CN116600888A - Carbon-coated lithium ion sieve for extracting lithium by electrochemical deintercalation method, and preparation method and application thereof - Google Patents
Carbon-coated lithium ion sieve for extracting lithium by electrochemical deintercalation method, and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 68
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 63
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 58
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000009831 deintercalation Methods 0.000 title abstract description 5
- 239000007772 electrode material Substances 0.000 claims abstract description 46
- -1 aldehyde compound Chemical class 0.000 claims abstract description 29
- 150000002989 phenols Chemical class 0.000 claims abstract description 25
- 239000011247 coating layer Substances 0.000 claims abstract description 24
- 239000004088 foaming agent Substances 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 22
- 239000002245 particle Substances 0.000 claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 9
- 238000010000 carbonizing Methods 0.000 claims abstract description 8
- 238000000605 extraction Methods 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 27
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 16
- 239000004604 Blowing Agent Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 238000003763 carbonization Methods 0.000 claims description 11
- 239000003208 petroleum Substances 0.000 claims description 10
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 4
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 4
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 4
- 239000007774 positive electrode material Substances 0.000 claims description 4
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 claims description 2
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 claims description 2
- 229930003836 cresol Natural products 0.000 claims description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 2
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000000527 sonication Methods 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 10
- 239000002994 raw material Substances 0.000 claims 1
- 150000003739 xylenols Chemical class 0.000 claims 1
- 239000006260 foam Substances 0.000 abstract description 21
- 238000012546 transfer Methods 0.000 abstract description 17
- 239000011148 porous material Substances 0.000 abstract description 16
- 238000001179 sorption measurement Methods 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 10
- 238000005187 foaming Methods 0.000 abstract description 8
- 238000000926 separation method Methods 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 35
- 239000000243 solution Substances 0.000 description 22
- 238000000576 coating method Methods 0.000 description 11
- 230000014759 maintenance of location Effects 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 10
- 239000003463 adsorbent Substances 0.000 description 9
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 8
- 239000005011 phenolic resin Substances 0.000 description 8
- 229920001568 phenolic resin Polymers 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 239000002033 PVDF binder Substances 0.000 description 6
- 239000012267 brine Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 3
- 239000008098 formaldehyde solution Substances 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 238000001132 ultrasonic dispersion Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical group [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 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 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003011 anion exchange membrane Substances 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 1
Classifications
-
- 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 application provides a carbon-coated lithium ion sieve for extracting lithium by an electrochemical deintercalation method, and a preparation method and application thereof, wherein the preparation method comprises the following steps: and mixing the electrode active material, the phenolic compound, the aldehyde compound, the physical foaming agent and the solvent, separating after reaction, and carbonizing the separated solid to obtain the carbon-coated lithium ion sieve. According to the application, the phenolic compound and the aldehyde compound are combined with the physical foaming agent, and a loose carbon coating layer with larger pore size is formed on the surface of the electrode active material by utilizing the foaming characteristic of the physical foaming agent, so that the electrode active material particles can be mutually communicated through the pores of the carbon coating layer, thereby forming a solution mass transfer channel, being beneficial to solution mass transfer and improving the adsorption and separation efficiency of lithium ions; and the formed foam net structure is compact, and can prevent the hole wall from tearing, so that the circulation stability of the material can be improved.
Description
Technical Field
The application belongs to the technical field of materials, and for example relates to a carbon-coated lithium ion sieve for extracting lithium by an electrochemical deintercalation method, a preparation method and application thereof.
Background
The development of power and energy storage batteries has prompted a worldwide continuous increase in demand for lithium resources, which has become an important strategic resource. Lithium resources in nature are mainly present in salt lake brine, seawater and ores, wherein the salt lake lithium resources account for about 70%, lithium ores are used as non-renewable resources, and are increasingly depleted and exhausted with continuous exploitation, so that the extraction of lithium from the salt lake brine has become a trend of lithium resource development.
The method for extracting lithium from brine mainly comprises a precipitation method, a solvent extraction method, an evaporation crystallization method, an electrodialysis method, an ion exchange adsorption method and the like, wherein the lithium ion sieve adsorption method has the advantages of simple process, high recovery rate, good selectivity and environmental friendliness, and is an important technology for extracting lithium from salt lakes.
