CN116237026A - Nano lithium extraction adsorbent, preparation method thereof and electrochemical reactor using nano lithium extraction adsorbent - Google Patents
Nano lithium extraction adsorbent, preparation method thereof and electrochemical reactor using nano lithium extraction adsorbent Download PDFInfo
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 89
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 239000003463 adsorbent Substances 0.000 title claims abstract description 75
- 238000000605 extraction Methods 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- -1 lithium-iron-cobalt-titanium oxide Chemical compound 0.000 claims abstract description 51
- 238000000034 method Methods 0.000 claims abstract description 36
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 25
- 239000002243 precursor Substances 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 13
- 150000001868 cobalt Chemical class 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 7
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 5
- 150000003608 titanium Chemical class 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- 238000003756 stirring Methods 0.000 claims description 28
- 239000008346 aqueous phase Substances 0.000 claims description 24
- 229910021538 borax Inorganic materials 0.000 claims description 23
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 23
- 239000004327 boric acid Substances 0.000 claims description 23
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 23
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 claims description 23
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- 239000003431 cross linking reagent Substances 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000012071 phase Substances 0.000 claims description 18
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 14
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 14
- 239000001110 calcium chloride Substances 0.000 claims description 14
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 14
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 10
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 8
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- OMOVVBIIQSXZSZ-UHFFFAOYSA-N [6-(4-acetyloxy-5,9a-dimethyl-2,7-dioxo-4,5a,6,9-tetrahydro-3h-pyrano[3,4-b]oxepin-5-yl)-5-formyloxy-3-(furan-3-yl)-3a-methyl-7-methylidene-1a,2,3,4,5,6-hexahydroindeno[1,7a-b]oxiren-4-yl] 2-hydroxy-3-methylpentanoate Chemical compound CC12C(OC(=O)C(O)C(C)CC)C(OC=O)C(C3(C)C(CC(=O)OC4(C)COC(=O)CC43)OC(C)=O)C(=C)C32OC3CC1C=1C=COC=1 OMOVVBIIQSXZSZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000853 adhesive Substances 0.000 claims description 6
- 230000001070 adhesive effect Effects 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 239000000661 sodium alginate Substances 0.000 claims description 5
- 235000010413 sodium alginate Nutrition 0.000 claims description 5
- 229940005550 sodium alginate Drugs 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 4
- 239000002086 nanomaterial Substances 0.000 claims description 4
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 claims description 4
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 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
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 235000019422 polyvinyl alcohol Nutrition 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
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 32
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000000975 co-precipitation Methods 0.000 abstract 1
- 238000002848 electrochemical method Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 23
- 239000012267 brine Substances 0.000 description 20
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 20
- 239000011777 magnesium Substances 0.000 description 7
- 239000013535 sea water Substances 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 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 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- OBTSLRFPKIKXSZ-UHFFFAOYSA-N lithium potassium Chemical compound [Li].[K] OBTSLRFPKIKXSZ-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/007—Contaminated open waterways, rivers, lakes or ponds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/08—Seawater, e.g. for desalination
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a nano lithium extraction adsorbent, a preparation method thereof and an electrochemical reactor using the nano lithium extraction adsorbent, wherein lithium salt, ferric salt, cobalt salt and titanium salt are used as raw materials, a precursor of lithium-iron-cobalt-titanium oxide is prepared by a coprecipitation method, and the nano lithium-iron-cobalt-titanium oxide is prepared through steps of washing, drying, high-temperature roasting and the like; then, the synthesized nanoscale lithium-iron-cobalt-titanium oxide is hybridized into a pore canal of the polymer-based material by adopting an in-situ crosslinking-polymerization method, so that the loss of the nanoscale lithium-iron-cobalt-titanium oxide component is prevented; finally, lithium ions in the nanoscale lithium-iron-cobalt-titanium oxide framework are intercalated and deintercalated by an electrochemical method to form memory vacancies of the lithium ions, and the novel nanoscale lithium extraction adsorbent is obtained. Under the electrochemical auxiliary condition, the nano lithium extraction adsorbent prepared by the invention has the advantages of high adsorption selectivity, high adsorption capacity, high adsorption rate and the like on lithium ions, and is suitable for large-scale industrial production and application.
