CN114887581B - Core-shell structured lithium ion sieve precursor and preparation method and application thereof - Google Patents
Core-shell structured lithium ion sieve precursor and preparation method and application thereof Download PDFInfo
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- CN114887581B CN114887581B CN202210432076.6A CN202210432076A CN114887581B CN 114887581 B CN114887581 B CN 114887581B CN 202210432076 A CN202210432076 A CN 202210432076A CN 114887581 B CN114887581 B CN 114887581B
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 171
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 169
- 239000002243 precursor Substances 0.000 title claims abstract description 108
- 239000011258 core-shell material Substances 0.000 title claims abstract description 91
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000001179 sorption measurement Methods 0.000 claims abstract description 29
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 claims abstract description 24
- 229910010586 LiFeO 2 Inorganic materials 0.000 claims abstract description 13
- 239000011162 core material Substances 0.000 claims description 65
- 229910052744 lithium Inorganic materials 0.000 claims description 58
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 57
- 238000000034 method Methods 0.000 claims description 44
- 239000000243 solution Substances 0.000 claims description 43
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 30
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 229910052742 iron Inorganic materials 0.000 claims description 14
- 238000001694 spray drying Methods 0.000 claims description 12
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 11
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 11
- 238000010304 firing Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 7
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 6
- 229930006000 Sucrose Natural products 0.000 claims description 6
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 6
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 claims description 6
- 239000005720 sucrose Substances 0.000 claims description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 5
- 239000008103 glucose Substances 0.000 claims description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 5
- 229940071264 lithium citrate Drugs 0.000 claims description 5
- WJSIUCDMWSDDCE-UHFFFAOYSA-K lithium citrate (anhydrous) Chemical compound [Li+].[Li+].[Li+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WJSIUCDMWSDDCE-UHFFFAOYSA-K 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 4
- 229960002413 ferric citrate Drugs 0.000 claims description 4
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 238000004090 dissolution Methods 0.000 abstract description 32
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 28
- 239000002253 acid Substances 0.000 abstract description 18
- 238000005260 corrosion Methods 0.000 abstract description 13
- 230000007797 corrosion Effects 0.000 abstract description 13
- 150000002500 ions Chemical class 0.000 abstract description 11
- 229910052596 spinel Inorganic materials 0.000 abstract description 7
- 239000011029 spinel Substances 0.000 abstract description 7
- 238000005554 pickling Methods 0.000 abstract description 5
- 239000010410 layer Substances 0.000 description 48
- 239000011257 shell material Substances 0.000 description 46
- 239000011572 manganese Substances 0.000 description 26
- 229910052748 manganese Inorganic materials 0.000 description 24
- 239000000463 material Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 229910052736 halogen Inorganic materials 0.000 description 7
- 150000002367 halogens Chemical class 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 7
- 239000012267 brine Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 6
- 239000011247 coating layer Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 150000002696 manganese Chemical class 0.000 description 5
- 229910001437 manganese ion Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 3
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 239000013535 sea water Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000009775 high-speed stirring Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- -1 hydrogen ions Chemical class 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 102100024452 DNA-directed RNA polymerase III subunit RPC1 Human genes 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 101000689002 Homo sapiens DNA-directed RNA polymerase III subunit RPC1 Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000012792 core layer Substances 0.000 description 1
- 239000007771 core particle Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052642 spodumene Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 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
- B01J20/04—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
- B01J20/041—Oxides or hydroxides
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28026—Particles within, immobilised, dispersed, entrapped in or on a matrix, e.g. a resin
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
- C22B3/24—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition by adsorption on solid substances, e.g. by extraction with solid resins
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a core-shell structure lithium ion sieve precursor, a preparation method and application thereof, wherein the core-shell structure lithium ion sieve precursor comprises a precursor inner core and a precursor shell layer coated on the surface of the precursor inner core, and the precursor inner core comprises LiMn 2 O 4 The precursor shell layer comprises LiFeO 2 . The invention is characterized in LiMn 2 O 4 The surface of the lithium ion sieve inner core is coated with a layer of LiFeO with compact structure and close fit 2 Shell layer, liFeO 2 The shell layer has good acid corrosion resistance and proper electric conductivity, and is coated on the surface of the inner core, so that the acid corrosion resistance of the lithium ion sieve can be improved, the direct contact between the pickling solution and the ion sieve is blocked, the manganese element dissolution loss is reduced, the stability of a spinel structure is improved, the adsorption capacity is improved, and the comprehensive performance of the core-shell structure lithium ion sieve prepared later is improved.
Description
Technical Field
The invention belongs to the technical field of materials, and relates to a core-shell structure lithium ion sieve precursor, a preparation method and application thereof.
Background
Lithium is an important strategic resource, is one of the most ideal materials in new energy development, is known as 'twenty-first century energy metal', 'element for promoting the world' and governments in various countries take the development of new lithium battery energy and materials as important emerging industries. With the increasing depletion and exhaustion of mineral resources such as spodumene in recent years, the specific gravity of lithium extracted from salt lake brine has increased to 90% or more in the current worldwide production of lithium salts. The salt lakes in China are numerous and rich in lithium resources, but the salt lake brine in China is low in lithium concentration, high in magnesium-lithium ratio and difficult to extract.