CN105289455a discloses a method of limiting the practical use capacity to increase the life of a lithium ion sieve adsorbent comprising: step 1, adding a substance with pH buffering capacity for controlling the solution environment into a solution containing lithium to be adsorbed for pretreatment; step 2, adsorption: fully mixing the pretreated solution containing lithium to be adsorbed with a lithium ion sieve adsorbent to finish the exchange adsorption of lithium ions; step 3, desorption: the adsorbent having completed adsorption is soaked with an acidic solution.
CN103316623a discloses a method for preparing spherical lithium ion sieve adsorbent, comprising: heating, dissolving and mixing the polysaccharide and a solvent, adding an ion sieve precursor into the solution, and uniformly stirring to obtain a viscous solution; dropping the viscous solution into the oil phase at 50-100 ℃ to obtain a solid spherical adsorbent with the particle size of 2-5 mm; placing the spherical adsorbent into a cross-linking agent, cross-linking for 10-30 hours at 20-80 ℃, filtering and washing to obtain cross-linked spherical adsorbent particles; eluting the adsorbent particles in a lithium removal solvent to finally prepare the spherical lithium ion sieve adsorbent.
However, the acid leaching process of the lithium ion sieve adsorption method has larger dissolution loss, and the equipment is corroded by a large amount of consumed acid. In recent years, many researchers at home and abroad have widely explored and studied new lithium extraction processes, and the electrochemical lithium extraction technology has good use value and application prospect.
The principle of electrochemical lithium extraction is that lithium ions are extracted from a working electrode by charging in LiCl solution to form a lithium ion sieve, lithium ions selectively enter the lithium ion sieve by discharging in saline water, and selective enrichment of lithium is realized by cyclic operation in a charging and discharging process. For the electrochemical lithium extraction method, the improvement of the lithium extraction efficiency and the circulation performance are important performance indexes, and the used electrode directly influences the lithium extraction efficiency and the circulation performance. The coating density of the currently used electrode is high, so that mass transfer of brine in the electrode is slow, and the lithium extraction rate is affected. Meanwhile, the cycle performance of the electrode determines the service life of the electrode, influences the cost, and has research significance.
Therefore, it is needed to solve the problem of slow mass transfer of brine in the electrode, and improve the cycle performance of the electrode, so as to prolong the service life of the electrode and reduce the cost.
Disclosure of Invention
The following is a summary of the subject matter described in detail herein. This summary is not intended to limit the scope of the claims.
The application provides a carbon-coated lithium ion sieve for extracting lithium by an electrochemical deintercalation method, and a preparation method and application thereof. According to the application, the phenolic compound and the aldehyde compound are combined with the physical foaming agent, and a loose carbon coating layer with larger pore size is formed on the surface of the electrode active material by utilizing the foaming characteristic of the physical foaming agent, so that the electrode active material particles can be mutually communicated through the pores of the carbon coating layer, thereby forming a solution mass transfer channel, being beneficial to solution mass transfer and improving the adsorption and separation efficiency of lithium ions; and the formed foam net structure is compact, and can prevent the hole wall from tearing, so that the circulation stability of the material can be improved.
To achieve the purpose, the application adopts the following technical scheme:
in a first aspect, an embodiment of the present application provides a method for preparing a carbon-coated lithium ion sieve, where the method includes:
and mixing the electrode active material, the phenolic compound, the aldehyde compound, the physical foaming agent and the solvent, separating after reaction, and carbonizing the separated solid to obtain the carbon-coated lithium ion sieve.
The embodiment of the application provides a preparation method of a carbon-coated lithium ion sieve, which combines a phenolic compound, an aldehyde compound and a physical foaming agent, wherein the physical foaming agent has the advantages of high foaming multiple, good foam stability and the like, can foam in the process of phenolic polycondensation, generates multiple holes and can effectively control the size of the foam holes, thereby forming a layer of uniform loose foam phenolic resin coating on the surface of an electrode active material; in addition, the foam structure of the coating layer is not changed any more during carbonization, so that a loose carbon coating layer with larger pore size can be formed on the surface of the electrode active material. The electrode active material particles can be communicated with each other through the air holes of the carbon coating layer, so that a solution mass transfer channel is formed, the solution mass transfer is facilitated, and the adsorption and separation efficiency of lithium ions is improved; and the formed foam net structure is compact, and can prevent the hole wall from tearing, so that the circulation stability of the material can be improved.
In one embodiment, the electrode active material includes a positive electrode active material.