Description
Technical Field
The invention belongs to the technical field of adsorption lithium extraction, and particularly relates to a nano lithium extraction adsorbent, a preparation method thereof and an electrochemical reactor using the nano lithium extraction adsorbent.
Background
Lithium has different chemical and physical properties from other metal elements and is very widely used. In recent years, as new energy electric automobiles are popularized, the demand for lithium ion batteries is continuously rising. Currently, the mainstream new energy electric automobile mainly uses a lithium ion battery as a driving battery. Lithium is an indispensable raw material (including a positive electrode material and an electrolyte) for producing a secondary lithium ion battery. Therefore, sufficient lithium resources are important for the development of new energy electric automobile industry.
At present, in the research of lithium extraction technology, a solvent extraction method and an adsorbent method are mainly applied. The adsorption method has simple process, high recovery rate and good selectivity, and the adsorbent method is considered as the most promising method for extracting lithium from low-lithium-concentration seawater or oilfield brine, and the key of the method is to find a proper adsorbent. Depending on the nature of the adsorbent: the method can be divided into an organic lithium extraction adsorbent and an inorganic lithium extraction adsorbent, and the organic lithium extraction adsorbent has low adsorption selectivity on lithium ions and is not suitable for use; the inorganic lithium extraction adsorbent has higher lithium ion adsorption selectivity, and can realize selective adsorption of lithium ions from seawater or oilfield brine. The inorganic lithium extraction adsorbent commonly used at present mainly comprises the following components: aluminum-based lithium-extracted adsorbent, manganese-based lithium-extracted adsorbent, and titanium-based lithium-extracted adsorbent.
The Chinese patent CN1511964A discloses a method for extracting lithium from brine by an adsorption method, and the Chinese patent CN101928828A discloses a method for extracting lithium from salt lake brine by a resin adsorption method, wherein the two methods comprise resin adsorption, elution and refining processes, and have the advantages of less consumption of chemical raw materials, simple process, easiness in operation, no pollution to the environment and the like. However, in both the above-mentioned adsorption methods, the adsorbent is filled in the fixed bed adsorber, resulting in a longer adsorption period and reduced adsorption efficiency.
From the prior art, the lithium extraction adsorbent synthesized at present mainly has the problems of high production cost, high dissolution loss rate, low adsorption capacity, poor selectivity, long adsorption period and the like; in addition, the lithium extraction from the seawater or the oilfield brine is difficult (the lithium ion concentration is low and is about 0.2-10 ppm), which also severely restricts the engineering application of the lithium extraction adsorbent in the aspect of extracting lithium from the salt lake brine, the seawater or the oilfield brine.
The present invention has been made to solve the above-mentioned problems occurring in the prior art.
Disclosure of Invention
Aiming at the technical problems, the invention provides a nano lithium extraction adsorbent, a preparation method thereof and an electrochemical reactor using the nano lithium extraction adsorbent, and the nano lithium-iron-cobalt-titanium oxide is hybridized into a pore canal of a high polymer material by adopting an in-situ crosslinking-polymerization method, and then the novel nano lithium extraction adsorbent is prepared by an electrochemical deintercalation method; the adsorbent is mainly applied to extracting lithium from salt lake brine, seawater or oilfield brine.