The lithium ion sieve exchange method is the method which has the most practical significance for extracting lithium from a dilute solution. The key to this technology is the development of adsorbents with excellent properties. The spinel type lithium manganese oxide ion sieve has good selectivity and unique three-dimensional tunnel structure, and is beneficial to Li + With H in acid + Ion exchange takes place, particularly suited to the reaction from c (Li + )<200mg·L -1 Extracting lithium from the raw halogen of (a) a manganese oxide ion sieve comprising LiMn 2 O 4 Etc.
CN112547004a discloses a cobalt-doped manganese-series lithium ion sieve compound and a preparation method thereof, and the patent discloses an electrolytic MnO 2 Powder heat treatment to obtain Mn 2 O 3 By Mn 2 O 3 LiCl and CoCl 2 Hydrothermal reaction in alkaline environment to obtain Li (MnCo) O 2 Li (MnCo) O 2 After heat treatment, a Co-doped lithium ion sieve precursor Li is obtained 1.6 (MnCo) 1.6 O 4 H is obtained by further acid washing 1.6 (MnCo) 1.6 O 4 The lithium ion sieve prepared by the method has good cycle life and lower manganese dissolution loss rate. CN112591798A discloses a columnar manganese series lithium ion sieve compound and a preparation method thereof, which mixes potassium permanganate with ethanol for hydrothermal reaction, then carries out heat treatment on a hydrothermal reaction product, carries out hydrothermal reaction and sintering again after adding a lithium source, and obtains the columnar lithium ion sieve after acid washing, thereby improving the adsorption capacity of the lithium ion sieve and reducing the manganese dissolution loss rate. CN108097198B discloses a conductive manganese-based lithium ion sieve, which coats a layer of conductive oxide, such as antimony doped tin dioxide, fluorine doped tin dioxide, indium doped tin dioxide, etc., on the surface of a manganese ion sieve precursor, so that the adsorption capacity and stability of the manganese-based lithium ion sieve are improved.
In the prior art, manganese series lithium ion sieves are prepared in various modes, but MnO is formed after lithium removal of a manganese oxide ion sieve 2 ·xH 2 O, which reacts in an acidic solution to cause manganese dissolution loss: mnO (MnO) 2 ·xH 2 O+4HCl→MnCl 2 +Cl 2 +(2+x)H 2 The dissolution loss of O and Mn can lead to unstable spinel structure and reduced circulation performance. Although the surface of the ion sieve is coated with an oxide such as ZrO 2 And TiO 2 Can prevent the direct contact between the lithium ion sieve and the acid, reduce the dissolution rate of manganese and improve the structural stability, but most of the oxides are insulators of ions and are tightly wrapped on the surface of the ion sieve, which is not beneficial to the migration of lithium ions, and the ion sieve coated with the oxides can not give consideration to the dissolution loss of manganeseAnd lithium adsorption capacity.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a core-shell structure lithium ion sieve precursor, and a preparation method and application thereof. The invention is characterized in LiMn 2 O 4 The surface of the lithium ion sieve inner core is coated with a layer of LiFeO with compact structure and close fit 2 Shell layer, liFeO 2 The shell layer has good acid corrosion resistance, and is coated on the surface of the inner core, so that the acid corrosion resistance of the lithium ion sieve can be improved, the direct contact between the pickling solution and the ion sieve is blocked, the dissolution loss of manganese element is reduced, the stability of a spinel structure is improved, the adsorption capacity is improved, and the comprehensive performance of the core-shell structure lithium ion sieve prepared later is improved.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the invention provides a core-shell structured lithium ion sieve precursor, which comprises a precursor inner core and a precursor shell layer coated on the surface of the precursor inner core, wherein the precursor inner core comprises LiMn 2 O 4 The precursor shell layer comprises LiFeO 2 。
The invention is characterized in LiMn 2 O 4 The surface of the lithium ion sieve inner core is coated with a layer of LiFeO with compact structure and close fit 2 Shell layer, liFeO 2 The shell layer has good acid corrosion resistance, and is coated on the surface of the inner core, so that the acid corrosion resistance of the lithium ion sieve can be improved, direct contact between pickling solution and the ion sieve is blocked, the dissolution loss of manganese element is reduced, the stability of a spinel structure is improved, and the adsorption capacity of the lithium ion sieve can be improved; at the same time, liFeO 2 Shell and LiMn 2 O 4 The inner core belongs to an orthorhombic crystal system, a compact and tightly attached coating layer is easy to form on the surface of the inner core of the precursor, the lithium ion transmission is facilitated, and the method is suitable for large-particle LiMn 2 O 4 The coating of the lithium ion sieve can reduce the consumption of coating materials and improve the comprehensive performance of the core-shell structure lithium ion sieve prepared later.
The invention solves the problems of poor acid corrosion resistance, large manganese dissolution loss, unstable structure, poor cycle performance and no adsorption capacity of the coating layer of the manganese series lithium ion sieve. The core-shell structure lithium ion sieve precursor prepared by the preparation method disclosed by the invention has the advantages of high lithium adsorption capacity, stable structure and long service life, and is a salt lake brine or seawater efficient lithium extraction adsorbent.
The mass of the precursor shell layer is preferably 0.5 to 1% of the mass of the precursor core, and may be, for example, 0.5%, 0.6%, 0.7%, 0.8%, 0.9% or 1%, and preferably 0.5 to 0.7%.
