CN108187606B - Conductive titanium lithium ion sieve and preparation method thereof - Google Patents
Conductive titanium lithium ion sieve and preparation method thereof Download PDFInfo
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 150
- SWAIALBIBWIKKQ-UHFFFAOYSA-N lithium titanium Chemical compound [Li].[Ti] SWAIALBIBWIKKQ-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 89
- 239000002243 precursor Substances 0.000 claims abstract description 54
- 238000003795 desorption Methods 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000000126 substance Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 238000002848 electrochemical method Methods 0.000 claims abstract description 7
- 229910009866 Ti5O12 Inorganic materials 0.000 claims abstract description 6
- 229910010252 TiO3 Inorganic materials 0.000 claims abstract description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 50
- 239000010936 titanium Substances 0.000 claims description 50
- 229910052719 titanium Inorganic materials 0.000 claims description 50
- 238000001179 sorption measurement Methods 0.000 claims description 31
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 26
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000011787 zinc oxide Substances 0.000 claims description 13
- 239000011701 zinc Substances 0.000 claims description 11
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 9
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 8
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 8
- 229920000742 Cotton Polymers 0.000 claims description 8
- 239000004917 carbon fiber Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 7
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 7
- 238000011049 filling Methods 0.000 claims description 7
- 239000004246 zinc acetate Substances 0.000 claims description 7
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 6
- 239000008139 complexing agent Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 230000003301 hydrolyzing effect Effects 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 229910000611 Zinc aluminium Inorganic materials 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- 239000006258 conductive agent Substances 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 238000009792 diffusion process Methods 0.000 claims description 2
- 239000002019 doping agent Substances 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 abstract description 9
- 238000005728 strengthening Methods 0.000 abstract description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 24
- 229910052744 lithium Inorganic materials 0.000 description 23
- 239000000243 solution Substances 0.000 description 19
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 14
- 238000011084 recovery Methods 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000003463 adsorbent Substances 0.000 description 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical group [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 239000012267 brine Substances 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 239000013535 sea water Substances 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- -1 zinc aluminate Chemical class 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 241001131796 Botaurus stellaris Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000006181 electrochemical material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0233—Compounds of Cu, Ag, Au
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/024—Compounds of Zn, Cd, Hg
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to a conductive titanium lithium ion sieve, in particular to a conductive titanium lithium ion sieve doped and coated with a nano conductive oxide, which can be used for strengthening the absorption and desorption process of lithium ions by an electrochemical method, wherein the conductive titanium lithium ion sieve comprises 75-85% by mass of the titanium lithium ion sieve, 3-5% by mass of the doped conductive oxide and 15-20% by mass of the surface-coated conductive oxide, and the chemical composition of a precursor of the titanium lithium ion sieve is L i2TiO3Or L i4Ti5O12One of them; the chemical composition of the conductive oxide is Zn1‑xAlxOAgyWherein x =0.05-0.2 and y = 0-0.05. The conductive titanium lithium ion sieve can be used for strengthening the absorption and desorption process of lithium ions by an electrochemical method, thereby improving the absorption capacity of the lithium ion sieve, the absorption and desorption speed and the desorption rate of the lithium ions.
Description
Technical Field
The invention relates to a conductive titanium lithium ion sieve and a preparation method thereof, in particular to a conductive titanium lithium ion sieve doped and coated with a nano conductive oxide and a preparation method thereof, belonging to the field of new energy materials.
Technical Field
Lithium resource has become an important strategic resource at home and abroad, is widely applied to industries such as ceramics, batteries, pharmacy and the like, and is called as an energy element in the 21 st century by people. Lithium and its compounds are mainly present in seawater, salt lake brine and mineral deposits. There are two main methods for producing lithium, one is to extract lithium from ore, and the other is to extract lithium from seawater or salt lake brine. The defects of complicated steps, high energy consumption and the like exist in the process of extracting lithium from ores, so the process of extracting lithium from a solution becomes a development direction of lithium extraction. The technical key of extracting lithium from solution is to synthesize a high-efficiency lithium adsorbent material, and certain performances are achieved in the aspects of adsorption and ion exchange lithium extraction at home and abroad. The adsorption method has simple process for extracting lithium, high recovery rate and good selectivity, is particularly suitable for extracting lithium from low-concentration lithium-containing aqueous solution, and has the key point of preparing the adsorbent with large adsorption capacity and good cycle performance.
