CN107051369A - In-situ oxidation reduction prepares HMn2O4Method - Google Patents
In-situ oxidation reduction prepares HMn2O4Method Download PDFInfo
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- CN107051369A CN107051369A CN201710156817.1A CN201710156817A CN107051369A CN 107051369 A CN107051369 A CN 107051369A CN 201710156817 A CN201710156817 A CN 201710156817A CN 107051369 A CN107051369 A CN 107051369A
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- Prior art keywords
- lithium
- ion sieve
- acid
- lithium ion
- hmn
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- 238000011065 in-situ storage Methods 0.000 title claims abstract description 9
- 230000033116 oxidation-reduction process Effects 0.000 title claims abstract description 5
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 26
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 18
- 239000011572 manganese Substances 0.000 claims abstract description 18
- 239000000243 solution Substances 0.000 claims abstract description 18
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 17
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims abstract description 16
- 229910004251 HMn2O4 Inorganic materials 0.000 claims abstract description 14
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 11
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 11
- 230000001476 alcoholic effect Effects 0.000 claims abstract description 6
- 239000012266 salt solution Substances 0.000 claims abstract description 6
- 238000005554 pickling Methods 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 6
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 6
- 239000012286 potassium permanganate Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 3
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- -1 Isobutyl alcohols Chemical class 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 2
- XKPJKVVZOOEMPK-UHFFFAOYSA-M lithium;formate Chemical compound [Li+].[O-]C=O XKPJKVVZOOEMPK-UHFFFAOYSA-M 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 2
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 2
- QDWNJWYHGDYFOG-UHFFFAOYSA-N [N+](=O)(O)[O-].[Li] Chemical compound [N+](=O)(O)[O-].[Li] QDWNJWYHGDYFOG-UHFFFAOYSA-N 0.000 claims 1
- OOSYCERWOGUQJY-UHFFFAOYSA-N calcium;dioxido(dioxo)manganese Chemical compound [Ca+2].[O-][Mn]([O-])(=O)=O OOSYCERWOGUQJY-UHFFFAOYSA-N 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 24
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 15
- 229910052744 lithium Inorganic materials 0.000 abstract description 15
- 150000002500 ions Chemical class 0.000 abstract description 10
- 229910015645 LiMn Inorganic materials 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 3
- 238000010828 elution Methods 0.000 abstract description 2
- 230000000274 adsorptive effect Effects 0.000 abstract 1
- 239000007772 electrode material Substances 0.000 abstract 1
- 238000000605 extraction Methods 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 8
- 229910006290 γ-MnOOH Inorganic materials 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 239000012043 crude product Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000012535 impurity Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000010532 solid phase synthesis reaction Methods 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 150000002927 oxygen compounds Chemical class 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 description 1
- 229910018613 MMnO4 Inorganic materials 0.000 description 1
- 229910018663 Mn O Inorganic materials 0.000 description 1
- 229910003176 Mn-O Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- 238000010327 methods by industry Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- LPUQAYUQRXPFSQ-DFWYDOINSA-M monosodium L-glutamate Chemical compound [Na+].[O-]C(=O)[C@@H](N)CCC(O)=O LPUQAYUQRXPFSQ-DFWYDOINSA-M 0.000 description 1
- 235000013923 monosodium glutamate Nutrition 0.000 description 1
- 239000004223 monosodium glutamate Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
HMn is prepared the present invention relates to a kind of reduction of in-situ oxidation2O4The method of ion sieve, it is comprised the following steps that：In hydrothermal reaction kettle, lithium salt solution (lithium source), permanganate (manganese source) are sequentially added by a certain percentage, stirring is to being completely dissolved；Then alcoholic solution is added, heated sealed to hydro-thermal reaction completely, obtains lithium ion sieve presoma LiMn2O4；It is finally de- with pickling, prepare HMn2O4Type lithium ion sieve.This invention uses the lithium ion sieve presoma LiMn that in-situ oxidation reduction technique is synthesized2O4, it has the nanostructured morphologies of the sheet hexagon of New Rule；The HMn obtained after elution2O4Ion sieve specific surface area is big, adsorption capacity high to the adsorptive selectivity of lithium is big and it is simple to operate take short, adsorption and purification and extraction available for lithium ion, its presoma can also as lithium ion battery electrode material.
