CN108187606A - A kind of electric conductivity titanium based lithium-ion sieve and preparation method thereof - Google Patents
A kind of electric conductivity titanium based lithium-ion sieve and preparation method thereof Download PDFInfo
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- CN108187606A CN108187606A CN201810057887.6A CN201810057887A CN108187606A CN 108187606 A CN108187606 A CN 108187606A CN 201810057887 A CN201810057887 A CN 201810057887A CN 108187606 A CN108187606 A CN 108187606A
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- lithium
- ion
- titanium based
- based lithium
- sieve
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 143
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 140
- 239000010936 titanium Substances 0.000 title claims abstract description 92
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title claims description 9
- 238000000034 method Methods 0.000 claims abstract description 24
- 238000001179 sorption measurement Methods 0.000 claims abstract description 16
- 238000002336 sorption--desorption measurement Methods 0.000 claims abstract description 16
- 230000008569 process Effects 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 238000003795 desorption Methods 0.000 claims abstract description 10
- 238000005253 cladding Methods 0.000 claims abstract description 9
- 230000005518 electrochemistry Effects 0.000 claims abstract description 6
- 229910002986 Li4Ti5O12 Inorganic materials 0.000 claims abstract description 5
- 229910007848 Li2TiO3 Inorganic materials 0.000 claims abstract description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 32
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 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 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 238000010521 absorption reaction Methods 0.000 claims description 16
- 239000011701 zinc Substances 0.000 claims description 14
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 12
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical class [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000011787 zinc oxide 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
- 238000003756 stirring Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 9
- 239000004917 carbon fiber Substances 0.000 claims description 9
- KHYBPSFKEHXSLX-UHFFFAOYSA-N iminotitanium Chemical compound [Ti]=N KHYBPSFKEHXSLX-UHFFFAOYSA-N 0.000 claims description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 9
- 229910001000 nickel titanium Inorganic materials 0.000 claims description 9
- 238000011084 recovery Methods 0.000 claims description 9
- 229920000742 Cotton Polymers 0.000 claims description 8
- 241001062009 Indigofera Species 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
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000003792 electrolyte Substances 0.000 claims description 7
- 239000004246 zinc acetate Substances 0.000 claims description 7
- 239000008139 complexing agent Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- -1 aluminium silver Chemical compound 0.000 claims description 5
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 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
- 229940043237 diethanolamine Drugs 0.000 claims description 2
- 238000009792 diffusion process Methods 0.000 claims description 2
- 239000002019 doping agent Substances 0.000 claims description 2
- 238000002848 electrochemical method Methods 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 230000003014 reinforcing effect Effects 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- 239000003292 glue Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 description 16
- 239000002253 acid Substances 0.000 description 11
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000004411 aluminium Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000002500 ions Chemical group 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000013535 sea water Substances 0.000 description 3
- 241001131796 Botaurus stellaris Species 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 229910010252 TiO3 Inorganic materials 0.000 description 2
- 239000000443 aerosol Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229940031098 ethanolamine Drugs 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical group [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910009866 Ti5O12 Inorganic materials 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 150000001450 anions Chemical class 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
- 235000013339 cereals Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 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
- 229920000831 ionic polymer Polymers 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000003041 laboratory chemical Substances 0.000 description 1
- 150000002641 lithium Chemical group 0.000 description 1
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 description 1
- 230000036244 malformation Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000012528 membrane Substances 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
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- NMJKIRUDPFBRHW-UHFFFAOYSA-N titanium Chemical compound [Ti].[Ti] NMJKIRUDPFBRHW-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- 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
Landscapes
- 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 present invention relates to a kind of electric conductivity titanium based lithium-ion sieve, the oxide-doped electric conductivity titanium based lithium-ion sieve with cladding of particularly a kind of conductive nano is capable of the adsorption desorption process that Applied Electrochemistry method strengthens lithium ion；The shared mass percent of titanium based lithium-ion sieve is 75% 85% in electric conductivity titanium based lithium-ion sieve, and the mass percent shared by the conductive oxide of doping is 3% 5%, and the mass percent shared by surface coated conductive oxide is 15% 20%；The presoma chemical composition of titanium based lithium-ion sieve is Li2TiO3Or Li4Ti5O12One of；The chemical composition of conductive oxide is Zn1‑xAlxOAgy, wherein, x=0.05 0.2, y=0 0.05.Electric conductivity titanium based lithium-ion of the present invention sieve can Applied Electrochemistry method strengthen the adsorption desorption process of lithium ion, so as to improve the adsorption desorption speed of the adsorption capacity of lithium ion sieve, lithium ion and desorption rate.