The lithium ion sieve is prepared by introducing template L i into inorganic compound+Heat treating to form lithium ion sieve precursor, and removing L i+Obtained lithium ion sieve due to size effect and sieving effect, pair L i+The ions have specific memory selectivity, and can be L i under the condition of coexistence of multiple ions+Separating ions from other ions, and using in L i in lithium-rich solution such as seawater or bittern+The common titanium lithium ion sieve precursor mainly comprises L i of monoclinic system2TiO3And L i of spinel structure4Ti5O12. World patent WO2017020090 discloses a process for extracting lithium from brine using a titanic acid adsorbent; chinese patent CN105238927(2016-01-13) discloses a metatitanic acid adsorbent and a preparation method of a precursor thereof. The titanium lithium ion sieve has the advantages of low dissolution loss rate, stable structure, good reusability and the like, but has the problems that the actual adsorption capacity is greatly lower than the theoretical adsorption capacity, the adsorption and desorption speeds are slow, the lithium ion desorption is not thorough, and the lithium removal amount is gradually reduced in use, so that the industrial application is hindered.
In order to overcome the defects in the application of the lithium ion sieve, a magnetic field, an electric field or ultrasonic waves can be applied to enhance the absorption and desorption process of the lithium ions, for example, the absorption and desorption process of the lithium ions is enhanced by an electrochemical method in chinese patents CN105408521(2016-03-16), CN105948081(2016-09-21) and CN102382984 (2012-03-21). Because the titanium-based lithium ion sieve and the precursor thereof are almost non-conductive semiconductor materials, the titanium-based lithium ion sieve and the precursor thereof are usually required to be mixed with graphite powder or metal powder to be molded into an electrode, and the lithium ion sieve and the precursor with conductivity are lacked.
Disclosure of Invention
The invention aims to provide a conductive titanium lithium ion sieve, in particular to a conductive titanium lithium ion sieve doped and coated with a nano conductive oxide, which can be used for strengthening the absorption and desorption process of lithium ions by an electrochemical method, wherein the conductive titanium lithium ion sieve comprises 75-85% of titanium lithium ion sieve by mass, 3-5% of doped conductive oxide by mass and 15-20% of surface-coated conductive oxide by mass, and the chemical composition of a precursor of the titanium lithium ion sieve is L i2TiO3Or L i4Ti5O12One, the conductive oxide is acid-resistant aluminum-doped zinc oxide or aluminum-silver-doped zinc oxide.
The chemical composition of the conductive oxide in the invention is as follows: zn1-xAlxOAgyWherein x =0.05-0.2, y =0-0.05, as a binder, a dopant, a capping agent, and a conductive agent of the lithium ion sieve and its precursor.
Zn in the invention2+、Al3+And Ag+Atoms with larger volume are doped into the titanium lithium ion sieve, so that the diffusion coefficient of lithium ions in the titanium lithium ion sieve is improved, and the adsorption and desorption speed and the desorption rate of the lithium ion sieve are improved.
The main conductive component of the conductive oxide in the invention is aluminum-doped zinc oxide, in Al3+When the doping mole fraction is less than 0.05, Al3+By substitution of Zn in the zinc oxide lattice2+The crystal structure of ZnO is kept; when Al is present3+When the doping molar fraction is more than 0.05, zinc aluminate (ZnAl) excellent in acid resistance is produced2O4) And the conductivity of the material is reduced. By adding silver atoms with good conductivity, the conductivity reduction of the aluminum-doped zinc oxide can be compensated, and the acid resistance of the aluminum-doped zinc oxide can be improved.
The conductive oxide film coated with the titanium lithium ion sieve is a porous film material, the size of lithium atoms is very small, and the conductive oxide film does not influence the adsorption and mass transfer process of lithium ions; in the high-temperature heat treatment process, precursor elements of the titanium-based lithium ion sieve are diffused into the conductive oxide film, so that lithium zincate, lithium aluminate and titanium zincate can be formed, and the precursor elements can also be used as precursors of the lithium ion sieve, so that the adsorption selectivity of the titanium-based lithium ion sieve is improved.