The technical scheme of the invention is as follows:
the invention provides a preparation method of a nano lithium extraction adsorbent, which comprises the following steps:
s1, dissolving lithium salt, ferric salt, cobalt salt and titanium salt in deionized water, stirring and mixing uniformly, adding sodium hydroxide to completely precipitate, and then filtering, washing and drying to obtain a lithium-iron-cobalt-titanium oxide precursor;
s2, transferring the precursor of the lithium-iron-cobalt-titanium oxide into a muffle furnace for roasting, and then cooling to obtain lithium-iron-cobalt-titanium oxide powder;
s3, adding an organic adhesive and lithium-iron-cobalt-titanium oxide powder into the water phase, and stirring at room temperature until the organic adhesive and the lithium-iron-cobalt-titanium oxide powder are completely dissolved to obtain a water phase solution A;
s4, adding a cross-linking agent into the water phase, and uniformly stirring to obtain a water phase solution B;
s5, dropwise adding the aqueous phase solution A formed in the step S3 into the aqueous phase solution B formed in the step S4, dispersing into droplets with the particle size of 0.3-1.0mm in the aqueous phase through stirring, carrying out a heating reaction, and then cooling and washing to obtain the lithium-iron-cobalt-titanium oxide precursor-loaded nano material;
and S6, applying current, and removing and inserting lithium ions in the nano material skeleton obtained in the step S5 to obtain the nano lithium extraction adsorbent.
Preferably, in the step S1, the molar ratio of the charged lithium salt is controlled to be: iron salt: cobalt salt: titanium salt=1:x:y:z, where x=0.05-1.00, y=0.05-1.00, z=0.05-1.00;
the lithium salt is at least one of lithium chloride, lithium sulfate, lithium acetate and lithium hydroxide; the ferric salt is at least one of ferric chloride, ferric sulfate and ferric nitrate; the cobalt salt is at least one of cobalt chloride, cobalt sulfate and cobalt nitrate; the titanium salt is at least one of titanium sulfate, titanium tetrachloride, titanyl sulfate and titanium nitrate.
Preferably, in the step S2, the roasting temperature is 600-1200 ℃ and the roasting time is 5-6h.
Preferably, in the step S3, the mass ratio of the organic binder to the lithium-iron-cobalt-titanium oxide powder is (1-5): (1-20), and the concentration of the organic binder in the aqueous phase solution A is 5-25g/L;
the organic adhesive is at least one of polyvinyl alcohol, hydroxyethyl cellulose, sodium alginate and polyacrylic acid.
Preferably, in the step S4, the concentration of the cross-linking agent in the aqueous phase solution B is 5.0-20.0g/L;
the cross-linking agent consists of a substance A and a substance B, wherein the substance A is boric acid and/or sodium borate, the substance B is at least one of aluminum chloride, calcium chloride and ferric chloride, and the mass ratio of the substance A to the substance B is 1:2-3:1.
Preferably, the crosslinking agent is one of boric acid, a mixture of sodium borate and aluminum chloride, a mixture of boric acid, sodium borate and calcium chloride, a mixture of boric acid and ferric chloride, and a mixture of sodium borate and calcium chloride, that is, the crosslinking agent may be one of (boric acid+sodium borate+aluminum chloride), (boric acid+sodium borate+calcium chloride), (boric acid+ferric chloride), and (sodium borate+calcium chloride).
Preferably, in the step S5, the temperature is raised to 60-80 ℃ and the reaction is carried out for 8-20 hours.
Preferably, in step S6, the applied current is 0.5mA-1.0mA.
The invention also provides a nano lithium extraction adsorbent which is prepared by adopting the preparation method. The nano lithium extraction adsorbent can be applied to the extraction of lithium from salt lake brine, seawater or oilfield brine, and has the advantages of high adsorption rate, high adsorption selectivity and good adsorption performance on high-concentration lithium and low-concentration lithium by adopting an electrochemical auxiliary process.
The invention also provides an electrochemical reactor, which adopts the nano lithium extraction adsorbent, lithium ions are selectively inlaid on the sites of the nano lithium extraction adsorbent in the charging process, and lithium ions are released from the sites of the nano lithium extraction adsorbent in the discharging process.
The beneficial effects of the invention are as follows:
(1) According to the invention, the nano-scale lithium-iron-cobalt-titanium oxide is hybridized into the pore canal of the high polymer material by an in-situ crosslinking-polymerization method, and then the novel nano-scale lithium extraction adsorbent is prepared by an electrochemical deintercalation method, and ions are not required to be eluted by acid, so that the preparation process is simple and has no pollution to the environment;
(2) Under the electrochemical auxiliary condition, the prepared lithium extraction adsorbent is applied to extracting lithium from salt lake brine, seawater or oilfield brine, has the advantages of high lithium ion selectivity, low dissolution loss rate, high adsorption capacity, high adsorption rate and the like, and does not need to use inorganic acid.