In the invention, under the preferable coating content, the specific coating material with good lithium ion conductivity is matched to be beneficial to Li + Diffusion mass transfer in the lithium ion sieve further improves the cyclic adsorption capacity of lithium.
Preferably, the precursor core has an average particle diameter of 500 to 1000nm, and may be 500nm, 550nm, 600nm, 650nm, 700nm, 750nm, 800nm, 850nm, 900nm, 950nm, 1000nm, or the like, for example.
Preferably, the thickness of the precursor shell layer is 40 to 80nm, and may be, for example, 40nm, 45nm, 50nm, 55nm, 60nm, 65nm, 70nm, 75nm, 80nm, or the like.
In the present invention, a suitable precursor shell layer thickness helps to closely adhere the shell layer to the LiMn 2 O 4 The surface of the inner core is improved, so that the stability of the lithium ion sieve is improved, and the loss of the adsorption capacity of lithium ions is reduced.
In a second aspect, the present invention provides a method for preparing the core-shell structure lithium ion sieve precursor according to the first aspect, where the preparation method includes:
(1) Mixing the core material, a lithium source and an iron source, and performing hydrothermal reaction;
(2) And (3) carrying out spray drying and roasting on the product of the hydrothermal reaction in the step (1) to obtain a core-shell structure lithium ion sieve precursor.
The core-shell structure lithium ion sieve precursor is prepared through hydrothermal reaction, spray drying and roasting, the preparation process is simple and clean, no side reaction exists in the preparation process, and the product performance is good, so that the preparation method is suitable for industrial production.
Preferably, the core material of step (1) comprises LiMn 2 O 4 。
Preferably, the lithium source in step (1) includes any one or a combination of at least two of lithium carbonate, lithium bicarbonate, lithium citrate and lithium acetate, for example, a combination of lithium carbonate and lithium bicarbonate, a combination of lithium citrate and lithium acetate, a combination of lithium bicarbonate, lithium citrate and lithium acetate, or a combination of lithium carbonate, lithium bicarbonate, lithium citrate and lithium acetate.
Preferably, the iron source in step (1) includes any one or a combination of at least two of ferric citrate, ferric acetate, ferric oxide and ferric oxide, for example, a combination of ferric citrate and ferric acetate, a combination of ferric oxide and ferric oxide, a combination of ferric acetate, ferric oxide and ferric oxide, or a combination of ferric citrate, ferric acetate, ferric oxide and ferric oxide, etc.
As a preferable technical scheme of the preparation method, the step (1) is carried out by mixing the core material, the lithium source and the iron source in the following manner:
the core material is dispersed in a solution containing a lithium source and an iron source and stirred.
Preferably, the solute in the solution comprises any one or a combination of at least two of polyvinyl alcohol, citric acid, glucose, sucrose and polyethylene glycol, for example, can be a combination of polyvinyl alcohol and citric acid, a combination of citric acid and glucose, a combination of sucrose and polyethylene glycol, or a combination of citric acid, glucose, sucrose and polyethylene glycol, etc.
In the invention, a proper mixing and dispersing mechanism is helpful for LiFeO 2 And the growth of the core-shell structure further improves the stability of the finally prepared lithium ion sieve.
Preferably, the molar ratio of the iron element in the iron source to the lithium element in the lithium source is 1 (1.2-3), and may be, for example, 1:1.2, 1:1:5, 1:1.8, 1:2, 1:2.2, 1:2.4, 1:2.6, 1:2.8, or 1:3, etc.
Preferably, the concentration of the solute in the solution is 10-30% by mass, for example, 10%, 12%, 14%, 16%, 18%, 20%, 22%, 24%, 26%, 28% or 30% by mass, etc.
Preferably, the ratio of the total mass of the iron source and the lithium source to the mass of the solution is 1 (5-10), for example, 1:5, 1:5.5, 1:6, 1:6.5, 1:7, 1:7.5, 1:8, 1:8.5, 1:9, 1:9.5, 1:10, etc.
Preferably, the stirring speed is 500-1000 r/min, for example, 500r/min, 550r/min, 600r/min, 650r/min, 700r/min, 750r/min, 800r/min, 850r/min, 900r/min, 950r/min or 1000r/min, etc.
Preferably, the stirring time is 30 to 60min, for example, 30min, 35min, 40min, 45min, 50min, 55min or 60min, etc.
Preferably, the temperature of the stirring is 30 to 50 ℃, for example, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃ or the like.
As a preferable mode of the production method of the present invention, the hydrothermal reaction in the step (1) is carried out at a temperature of 80 to 100℃and may be carried out at 80℃and 85℃and 90℃and 95℃or 100℃for example.
Preferably, the time of the hydrothermal reaction is 120-180 min, for example, 120min, 130min, 140min, 150min, 160min, 170min or 180min, etc.
Preferably, stirring is performed in the hydrothermal reaction process, and the stirring rotation speed is 1000-1800 r/min, for example, 1000r/min, 1100r/min, 1200r/min, 1300r/min, 1400r/min, 1500r/min, 1600r/min, 1700r/min, 1800r/min or the like.
In the invention, liMn 2 O 4 When dispersing in solution containing lithium source and iron source, stirring at low speed (500-1000 r/min) for a certain time at a proper temperature to realize primary mixing of materials, then carrying out hydrothermal reaction, and simultaneously carrying out high-speed stirring (1000-1800 r/min) while carrying out hydrothermal reaction.