The formation, doping and film forming of the conductive oxide are completed in one step in the high-temperature heat treatment process, the conductive oxide is mixed with titanium lithium ion sieve powder in the form of nano sol, Zn2+、Al3+And Ag+Doping into a titanium lithium ion sieve crystal structure to deform the lithium ion sieve structure, so that the adsorption capacity, stability and conductivity of the lithium ion sieve are improved, and the doping amount mainly depends on the heat treatment temperature; in the high-temperature heat treatment process, the conductive oxide nanoparticles which are not doped into the crystal structure of the titanium-based lithium ion sieve are coated on the surface of the titanium-based lithium ion sieve to form an acid-resistant conductive oxide film, so that the titanium-based lithium ion sieve is endowed with good conductivity, and the conductivity not only depends on the doping amount of aluminum and silver, but also is influenced by the process conditions such as heat treatment temperature, time and the like.
The conductive titanium lithium ion sieve can selectively adsorb lithium ions from a lithium-containing solution, and can also be conveniently assembled into an electrode, and the adsorption of positive ions in the solution is enhanced by adopting an electric field to promote the adsorption of the lithium ions on the negative electrode of the lithium ion sieve; the lithium ions can be eluted and adsorbed by adopting inorganic acid, or the desorption of the lithium ions in the positive electrode of the lithium ion sieve can be promoted by adopting electric field enhancement by taking the conductive titanium lithium ion sieve as an electrode. The electrochemical adsorption and desorption of the lithium ion sieve is less influenced by the concentration and acidity of the solution, and the adsorption capacity, the lithium ion adsorption and desorption speed and the recovery rate of the lithium ion sieve are high even in the dilute solution.
The invention relates to a conductive titanium lithium ion sieve, which is based on the research of a solar cell transparent conductive film and an inorganic nano material by the inventor for a long time and is essentially different from the method for doping and coating the lithium ion sieve by the inorganic nano material in the prior art. Fully utilizes the characteristic that the aluminum or aluminum-silver doped nano ZnO has conductivity, the proportion of doping elements aluminum and ZnO exceeds the limit of the prior art, and the excessive aluminum and zinc form acid resistanceThe excellent zinc aluminate ensures that the aluminum-doped zinc oxide conductive film has good acid resistance, and the conductivity is reduced by silver doping compensation. The nano conductive oxide and the titanium lithium ion sieve are not simply physically coated, and mainly subjected to high-temperature thermochemical reaction. In the heat treatment process, components of the nanometer conductive oxide and the titanium-based lithium ion sieve precursor diffuse mutually at high temperature, and zinc and aluminum components enter a crystal structure of the titanium-based lithium ion sieve to form a doped titanium-based lithium ion sieve; titanium and lithium components enter a crystal structure of the conductive oxide to form a transition layer of the conductive oxide doped with lithium zincate, lithium aluminate and titanium zincate, the roughness of the conductive oxide is changed by multi-element doping, so that the conductive oxide has good acid resistance, and the chemical component formed by sintering the undoped conductive oxide is Zn1-xAlxOAgyThe invention has creativity and practicability.
