CN108097198A - A kind of manganese systems lithium ion sieve of conduction and preparation method thereof - Google Patents
A kind of manganese systems lithium ion sieve of conduction and preparation method thereof Download PDFInfo
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- CN108097198A CN108097198A CN201810057955.9A CN201810057955A CN108097198A CN 108097198 A CN108097198 A CN 108097198A CN 201810057955 A CN201810057955 A CN 201810057955A CN 108097198 A CN108097198 A CN 108097198A
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- lithium ion
- ion sieve
- manganese systems
- conductive
- oxide
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 153
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 150
- 239000011572 manganese Substances 0.000 title claims abstract description 105
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 97
- 238000002360 preparation method Methods 0.000 title claims description 9
- 238000001179 sorption measurement Methods 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 16
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000011084 recovery Methods 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 12
- 238000005253 cladding Methods 0.000 claims abstract description 11
- 238000002336 sorption--desorption measurement Methods 0.000 claims abstract description 9
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 5
- 239000011029 spinel Substances 0.000 claims abstract description 5
- 229910009343 Li1.33 Mn1.67 O4 Inorganic materials 0.000 claims abstract description 4
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims abstract description 4
- 238000005728 strengthening Methods 0.000 claims abstract description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 24
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 17
- 238000010521 absorption reaction Methods 0.000 claims description 14
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical class [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 14
- 239000010936 titanium Substances 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 9
- 239000004917 carbon fiber Substances 0.000 claims description 9
- 239000003792 electrolyte Substances 0.000 claims description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 230000002378 acidificating effect Effects 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 238000003795 desorption Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 229910004209 O2−zFz Inorganic materials 0.000 claims description 5
- 229910009371 Sn1-xSbx Inorganic materials 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000000274 adsorptive effect Effects 0.000 claims description 4
- 239000000908 ammonium hydroxide Substances 0.000 claims description 4
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 230000005518 electrochemistry Effects 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000001935 peptisation Methods 0.000 claims description 3
- 239000000443 aerosol Substances 0.000 claims description 2
- 230000032683 aging Effects 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 238000002848 electrochemical method Methods 0.000 claims description 2
- 239000002105 nanoparticle Substances 0.000 claims description 2
- 229940071182 stannate Drugs 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims 1
- 239000007789 gas Substances 0.000 description 6
- KHYBPSFKEHXSLX-UHFFFAOYSA-N iminotitanium Chemical compound [Ti]=N KHYBPSFKEHXSLX-UHFFFAOYSA-N 0.000 description 5
- 229910001000 nickel titanium Inorganic materials 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 3
- 241001131796 Botaurus stellaris Species 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- 229910015645 LiMn Inorganic materials 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- -1 covering Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229920000831 ionic polymer Polymers 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- UIDWHMKSOZZDAV-UHFFFAOYSA-N lithium tin Chemical compound [Li].[Sn] UIDWHMKSOZZDAV-UHFFFAOYSA-N 0.000 description 1
- 230000036244 malformation Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 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
- B01J20/0203—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
- B01J20/0222—Compounds of Mn, Re
-
- 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
- B01J20/0251—Compounds of Si, Ge, Sn, Pb
-
- 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
- B01J20/0259—Compounds of N, P, As, Sb, Bi
-
- 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
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
Abstract
The present invention relates to a kind of manganese systems lithium ion sieves of conduction, the oxide-doped conductive manganese systems lithium ion sieve with cladding of particularly a kind of conductive nano, mass percent shared by manganese systems lithium ion sieve is 75% 85%, mass percent shared by the conductive oxide of doping is 5% 10%, mass percent shared by surface coated conductive oxide is 10% 15%, the presoma of the manganese systems lithium ion sieve is spinel structure, chemical composition LiMn2O4、Li1.33Mn1.67O4Or Li1.6Mn1.6O4One of, the conductive oxide is one of antimony-doped stannic oxide, fluorine-doped tin dioxide, indium-doped stannic oxide or its mixture.Invention both improves the adsorption capacity and stability of manganese systems lithium ion sieve, and manganese systems lithium ion sieve electric conductivity is assigned, applied to the electrochemically strengthening adsorption desorption of lithium ion, the rate of recovery that lithium ion is extracted from weak solution is high.
Description
Technical field
The present invention relates to a kind of manganese systems lithium ion sieves of conduction and preparation method thereof, particularly a kind of conductive nano oxide
Conductive manganese systems lithium ion sieve of doping and cladding and preparation method thereof, belongs to new energy materials field.