Preferably, the spray drying in step (2) has an inlet temperature of 130 to 180℃and may be, for example, 130℃140℃150℃160℃170℃180℃or the like.
Preferably, the outlet temperature of the spray drying in the step (2) is 120 to 150 ℃, and for example, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃ or the like can be used.
In the invention, the optimal conditions of the spray drying are properly adjusted according to the types and the amounts of the iron source, the lithium source and the solution, and the product prepared at the optimal spray drying temperature has the best effect.
Preferably, the firing of step (2) is performed as follows:
carrying out first roasting on the spray-dried product, and carrying out second roasting at a high temperature;
preferably, the temperature of the first firing is 200 to 300 ℃, and may be 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃, 300 ℃, or the like, for example.
Preferably, the time of the first calcination is 3 to 6 hours, and may be, for example, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, or 6 hours.
Preferably, the temperature of the second firing is 400 to 600 ℃, and may be 400 ℃, 420 ℃, 440 ℃, 460 ℃, 480 ℃, 500 ℃, 520 ℃, 540 ℃, 560 ℃, 580 ℃, 600 ℃, or the like, for example.
Preferably, the second calcination time is 5 to 8 hours, and may be, for example, 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours, or 8 hours.
In the invention, the spray-dried product is preferably roasted for a certain time at a medium temperature (200-300 ℃), then is roasted at a high temperature (400-600 ℃), and the proper temperature control mode can save energy, avoid the rapid expansion of materials to cause cracking, promote the migration of a proper amount of shell-core elements and ensure the closer bonding.
In the present invention, the air flow rate at the time of baking is 12 to 40L/min/kg, for example, 12L/min/kg, 15L/min/kg, 20L/min/kg, 25L/min/kg, 30L/min/kg, 35L/min/kg, 40L/min/kg, or the like, and the optimum air flow rate is appropriately adjusted according to the material pot thickness, by cooling to 100℃or less at 5℃per minute.
In a third aspect, the invention provides a core-shell structure lithium ion sieve, wherein the core-shell structure lithium ion sieve is prepared by adopting the core-shell structure lithium ion sieve precursor, the core-shell structure lithium ion sieve comprises a lithium ion sieve core and a lithium ion sieve shell layer, and the lithium ion sieve core comprises HMn 2 O 4 The lithium ion sieve shell layer comprises LiFeO 2 。
The invention solves the problems of poor acid corrosion resistance, large manganese dissolution loss, unstable structure, poor circulation performance and no adsorption capacity of a coating layer of the manganese series lithium ion sieve, and the obtained core-shell structure lithium ion sieve has high lithium adsorption capacity, stable structure and long service life, and is a salt lake brine or seawater efficient lithium extraction adsorbent.
The invention has LiFeO 2 The shell-layer core-shell structure lithium ion sieve has black powder appearance, and the saturated adsorption capacity of lithium in raw halogen is 28-32 mg.g -1 The first manganese dissolution loss is 0.2-0.5%, and after 100 times of circulation, the lithium adsorption capacity in the salt lake brine is kept at 24-28 mg.g -1 The manganese dissolution loss rate is 0.3-0.45%. Compared with the ionic sieve reported in the literature, the ionic sieve has the advantages of good recycling performance, low manganese dissolution loss, high retention rate of circulating adsorption capacity and stable structure.
In a fourth aspect, the invention provides a preparation method of the core-shell structured lithium ion sieve, which comprises the following steps:
and carrying out lithium removal treatment on the precursor of the lithium ion sieve with the core-shell structure to obtain the lithium ion sieve with the core-shell structure.
In the invention, lithium ions are desorbed from crystal lattices of a core-shell structure lithium ion sieve precursor (lithium manganese oxide), channels and positions which are equivalent to the sizes of the lithium ions are still kept in a framework, the channels and positions only allow the free entry and exit of the lithium ions and hydrogen ions, other metal ions such as magnesium, sodium, potassium and the like cannot be adsorbed into the crystal lattices, and after the lithium ions are intercalated, the lithium ion sieve is converted into the lithium manganese oxide again.
Preferably, the lithium removal treatment is performed by dispersing the core-shell structure lithium ion sieve precursor in a lithium removal solution.
Preferably, the lithium removing solution includes any one or a mixture of at least two of acetic acid, sulfuric acid, hydrochloric acid and nitric acid, for example, a mixture of acetic acid and sulfuric acid, a mixture of hydrochloric acid and nitric acid, a mixture of sulfuric acid, hydrochloric acid and nitric acid, or a mixture of acetic acid, sulfuric acid and hydrochloric acid, etc.
Preferably, the pH of the lithium removal solution is 1 to 4, and may be 1, 2, 3, 4, or the like, for example.
The invention preferably adopts acid with weaker anion complexing ability to carry out lithium removal treatment, so as to avoid corroding the skeleton structure of the precursor of the core-shell structure lithium ion sieve; although the pH of the weakly acidic aqueous solution is preferably 1 to 4, the hydrogen ion concentration is high, liFeO 2 The core-shell structure can effectively prevent hydrogen ions from eroding LiMn 2 O 4 The lithium ion sieve inner core greatly reduces the first manganese dissolution loss, improves the structural stability of the material and increases the recycling performance.