Description
Technical field
The present invention relates to a kind of electric conductivity titanium based lithium-ion sieve and preparation method thereof, particularly a kind of conductive nano oxides
The electric conductivity titanium based lithium-ion of doping and cladding sieve and preparation method thereof, belongs to new energy materials field.
Technical background
Lithium resource has become domestic and international important strategic resource, is widely used in the industries such as ceramics, battery, pharmacy, people
It is referred to as " the energy source elements in 21st century ".Lithium and its compound are primarily present in seawater, salt lake bittern and mineral deposit.Lithium
Production method there are mainly two types of, one kind is that lithium is extracted from ore, and another kind is to extract lithium from seawater or salt lake bittern.
Extracted from ore lithium there are complex steps, energy consumption is larger the shortcomings of, therefore extract lithium from solution will be as proposing the development of lithium
Direction.The key problem in technology that lithium is extracted from solution is the lithium adsorbent material of synthesizing efficient, both at home and abroad in absorption and ion exchange
Certain achievement is achieved in terms of carrying lithium.Absorption method extraction lithium is simple for process, the rate of recovery is high, selectivity is good, is particularly suitable for from low
Concentration extracts lithium in aqueous solution containing lithium, the key of this method is to prepare that adsorption capacity is big and the good adsorbent of cycle performance.
Lithium ion sieve is by importing template Li into inorganic compound+, lithium ion sieve presoma is treated thermally to produce, so
After remove Li therein+It obtains.Lithium ion sieve is due to dimensional effect and sieve effect, to Li+There is ion specific memory to select
Property, it can be under polyion Coexistence Situation by Li+Ion comes with other ion isolations, is usually used in the rich lithium solution such as seawater or brine
Middle Li+Selective extraction.Lithium ion sieve mainly has manganese systems lithium ion sieve, titanium based lithium-ion sieve and other based lithium-ions sieve etc..
Common titanium based lithium-ion sieve presoma mainly has the Li of monoclinic system2TiO3With the Li of spinel structure4Ti5O12.The world
Patent WO2017020090 discloses the method for extracting lithium from brine using metatitanic acid adsorbent；Chinese patent CN105238927
(2016-01-13) discloses the preparation method of a kind of metatitanic acid adsorbent and its presoma.Titanium based lithium-ion sifter device has molten loss rate
The advantages that low, stable structure, reusability are good, but in the presence of practical adsorption capacity be significantly less than theoretical adsorption capacity, absorption and
Desorption rate is slower, and lithium ion desorption is not thorough, and the problem of lithium amount is gradually reduced is taken off in use, hinders industrial applications.
It is insufficient present in lithium ion sieve application to overcome, it is strong that the modes such as application magnetic field, electric field or ultrasonic wave may be used
Change the adsorption desorption process of lithium ion, for example, Chinese patent CN105408521 (2016-03-16), CN105948081 (2016-
Adsorption desorption lithium ion 09-21) and disclosed in CN102382984 (2012-03-21) is strengthened using electrochemical method.Due to titanium system
Lithium ion sieve and its presoma are almost nonconducting semi-conducting materials, it usually needs and graphite powder or metal powder mixing molding
Electrode is made, lacks conductive lithium ion sieve and presoma.