Description
Technical field
HMn is prepared the present invention relates to a kind of in-situ oxidation-reduction2O4The method of ion sieve, i.e., a kind of adsorption effect is excellent,
The preparation method of the fast ion sieve adsorbant of the rate of adsorption.
Background technology
Lithium and its compound are described as " industrial monosodium glutamate ", and it is widely used in battery, ceramics, glass, aluminium, lubricant, system
The emerging field such as cryogen and nuclear industry, it has also become national economy and the grand strategy resource of national defense construction.
The advantages of ion sieve absorption method is with its selectivity good, relative inexpensiveness is acknowledged as most promising green and carries lithium
Method.Not only Selective adsorption is good but also adsorption capacity is big for the lithium ion sieve of spinel structure, cyclic utilization rate is high, is most
The ideal material of prospects for commercial application.In spinel lithium manganese and oxygen compound, LiMn2O4Before being a kind of adsorbent studied earliest
Drive body.Solid phase method and liquid phase method (also known as soft chemical method) are broadly divided into from technique preparation process.
Solid phase method uses different solid lithium source and manganese source for raw material, and ion sieve is prepared with reference to high-temperature calcination.Reported in document
Road has with Li2CO3And MnCO3For raw material, mixed calcining is prepared for ion sieve presoma LiMn2O4(sea lake salt and chemical industry,
2005,34 (1)：6-9), with Li2CO3And MnO2For raw material, first microwave premix is calcined again is prepared for ion sieve presoma LiMn2O4
(Yunnan University's journal, 2005,27 (5A)：465-467).Liquid phase method includes sol-gal process, infusion process, hydro-thermal method etc., and it is more
Product uniformity caused by inequality is mixed in solid phase method is mended bad, the larger deficiency of crystallite size.Using sol-gel with forging
Burn the method being combined and be prepared for presoma LiMn2O4(functional material, 2013,4 (44)：498-506), also have with Mn (NO3)2,
LiOH,H2O2For raw material, the presoma LiMn of 1-dimention nano cable architecture has been synthesized by hydro-thermal reaction2O4(process engineering journal,
2010,10 (1)：185-189), the product of above method synthesis has slight crystal agglomeration so that adsorption area reduces, and inhales
Attached rate reduction.
The content of the invention
Purpose of the present invention formula provides a kind of in-situ oxidation-reducing process reaction in order to improve the deficiencies in the prior art and prepared
HMn2O4Type lithium ion sieve method.
The technical scheme is that：First using permanganate as manganese source, organic or inorganic lithium salts is lithium source, and alcohol-water is made
For reaction solution, using the strong oxidizing property of permanganate in itself, preferential reaction generation organic acid and γ-MnOOH；Then permanganic acid
Salt continues to react with γ-MnOOH, and lithium ion is embedded during Mn-O keys are formed, and generates LiMn2O4Presoma；It has
The nanostructured morphologies of the sheet hexagon of New Rule；Finally it is eluted with acid, so that being formed stable has three
The ion sieve HMn of dimension space structure2O4。
The present invention concrete technical scheme be：In-situ oxidation-reduction prepares HMn2O4The method of type lithium ion sieve, its is specific
Step is as follows：In hydrothermal reaction kettle, lithium salt solution (lithium source), permanganate (manganese source) are sequentially added by a certain percentage, are stirred
To being completely dissolved；Then alcoholic solution is added, heated sealed to hydro-thermal reaction completely, obtains lithium ion sieve presoma LiMn2O4；Most
It is de- with pickling afterwards, prepare HMn2O4Type lithium ion sieve.