Optionally, after the lithium removal treatment, the method further comprises the steps of solid-liquid separation, washing and drying.
In a fifth aspect, the invention provides an application of the core-shell structured lithium ion sieve in the field of lithium adsorption.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention is characterized in LiMn 2 O 4 The surface of the lithium ion sieve inner core is coated with a layer of LiFeO with compact structure and close fit 2 Shell layer, liFeO 2 The shell layer has good acid corrosion resistance and proper electric conductivity, can improve the acid corrosion resistance of the lithium ion sieve, prevent the pickling solution from directly contacting with the ion sieve, reduce the dissolution loss of manganese element, improve the stability of spinel structure and improve the adsorption capacity of the lithium ion sieve; at the same time, liFeO 2 Shell and LiMn 2 O 4 The inner core belongs to an orthorhombic crystal system, a compact and tightly attached coating layer is easy to form on the surface of the inner core of the precursor, the lithium ion transmission is facilitated, and the method is suitable for large-particle LiMn 2 O 4 Can reduce the consumption of coating materials and improve the lithium with the core-shell structure obtained by subsequent preparationThe combination property of the ion sieve.
(2) The invention solves the problems of poor acid corrosion resistance, large manganese dissolution loss, unstable structure, poor cycle performance and no adsorption capacity of the coating layer of the manganese series lithium ion sieve. The core-shell structure lithium ion sieve precursor prepared by the preparation method disclosed by the invention has the advantages of high lithium adsorption capacity, stable structure and long service life, and is a salt lake brine or seawater efficient lithium extraction adsorbent.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a core-shell structure lithium ion sieve, wherein the core-shell structure lithium ion sieve comprises a lithium ion sieve core and a lithium ion sieve shell layer, and the lithium ion sieve core comprises HMn 2 O 4 The lithium ion sieve shell layer comprises LiFeO 2 。
The lithium ion sieve with the core-shell structure is prepared from a precursor of the lithium ion sieve with the core-shell structure, and the precursor of the lithium ion sieve with the core-shell structure comprises a precursor inner core LiMn 2 O 4 And a precursor shell layer LiFeO coated on the surface of the precursor inner core 2 The average particle diameter of the precursor core is 500nm, the thickness of the precursor shell layer is 40nm, and the mass of the precursor shell layer is 0.5% of the mass of the precursor core.
The embodiment also provides a preparation method of the core-shell structure lithium ion sieve, which comprises the following steps:
(1) Preparing a core-shell structured lithium ion sieve precursor: weighing 194g of iron acetate, 130g of lithium acetate and 1650g of glucose solution with concentration of 20%, and stirring at 30deg.C for 800 r.min -1 Stirring at a rotating speed for 30min to realize primary mixing of materials; then carrying out hydrothermal reaction at 90 ℃ for 150min, and stirring the mixture at the same time, wherein the stirring speed is 1500 r.min -1 The method comprises the steps of carrying out a first treatment on the surface of the Then spray drying the prepared solution to remove solvent, wherein the spray inlet temperature is 135 ℃ and the spray outlet temperature is 125 ℃; loading the spray-dried material into a pot, and loadingThe thickness of the pot is 4cm, the air flow rate is 12L/min.kg, the first roasting is carried out for 6 hours at the medium temperature of 200 ℃, then the second roasting is carried out for 5 hours at the high temperature of 600 ℃, and finally the temperature is reduced to below 100 ℃ at the speed of 5 ℃ per minute, so as to obtain the precursor of the lithium ion sieve with the core-shell structure;
(2) And (3) cooling and crushing the precursor of the core-shell structure lithium ion sieve prepared in the step (1), and dispersing the crushed precursor into a lithium removing solution, wherein the lithium removing solution is an acetic acid solution with a pH value of 3.0, so as to obtain the core-shell structure lithium ion sieve.
In the embodiment, when the core-shell structure lithium ion sieve precursor is adopted to prepare the core-shell structure lithium ion sieve, the first manganese dissolution loss rate is 0.2%; the prepared core-shell structured lithium ion sieve is used for absorbing original halogen lithium ions, then acetic acid solution with the pH value of 3.0 is used for eluting, and after repeating 100 times, the lithium ion absorption capacity retention rate is 95.4%, and the manganese ion dissolution loss rate is 0.3%.
Example 2
The embodiment provides a core-shell structure lithium ion sieve, wherein the core-shell structure lithium ion sieve comprises a lithium ion sieve core and a lithium ion sieve shell layer, and the lithium ion sieve core comprises HMn 2 O 4 The lithium ion sieve shell layer comprises LiFeO 2 。
The lithium ion sieve with the core-shell structure is prepared from a precursor of the lithium ion sieve with the core-shell structure, and the precursor of the lithium ion sieve with the core-shell structure comprises a precursor inner core LiMn 2 O 4 And a precursor shell layer LiFeO coated on the surface of the precursor inner core 2 The average particle diameter of the precursor core is 700nm, the thickness of the precursor shell layer is 80nm, and the mass of the precursor shell layer is 0.9% of the mass of the precursor core.