Invention content
The object of the present invention is to provide a kind of electric conductivity titanium based lithium-ion sieves, and particularly a kind of conductive nano is oxide-doped
It is sieved with the electric conductivity titanium based lithium-ion of cladding, is capable of the adsorption desorption process of Applied Electrochemistry method reinforcing lithium ion；Electric conductivity titanium
Titanium based lithium-ion sieves shared mass percent as 75%-85% in based lithium-ion sieve, the quality shared by the conductive oxide of doping
Percentage is 3%-5%, the mass percent shared by surface coated conductive oxide be 15%-20%, the titanium based lithium-ion
The presoma chemical composition of sieve is Li2TiO3Or Li4Ti5O12One of, the conductive oxide is acidproof aluminium doping oxidation
Zinc or aluminium silver doped zinc oxide.
The chemical composition of conductive oxide is in the present invention：Zn1-xAlxOAgy, wherein, x=0.05-0.2, y=0-0.05,
As the adhesive of lithium ion sieve and its presoma, dopant, covering and conductive agent.
Zn in the present invention2+、Al3+And Ag+Isometric larger atom is incorporated into titanium based lithium-ion sieve, improves lithium ion
Diffusion coefficient wherein, so as to improve the adsorption desorption speed of lithium ion sieve and desorption rate.
The main conductive component of conductive oxide is aluminium-doped zinc oxide in the present invention, in Al3+Doping molar fraction is less than
When 0.05, Al3+Replace the Zn in zinc oxide lattice2+, maintain the crystal structure of ZnO；Work as Al3+Doping molar fraction is more than
When 0.05, the fabulous zinc aluminate (ZnAl of generation acid resistance2O4) phase, make the reduction of materials conductive performance.It is good by adding electric conductivity
Good silver atoms, can compensate the electric conductivity of Al-Doped ZnO reduces, while improve its acid resistance.
The conductive oxide film that titanium based lithium-ion sieve is coated in the present invention is porous film material, and lithium atom is small-sized, leads
Electroxidation object film has no effect on lithium ion absorption mass transport process；In high-temperature heat treatment process, titanium based lithium-ion sieve forerunner's volume elements
Element is diffused into conductive oxide film, zincic acid lithium, lithium aluminate and zincic acid titanium can be formed, before they can also be used as lithium ion sieve
Body is driven, improves the adsorptive selectivity of titanium based lithium-ion sieve.
Formation, doping and the film forming of conductive oxide are that a step is completed in high-temperature heat treatment process in the present invention, are led
Electroxidation object is mixed in the form of Nano sol with titanium based lithium-ion sieve powder, Zn2+、Al3+And Ag+Doping enters titanium based lithium-ion and sieves
In crystal structure, make lithium ion sieve malformation, so as to improve its adsorption capacity, stability and electric conductivity, doping mainly takes
Certainly in heat treatment temperature；Undoped with the conductive oxide nanometer for entering titanium based lithium-ion sieve crystal structure in high-temperature heat treatment process
Particle is coated on titanium based lithium-ion sieve surface and forms acidproof conductive oxide film, assigns titanium based lithium-ion and sieves good electric conductivity,
Electric conductivity depends not only on the doping of aluminium silver, is also influenced by process conditions such as heat treatment temperature and times.
In the present invention electric conductivity titanium based lithium-ion sieve can from lithium-containing solution selective absorption lithium ion, can also facilitate
Electric conductivity titanium based lithium-ion sieve is assembled into electrode by ground, using the absorption of electric field-enhanced anions in solution, lithium ion is promoted to exist
The absorption of lithium ion sieve cathode；The lithium ion of inorganic acid elution absorption may be used, electric conductivity titanium based lithium-ion can also be sieved
As electrode, using the desorption of lithium ion in electric field-enhanced promotion lithium ion sieve anode.Lithium ion sieve electrochemistry adsorption desorption is by molten
The concentration and Effect of Acidity On Absorption of liquid are smaller, even if lithium ion sieve adsorption capacity, lithium ion adsorption desorption speed and recycling in weak solution
Rate is also very high.