Drawings
The invention is further described below with reference to the accompanying drawings and examples:
FIG. 1 is a process route diagram of the preparation of the nano lithium extraction adsorbent of the present invention;
FIG. 2 is a schematic diagram of an electrochemical reactor employing nano-lithium-extracted sorbents according to the invention;
fig. 3 is a graph of adsorption rate of electrochemical assisted salt lake brine extraction of lithium.
Detailed Description
The objects, technical solutions and advantages of the present invention will become more apparent by the following detailed description of the present invention with reference to the accompanying drawings. It should be understood that the description is only illustrative and is not intended to limit the scope of the invention. In addition, in the following description, descriptions of well-known structures and techniques are omitted so as not to unnecessarily obscure the present invention.
Example 1
As shown in fig. 1, the process for preparing the nano lithium extraction adsorbent in this example is as follows:
the first step: preparation of nanoscale lithium-iron-cobalt-titanium oxide powder
1) Dissolving 1.0mol of lithium chloride, 0.5mol of ferric chloride, 0.2mol of cobalt chloride and 0.3mol of titanium tetrachloride in 100mL of deionized water according to the mol ratio of 1:0.5:0.2:0.3, stirring and mixing uniformly, adding sodium hydroxide to completely precipitate, and filtering, washing and drying to obtain a lithium-iron-cobalt-titanium oxide precursor;
2) Transferring the lithium-iron-cobalt-titanium oxide precursor into a muffle furnace, roasting for 5 hours at 650 ℃, and cooling to obtain lithium-iron-cobalt-titanium oxide powder;
and a second step of: preparation of Supported nanoscale lithium-iron-cobalt-titanium oxides
1) Adding 0.5g of sodium alginate into a 100mL beaker, adding 50mL of deionized water, adding 10g of lithium-iron-cobalt-titanium oxide powder, and uniformly stirring to obtain aqueous phase solution A;
2) Adding deionized water and a cross-linking agent into a 1L flask with a stirring and temperature controlling device, stirring at room temperature until the mixture is dissolved to form a water phase to obtain a water phase solution B, wherein 500mL of deionized water and a mass ratio of the cross-linking agent (boric acid+sodium borate+calcium chloride, (boric acid and sodium borate) to calcium chloride is 1:2, and the mass ratio of the boric acid to the sodium borate is 1:1) is 3.0g;
3) Dropwise adding the aqueous phase solution A formed in the step (1) into the aqueous phase solution B formed in the step (2), dispersing into droplets with the particle size of 0.3-1.0mm in the aqueous phase by vigorously stirring, then carrying out heating reaction, heating to 60 ℃, and reacting for 8 hours; finally, cooling and washing to obtain the supported lithium-iron-cobalt-titanium oxide (namely HP-LFCT-A);
and a third step of: preparation of lithium extraction adsorbent
And (3) applying 0.5mA current to desorb and intercalate lithium ions in the HP-LFCT-A framework, thus preparing the novel nano lithium extraction adsorbent A (namely HP-FCT-A).