In one embodiment, the positive electrode active material includes at least one of lithium iron phosphate, lithium manganese iron phosphate, lithium manganate, lithium cobaltate, and lithium nickel cobalt manganate.
In one embodiment, the phenolic compound comprises at least one of resorcinol, phenol, cresol, and xylenol.
In one embodiment, the aldehyde compound includes at least one of formaldehyde, furfural, and acrolein.
In one embodiment, the physical blowing agent comprises at least one of n-pentane, isopentane, cyclopentane, dichloromethane, and petroleum ether.
In one embodiment, the solvent comprises water and/or ethanol.
In one embodiment, a catalyst is also included in the mixed feedstock.
In one embodiment, the catalyst comprises a basic catalyst or an acidic catalyst.
In one embodiment, the basic catalyst comprises ammonia and/or sodium hydroxide.
In one embodiment, the acidic catalyst comprises hydrochloric acid and/or oxalic acid.
In one embodiment, the mass fraction of the electrode active material is 70-80%, for example, 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79% or 80%, etc., based on the total mass of the electrode active material, phenolic compound, aldehyde compound, and physical blowing agent.
In one embodiment, the mass fraction of the phenolic compound is 15-25%, such as 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, etc., based on the total mass of the electrode active material, phenolic compound, aldehyde compound, and physical blowing agent.
In one embodiment, the mass fraction of the aldehyde compound is 6-10%, for example, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, etc., based on the total mass of the electrode active material, the phenol compound, the aldehyde compound, and the physical blowing agent.
In one embodiment, the mass fraction of the physical blowing agent is 1-5%, for example, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, or 5%, etc., based on the total mass of the electrode active material, phenolic compound, aldehyde compound, and physical blowing agent.
In the embodiment of the application, if the mass fraction of the physical foaming agent is smaller, the foaming degree is small, the foam density is large, and the pore diameter of the coating layer is small; if the mass fraction of the physical foaming agent is large, the foam pores are large, and the strength of the coating layer is low.
In one embodiment, the mixing of the electrode active material, the phenolic compound, the aldehyde compound, the physical blowing agent, and the solvent comprises the steps of:
(1) Mixing the electrode active material with a solvent to obtain a first mixture;
(2) Mixing the first mixture with a phenolic compound to obtain a second mixture;
(3) And mixing the second mixture with an aldehyde compound, a catalyst and a physical foaming agent.
In one embodiment, the mixing of step (1) is accompanied by sonication.
In one embodiment, the time of the ultrasonic treatment is 20-50min, for example, 20min, 30min, 40min or 50min, etc.
In one embodiment, the mixing of step (2) is accompanied by stirring.
In one embodiment, during the mixing of step (2), the stirring rate is 100-500rpm, which may be, for example, 100rpm, 150rpm, 200rpm, 250rpm, 300rpm, 350rpm, 400rpm, 450rpm, 500rpm, etc.; the stirring time is 0.5-1.5h, and can be, for example, 0.5h, 0.6h, 0.7h, 0.8h, 0.9h, 1h, 1.1h, 1.2h, 1.3h, 1.4h or 1.5h, etc.
In one embodiment, the temperature of the reaction is room temperature, which may range from 20 to 35 ℃, such as 20 ℃, 22 ℃, 25 ℃, 27 ℃, 30 ℃, 32 ℃, 35 ℃, or the like.
In one embodiment, the reaction time is 10-15h, which may be, for example, 10h, 10.5h, 11h, 11.5h, 12h, 12.5h, 13h, 13.5h, 14h, 14.5h, 15h, or the like.
In one embodiment, the reaction is accompanied by stirring at a rate of 100-500rpm, which may be, for example, 100rpm, 150rpm, 200rpm, 250rpm, 300rpm, 350rpm, 400rpm, 450rpm, 500rpm, or the like.
In the embodiment of the application, if the stirring speed is too low in the reaction process, insufficient contact of reactants can be caused, the reaction speed is low, and a uniform coating layer can not be formed on the surface of electrode active material particles; if the rate is too high, the micelle nucleation probability is reduced, the reaction center is reduced, and the polymerization reaction rate is reduced, so that the generated phenolic resin coating is less, and mass transfer channels formed after high-temperature carbonization are less.
In one embodiment, the means of separation comprises centrifugation.
In one embodiment, the method of preparing further comprises: a step of drying is performed between the steps of separating and carbonizing.
In one embodiment, between the separating and the drying steps, a washing step is performed.