The Pathway of Creation that electric conductivity titanium based lithium-ion sieves in the present invention is inventor's long campaigns solar cell electrically conducting transparent
Based on film and inorganic nano material research, with using inorganic nano material doping and coated lithium ion sifter device in the prior art
There is the difference of essence.Take full advantage of aluminium or aluminium Ag doping nano-ZnO it is conductive the characteristics of, doped chemical aluminium and ZnO
Ratio have exceeded the limitation of the prior art, excessive aluminum and zinc is made to form the fabulous zinc aluminate of acid resistance, makes Al-Doped ZnO
Conductive film has good acid resistance, and compensates electric conductivity by Ag doping and decline.Conductive nano oxide and titanium based lithium-ion
It is not simple physics cladding, mainly high temperature thermal chemical reaction between sieve.In heat treatment process conductive nano oxide and
Titanium based lithium-ion sieves the component phase counterdiffusion at high temperature of presoma, and zinc and aluminium component enter titanium based lithium-ion sieve crystal structure
In, the titanium based lithium-ion for forming doping sieves；Titanium and lithium component enter in conductive oxide crystal structure, form zincic acid lithium, aluminic acid
Lithium and the titanium doped conductive oxide transition zone of zincic acid, multi-element doping change the roughness of conductive oxide, make it have
Good acid resistance, undoped conductive oxide are sintered to form chemical composition as Zn1-xAlxOAgyAcidproof conductive oxide film,
So creative and practicability of the invention.
It is a further object of the present invention to provide a kind of preparation method of electric conductivity titanium based lithium-ion sieve, technical solution includes receiving
It is prepared by rice conductive oxide colloidal sol, the doping of titanium based lithium-ion sieve presoma, the sintering of electric conductivity titanium based lithium-ion sieve presoma,
The preparation of electric conductivity based lithium-ion sieve, the specific steps are：
（1）Isopropanol, complexing agent, the aqueous isopropanol of zinc acetate, aluminium isopropoxide are separately added into reactor under stiring
Aqueous isopropanol, silver nitrate and deionized water, control raw material molar ratio are：Zinc acetate：Aluminium isopropoxide：Silver nitrate：Complexing
Agent：Isopropanol：Water=1：0.05-0.25：0-0.05：1-1.2：10-40：5-10, the heating hydrolysis 1-2h at 60-70 DEG C, then
Concentration forms the conductive nano oxide sol of a concentration of 10%-15% of solid masses, grain size 20-30nm, room temperature ageing 24-
72h is spare, chemical composition Zn1-xAlxOAgy, wherein, x=0.05-0.2, y=0-0.05, the complexing agent are ethyl alcohol
One of amine, diethanol amine, triethanolamine or acetylacetone,2,4-pentanedione；
（2）By titanium based lithium-ion sieve presoma be impregnated into conductive nano oxide sol, make conductive nano it is oxide-doped and
It is coated on titanium based lithium-ion sieve presoma, stirring 1-2h forms gel, and the control solid masses ratio that feeds intake is：Lithium ion sieve：It leads
Electroxidation object=1：0.17-0.35；
（4）Titanium based lithium-ion that is conductive nano is oxide-doped and coating sieves presoma drying, Ran Houfang at 100-150 DEG C
Enter in high temperature furnace, 8-12h is heat-treated at 600-800 DEG C, form electric conductivity titanium based lithium-ion sieve presoma agglomerate；
（5）By the sieve presoma agglomerate cutting of electric conductivity titanium based lithium-ion, and titanium the moon is loaded into after being coated with electric conduction of carbon fiber cotton
Extremely in basket, insoluble Ni―Ti anode indigo plant is used to electrode, using the hydrochloric acid solution of 0.1-0.5mol/L as electrolyte, to be passed through gas
Hydrochloric acid solution is stirred, collectively constitutes electrochemical cell, applies the DC voltage of 0-2V in two interpolars, makes in lithium ion sieve presoma
Lithium ion is desorbed, and is then cleaned with deionized water, obtains electric conductivity titanium based lithium-ion sieve；
（6）It is loaded into insoluble Ni―Ti anode basket, uses after electric conductivity titanium based lithium-ion sieve is coated with electric conduction of carbon fiber cotton
Ti cathode indigo plant is to electrode, using 200mg/L lithium chlorides as electrolyte, is passed through Gas Stirring lithium chloride solution, collectively constitutes electrification
Slot is learned, applies the DC voltage of 0-2V in two interpolars, lithium ion sieve is made to reach saturation absorption, measures its adsorption capacity as 52-
58mg/g, lithium rate of recovery 92%-96%, adsorption capacity and the lithium ion rate of recovery are not substantially reduced after adsorption desorption 10 times.