Technical background
With lithium-containing materials market price continuous rise, lithium Source Study also carries lithium from traditional lithium ore and is expanded to salt lake
On the liquid lithium resource such as bittern, seawater and GEOTHERMAL WATER.Absorption-ion-exchange is simple for process, the rate of recovery is high, selectivity is good, special
Lithium Shi He not be extracted from low concentration aqueous solution containing lithium, the key of this method is to prepare that adsorption capacity is big and cycle performance is good
Adsorbent.Lithium ion sieve is that template Li is imported into inorganic compound+, lithium ion sieve presoma is treated thermally to produce, is then gone
Fall Li therein+It obtains.Lithium ion sieve is due to dimensional effect and sieve effect, to Li+Ion has specific memory selectivity,
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 bittern
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..It grinds
Studying carefully more manganese systems lithium ion sieve presoma mainly has the LiMn of oxidation-reduction type spinel structure2O4, ion-exchange type spinelle
The Li of structure1.33Mn1.67O4With the Li of spinel-like structural1.6Mn1.6O4.The Li of spinel-like structural1.6Mn1.6O4It is obtained through overpickling
To MnO2·0.5H2O-shaped lithium ion sieve contains only 4 valency manganese in this lithium ion sieve, has the molten loss rate of manganese small in and cycle
The advantages that performance is good.Since manganese systems ion sieve Research foundation is sturdy, low raw-material cost is that professional is universal in industry
It is good, there is industrialization prospect.
The solution loss when the key technical indexes of lithium ion sieve is adsorption capacity, adsorption capacity stability, reclaiming
Rate and cycle life.For molten damage problem of the manganese systems lithium ion sieve when acidity is desorbed, Chinese patent CN103991908 (2014-
The method for regulating and controlling lithium ion sieve stability by cation doping 08-20) is disclosed, is mixed based on manganese systems lithium ion sieve
Miscellaneous modified reduction Mn3+Content, doped chemical mainly has Cr3+、Co3+、Al3+、Ni2+ 、Ti2+、Zr4+Deng.Chinese patent
A kind of preparation side of the long-life lithium ion sieve adsorbant of nano-oxide cladding disclosed in CN106076244 (2016-11-09)
Method is granulated with nano silicon dioxide, titanium dioxide or alumina-coated manganese systems lithium ion sieve, then with organic polymer, improves
The stability and service life of lithium ion sieve.
For overcome lithium ion sieve extracted in low concentration aqueous solution lithium the rate of recovery is low, adsorption time is long, lithium ion saturation
The defects of de- lithium process consumes a large amount of inorganic acids, Chinese patent CN105408521 (2016-03-16), CN105948081
Adsorption desorption lithium ion is strengthened using electrochemical method disclosed in (2016-09-21) and CN102382984 (2012-03-21), by
In manganese systems lithium ion sieve and its presoma be almost nonconducting semi-conducting material, it usually needs mixed with graphite powder or metal powder
Molding is pressed into electrode, and market needs to develop conductive lithium ion sieve.
The content of the invention
The object of the present invention is to provide a kind of manganese systems lithium ion sieve of conduction, a kind of particularly conductive nano is oxide-doped
With the conductive manganese systems lithium ion sieve of cladding, the adsorption capacity of manganese systems lithium ion sieve and stability and manganese systems can be improved
Lithium ion sieve electric conductivity can be applied to the electrochemically strengthening adsorption desorption of lithium ion；Manganese in conductive manganese systems lithium ion sieve
The shared mass percent of based lithium-ion sieve is 75%-85%, and the mass percent shared by the conductive oxide of doping is 5%-10%,
Mass percent shared by surface coated conductive oxide is 10%-15%, and the presoma of the manganese systems lithium ion sieve is point
Spar type structure, chemical composition LiMn2O4、Li1.33Mn1.67O4Or Li1.6Mn1.6O4One of, the conductive oxide is to mix
One of antimony stannic oxide, fluorine-doped tin dioxide or its mixture.
The chemical composition of conductive oxide is in the present invention：Sn1-xSbxO2-zFz, wherein, x=0-0.07, z=0-0.2, but x
0 cannot be equal to simultaneously with z, as the adhesive of lithium ion sieve and its presoma, dopant, covering, conductive agent and skeleton material
Material.
