solution prepared in the step 2 into the collagen fiber solution prepared in the step 1, continuously stirring for 10 hours by using a magnetic stirrer at normal temperature, then adjusting the pH value of the solution to 5.0 by using a saturated sodium bicarbonate solution, then carrying out water bath for 4 hours at 40 ℃, centrifuging for 5 minutes under the condition of 4000r/min, washing the precipitate for four times by using distilled water, then washing the precipitate for two times by using ethanol, then soaking the precipitate for 4 hours in the ethanol, wherein the dosage of the ethanol needs to be completely soaked and precipitated;
and 4, step 4: weighing 5.32g (0.072mol) of lithium carbonate in the ethanol in the step 3, then supplementing anhydrous ethanol, stirring and stirring for 6 hours by using a magnetic stirrer at normal temperature, then carrying out ultrasonic treatment for 25 minutes, centrifuging once, and drying at the temperature of 80 ℃. Wherein, the amount of the added absolute ethyl alcohol is 20-30mL, so that the magnetic stirring can be normally carried out.
And 5: and (4) calcining the dried material in the step (4) at 750 ℃ for 6h by using a muffle furnace, wherein the heating rate is about 5 ℃/min, and cooling to room temperature along with the furnace after calcining to obtain the fibrous lithium titanate.
Comparative example 1
Compared with the embodiment 1, the comparison method adds the inorganic titanium solution and the lithium acetate into the collagen fiber solution at the same time, and comprises the following specific steps:
step 1 and step 2 are the same as in example 1;
and step 3: adding 2.04g of lithium acetate and the inorganic titanium solution prepared in the step 2 into the collagen fiber solution prepared in the step 1, continuously stirring for 8 hours by using a magnetic stirrer at normal temperature, then adjusting the pH value of the solution to 4.0 by using a saturated sodium bicarbonate solution, then carrying out water bath for 2 hours at 38 ℃, centrifuging for 5 minutes under the condition of 4000r/min, washing the precipitate for four times by using distilled water, then washing for two times by using ethanol, then soaking for 4 hours in absolute ethanol, completely soaking the precipitate by using the amount of the ethanol, then centrifuging, and drying the centrifuged precipitate at 60 ℃.
And 4, step 4: and (3) calcining the dried material in the step (3) at 700 ℃ for 8h by using a muffle furnace, wherein the heating rate is about 5 ℃/min, and cooling the calcined material along with the furnace to obtain a sample named D1.
The XRD patterns of the D1 samples prepared in this example are shown in FIG. 7, which shows that D1 has the crystalline phase composition of titanium dioxide and does not have the crystalline phase composition of lithium titanate.
The SEM image of the D1 sample prepared in this example is shown in FIG. 8, and the result shows that D1 has a fibrous structure.
The results show that the method of the comparative example can only load the titanium source on the collagen fibers, but can not load the lithium source on the collagen fibers, and finally the prepared titanium dioxide is fibrous, and fibrous lithium titanate cannot be prepared.
Comparative example 2
Compared with the embodiment 1, the comparative example prepares fibrous titanium dioxide, and then adds lithium acetate to calcine, and the specific steps are as follows:
step 1 to step 3 are the same as in example 1;
then soaking in absolute ethyl alcohol for 4 hours, wherein the dosage of the ethyl alcohol needs to be completely soaked and precipitated;
and 4, step 4: and (3) centrifuging the precipitate soaked in the step (3), drying the centrifuged precipitate at 60 ℃, calcining the dried material at 700 ℃ for 8 hours by using a muffle furnace, wherein the heating rate is about 5 ℃/min, and cooling the calcined material along with the furnace to prepare the fibrous titanium dioxide.
And 5: and (3) adding 2.04g of lithium acetate into the fibrous titanium dioxide prepared in the step (4), uniformly mixing, calcining for 8 hours at 700 ℃ by using a muffle furnace at the heating rate of about 5 ℃/min, and cooling along with the furnace after calcining to obtain a sample named D2.
The XRD pattern of the D2 sample prepared in this comparative example is shown in fig. 9, and the result shows that D2 has the crystalline phase composition of lithium titanate.
The SEM image of the D2 sample prepared in this comparative example is shown in FIG. 10, and the result shows that D2 has no fibrous structure.
The results show that the method of this comparative example can produce lithium titanate, but the fibrous structure is destroyed by high-temperature calcination, and therefore, fibrous lithium titanate cannot be produced.