The invention also aims to provide a preparation method of the conductive titanium lithium ion sieve, which adopts the technical scheme that the preparation method comprises the steps of preparing nano conductive oxide sol, doping a titanium lithium ion sieve precursor, sintering the conductive titanium lithium ion sieve precursor and preparing the conductive titanium lithium ion sieve, and comprises the following specific steps:
(1) respectively adding isopropanol, a complexing agent, an isopropanol solution of zinc acetate, an isopropanol solution of aluminum isopropoxide, silver nitrate and deionized water into a reactor under stirring, and controlling the feeding molar ratio of the raw materials as follows: zinc acetate: aluminum isopropoxide: silver nitrate: complexing agent: isopropyl alcohol: water = 1: 0.05-0.25: 0-0.05: 1-1.2: 10-40: 5-10, heating and hydrolyzing for 1-2h at 60-70 ℃, then concentrating to form nano conductive oxide sol with solid mass concentration of 10-15%, the particle size is 20-30nm, aging for 24-72h at room temperature for standby, and the chemical composition of the nano conductive oxide sol is Zn1-xAlxOAgyWherein x =0.05-0.2, y =0-0.05, and the complexing agent is one of ethanolamine, diethanolamine, triethanolamine or acetylacetone;
(2) soaking a titanium-based lithium ion sieve precursor into the nano conductive oxide sol to dope and coat the nano conductive oxide on the titanium-based lithium ion sieve precursor, stirring for 1-2h to form gel, and controlling the mass ratio of fed solids as follows: lithium ion sieve: conductive oxide = 1: 0.17-0.35;
(4) drying the titanium-based lithium ion sieve precursor doped and coated with the nano conductive oxide at the temperature of 100-150 ℃, then placing the dried precursor into a high-temperature furnace, and carrying out heat treatment for 8-12h at the temperature of 600-800 ℃ to form a conductive titanium-based lithium ion sieve precursor sintered block;
(5) cutting a conductive titanium lithium ion sieve precursor sintered block, coating the conductive titanium lithium ion sieve precursor sintered block with carbon fiber conductive cotton, filling the conductive titanium lithium ion sieve precursor sintered block into titanium cathode blue, taking insoluble titanium anode blue as a counter electrode, taking 0.1-0.5 mol/L hydrochloric acid solution as electrolyte, introducing gas, stirring the hydrochloric acid solution to jointly form an electrochemical cell, applying 0-2V direct current voltage between the two electrodes to desorb lithium ions in the lithium ion sieve precursor, and then washing with deionized water to obtain the conductive titanium lithium ion sieve;
(6) the method comprises the steps of coating a conductive titanium lithium ion sieve with carbon fiber conductive cotton, filling the coated conductive titanium lithium ion sieve into insoluble titanium anode blue, using titanium cathode blue as a counter electrode, using 200 mg/L lithium chloride as electrolyte, introducing gas to stir lithium chloride solution to jointly form an electrochemical cell, applying 0-2V direct current voltage between the two electrodes to enable the lithium ion sieve to achieve saturated adsorption, measuring that the adsorption capacity of the lithium ion sieve is 52-58mg/g, the lithium recovery rate is 92-96%, and the adsorption capacity and the lithium ion recovery rate are not obviously reduced after 10 times of adsorption and desorption.
The adsorption capacity and the lithium ion recovery rate of the conductive titanium lithium ion sieve are obtained by measuring the lithium ion concentration in the electrolyte before and after adsorption by adopting an ion chromatography.
The experimental raw materials used in the invention, namely zinc acetate, aluminum isopropoxide, ethanolamine, isopropanol, lithium hydroxide, hydrochloric acid and lithium chloride are all commercially available chemically pure reagents, and the precursor L i of the used titanium lithium ion sieve2TiO3And L i4Ti5O12Prepared by referring to the prior method. Insoluble titanium anode blue, titanium cathode blue, carbon fiber conductive cotton and a dc power source are commercially available laboratory-generic electrochemical materials and equipment.
The invention has the beneficial effects that:
(1) conductive titanium-based lithium ion sieveBy Zn2+、Al3+And Ag+Doping improves the adsorption and desorption speed and desorption rate of lithium ions;
(2) the electrochemical method is applied to strengthen the absorption and desorption process of the lithium ions, so that the absorption capacity of the lithium ion sieve is improved;
(3) the sol-gel method for preparing the aluminum-resistant doped conductive zinc oxide film has the advantages of simple process, low production cost and application prospect.
Detailed Description
Example 1
Adding 60g (1.0mol) of isopropanol, 7.3g (0.12mol) of ethanolamine, 16.5g (0.09mol) of zinc acetate, 2.0g (0.01mol) of isopropanol solution of aluminum isopropoxide, 0.85g (0.005mol) of silver nitrate and 9.0g (0.5mol) of deionized water into a reactor respectively under stirring, heating and hydrolyzing for 2h at 60-70 ℃, then concentrating to form 87.0g of nano conductive oxide sol with the solid mass percentage concentration of 10%, wherein the particle diameter of the sol is 20-30nm, and aging for 24h at room temperature, and the chemical composition of the sol is Zn0.9Al0.1OAg0.05。
Titanium-based lithium ion sieve precursor L i2TiO335.0g of sol of 10 percent of nano conductive oxide is soaked to 87.0g of sol of 10 percent of nano conductive oxide, so that the nano conductive oxide is doped and coated on the precursor of the titanium-based lithium ion sieve, and the gel is formed after stirring for 2 hours. Drying the titanium-based lithium ion sieve precursor doped and coated with the nano conductive oxide at the temperature of 100 ℃ and 150 ℃, then placing the dried precursor into a high-temperature furnace, and carrying out heat treatment for 8 hours at the temperature of 700 ℃ to form 43.7g of conductive titanium-based lithium ion sieve precursor sintered blocks.