The embodiment also provides a preparation method of the core-shell structure lithium ion sieve, which comprises the following steps:
(1) Preparing a core-shell structured lithium ion sieve precursor: weighing 194g of iron acetate, 130g of lithium carbonate and 1650g of sucrose solution with concentration of 30%, and heating at 50deg.C for 1000 r.min -1 Stirring at a rotating speed for 60min to realize primary mixing of materials; then carrying out hydrothermal reaction for 130min at the temperature of 70 ℃, and stirring the mixture at the same time, wherein the stirring speed is 1700 r.min -1 The method comprises the steps of carrying out a first treatment on the surface of the Then spray drying the prepared solution to remove solvent,the spray inlet temperature is 125 ℃ and the spray outlet temperature is 135 ℃; loading the spray-dried material into a bowl with the bowl thickness of 7cm and the air flow rate of 30L/min-kg, performing first roasting for 3 hours at the medium temperature of 300 ℃, performing second roasting for 5 hours at the high temperature of 500 ℃, and finally cooling to below 100 ℃ at the speed of 5 ℃/min to obtain a core-shell structure lithium ion sieve precursor;
(2) And (3) cooling and crushing the precursor of the core-shell structure lithium ion sieve prepared in the step (1), and dispersing the crushed precursor in a lithium removing solution, wherein the lithium removing solution is a hydrochloric acid solution with a pH value of 2.0, so as to obtain the core-shell structure lithium ion sieve.
In the embodiment, when the core-shell structure lithium ion sieve precursor is adopted to prepare the core-shell structure lithium ion sieve, the first manganese dissolution loss rate is 0.3%; the prepared core-shell structured lithium ion sieve is used for absorbing original halogen lithium ions, and then is eluted by hydrochloric acid solution with the pH value of 2.0, and after repeating 100 times, the lithium ion absorption capacity retention rate is 94.1%, and the manganese ion dissolution loss rate is 0.5%.
Example 3
The embodiment provides a core-shell structure lithium ion sieve, wherein the core-shell structure lithium ion sieve comprises a lithium ion sieve core and a lithium ion sieve shell layer, and the lithium ion sieve core comprises HMn 2 O 4 The lithium ion sieve shell layer comprises LiFeO 2 。
The lithium ion sieve with the core-shell structure is prepared from a precursor of the lithium ion sieve with the core-shell structure, and the precursor of the lithium ion sieve with the core-shell structure comprises a precursor inner core LiMn 2 O 4 And a precursor shell layer LiFeO coated on the surface of the precursor inner core 2 The average particle diameter of the precursor core is 900nm, the thickness of the precursor shell layer is 70nm, and the mass of the precursor shell layer is 0.7% of the mass of the precursor core.
The embodiment also provides a preparation method of the core-shell structure lithium ion sieve, which comprises the following steps:
(1) Preparing a core-shell structured lithium ion sieve precursor: weighing 194g of ferric oxide, 130g of lithium bicarbonate and 1650g of sucrose solution with concentration of 10 percent, and heating at 40 ℃ for 600 r.min -1 Stirring at a rotating speed for 45min to realize primary mixing of materials; then carrying out hydrothermal reaction at 80 ℃ for 160min, and stirring the mixture at the same timeThe rotation speed of the stirring is 1300 r.min -1 The method comprises the steps of carrying out a first treatment on the surface of the Then spray drying the prepared solution to remove solvent, wherein the spray inlet temperature is 140 ℃ and the spray outlet temperature is 150 ℃; loading the spray-dried material into a bowl with the bowl thickness of 7cm and the air flow rate of 40L/min.kg, performing first roasting for 4 hours at the medium temperature of 250 ℃, performing second roasting for 8 hours at the high temperature of 400 ℃, and finally cooling to below 100 ℃ at the speed of 5 ℃/min to obtain a core-shell structure lithium ion sieve precursor;
(2) And (3) cooling and crushing the precursor of the core-shell structure lithium ion sieve prepared in the step (1), and dispersing the crushed precursor into a lithium removing solution, wherein the lithium removing solution is a sulfuric acid solution with a pH value of 2.0, so as to obtain the core-shell structure lithium ion sieve.
In the embodiment, when the core-shell structure lithium ion sieve precursor is adopted to prepare the core-shell structure lithium ion sieve, the first manganese dissolution loss rate is 0.25%; the prepared core-shell structured lithium ion sieve is used for absorbing original halogen lithium ions, and then is eluted by sulfuric acid solution with the pH value of 2.0, and after repeating 100 times, the lithium ion absorption capacity retention rate is 94.5%, and the manganese ion dissolution loss rate is 0.45%.
Example 4
The procedure of example 1 was followed except that the thickness of the precursor shell layer was 100nm, and the mass of the precursor shell layer was 1.5% of the mass of the precursor core.
Example 5
The procedure of example 1 was followed except that the thickness of the precursor shell layer was 30nm, and the mass of the precursor shell layer was 0.3% of the mass of the precursor core.
Example 6
The procedure of example 1 was followed except that the precursor core had an average particle diameter of 300 nm.
Example 7
The procedure of example 1 was followed except that the precursor core had an average particle diameter of 1200 nm.
Example 8
The procedure of example 1 was repeated except that the hydrothermal reaction temperature was 50 ℃.
Example 9
The procedure of example 1 was repeated except that the hydrothermal reaction temperature was 120 ℃.
Example 10
The procedure of example 1 was repeated except that the temperature of the first firing was 600 ℃.