The adsorption capacity and the lithium ion rate of recovery that electric conductivity titanium based lithium-ion sieves in the present invention are surveyed using the chromatography of ions
Lithium concentration is calculated in electrolyte before and after fixed absorption.
Experimental raw zinc acetate, aluminium isopropoxide, ethanol amine, isopropanol, lithium hydroxide, hydrochloric acid and chlorination used in the present invention
Lithium is commercially available chemically pure reagent.The presoma Li of titanium based lithium-ion sieve used2TiO3And Li4Ti5O12With reference to existing method
It is prepared.Insoluble Ni―Ti anode is blue, Ti cathode is blue, electric conduction of carbon fiber cotton and DC power supply are commercially available the general electricity in laboratory
Chemical material and equipment.
The beneficial effects of the invention are as follows：
（1）Electric conductivity titanium based lithium-ion sieve passes through Zn2+、Al3+And Ag+Doping improves the adsorption desorption speed and desorption of lithium ion
Rate；
（2）Applied Electrochemistry method strengthens the adsorption desorption process of lithium ion, improves the adsorption capacity of lithium ion sieve；
（3）Sol-gal process prepare alumite doping conductive zinc oxide membrane process it is simple, production cost is low, have application prospect.
Specific embodiment
Embodiment 1
Isopropanol 60g (1.0mol), ethanol amine 7.3g (0.12mol), zinc acetate are separately added into reactor under stiring
16.5g (0.09mol), the aqueous isopropanol of aluminium isopropoxide 2.0g (0.01mol), silver nitrate 0.85g (0.005mol) and go from
Sub- water 9.0g (0.5mol), the heating hydrolysis 2h at 60-70 DEG C, it is 10% to receive that then concentration, which forms solid masses percentage concentration,
Rice conductive oxide colloidal sol 87.0g, aerosol particle size 20-30nm, for 24 hours, chemical composition is for room temperature ageing
Zn0.9Al0.1OAg0.05。
By titanium based lithium-ion sieve presoma Li2TiO335.0g is impregnated into 10% conductive nano oxide sol 87.0g, makes
Conductive nano is oxide-doped and is coated on titanium based lithium-ion sieve presoma, and stirring 2h forms gel.Conductive nano is aoxidized
Object adulterates and the titanium based lithium-ion of cladding sieves presoma drying at 100-150 DEG C, is then placed in high temperature furnace, at 700 DEG C
8h is heat-treated, forms electric conductivity titanium based lithium-ion sieve presoma agglomerate 43.7g.