In one embodiment, the reagent used for the washing comprises ethanol and/or water.
In one embodiment, the number of times of washing is 3 or more, for example, 3 times, 4 times, 6 times, 10 times, or the like.
In one embodiment, the drying temperature is 60-100deg.C, such as 60 deg.C, 65 deg.C, 70 deg.C, 75 deg.C, 80 deg.C, 85 deg.C, 90 deg.C, 95 deg.C, or 100deg.C.
In one embodiment, the drying time is 10-15h, for example, 10h, 10.5h, 11h, 11.5h, 12h, 12.5h, 13h, 13.5h, 14h, 14.5h, 15h, etc.
In one embodiment, the carbonization temperature rise rate is 3-8deg.C/min, which may be, for example, 3deg.C/min, 4deg.C/min, 5deg.C/min, 6deg.C/min, 7deg.C/min, 8deg.C/min, etc.
In one embodiment, the carbonization temperature is 400-800 ℃, and may be 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, or the like, for example.
In one embodiment, the carbonization time is 4-10h, for example, 4h, 5h, 6h, 7h, 8h, 9h, 10h, etc.
In one embodiment, the carbonization atmosphere is an inert atmosphere.
In one embodiment, the gas in the inert atmosphere comprises nitrogen.
As an alternative technical scheme of the embodiment of the application, the preparation method comprises the following steps:
ultrasonically treating an electrode active material and a solvent for 20-50min to obtain a first mixture, stirring the first mixture and a phenolic compound at a speed of 100-500rpm for 0.5-1.5h to obtain a second mixture, mixing the second mixture with an aldehyde compound, a catalyst and a physical foaming agent, and reacting at room temperature for 10-15h to obtain a reaction product;
and (II) separating the reaction product, drying the separated solid for 10-15 hours at 60-100 ℃, and carbonizing for 4-10 hours at 400-800 ℃ to obtain the carbon-coated lithium ion sieve.
In a second aspect, an embodiment of the present application provides a carbon-coated lithium ion sieve, where the carbon-coated lithium ion sieve is prepared by the preparation method described in the first aspect.
In one embodiment, the carbon-coated lithium ion screen includes an electrode active material core, and a carbon coating layer coated on a surface of the core.
In one embodiment, the average particle size of the carbon-coated lithium ion sieve is 0.5-20 μm, and may be, for example, 0.5 μm, 0.7 μm, 1 μm, 2 μm, 5 μm, 7 μm, 10 μm, 12 μm, 15 μm, 17 μm, 20 μm, or the like.
In a third aspect, embodiments of the present application provide an application of the carbon-coated lithium ion sieve according to the second aspect, where the carbon-coated lithium ion sieve is applied to electrochemical lithium extraction.
The numerical ranges recited herein include not only the above-listed point values, but also any point values between the above-listed numerical ranges that are not listed, and are limited in space and for the sake of brevity, the present application is not intended to be exhaustive of the specific point values that the stated ranges include.
Compared with the related art, the application has the beneficial effects that:
(1) The application provides a preparation method of a carbon-coated lithium ion sieve, which combines a phenolic compound, an aldehyde compound and a physical foaming agent, wherein the physical foaming agent has the advantages of high foaming multiple, good foam stability and the like, can foam in the process of phenolic polycondensation, generates multiple holes and can effectively control the size of the foam holes, thereby forming a layer of uniform loose foam phenolic resin coating on the surface of an electrode active material; in addition, the foam structure of the coating layer is not changed any more during carbonization, so that a loose carbon coating layer with larger pore size can be formed on the surface of the electrode active material. The electrode active material particles can be communicated with each other through the air holes of the carbon coating layer, so that a solution mass transfer channel is formed, the solution mass transfer is facilitated, and the adsorption and separation efficiency of lithium ions is improved; the formed foam net structure is compact, and can prevent the hole wall from tearing, so that the circulation stability of the material can be improved;
(2) The application provides a carbon-coated lithium ion sieve, which comprises an electrode active material inner core and a carbon coating layer coated on the surface of the inner core, wherein the average particle size of the carbon-coated lithium ion sieve is 0.5-20 mu m.
Other aspects will become apparent upon reading and understanding the accompanying drawings and detailed description.
Drawings
The accompanying drawings are included to provide a further understanding of the technology herein, and are incorporated in and constitute a part of this specification, illustrate technology herein and together with the description serve to explain, without limitation, the technology herein.