Example 11
The procedure of example 1 was repeated except that the temperature of the first firing was 200 ℃.
Comparative example 1
The comparative example directly uses LiMn 2 O 4 Namely, a precursor inner core which is not coated is dispersed in a lithium removal solution, wherein the lithium removal solution is hydrochloric acid solution with the pH value of 2.0, so that a lithium ion sieve with a core-shell-free structure is obtained, and the first manganese dissolution loss rate is 0.8%; the prepared lithium ion sieve without the core-shell structure is used for adsorbing the original halogen lithium ions, then the original halogen lithium ions are eluted by hydrochloric acid solution with the pH value of 2.0, and after the operation is repeated for 100 times, the retention rate of the adsorption capacity of the lithium ions is 90.5%, and the dissolution loss rate of the manganese ions is 5.5%.
Comparative example 2
Except that the lithium ion sieve shell is replaced by Li 2 ZrO 3 Except for this, the procedure was the same as in example 1.
The performance data of the lithium ion sieves of the examples and comparative examples of the present invention are summarized as shown in table 1.
TABLE 1
As can be seen from examples 1-11, the present invention is described in LiMn 2 O 4 The surface of the lithium ion sieve inner core is coated with a layer of LiFeO with compact structure and close fit 2 Shell layer, liFeO 2 The shell layer has good acid corrosion resistance and proper electric conductivity, and is coated on the surface of the inner core, so that the acid corrosion resistance of the lithium ion sieve can be improved, direct contact between pickling solution and the ion sieve is blocked, the manganese element dissolution loss is reduced, the stability of a spinel structure is improved, the adsorption capacity is improved, and the subsequent adsorption capacity is improvedThe prepared core-shell structured lithium ion sieve has comprehensive performance.
As can be seen from a comparison of examples 4-7 and example 1, the particle size of the precursor core and the thickness of the precursor shell layer in the present invention are in the most suitable range, and the suitable core particle size and shell layer thickness are matched to help to make LiFeO 2 The shell layer is tightly attached to LiMn 2 O 4 The surface of the inner core is provided with improved stability of the ion sieve and reduced loss of lithium ion adsorption capacity; thus, the lithium ion sieve of example 1 has a higher structural stability than examples 4-7.
As can be seen from comparison of examples 8-9 and example 1, the temperature of the hydrothermal reaction in the invention affects the performance of the prepared material, and the invention can improve the uniformity of the reaction, improve the lithium adsorption performance of the lithium ion sieve with the core-shell structure and reduce the manganese dissolution loss rate by matching a low-speed-high-speed stirring and mixing mechanism with a specific hydrothermal temperature, so that the adsorption capacity retention rate performance of examples 8-9 is slightly poorer than that of example 1.
As can be seen from comparison of examples 10-11 and example 1, the invention can save energy by adopting the medium-high temperature roasting mode at a specific temperature and matching with the specific shell layer material in the invention, avoid rapid expansion of the material to cause cracking, promote migration of a proper amount of shell-core layer elements and make the bonding more compact, so that the structural stability of example 1 is higher than that of examples 10-11.
As can be seen from a comparison of comparative example 1 and example 2, in the present invention LiMn 2 O 4 The surface of the inner core is coated with LiFeO 2 The shell layer of the lithium ion sieve can improve the adsorption capacity and the circulation stability of the lithium ion sieve, and the manganese dissolution loss rate is reduced, but the shell layer is not adopted for coating in the comparative example 1, the manganese dissolution loss rate for the first time is higher than that of the example 2, and after the lithium ion sieve is particularly circulated for 100 times, the manganese dissolution loss reaches 5.5%, the lithium adsorption capacity is 90.5%, and the manganese dissolution loss rate is obviously lower than that of the example 2.
As can be seen from a comparison of comparative example 2 and example 1, a specific LiFeO was used in the present invention 2 Shell layer matching of LiMn 2 O 4 The lithium ion sieve prepared by the inner core has the best performance. The shell material of the lithium ion sieve in comparative example 2 is Li 2 ZrO 3 The first manganese dissolution loss rate is up to 0.9%, the lithium ion adsorption capacity retention rate is obviously reduced after 100 times of circulation, and the circulation stability is inferior to that of the embodiment 1 of the invention, so that the core-shell structure lithium ion sieve prepared by matching the core-shell structure with the lithium ion sieve inner core has the best performance.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that fall within the technical scope of the present invention disclosed herein are within the scope of the present invention.
Claims (29)
1. The precursor of the lithium ion sieve with the core-shell structure is characterized by comprising a precursor inner core and a precursor shell layer coated on the surface of the precursor inner core, wherein the precursor inner core is LiMn 2 O 4 The precursor shell layer is LiFeO 2 The method comprises the steps of carrying out a first treatment on the surface of the The mass of the precursor shell layer is 0.5-0.9% of the mass of the precursor inner core; the average particle size of the precursor inner core is 500-1000 nm; the thickness of the precursor shell layer is 45-80 nm.
2. The core-shell structured lithium ion sieve precursor according to claim 1, wherein the mass of the precursor shell layer is 0.5-0.7% of the mass of the precursor inner core.