Electric conductivity titanium based lithium-ion sieve presoma agglomerate is crushed, and is loaded into after being coated with electric conduction of carbon fiber cotton insoluble
In Ni―Ti anode basket, Ti cathode indigo plant is used to electrode, using the hydrochloric acid solution of 0.1mol/L as electrolyte, to be passed through Gas Stirring hydrochloric acid
Solution collectively constitutes electrochemical cell, applies the DC voltage of 1.5V in two interpolars, takes off the lithium ion in lithium ion sieve presoma
It is attached, it is then cleaned with deionized water, obtains electric conductivity titanium based lithium-ion sieve.By electric conductivity titanium based lithium-ion sieve electric conduction of carbon fiber
It is loaded into Ti cathode basket after cotton cladding, it is to electrode, using 200mg/L lithium chlorides to be electrolysed to use insoluble Ni―Ti anode indigo plant
Liquid is passed through Gas Stirring lithium chloride solution, collectively constitutes electrochemical cell, two interpolars apply 1.5V DC voltage, make lithium from
Son sieve reaches saturation absorption, measures its adsorption capacity as 58mg/g, the lithium rate of recovery 96%, adsorption capacity and lithium after adsorption desorption 10 times
The ion rate of recovery is not substantially reduced.
Embodiment 2
Isopropanol 60g (1.0mol), acetylacetone,2,4-pentanedione 12g (0.12mol), zinc acetate are separately added into reactor under stiring
17.4g (0.095mol), the aqueous isopropanol of aluminium isopropoxide 1.0g (0.005mol) and deionized water 9.0g (0.5mol),
Heating hydrolysis 1h at 60-70 DEG C, then concentration form the conductive nano oxide sol that solid masses percentage concentration is 10%
79.9g, aerosol particle size 20-30nm, room temperature are aged for 24 hours, chemical composition Zn0.95Al0.05O。
By titanium based lithium-ion sieve presoma Li4Ti5O1235.0g is impregnated into 10% conductive nano oxide sol 79.9g,
Make conductive nano oxide-doped and be coated on titanium based lithium-ion sieve presoma, stirring 2h forms gel.By conductive nano oxygen
Compound is adulterated and the titanium based lithium-ion of cladding sieves presoma drying at 100-150 DEG C, is then placed in high temperature furnace, at 600 DEG C
Lower heat treatment 12h forms electric conductivity titanium based lithium-ion sieve presoma agglomerate 43.0g.
Electric conductivity titanium based lithium-ion sieve presoma agglomerate is crushed, and is loaded into after being coated with electric conduction of carbon fiber cotton insoluble
In the Ni―Ti anode basket of property, Ti cathode indigo plant is used to electrode, using the hydrochloric acid solution of 0.1mol/L as electrolyte, to be passed through Gas Stirring
Hydrochloric acid solution collectively constitutes electrochemical cell, applies the DC voltage of 1.5V in two interpolars, make lithium in lithium ion sieve presoma from
Son desorption, is then cleaned with deionized water, obtains electric conductivity titanium based lithium-ion sieve.By electric conductivity titanium based lithium-ion sieve carbon fiber
It is loaded into Ti cathode basket after conductive sponge cladding, it is to electrode, using 200mg/L lithium chlorides to be electric to use insoluble Ni―Ti anode indigo plant
Liquid is solved, Gas Stirring lithium chloride solution is passed through, collectively constitutes electrochemical cell, applies the DC voltage of 1.5V in two interpolars, makes lithium
Ion sieve reaches saturation absorption, measures its adsorption capacity as 52mg/g, the lithium rate of recovery 92%.
Claims (5)
1. a kind of electric conductivity titanium based lithium-ion sieve, it is characterised in that using conductive nano is oxide-doped and cladding titanium based lithium-ion
Sieve is capable of the adsorption desorption process of Applied Electrochemistry method reinforcing lithium ion；Titanium based lithium-ion sieves in electric conductivity titanium based lithium-ion sieve
Shared mass percent is 75%-85%, and the mass percent shared by the conductive oxide of doping is 3%-5%, surface coated
Mass percent shared by conductive oxide is 15%-20%, and the presoma chemical composition of titanium based lithium-ion sieve is
Li2TiO3Or Li4Ti5O12One of, the conductive oxide is acidproof aluminium-doped zinc oxide or aluminium silver doped zinc oxide.
2. electric conductivity titanium based lithium-ion according to claim 1 sieve, it is characterised in that the chemical composition of conductive oxide is：
Zn1-xAlxOAgy, wherein, x=0.05-0.2, y=0-0.05, as the adhesive of lithium ion sieve and its presoma, doping
Agent, covering and conductive agent.