Sn in the present invention4+And Sb5+Highly charged ions are incorporated into manganese systems lithium ion sieve and have stabilized and increased manganese valence,
The stability of spinel structure is improved, improves the diffusion coefficient of lithium ion wherein, improves the conduction of lithium ion sieve
Property.Fluorine ion is incorporated into manganese systems lithium ion sieve instead of part oxygen, since the electronegativity of fluorine is bigger than oxygen and electron-withdrawing power is strong,
So as to reduce the dissolubility of manganese, make the more uniform stabilization of spinel structure, but additive amount can excessively make Mn3+Content carries
Height should take cationic indemnifying measure simultaneously.
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 received
Rice conductive oxide mix in the form of the hydrosol with manganese systems lithium ion sieve powder, then high-temperature heat treatment adulterate enter manganese systems lithium from
In son sieve crystal structure, make lithium ion sieve malformation, so as to improve its adsorption capacity, stability and electric conductivity；At high warm
During reason manganese systems lithium ion sieve is coated on undoped with the conductive nano oxide particle into manganese systems lithium ion sieve crystal structure
Surface forms conductive nano oxidation film, assigns the good electric conductivity of manganese systems lithium ion sieve.
The conductive nano oxidation film of the manganese systems lithium ion sieve coated in the present invention is porous film material, have no effect on lithium from
Son absorption mass transport process；In high-temperature heat treatment process, manganese systems lithium ion sieve presoma elements diffusion into conductive oxide film,
Lithium stannate, metaantimmonic acid lithium and metaantimmonic acid tin can be formed, they are also classical lithium ion sieve presoma, can improve manganese systems lithium ion
The adsorptive selectivity of sieve.
In the present invention conductive manganese systems lithium ion sieve can from lithium-containing solution selective absorption lithium ion, can also facilitate
Conductive manganese systems lithium ion sieve is processed as 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 employed, it can also be by conductive manganese systems lithium ion sieve
As anode, using the desorption of lithium ion in electric field-enhanced promotion lithium ion sieve anode.Lithium ion sieve electrochemistry adsorption desorption process
Concentration and Effect of Acidity On Absorption by solution is smaller, and the rate of recovery height of lithium ion is extracted in weak solution, is particularly suitable in complex system
Using.
Conductive manganese systems lithium ion sieve Pathway of Creation is inventor's long campaigns solar cell transparent conductive film in the present invention
Based on being studied with inorganic nano material, in the prior art inorganic nano material coated lithium ion sifter device being used to have essence
It is different.Take full advantage of the nano SnO of antimony, fluorine or the doping of its mixture2The characteristics of conductive, doped chemical and nanometer
SnO2Composition ratio have stringent limitation, the heat-treatment temperature range for adulterating process also has stringent limitation.Conductive nano oxide
It is not simple physics cladding, mainly high temperature thermal chemical reaction between manganese systems lithium ion sieve.The nanometer in heat treatment process
The component phase counterdiffusion at high temperature of conductive oxide and manganese systems lithium ion sieve presoma, antimony and tin component enter manganese systems lithium ion
It sieves in crystal structure, forms the manganese systems lithium ion sieve of doping；Manganese and lithium component enter in conductive oxide crystal structure, form tin
The transition zone of sour manganese lithium, metaantimmonic acid manganese lithium and metaantimmonic acid tin lithium doping improves the adsorptive selectivity of manganese systems lithium ion sieve, undoped
Conductive oxide is sintered to form chemical composition as Sn1-xSbxO2-zFzConductive film, so, the present invention it is creative and practical
Property.