Example 2
As shown in fig. 1, the process for preparing the nano lithium extraction adsorbent in this example is as follows:
the first step: preparation of nanoscale lithium-iron-cobalt-titanium oxide powder
1) Dissolving 1.0mol of lithium chloride, 0.3mol of ferric nitrate, 0.3mol of cobalt nitrate and 0.3mol of titanium tetrachloride in 100mL of deionized water according to the mol ratio of 1:0.3:0.3:0.3:0.3, stirring and mixing uniformly, adding sodium hydroxide to completely precipitate, and filtering, washing and drying to obtain a lithium-iron-cobalt-titanium oxide precursor;
2) Transferring the precursor of the lithium-iron-cobalt-titanium oxide into a muffle furnace, roasting for 5 hours at 850 ℃, and cooling to obtain lithium-iron-cobalt-titanium oxide powder;
and a second step of: preparation of Supported nanoscale lithium-iron-cobalt-titanium oxides
1) Adding 1.0g of polyvinyl alcohol into a 100mL beaker, adding 50mL of deionized water, adding 15g of lithium-iron-cobalt-titanium oxide powder, and uniformly stirring to obtain aqueous phase solution A;
2) Adding deionized water and a cross-linking agent into a 1L flask with a stirring and temperature controlling device, and stirring at room temperature until the deionized water and the cross-linking agent are dissolved to form a water phase, so as to obtain a water phase solution B; wherein 200mL of deionized water, and the mass ratio of the cross-linking agent (boric acid+sodium borate+calcium chloride, (boric acid and sodium borate) to calcium chloride is 3:1, and the mass ratio of boric acid to sodium borate is 1:1) is 4.0g;
3) Dropwise adding the aqueous phase solution A formed in the step (1) into the aqueous phase solution B formed in the step (2), dispersing into droplets with the particle size of 0.3-1.0mm in the aqueous phase by vigorously stirring, then carrying out heating reaction, heating to 60 ℃, and reacting for 8 hours; finally, cooling and washing to obtain the supported lithium-iron-cobalt-titanium oxide (namely HP-LFCT-B);
and a third step of: preparation of lithium extraction adsorbent
And (3) applying 0.5mA current to desorb and intercalate lithium ions in the HP-FCT-B framework, thus preparing the novel nano lithium extraction adsorbent B (namely HP-FCT-B).
Example 3
As shown in fig. 1, the process for preparing the nano lithium extraction adsorbent in this example is as follows:
the first step: preparation of nanoscale lithium-iron-cobalt-titanium oxide powder
1) Dissolving 1.0mol of lithium hydroxide, 0.6mol of ferric nitrate, 0.2mol of cobalt chloride and 0.2mol of titanium sulfate in 100mL of deionized water according to the mol ratio of 1:0.6:0.2:0.2, stirring and mixing uniformly, adding sodium hydroxide to completely precipitate, and filtering, washing and drying to obtain a lithium-iron-cobalt-titanium oxide precursor;
2) Transferring the lithium-iron-cobalt-titanium oxide precursor into a muffle furnace, roasting for 6 hours at 1050 ℃, and cooling to obtain lithium-iron-cobalt-titanium oxide powder;
and a second step of: preparation of Supported nanoscale lithium-iron-cobalt-titanium oxides
1) Adding 0.75g of polyvinyl alcohol plus 0.25g of sodium alginate into a 100mL beaker, adding 50mL of deionized water, adding 20g of lithium-iron-cobalt-titanium oxide powder, and uniformly stirring to obtain a water phase solution B;
2) Adding deionized water and a cross-linking agent into a 1L flask with a stirring and temperature controlling device, and stirring at room temperature until the deionized water and the cross-linking agent are dissolved to form a water phase, so as to obtain a water phase solution B; wherein 300mL of deionized water, and the mass ratio of the cross-linking agent (boric acid+sodium borate+aluminum chloride, (boric acid and sodium borate) to calcium chloride is 1:1, and the mass ratio of boric acid to sodium borate is 1:1) is 5.0g;
3) Dropwise adding the aqueous phase solution A formed in the step (1) into the aqueous phase solution B formed in the step (2), dispersing into droplets with the particle size of 0.3-1.0mm in the aqueous phase by vigorously stirring, then carrying out heating reaction, heating to 60 ℃, and reacting for 8 hours; finally, cooling and washing to obtain the supported lithium-iron-cobalt-titanium oxide (namely HP-LFCT-C);
and a third step of: preparation of lithium extraction adsorbent
And (3) applying 0.5mA current to desorb and intercalate lithium ions in the HP-LFCT-C framework, thus preparing the novel nano lithium extraction adsorbent C (namely HP-FCT-C).