3. electric conductivity titanium based lithium-ion sieve according to claim 1, it is characterised in that Zn2+、Al3+And Ag+Volume is larger
Atom is incorporated into titanium based lithium-ion sieve, improves the diffusion coefficient of lithium ion, so as to improve the adsorption capacity of lithium ion sieve,
Adsorption desorption speed and desorption rate.
4. electric conductivity titanium based lithium-ion sieve according to claim 1, it is characterised in that inorganic acid desorption absorption may be used
Lithium ion, can also use electrochemical method strengthen desorption absorption lithium ion.
5. a kind of preparation method of electric conductivity titanium based lithium-ion sieve, it is characterised in that it is molten that technical solution includes conductive nano oxide
Prepared by glue, titanium based lithium-ion sieves the doping of presoma, electric conductivity titanium based lithium-ion sieves the sintering of presoma, electric conductivity based lithium-ion
The preparation of sieve, the specific steps are：
（1）Isopropanol, complexing agent, the aqueous isopropanol of zinc acetate, aluminium isopropoxide are separately added into reactor under stiring
Aqueous isopropanol, silver nitrate and deionized water, control raw material molar ratio are：Zinc acetate：Aluminium isopropoxide：Silver nitrate：Complexing
Agent：Isopropanol：Water=1：0.05-0.25：0-0.05：1-1.2：10-40：5-10, the heating hydrolysis 1-2h at 60-70 DEG C, then
Concentration forms the conductive nano oxide sol of a concentration of 10%-15% of solid masses, grain size 20-30nm, room temperature ageing 24-
72h is spare, chemical composition Zn1-xAlxOAgy, wherein, x=0.05-0.2, y=0-0.05, the complexing agent are ethyl alcohol
One of amine, diethanol amine, triethanolamine or acetylacetone,2,4-pentanedione；
（2）By titanium based lithium-ion sieve presoma be impregnated into conductive nano oxide sol, make conductive nano it is oxide-doped and
It is coated on titanium based lithium-ion sieve presoma, stirring 1-2h forms gel, and the control solid masses ratio that feeds intake is：Lithium ion sieve：It leads
Electroxidation object=1：0.17-0.35；
（4）Titanium based lithium-ion that is conductive nano is oxide-doped and coating sieves presoma drying, Ran Houfang at 100-150 DEG C
Enter in high temperature furnace, 8-12h is heat-treated at 600-800 DEG C, form electric conductivity titanium based lithium-ion sieve presoma agglomerate；
（5）By the sieve presoma agglomerate cutting of electric conductivity titanium based lithium-ion, and it is loaded into after being coated with electric conduction of carbon fiber cotton insoluble
In the Ni―Ti anode basket of property, Ti cathode indigo plant is used to electrode, using the hydrochloric acid solution of 0.1-0.5mol/L as electrolyte, to be passed through gas
Hydrochloric acid solution is stirred, collectively constitutes electrochemical cell, applies the DC voltage of 0-2V in two interpolars, makes in lithium ion sieve presoma
Lithium ion is desorbed, and is then cleaned with deionized water, obtains electric conductivity titanium based lithium-ion sieve；
（6）It is loaded into Ti cathode basket after electric conductivity titanium based lithium-ion sieve is coated with electric conduction of carbon fiber cotton, use is insoluble
Ni―Ti anode indigo plant is to electrode, using 200mg/L lithium chlorides as electrolyte, is passed through Gas Stirring lithium chloride solution, collectively constitutes electrification
Slot is learned, applies the DC voltage of 0-2V in two interpolars, lithium ion sieve is made to reach saturation absorption, measures its adsorption capacity as 52-
58mg/g, lithium rate of recovery 92%-96%, adsorption capacity and the lithium ion rate of recovery are not substantially reduced after adsorption desorption 10 times.
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