The reaction prepares lithium ion sieve HMn by three course one-step synthesis2O4, reaction principle is as follows：
R-CH2OH+M-MnO4→R-COOH+γ-MnOOH
MMnO4+γ-MnOOH+LiCl→LiMn2O4
LiMn2O4+H+→HMn2O4+Li+
Wherein, R=H, C1-4；M=K, Na, Mg, Ca etc..
It is preferred that above-mentioned lithium salts be lithium inorganic or acylate, more preferably lithium chloride, lithium bromide, lithium fluoride, lithium nitrate,
Lithium sulfate, lithium acetate or lithium formate.It is preferred that the concentration of lithium salts is 7-15mol/L in lithium salt solution.
It is preferred that it is+7 valencys that above-mentioned permanganate, which is the common chemical valence such as potassium permanganate, magnesium permanganate or acerdol,
Manganese and oxygen compound.
It is preferred that lithium manganese mol ratio is (10-50):1.
It is preferred that alcoholic solution is low molecule primary and secondary alcohol, such as methanol, ethanol, propyl alcohol, butanol, isopropanol or isobutyl alcohols.
Preferred alcohols manganese mol ratio is (1-3):1.
It is preferred that hydrothermal temperature is 130-160 DEG C；The hydro-thermal reaction time is 10-15h.
The acid of preferred acid elution is hydrochloric acid, dilute sulfuric acid, phosphoric acid, phosphorous acid, nitric acid, sulfurous acid, citric acid or oxalic acid etc.
Inorganic and organic acid.
Beneficial effect：
1st, HMn is prepared present invention firstly discloses a kind of in-situ oxidation based on manganese element-restoring method2O4Technology, core
It is that the manganese of the valency of chemical valence+7, as oxidant, the alkali formula manganese oxide for becoming chemical valence+trivalent is reduced by alcohol, then alkali formula oxygen
Change manganese by permanganate oxidation, the LiMn that generation chemical valence is+3.52O4, then through the de- obtained HMn of pickling2O4, so far, nothing
Pertinent literature or the patent report preparation method.
2nd, the present invention has prepared novel sheet hexagonal structure first from the reduction of manganese source using one step hydro thermal method
LiMn2O4, elute and HMn be made2O4, it has adsorption capacity big, and the rate of adsorption is fast, it is easy to which what is eluted and reuse is excellent
Point.
Brief description of the drawings
Fig. 1 is the Hydrothermal Synthesiss HMn of the embodiment of the present invention 12O4XRD spectra.
Fig. 2 is the Hydrothermal Synthesiss HMn of the embodiment of the present invention 12O4SEM spectrograms.
Embodiment
Embodiment 1：
In hydrothermal reaction kettle, 10mol/L LiCl.H is added2O deionized water solution 150mL (1.5 mol), slowly
Potassium permanganate 4.94g (0.031mol), lithium concentration 10mol/L, manganese concentration 0.2mol/L are added, 11.03mL (0.05mol) is added
Product is filtered, washed, dried, obtain lithium ion sieve presoma crude product to 160 DEG C of reaction 14h by ethanol solution, heated sealed
5.1g.Further sample is eluted with hydrochloric acid, lithium ion sieve is obtained, XRD signs are carried out to it, collection of illustrative plates shows sample peak shape
Sharply, it is pure phase HMn2O4, concrete outcome is shown in Fig. 1, and continuation carries out SEM signs to it, it can be seen that ion sieve is novel sheet six
Side shape structure, concrete outcome is shown in Fig. 2, carries out adsorption experiment, and ICP measurement results show that adsorption capacity is 23.4mg/g.