It is a further object of the present invention to provide a kind of preparation method of the manganese systems lithium ion sieve of conduction, technical solution includes receiving
It is prepared by the rice conductive oxide hydrosol, the coating of manganese systems lithium ion sieve presoma, the burning of conductive manganese systems lithium ion sieve presoma
The preparation of knot, conductive manganese systems lithium ion sieve, concretely comprises the following steps：
（1）Ammonium hydroxide to the solution for adding in 1mol/L into the stannic chloride of 1mol/L and the aqueous solution of antimony chloride respectively under stiring is shown
Alkalescence is separated by filtration the hydroxide precipitation of generation, is cleaned with deionized water and be precipitated to not chloride ion-containing, precipitation is added in
In the oxalic acid aqueous solution of 0.5mol/L, peptization 1-2h is heated at 60-70 DEG C, forms nanometer Sn (OH)4With Sb (OH)5Acidity
The hydrosol；
（2）A nanometer Sn (OH) is separately added into the reactor4、Sb(OH)5Acidic aqueous sol and HF aqueous solutions, are heated to reflux 12-
16h makes nano-particle aging and mutually doping, and then vacuum concentration forms the nanometer that solid masses percentage concentration is 5%-10% and leads
Electroxidation object acidic aqueous sol, aerosol particle size 10-20nm, colloidal sol chemical composition are：Sn1-xSbxO2-zFz, wherein, x=0-
0.07, z=0-0.2, but x and z cannot be equal to 0 simultaneously；
（3）The manganese systems lithium ion sieve presoma prepared using classical way is impregnated into conductive nano oxide acidic aqueous sol
In, the hydro-thermal process 12-16h at 100-120 DEG C makes conductive nano oxide-doped and is coated on manganese systems lithium ion sieve presoma
On, control the mass ratio that feeds intake to be：Lithium ion sieve：Conductive oxide=1：0.18-0.33；
（4）By oxide-doped dry at 100-150 DEG C, the Ran Houfang with the manganese systems lithium ion sieve presoma of cladding of conductive nano
Enter in high temperature furnace, 8-12h is heat-treated at 450-550 DEG C, form conductive manganese systems lithium ion sieve presoma agglomerate；
（5）It will be coated after conductive manganese systems lithium ion sieve presoma agglomerate cutting with carbon fiber felt, be loaded into insoluble titanium
In anode basket, use Ti cathode blue to electrode, using the hydrochloric acid solution of 0.1-0.5mol/L as electrolyte, to collectively constitute electrochemistry
Slot is passed through Gas Stirring hydrochloric acid solution, collectively constitutes electrochemical cell, applies the DC voltage of 0-2V in two interpolars, makes lithium ion
The lithium ion desorption in presoma is sieved, is then cleaned with deionized water, obtains conductive manganese systems lithium ion sieve；
（6）It is loaded into after conductive manganese systems lithium ion sieve is coated with carbon fiber felt in Ti cathode basket, using insoluble titanium sun
Extremely blue is to electrode, using 200mg/L lithium chlorides as electrolyte, is passed through Gas Stirring lithium chloride solution, collectively constitutes electrochemical cell,
Apply the DC voltage of 0-2V in two interpolars, lithium ion sieve made to reach saturation absorption, measure its adsorption capacity as 42-47mg/g,
Lithium rate of recovery 90%-94%, 10 adsorption capacities of adsorption desorption and the lithium ion rate of recovery are not substantially reduced.
The adsorption capacity of conductive manganese systems lithium ion sieve and the lithium ion rate of recovery are surveyed using the chromatography of ions in the present invention
Lithium concentration is calculated in electrolyte before and after fixed absorption.
Experimental raw stannic chloride, antimony chloride, oxalic acid, lithium hydroxide, ammonium hydroxide and lithium chloride used in the present invention are commercially available
Chemically pure reagent.Spinel-type manganese systems lithium ion sieve LiMn used2O4、Li1.33Mn1.67O4And Li1.6Mn1.6O4With reference to classics side
Method is prepared.Insoluble Ni―Ti anode is blue, Ti cathode is blue, carbon fiber felt and DC power supply are commercially available the general electrification in laboratory
Learn material and facility.
The beneficial effects of the invention are as follows：
（1）Not only the adsorption capacity and stability of manganese systems lithium ion sieve had been improved, but also has assigned manganese systems lithium ion sieve electric conductivity, it can
Enough it is applied to the electrochemically strengthening adsorption desorption process of lithium ion；
（2）Conductive manganese systems lithium ion sieve can improve the adsorptive selectivity of lithium ion sieve, and lithium ion is extracted from weak solution
The rate of recovery is high, is particularly suitable for using in complex system.