Comparative example 3
In this comparative example, the calcination temperature in step 5 was different from that in comparative example 2, and the calcination was carried out in a muffle furnace at 600 ℃ for 8 hours, and the other conditions were the same.
The sample prepared in this comparative example was designated as D3.
The XRD pattern of the D3 sample obtained in this comparative example is shown in fig. 11, and the results show that D3 contains other impurities in addition to the crystal phase composition of lithium titanate, and that lithium titanate has low crystallinity because the calcination temperature is too low and the product transformation is incomplete.
The SEM image of the D3 sample prepared in this comparative example is shown in FIG. 12, and the result shows that D3 has a fibrous structure.
The results show that the material produced by the process of this comparative example, although having a fibrous structure, is not a single lithium titanate. A single fibrous lithium titanate could not be obtained with the process of comparative example 3.
The above-mentioned embodiment is only one of the preferred embodiments of the present invention, and should not be used to limit the scope of the present invention, but all the insubstantial modifications or changes made within the spirit and scope of the main design of the present invention, which still solve the technical problems consistent with the present invention, should be included in the scope of the present invention.
Claims (10)
1. A preparation method of fibrous lithium titanate is characterized in that collagen fibers are used as templates, an inorganic titanium source is used as a titanium tanning agent, lithium salt is used as a lithium source, the titanium source is firstly loaded on the collagen fibers, and then the lithium source is combined with the titanium source, so that the preparation of the fibrous lithium titanate is realized.
2. The method for producing fibrous lithium titanate according to claim 1, wherein the collagen fiber is a collagen fiber;
the inorganic titanium source is selected from titanium sulfate;
the lithium source is one or two of lithium acetate and lithium carbonate.
3. The method for preparing fibrous lithium titanate as claimed in claim 1, wherein the molar ratio of titanium to lithium in the inorganic titanium source and lithium salt is 1: 2-4.
4. The method for producing fibrous lithium titanate according to claim 1, wherein the amount of the collagen fiber is equal to or greater than the mass of the fibrous lithium titanate produced.
5. The method for preparing fibrous lithium titanate according to claim 1 or 2, comprising the steps of:
step 1, preparing a collagen fiber solution: adding water and sodium chloride into collagen fiber raw material, mixing, adding acid to adjust pH value to 1.0-4.0, and stirring;
step 2, preparing an inorganic titanium solution: adding buffer solution into inorganic titanium for dissolving, and then adding alkali solution to adjust the pH value to 1.0-4.0;
step 3, adding the inorganic titanium solution prepared in the step 2 into the collagen fiber solution prepared in the step 1, continuously stirring, adding an alkali solution to adjust the pH value to 3.0-5.0, reacting for a period of time, centrifuging, washing, and soaking in ethanol;
step 4, adding lithium salt into the ethanol obtained in the step 3, stirring, then carrying out ultrasonic treatment, centrifuging and drying;
and 5, calcining the dried material obtained in the step 4, and cooling to room temperature to obtain the fibrous lithium titanate.
6. The method for preparing fibrous lithium titanate according to claim 5, wherein the acid solution in the step 1 is prepared from 25 mass percent of dilute sulfuric acid and 25 mass percent of formic acid according to a mass ratio of 3: 1;
the buffer solution in the step 2 is a citric acid-trisodium citrate buffer solution;
and the alkali solutions in the step 2 and the step 3 are both saturated sodium bicarbonate solutions.
7. The method for producing fibrous lithium titanate according to claim 5, wherein the stirring in step 1 is performed at room temperature for 2 to 6 hours;
the stirring in the step 3 is stirring for 6 to 10 hours at normal temperature;
and the stirring in the step 4 is carried out for 2 to 6 hours at normal temperature.
8. The method for producing fibrous lithium titanate as claimed in claim 5, wherein in the step 3, after adjusting the pH to 3.0-5.0 with an alkali solution, the fibrous lithium titanate is reacted at 35-40 ℃ for 1-4 hours;
in the step 4, the ultrasonic treatment time is 15-25 min; drying at 50-80 deg.C.
9. The method as claimed in claim 5, wherein the step 5 of calcining comprises calcining in a muffle furnace at 800 ℃ for 6-10h at a temperature rise rate of 5 ℃/min at 600 ℃. The step of calcining is followed by cooling to room temperature to obtain the fibrous lithium titanate.
10. Fibrous lithium titanate produced by the process according to any one of claims 1 to 9.
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