3. A method of preparing a core-shell structured lithium ion sieve precursor according to claim 1 or 2, comprising:
(1) Mixing a core material, a lithium source and an iron source, wherein the core material is LiMn 2 O 4 Carrying out hydrothermal reaction;
(2) Spray drying and roasting the product of the hydrothermal reaction in the step (1) to form a precursor shell layer LiFeO 2 And obtaining the core-shell structure lithium ion sieve precursor.
4. The method of claim 3, wherein the lithium source of step (1) comprises any one or a combination of at least two of lithium carbonate, lithium bicarbonate, lithium citrate, and lithium acetate.
5. The method of claim 3, wherein the iron source of step (1) comprises any one or a combination of at least two of ferric citrate, ferric acetate, ferric oxide, and ferric oxide.
6. A method of preparing according to claim 3, wherein the mixing of the core material, the lithium source and the iron source in step (1) is performed as follows:
the core material is dispersed in a solution containing a lithium source and an iron source and stirred.
7. The method of claim 6, wherein the solute in the solution comprises any one or a combination of at least two of polyvinyl alcohol, citric acid, glucose, sucrose, and polyethylene glycol.
8. The method according to claim 3, wherein the molar ratio of the iron element in the iron source to the lithium element in the lithium source is 1 (1.2 to 3).
9. The method according to claim 6, wherein the concentration of the solute in the solution is 10-30% by mass.
10. The method according to claim 6, wherein the ratio of the total mass of the iron source and the lithium source to the mass of the solution is 1 (5-10).
11. The method according to claim 6, wherein the stirring speed is 500-1000 r/min.
12. The method according to claim 6, wherein the stirring time is 30-60 min.
13. The method according to claim 6, wherein the temperature of stirring is 30-50 ℃.
14. The method according to claim 3, wherein the hydrothermal reaction in the step (1) is performed at a temperature of 80 to 100 ℃.
15. The preparation method of claim 3, wherein the hydrothermal reaction time is 120-180 min.
16. The preparation method according to claim 3, wherein stirring is performed in the hydrothermal reaction process, and the stirring speed is 1000-1800 r/min.
17. The method of claim 3, wherein the spray-drying inlet temperature in step (2) is 130-180 ℃.
18. The method according to claim 3, wherein the spray-drying outlet temperature in the step (2) is 120-150 ℃.
19. A production method according to claim 3, wherein the firing in step (2) is performed as follows:
and (3) carrying out first roasting on the spray-dried product, and carrying out second roasting at the temperature.
20. The method according to claim 19, wherein the first firing temperature is 200 to 300 ℃.
21. The method of claim 19, wherein the first firing time is 3 to 6 hours.
22. The method according to claim 19, wherein the second firing temperature is 400-600 ℃.
23. The method of claim 19, wherein the second firing time is 5 to 8 hours.
24. A core-shell structured lithium ion sieve, characterized in that the core-shell structured lithium ion sieve is prepared by using the core-shell structured lithium ion sieve precursor according to claim 1 or 2, the core-shell structured lithium ion sieve comprises a lithium ion sieve core and a lithium ion sieve shell layer, and the lithium ion sieve core comprises HMn 2 O 4 The lithium ion sieve shell layer comprises LiFeO 2 。
25. A method of preparing a core-shell structured lithium ion sieve according to claim 24, comprising:
and carrying out lithium removal treatment on the precursor of the lithium ion sieve with the core-shell structure to obtain the lithium ion sieve with the core-shell structure.
26. The method for preparing a lithium ion sieve with a core-shell structure according to claim 25, wherein the lithium removal treatment is performed by dispersing the precursor of the lithium ion sieve with a core-shell structure in a lithium removal solution.
27. The method for preparing a core-shell structured lithium ion sieve according to claim 26, wherein the delithiated solution comprises any one or a mixed solution of at least two of acetic acid, sulfuric acid, hydrochloric acid and nitric acid.
28. The method for preparing a lithium ion sieve with a core-shell structure according to claim 26, wherein the pH value of the lithium removal solution is 1-4.
29. Use of the core-shell structured lithium ion sieve of claim 24 in the field of lithium adsorption.
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| CN105702949A (en) * | 2014-11-28 | 2016-06-22 | Tdk株式会社 | Positive active substance, positive electrode employing same and lithium ion secondary battery |
| CN109999750A (en) * | 2018-01-05 | 2019-07-12 | 中南大学 | A kind of lithium zirconate cladding manganese systems lithium ion sieve and its preparation and application |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105702949A (en) * | 2014-11-28 | 2016-06-22 | Tdk株式会社 | Positive active substance, positive electrode employing same and lithium ion secondary battery |
| CN109999750A (en) * | 2018-01-05 | 2019-07-12 | 中南大学 | A kind of lithium zirconate cladding manganese systems lithium ion sieve and its preparation and application |
Non-Patent Citations (2)
| Title |
|---|
| Effect of Cation Arrangement on the Magnetic Properties of Lithium Ferrites (LiFeO2) Prepared by Hydrothermal Reaction and Post-annealing Method;Mitsuharu Tabuchi等;《JOURNAL OF SOLID STATE CHEMISTRY》;第第140卷卷;第159-167页 * |
| LiFeO2 包覆锂离子正极材料Li[Li0.2Mn0.54Ni0.13Co0.13]O2制备及性能表征;陈佚等;《电源技术研究与设计》;第第38卷卷(第第6期期);第1018-1021页 * |
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