Comparative example 1
The first step: preparation of nanoscale lithium-iron-cobalt-titanium oxide powder
1) Dissolving 1.0mol of lithium hydroxide, 0.6mol of ferric nitrate, 0.2mol of cobalt chloride and 0.2mol of titanium sulfate in 100mL of deionized water according to the mol ratio of 1:0.6:0.2:0.2, stirring and mixing uniformly, adding sodium hydroxide to completely precipitate, and filtering, washing and drying to obtain a lithium-iron-cobalt-titanium oxide precursor;
2) Transferring the lithium-iron-cobalt-titanium oxide precursor into a muffle furnace, roasting for 6 hours at 1050 ℃, and cooling to obtain lithium-iron-cobalt-titanium oxide powder;
and a second step of: preparation of Supported nanoscale lithium-iron-cobalt-titanium oxides
1) Adding 0.75g of polyvinyl alcohol plus 0.25g of sodium alginate into a 100mL beaker, adding 50mL of deionized water, adding 20g of lithium-iron-cobalt-titanium oxide powder, and uniformly stirring to obtain a water phase solution B;
2) Adding deionized water and a cross-linking agent into a 1L flask with a stirring and temperature controlling device, and stirring at room temperature until the deionized water and the cross-linking agent are dissolved to form a water phase, so as to obtain a water phase solution B; wherein 300mL of deionized water, and the mass ratio of the cross-linking agent (boric acid+sodium borate+aluminum chloride, (boric acid and sodium borate) to calcium chloride is 1:1, and the mass ratio of boric acid to sodium borate is 1:1) is 5.0g;
3) Dropwise adding the aqueous phase solution A formed in the step (1) into the aqueous phase solution B formed in the step (2), dispersing into droplets with the particle size of 0.3-1.0mm in the aqueous phase by vigorously stirring, then carrying out heating reaction, heating to 60 ℃, and reacting for 8 hours; finally, cooling and washing to obtain the supported lithium-iron-cobalt-titanium oxide (namely HP-LFCT-D);
and a third step of: preparation of lithium extraction adsorbent
And eluting lithium ions in the HP-LFCT-C framework by using 1.0% hydrochloric acid to prepare the nano lithium extraction adsorbent D (namely HP-FCT-D).
Examples 1-3 extraction of lithium from salt lake brine of lithium adsorbent:
1. 0.1L of the novel nano lithium extraction adsorbent prepared in examples 1-3 was filled into an electrochemical reactor as shown in FIG. 2.
The electrochemical reactor mainly comprises a special electrode, a semipermeable membrane and a novel nano lithium extraction adsorbent; in the charging process, lithium ions are selectively inlaid on the sites of the novel nano lithium extraction adsorbent, and in the discharging process, lithium ions are rapidly deintercalated from the sites of the novel nano lithium extraction adsorbent. Realizing the rapid and efficient separation of lithium ions and impurity ions.
2. At a flow rate of 0.3L/h, 16L of salt lake brine (Li + :120ppm，Mg 2+ :63240ppm，Na + :752331ppm，K + 8546732 ppm) was passed through an electrochemical reactor as shown in FIG. 2.
3. After electrochemical auxiliary lithium extraction, the concentration of lithium, sodium, magnesium and potassium is measured, and the lithium adsorption capacity is calculated. The adsorption rate of the electrochemical auxiliary salt lake brine for extracting lithium is shown in figure 3, wherein no electrochemical auxiliary is added, and 1.0% hydrochloric acid is used as eluent.
Comparative example 1 extraction of lithium from salt lake brine of lithium adsorbent:
1. 0.1L of the nano lithium-extracted adsorbent prepared in comparative example 1 was charged into an electrochemical reactor as shown in FIG. 2.
2. At a flow rate of 0.3L/h, 16L of salt lake brine (Li + :120ppm，Mg 2+ :63240ppm，Na + :752331ppm，K + 8546732 ppm) was passed through an electrochemical reactor as shown in FIG. 2.
3. After elution with 1.0% hydrochloric acid, the concentrations of lithium, sodium, magnesium and potassium were measured, and the lithium adsorption capacity was calculated.