Embodiment 2：
In hydrothermal reaction kettle, 10mol/L LiCl.H is added2O deionized water solution 150mL (1.5 mol), slowly
Potassium permanganate 19.8g (0.125mol), lithium concentration 10mol/L, manganese concentration 0.83mol/L are added, 44.2mL (0.2mol) is added
Product is filtered, washed, dried, obtain lithium ion sieve presoma crude product to 160 DEG C of reaction 14h by ethanol solution, heated sealed
17.6g.XRD is carried out to sample and characterizes display sample with γ-MnOOH impurity.Further with citric acid to LiMn2O4Washed
It is de-, obtain HMn2O4Lithium ion sieve, carries out adsorption experiment, and ICP measurement results show that adsorption capacity is 14.8mg/g.
Embodiment 3：
In hydrothermal reaction kettle, 10mol/L LiBr deionized water solution 150mL (1.5mol) is added, is slowly added into
Potassium permanganate 4.94g (0.031mol), lithium concentration 10mol/L, manganese concentration 0.2mol/L add 19.83mL (0.09mol) second
Product is filtered, washed, dried, obtain lithium ion sieve presoma crude product to 130 DEG C of reaction 14h by alcoholic solution, heated sealed
4.2g.XRD is carried out to sample and characterizes display sample with γ-MnOOH impurity.Further with dilute sulfuric acid to LiMn2O4Washed
It is de-, obtain HMn2O4Lithium ion sieve, carries out adsorption experiment, and ICP measurement results show that adsorption capacity is 12.5mg/g.
Embodiment 4：
In hydrothermal reaction kettle, the deionized water solution 150mL (2.1mol) of 14mol/L lithium acetate is added, is slowly added
Enter six water magnesium permanganate 9.25g (0.05mol), lithium concentration 14mol/L, manganese concentration 0.33mol/L, add 12.13mL
Product is filtered, washed, dried, obtain before lithium ion sieve to 160 DEG C of reaction 14h by (0.055mol) methanol solution, heated sealed
Drive body crude product 8.2g.It is pure phase presoma that XRD is carried out to sample and characterizes display sample.Further with hydrochloric acid to LiMn2O4Washed
It is de-, obtain HMn2O4Lithium ion sieve, carries out adsorption experiment, and ICP measurement results show that adsorption capacity is 21.4mg/g.
Embodiment 5：
In hydrothermal reaction kettle, 7mol/L LiCl.H is added2O deionized water solution 150mL (1.05mol), slowly
Potassium permanganate 8g (0.05mol), lithium concentration 7mol/L, manganese concentration 0.33mol/L are added, 12.13 mL (0.055mol) are added different
Product is filtered, washed, dried, obtain lithium ion sieve presoma crude product to 160 DEG C of reaction 12h by butanol solution, heated sealed
8.9g.XRD is carried out to sample and characterizes display sample with γ-MnOOH impurity.Further with sulfurous acid to LiMn2O4Washed
It is de-, obtain HMn2O4Lithium ion sieve, carries out adsorption experiment, and ICP measurement results show that adsorption capacity is 15.9mg/g.
Embodiment 6：
In hydrothermal reaction kettle, 10mol/L LiF deionized water solution 150mL (1.5mol) is sequentially added, is slowly added
Enter six water magnesium permanganate 9.25g (0.05mol), lithium concentration 10mol/L, manganese concentration 0.33mol/L, add 11.03mL
Product is filtered, washed, dried, obtain before lithium ion sieve to 160 DEG C of reaction 10h by (0.05mol) ethanol solution, heated sealed
Drive body crude product 8.1g.It is with γ-MnOOH impurity that XRD is carried out to sample and characterizes display sample.Further with oxalic acid to LiMn2O4
Eluted, obtain HMn2O4Lithium ion sieve, carries out adsorption experiment, and ICP measurement results show that adsorption capacity is 19.8mg/g.
Embodiment 7：
This example illustrates LiMn of the present invention2O4Presoma XRD characterizes structure and HMn2O4Ion sieve absorption property, adsorbance
Measure using ICP measure, using embodiment 1-6 prepare ion sieve to lithium salt solution (amount containing lithium 50mg/L, PH=9) progress
Adsorption experiment, adsorption capacity measurement result is as shown in table 1 at ambient temperature.