Crushing a conductive titanium lithium ion sieve precursor sinter, coating the conductive titanium lithium ion sieve precursor sinter with carbon fiber conductive cotton, filling the coated conductive titanium lithium ion sieve precursor sinter into insoluble titanium anode blue, taking titanium cathode blue as a counter electrode, taking 0.1 mol/L hydrochloric acid solution as electrolyte, introducing gas to stir hydrochloric acid solution to jointly form an electrochemical cell, applying 1.5V direct current voltage between the two electrodes to desorb lithium ions in the lithium ion sieve precursor, then washing with deionized water to obtain the conductive titanium lithium ion sieve, coating the conductive titanium lithium ion sieve with carbon fiber conductive cotton, filling the coated conductive titanium lithium ion sieve into the titanium cathode blue, taking insoluble titanium anode blue as the counter electrode, taking 200 mg/L lithium chloride as electrolyte, introducing gas to stir lithium chloride solution to jointly form the electrochemical cell, applying 1.5V direct current voltage between the two electrodes to ensure that the lithium ion sieve is adsorbed in saturation, measuring the adsorption capacity of 58mg/g and the lithium ion recovery rate of 96%, and not obviously reducing the adsorption capacity and the lithium ion recovery rate after 10 times of adsorption and desorption.
Example 2
Respectively adding 60g (1.0mol) of isopropanol, 12g (0.12mol) of acetylacetone, 17.4g (0.095mol) of zinc acetate, 1.0g (0.005mol) of aluminum isopropoxide and 9.0g (0.5mol) of deionized water into a reactor under stirring, heating and hydrolyzing at 60-70 ℃ for 1h, concentrating to form 79.9g of nano conductive oxide sol with the solid mass percentage concentration of 10%, wherein the sol has the particle size of 20-30nm, and aging at room temperature for 24h, and the chemical composition of the sol is Zn0.95Al0.05O。
Titanium-based lithium ion sieve precursor L i4Ti5O1235.0g of the sol is dipped into 79.9g of 10 percent nano conductive oxide sol, so that the nano conductive oxide is doped and coated on the precursor of the titanium lithium ion sieve, and the gel is formed after stirring for 2 hours. Drying the titanium-based lithium ion sieve precursor doped and coated with the nano conductive oxide at the temperature of 100 ℃ and 150 ℃, then placing the dried precursor into a high-temperature furnace, and carrying out heat treatment for 12 hours at the temperature of 600 ℃ to form 43.0g of conductive titanium-based lithium ion sieve precursor sintered blocks.
Crushing a conductive titanium lithium ion sieve precursor sinter, coating the conductive titanium lithium ion sieve precursor sinter with carbon fiber conductive cotton, filling the coated conductive titanium lithium ion sieve precursor sinter into insoluble titanium anode blue, taking titanium cathode blue as a counter electrode, taking 0.1 mol/L hydrochloric acid solution as electrolyte, introducing gas to stir hydrochloric acid solution to jointly form an electrochemical cell, applying 1.5V direct current voltage between the two electrodes to desorb lithium ions in the lithium ion sieve precursor, then cleaning the electrochemical cell with deionized water to obtain the conductive titanium lithium ion sieve, coating the conductive titanium lithium ion sieve with the carbon fiber conductive cotton, filling the coated conductive titanium lithium ion sieve into the titanium cathode blue, taking insoluble titanium anode blue as the counter electrode, taking 200 mg/L lithium chloride as electrolyte, introducing gas to stir lithium chloride solution to jointly form the electrochemical cell, applying 1.5V direct current voltage between the two electrodes to ensure that the lithium ion sieve is adsorbed in saturation, and measuring the adsorption capacity of the electrochemical cell to be 52mg/g and the lithium recovery rate to be 92%.