TABLE 1 Table of the compositions of lithium, sodium, magnesium and Potassium in salt lake brine
TABLE 2 lithium adsorption Capacity (g/L) and lithium, sodium, magnesium and Potassium ratio before and after adsorption
| Name of the name | Saturated adsorption capacity | Magnesium to lithium ratio (front/back) | Sodium to lithium ratio (front/back) | Potassium-lithium ratio (front/rear) |
| A | 12.3g/L | 527/266050 | 6270/542153 | 71223/781236 |
| B | 14.2g/L | 527/251050 | 6270/351150 | 71223/831463 |
| C | 17.9g/L | 527/291050 | 6270/610250 | 71223/911325 |
| D | 8.1g/L | 527/210214 | 6270/310852 | 71223/635214 |
The nano lithium extraction adsorbent synthesized by the invention has the advantages of high adsorption capacity, high adsorption selectivity, high adsorption rate and the like for lithium ions. Under the electrochemical auxiliary condition, the novel nano lithium-extracting adsorbent prepared by the invention can fundamentally solve the defects of high production cost, poor mechanical strength, high dissolution loss rate, slow adsorption rate, difficult engineering and the like of the traditional aluminum lithium-extracting adsorbent, manganese lithium-extracting adsorbent and titanium lithium-extracting adsorbent. In addition, the method has the advantages of simple operation, low energy consumption, stable water output, high concentration ratio, high purity of the prepared lithium carbonate and the like.
It is to be understood that the above-described embodiments of the present invention are merely illustrative of or explanation of the principles of the present invention and are in no way limiting of the invention. Accordingly, any modification, equivalent replacement, improvement, etc. made without departing from the spirit and scope of the present invention should be included in the scope of the present invention. Furthermore, the appended claims are intended to cover all such changes and modifications that fall within the scope and boundary of the appended claims, or equivalents of such scope and boundary.
Claims (10)
1. The preparation method of the nano lithium extraction adsorbent is characterized by comprising the following steps of:
s1, dissolving lithium salt, ferric salt, cobalt salt and titanium salt in deionized water, stirring and mixing uniformly, adding sodium hydroxide to completely precipitate, and then filtering, washing and drying to obtain a lithium-iron-cobalt-titanium oxide precursor;
s2, transferring the precursor of the lithium-iron-cobalt-titanium oxide into a muffle furnace for roasting, and then cooling to obtain lithium-iron-cobalt-titanium oxide powder;
s3, adding an organic adhesive and lithium-iron-cobalt-titanium oxide powder into the water phase, and stirring at room temperature until the organic adhesive and the lithium-iron-cobalt-titanium oxide powder are completely dissolved to obtain a water phase solution A;
s4, adding a cross-linking agent into the water phase, and uniformly stirring to obtain a water phase solution B;
s5, dropwise adding the aqueous phase solution A formed in the step S3 into the aqueous phase solution B formed in the step S4, dispersing into droplets with the particle size of 0.3-1.0mm in the aqueous phase through stirring, carrying out a heating reaction, and then cooling and washing to obtain the lithium-iron-cobalt-titanium oxide precursor-loaded nano material;
and S6, applying current, and removing and inserting lithium ions in the nano material skeleton obtained in the step S5 to obtain the nano lithium extraction adsorbent.
2. The method for preparing the nano lithium extraction adsorbent according to claim 1, wherein in the step S1, the molar ratio of the charged lithium salt is controlled to be: iron salt: cobalt salt: titanium salt=1:x:y:z, where x=0.05-1.00, y=0.05-1.00, z=0.05-1.00;
the lithium salt is at least one of lithium chloride, lithium sulfate, lithium acetate and lithium hydroxide; the ferric salt is at least one of ferric chloride, ferric sulfate and ferric nitrate; the cobalt salt is at least one of cobalt chloride, cobalt sulfate and cobalt nitrate; the titanium salt is at least one of titanium sulfate, titanium tetrachloride, titanyl sulfate and titanium nitrate.
3. The method for preparing nano lithium extraction adsorbent according to claim 1, wherein in the step S2, the roasting temperature is 600-1200 ℃ and the roasting time is 5-6h.