Specific embodiment
Embodiment 1
Add in the ammonium hydroxide 400- of 1mol/L into the stannic chloride of 1mol/L and the aqueous solution 100mL of antimony chloride respectively under stiring
500mL shows alkalescence to solution, is separated by filtration the hydroxide precipitation of generation, is cleaned with deionized water and be precipitated to not chloride ion-containing,
Precipitation is separately added into the oxalic acid aqueous solution 120mL of 0.5mol/L, peptization 1h is heated at 60-70 DEG C, forms nanometer Sn
(OH)4With Sb (OH)5Acidic aqueous sol 0.1moL.A nanometer Sn (OH) is separately added into the reactor4Acidic aqueous sol
0.095moL and Sb (OH)5Acidic aqueous sol 0.005moL is heated to reflux 12h, is then concentrated in vacuo and forms solid masses percentage
Concentration is 10% conductive nano oxide acidic aqueous sol 151g, and chemical composition is：Sn0.95Sb0.05O2。
By manganese systems lithium ion sieve presoma LiMn2O480g is impregnated into more than conductive nano oxide acidic aqueous sol,
Hydro-thermal process 12h at 100-120 DEG C makes conductive nano oxide-doped and is coated on manganese systems lithium ion sieve presoma, is formed
It is dried after gel, it is further dry at 100-150 DEG C, it is then placed in high temperature furnace, 12h, shape is heat-treated at 450-550 DEG C
Into conductive manganese systems lithium ion sieve presoma agglomerate 95g.It will be used after conductive manganese systems lithium ion sieve presoma agglomerate cutting
Carbon fiber felt coats, and is then loaded into insoluble Ni―Ti anode basket, uses Ti cathode blue for electrode, with the salt of 0.5mol/L
Acid solution is electrolyte, is passed through Gas Stirring hydrochloric acid solution, collectively constitutes electrochemical cell, applies the direct current of 1.5V in two interpolars
Pressure, is desorbed the lithium ion in lithium ion sieve presoma, is then cleaned with deionized water, obtains conductive manganese systems lithium ion sieve.
Be loaded into after conductive manganese systems lithium ion sieve is coated with carbon fiber felt in Ti cathode basket, use insoluble Ni―Ti anode blue for pair
Electrode using 200mg/L lithium chlorides as electrolyte, is passed through Gas Stirring lithium chloride solution, collectively constitutes electrochemical cell, in two interpolars
Apply the DC voltage of 1.5V, lithium ion sieve is made to reach saturation absorption, measure its adsorption capacity as 42mg/g, the lithium rate of recovery 90%.
Embodiment 2
The nanometer Sn (OH) that in embodiment 1 prepared by method is separately added into the reactor4Acidic aqueous sol 0.095moL, Sb
(OH)5Acidic aqueous sol 0.005moL and HF 0.01moL, is heated to reflux 12h, is then concentrated in vacuo and forms solid masses percentage
Concentration is 10% conductive nano oxide acidic aqueous sol 145g, and chemical composition is：Sn0.95Sb0.05O1.9F0.1.By manganese systems
Lithium ion sieve presoma Li1.6Mn1.6O4 45g is impregnated into more than conductive nano oxide acidic aqueous sol, at 100-120 DEG C
Hydro-thermal process 12h makes conductive nano oxide-doped and is coated on manganese systems lithium ion sieve presoma, is dried after forming gel,
It is further dry at 100-150 DEG C, it is then placed in high temperature furnace, 12h is heat-treated at 450-550 DEG C, form conductive manganese
Based lithium-ion sieve presoma agglomerate 59.5g.
It will be coated, be then loaded into insoluble with carbon fiber felt after conductive manganese systems lithium ion sieve presoma agglomerate cutting
Ni―Ti anode basket in, use Ti cathode blue to electrode, using the hydrochloric acid solution of 0.5mol/L as electrolyte, to be passed through Gas Stirring salt
Acid solution collectively constitutes electrochemical cell, applies the DC voltage of 1.5V in two interpolars, makes the lithium ion in lithium ion sieve presoma
Desorption, is then cleaned with deionized water, obtains conductive manganese systems lithium ion sieve.By conductive manganese systems lithium ion sieve carbon fiber felt
It is loaded into after cladding in Ti cathode basket, uses insoluble Ni―Ti anode blue for electrode, using 200mg/L lithium chlorides as electrolyte,
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
Reach saturation absorption, measure its adsorption capacity as 47mg/g, the lithium rate of recovery 94%, 10 adsorption capacities of adsorption desorption and lithium ion return
Yield is not substantially reduced.
Claims (5)
1. a kind of manganese systems lithium ion sieve of conduction, it is characterised in that using conductive nano it is oxide-doped and cladding manganese systems lithium ion
Sieve can improve the adsorption capacity of manganese systems lithium ion sieve and stability and manganese systems lithium ion sieve electric conductivity, can answer
For the electrochemically strengthening adsorption desorption process of lithium ion；Quality hundred in conductive manganese systems lithium ion sieve shared by manganese systems lithium ion sieve
Point than for 75%-85%, the mass percent shared by the conductive oxide of doping is 5%-10%, shared by the conductive oxide of cladding
Mass percent is 10%-15%, and the presoma of the manganese systems lithium ion sieve is spinel structure, and chemical composition is
LiMn2O4、Li1.33Mn1.67O4Or Li1.6Mn1.6O4One of, the conductive oxide is antimony-doped stannic oxide, fluorine doped titanium dioxide
One of tin or its mixture.