The adsorption capacity of table 1. and XRD characterization result summary sheets.
Claims (9)
1. in-situ oxidation-reduction prepares HMn2O4The method of type lithium ion sieve, it is comprised the following steps that：In hydrothermal reaction kettle, press
Certain proportion sequentially adds lithium salt solution, permanganate, and stirring is to being completely dissolved；Then alcoholic solution, heated sealed to water are added
Thermal response completely, obtains lithium ion sieve presoma LiMn2O4；It is finally de- with pickling, prepare HMn2O4Type lithium ion sieve.
2. according to the method described in claim 1, it is characterised in that described lithium salts is lithium chloride, lithium bromide, lithium fluoride, nitric acid
Lithium, lithium sulfate, lithium acetate or lithium formate.
3. according to the method described in claim 1, it is characterised in that described permanganate is potassium permanganate, magnesium permanganate or height
Calcium manganate.
4. according to the method described in claim 1, it is characterised in that lithium manganese mol ratio is (10-50):1.
5. according to the method described in claim 1, it is characterised in that the concentration of lithium salts is 7-15mol/L in lithium salt solution.
6. according to the method described in claim 1, it is characterised in that alcoholic solution be methanol, ethanol, propyl alcohol, butanol, isopropanol or
Isobutyl alcohols.
7. according to the method described in claim 1, it is characterised in that alcohol manganese mol ratio is (1-3):1.
8. according to the method described in claim 1, it is characterised in that hydrothermal temperature is 130-160 DEG C；The hydro-thermal reaction time
For 10-15h.
9. according to the method described in claim 1, it is characterised in that the de- acid of pickling is hydrochloric acid, dilute sulfuric acid, phosphoric acid, phosphorous
Acid, nitric acid, sulfurous acid, citric acid or oxalic acid.
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| CN109289757A (en) * | 2018-12-07 | 2019-02-01 | 中国科学院青海盐湖研究所 | Six square bar shape manganese systems lithium ion sieve adsorbants of one kind and preparation method thereof |
| CN109289756A (en) * | 2018-12-07 | 2019-02-01 | 中国科学院青海盐湖研究所 | A kind of porous manganese systems lithium ion sieve adsorbant and preparation method thereof |
| CN109384262A (en) * | 2018-11-12 | 2019-02-26 | 南京工业大学 | A kind of sheet Li4Mn5O12The preparation method of ion sieve presoma and ion sieve |
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| CN104925836A (en) * | 2015-05-22 | 2015-09-23 | 中国科学院青海盐湖研究所 | Method for extracting lithium from lithium-containing brine |
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| HONGYUAN ZHAO等: ""A simple, low-cost and eco-friendly approach to synthesize single-crystalline LiMn2O4 nanorods with high electrochemical performance for lithium-ion batteries"", 《ELECTROCHIMICA ACTA》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109384262A (en) * | 2018-11-12 | 2019-02-26 | 南京工业大学 | A kind of sheet Li4Mn5O12The preparation method of ion sieve presoma and ion sieve |
| CN109289757A (en) * | 2018-12-07 | 2019-02-01 | 中国科学院青海盐湖研究所 | Six square bar shape manganese systems lithium ion sieve adsorbants of one kind and preparation method thereof |
| CN109289756A (en) * | 2018-12-07 | 2019-02-01 | 中国科学院青海盐湖研究所 | A kind of porous manganese systems lithium ion sieve adsorbant and preparation method thereof |
| CN109289757B (en) * | 2018-12-07 | 2021-03-16 | 中国科学院青海盐湖研究所 | Hexagonal dendritic manganese lithium ion sieve adsorbent and preparation method thereof |
| CN109289756B (en) * | 2018-12-07 | 2021-07-16 | 中国科学院青海盐湖研究所 | Porous manganese-based lithium ion sieve adsorbent and preparation method thereof |
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