4. The preparation method of the nano lithium extraction adsorbent according to claim 1, wherein in the step S3, the mass ratio of the organic binder to the lithium-iron-cobalt-titanium oxide powder is (1-5): (1-20), and the concentration of the organic binder in the aqueous phase solution A is 5-25g/L;
the organic adhesive is at least one of polyvinyl alcohol, hydroxyethyl cellulose, sodium alginate and polyacrylic acid.
5. The method for preparing nano lithium extraction adsorbent according to claim 1, wherein in the step S4, the concentration of the cross-linking agent in the aqueous phase solution B is 5.0-20.0g/L;
the cross-linking agent consists of a substance A and a substance B, wherein the substance A is boric acid and/or sodium borate, the substance B is at least one of aluminum chloride, calcium chloride and ferric chloride, and the mass ratio of the substance A to the substance B is 1:2-3:1.
6. The method for preparing nano-lithium extraction adsorbent according to claim 5, wherein the cross-linking agent is one of boric acid, a mixture of sodium borate and aluminum chloride, a mixture of boric acid, sodium borate and calcium chloride, a mixture of boric acid and ferric chloride, and a mixture of sodium borate and calcium chloride.
7. The method for preparing nano lithium extraction adsorbent according to claim 1, wherein in the step S5, the temperature is raised to 60-80 ℃ and the reaction is carried out for 8-20 hours.
8. The method for preparing nano-lithium-extracted adsorbent according to claim 1, wherein in the step S6, the applied current is 0.5mA-1.0mA.
9. A nano lithium extraction adsorbent prepared by the preparation method of any one of claims 1-8.
10. An electrochemical reactor, characterized in that the nano lithium extraction adsorbent according to claim 9 is adopted, lithium ions are selectively inlaid in the sites of the nano lithium extraction adsorbent during charging, and lithium ions are deintercalated from the sites of the nano lithium extraction adsorbent during discharging.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102631897A (en) * | 2012-02-14 | 2012-08-15 | 西安蓝晓科技新材料股份有限公司 | Method for preparing lithium adsorbent resin |
| US20130052489A1 (en) * | 2011-08-30 | 2013-02-28 | Aruna Zhamu | Surface-mediated lithium ion-exchanging energy storage device |
| CN108187606A (en) * | 2018-01-22 | 2018-06-22 | 天津市职业大学 | A kind of electric conductivity titanium based lithium-ion sieve and preparation method thereof |
| CN110759379A (en) * | 2019-10-31 | 2020-02-07 | 湘潭大学 | Preparation method and application of 0D/2D heterostructure composite negative electrode material |
| CN113842877A (en) * | 2021-09-24 | 2021-12-28 | 中国科学院青海盐湖研究所 | Carbon-based adsorbent particle for extracting liquid lithium resource, preparation method and preparation device |
| CN115637156A (en) * | 2022-09-15 | 2023-01-24 | 华南理工大学 | Core-shell structure oxidant sustained-release material and preparation method and application thereof |
-
2023
- 2023-03-31 CN CN202310336011.6A patent/CN116237026A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130052489A1 (en) * | 2011-08-30 | 2013-02-28 | Aruna Zhamu | Surface-mediated lithium ion-exchanging energy storage device |
| CN102631897A (en) * | 2012-02-14 | 2012-08-15 | 西安蓝晓科技新材料股份有限公司 | Method for preparing lithium adsorbent resin |
| CN108187606A (en) * | 2018-01-22 | 2018-06-22 | 天津市职业大学 | A kind of electric conductivity titanium based lithium-ion sieve and preparation method thereof |
| CN110759379A (en) * | 2019-10-31 | 2020-02-07 | 湘潭大学 | Preparation method and application of 0D/2D heterostructure composite negative electrode material |
| CN113842877A (en) * | 2021-09-24 | 2021-12-28 | 中国科学院青海盐湖研究所 | Carbon-based adsorbent particle for extracting liquid lithium resource, preparation method and preparation device |
| CN115637156A (en) * | 2022-09-15 | 2023-01-24 | 华南理工大学 | Core-shell structure oxidant sustained-release material and preparation method and application thereof |
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