2. the manganese systems lithium ion sieve of conduction according to claim 1, it is characterised in that the chemical composition of conductive oxide is：
Sn1-xSbxO2-zFz, wherein, x=0-0.07, z=0-0.2, but x and z cannot be equal to 0 simultaneously.
3. the manganese systems lithium ion sieve of conduction according to claim 1, it is characterised in that the nanometer of cladding manganese systems lithium ion sieve
Conductive oxide film is porous film material, and lithium stannate, metaantimmonic acid lithium and metaantimmonic acid tin can be formed in high-temperature heat treatment process, they
And lithium ion sieve presoma, the adsorptive selectivity of lithium ion sieve can be improved, has no effect on lithium ion absorption mass transport process.
4. the manganese systems lithium ion sieve of conduction according to claim 1, it is characterised in that inorganic acid desorption absorption may be employed
Lithium ion, can also use electrochemical method strengthen desorption absorption lithium ion.
5. a kind of preparation method of the manganese systems lithium ion sieve of conduction, it is characterised in that technical solution includes conductive nano oxide water
It is prepared by colloidal sol, the coating of manganese systems lithium ion sieve presoma, being sintered of conductive manganese systems lithium ion sieve presoma, conductive manganese systems lithium
The preparation of ion sieve, concretely comprises the following steps：
（1）Ammonium hydroxide to the solution for adding in 1mol/L into the stannic chloride of 1mol/L and the aqueous solution of antimony chloride respectively under stiring is shown
Alkalescence is separated by filtration the hydroxide precipitation of generation, is cleaned with deionized water and be precipitated to not chloride ion-containing, precipitation is added in
In the oxalic acid aqueous solution of 0.5mol/L, peptization 1-2h is heated at 60-70 DEG C, forms nanometer Sn (OH)4With Sb (OH)5Acidity
The hydrosol；
（2）A nanometer Sn (OH) is separately added into the reactor4、Sb(OH)5Acidic aqueous sol and HF aqueous solutions, are heated to reflux 12-
16h makes nano-particle aging and mutually doping, and then vacuum concentration forms the nanometer that solid masses percentage concentration is 5%-10% and leads
Electroxidation object acidic aqueous sol, aerosol particle size 10-20nm, colloidal sol chemical composition are：Sn1-xSbxO2-zFz, wherein, x=0-
0.07, z=0-0.2, but x and z cannot be equal to 0 simultaneously；
（3）The manganese systems lithium ion sieve presoma prepared using classical way is impregnated into conductive nano oxide acidic aqueous sol
In, the hydro-thermal process 12-16h at 100-120 DEG C makes conductive nano oxide-doped and is coated on manganese systems lithium ion sieve presoma
On, control the mass ratio that feeds intake to be：Lithium ion sieve：Conductive oxide=1：0.18-0.33；
（4）By oxide-doped dry at 100-150 DEG C, the Ran Houfang with the manganese systems lithium ion sieve presoma of cladding of conductive nano
Enter in high temperature furnace, 8-12h is heat-treated at 450-550 DEG C, form conductive manganese systems lithium ion sieve presoma agglomerate；
（5）It will be coated after conductive manganese systems lithium ion sieve presoma agglomerate cutting with carbon fiber felt, be loaded into insoluble titanium
In anode basket, use Ti cathode blue to electrode, using the hydrochloric acid solution of 0.1-0.5mol/L as electrolyte, to collectively constitute electrochemistry
Slot is passed through Gas Stirring hydrochloric acid solution, collectively constitutes electrochemical cell, applies the DC voltage of 0-2V in two interpolars, makes lithium ion
The lithium ion desorption in presoma is sieved, is then cleaned with deionized water, obtains conductive manganese systems lithium ion sieve；
（6）It is loaded into after conductive manganese systems lithium ion sieve is coated with carbon fiber felt in Ti cathode basket, using insoluble titanium sun
Extremely blue is to electrode, using 200mg/L lithium chlorides as electrolyte, is passed through Gas Stirring lithium chloride solution, collectively constitutes electrochemical cell,
Apply the DC voltage of 0-2V in two interpolars, lithium ion sieve made to reach saturation absorption, measure its adsorption capacity as 42-47mg/g,
Lithium rate of recovery 90%-94%, 10 adsorption capacities of adsorption desorption and the lithium ion rate of recovery are not substantially reduced.
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