Claims (5)
1. A conductive titanium lithium ion sieve is characterized in that a nanometer conductive oxide is adopted to dope and coat the titanium lithium ion sieve, the adsorption and desorption process of lithium ions can be enhanced by an electrochemical method, the mass percentage of the titanium lithium ion sieve in the conductive titanium lithium ion sieve is 75-85%, the mass percentage of the doped conductive oxide is 3-5%, the mass percentage of the surface-coated conductive oxide is 15-20%, and the chemical composition of a precursor of the titanium lithium ion sieve is L i2TiO3Or L i4Ti5O12One of them; the conductive oxide is acid-resistant aluminum-doped zinc oxide or aluminum-silver-doped zinc oxide, and the chemical composition of the conductive oxide is as follows: zn1-xAlxOAgyWherein x =0.05-0.2 and y = 0-0.05.
2. The conductive titanium-based lithium ion sieve of claim 1, wherein the conductive oxide serves as a binder, a dopant, a coating agent, and a conductive agent for the lithium ion sieve and a precursor thereof.
3. The conductive titanium-based lithium ion sieve of claim 1, wherein Zn is2+、Al3+And Ag+Atoms with larger volume are doped into the titanium lithium ion sieve, so that the diffusion coefficient of lithium ions is improved, and the adsorption capacity, adsorption and desorption speed and desorption rate of the lithium ion sieve are improved.
4. The conductive titanium-based lithium ion sieve of claim 1, wherein inorganic acid is used for desorption and adsorption of lithium ions, or electrochemical methods are used for enhanced desorption and adsorption of lithium ions.
5. A preparation method of a conductive titanium lithium ion sieve is characterized by comprising the steps of preparing a nano conductive oxide sol, doping a titanium lithium ion sieve precursor, sintering the conductive titanium lithium ion sieve precursor and preparing the conductive titanium lithium ion sieve, and comprises the following specific steps:
(1) respectively adding isopropanol, a complexing agent, an isopropanol solution of zinc acetate, an isopropanol solution of aluminum isopropoxide, silver nitrate and deionized water into a reactor under stirring, and controlling the feeding molar ratio of the raw materials as follows: zinc acetate: aluminum isopropoxide: silver nitrate: complexing agent: isopropyl alcohol: water = 1: 0.05-0.25: 0-0.05: 1-1.2: 10-40: 5-10, heating and hydrolyzing for 1-2h at 60-70 ℃, then concentrating to form nano conductive oxide sol with solid mass concentration of 10-15%, the particle size is 20-30nm, aging for 24-72h at room temperature for standby, and the chemical composition of the nano conductive oxide sol is Zn1-xAlxOAgyWherein x =0.05-0.2, y =0-0.05, and the complexing agent is one of ethanolamine, diethanolamine, triethanolamine or acetylacetone;
(2) soaking a titanium-based lithium ion sieve precursor into the nano conductive oxide sol to dope and coat the nano conductive oxide on the titanium-based lithium ion sieve precursor, stirring for 1-2h to form gel, and controlling the mass ratio of fed solids as follows: lithium ion sieve: conductive oxide = 1: 0.17-0.35;
(4) drying the titanium-based lithium ion sieve precursor doped and coated with the nano conductive oxide at the temperature of 100-150 ℃, then placing the dried precursor into a high-temperature furnace, and carrying out heat treatment for 8-12h at the temperature of 600-800 ℃ to form a conductive titanium-based lithium ion sieve precursor sintered block;
(5) cutting the sintered blocks of the precursor of the conductive titanium-based lithium ion sieve, coating the sintered blocks with carbon fiber conductive cotton, filling the coated sintered blocks into insoluble titanium anode blue, taking titanium cathode blue as a counter electrode, taking 0.1-0.5 mol/L hydrochloric acid solution as electrolyte, introducing gas, stirring the hydrochloric acid solution to jointly form an electrochemical cell, applying 0-2V direct current voltage between the two electrodes to desorb lithium ions in the precursor of the lithium ion sieve, and then washing with deionized water to obtain the conductive titanium-based lithium ion sieve.
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| CN113117635B (en) * | 2021-03-04 | 2022-07-26 | 广东省科学院稀有金属研究所 | Preparation method of titanium-based lithium ion sieve |
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