Fig. 1 is a graph showing the relationship between the anode lithium concentration and time at the time of extracting lithium by using the electrodes provided in examples 1 to 3, comparative examples 1 to 2 and comparative example 5 according to the present application.
Detailed Description
The technical scheme of the application is further described by the following specific embodiments.
Example 1
The embodiment provides a preparation method of a carbon-coated lithium ion sieve, which comprises the following steps:
(1) Placing 1.0g of lithium iron phosphate with the average particle size of 0.5 mu m in a three-neck flask, adding 35mL of deionized water and 15mL of absolute ethyl alcohol, adding 0.2g of resorcinol after ultrasonic dispersion for 30min, magnetically stirring for 1h at a speed of 100rpm, sequentially dripping 0.3mL of formaldehyde solution with the mass fraction of 37% and 5mL of ammonia water solution with the mass fraction of 30%, uniformly stirring, adding 10mg of petroleum ether, continuously stirring at a speed of 100rpm at room temperature for reacting for 12h, centrifuging, washing the solid obtained by centrifugation with absolute ethyl alcohol and deionized water for three times, and drying at 80 ℃ for 12h to obtain the porous foam-shaped phenolic resin coated electrode active material;
(2) And (3) placing the material obtained in the step (1) in a tube furnace, heating to 400 ℃ at a heating rate of 5 ℃/min under nitrogen atmosphere, and preserving heat at 400 ℃ for 10 hours, wherein resin is cracked and carbonized in the heat preservation process, so that the carbon-coated lithium ion sieve with the average particle size of 0.52 mu m is obtained.
Example 2
The embodiment provides a preparation method of a carbon-coated lithium ion sieve, which comprises the following steps:
(1) Placing 1.0g of lithium manganate with the average particle size of 4 mu m in a three-neck flask, adding 35mL of deionized water and 15mL of absolute ethyl alcohol, adding 0.3g of resorcinol after ultrasonic dispersion for 30min, magnetically stirring for 1h at the speed of 500rpm, sequentially dripping 0.3mL of formaldehyde solution with the mass fraction of 37% and 5mL of ammonia water solution with the mass fraction of 30%, uniformly stirring, adding 20mg of n-pentane, continuously stirring at the speed of 500rpm at room temperature for reacting for 12h, centrifuging, washing the solid obtained by centrifugation with absolute ethyl alcohol and deionized water for three times, and drying at 80 ℃ for 12h to obtain the porous foam-shaped phenolic resin coated electrode active material;
(2) And (3) placing the material obtained in the step (1) in a tube furnace, heating to 800 ℃ at a heating rate of 5 ℃/min under nitrogen atmosphere, and preserving heat at 800 ℃ for 4 hours, wherein resin is cracked and carbonized in the heat preservation process, so that the carbon-coated lithium ion sieve with an average particle size of 4.03 mu m is obtained.
Example 3
The embodiment provides a preparation method of a carbon-coated lithium ion sieve, which comprises the following steps:
(1) Placing 1.0g of lithium manganate with the average particle size of 5 mu m in a three-neck flask, adding 35mL of deionized water and 15mL of absolute ethyl alcohol, adding 0.18g of resorcinol after ultrasonic dispersion for 30min, magnetically stirring for 1h at the speed of 200rpm, sequentially dripping 0.3mL of 37 mass percent formaldehyde solution and 5mL of 30 mass percent ammonia water solution, uniformly stirring, adding 15mg of n-pentane, continuously stirring at the speed of 200rpm at room temperature for reacting for 12h, centrifuging, washing the solid obtained by centrifugation with absolute ethyl alcohol and deionized water for three times, and drying at 80 ℃ for 12h to obtain the porous foam phenolic resin coated electrode active material;
(2) And (3) placing the material obtained in the step (1) in a tube furnace, heating to 600 ℃ at a heating rate of 5 ℃/min under nitrogen atmosphere, and preserving heat at 600 ℃ for 8 hours, wherein resin is cracked and carbonized in the heat preservation process, so that the carbon-coated lithium ion sieve with an average particle size of 5.02 mu m is obtained.
Example 4
This example differs from example 1 in that in step (1), the mass of petroleum ether was adjusted to 2.5mg, and the remainder was exactly the same as in example 1.
Example 5
This example differs from example 1 in that in step (1), the mass of petroleum ether was adjusted to 90mg, and the remainder was exactly the same as in example 1.
Example 6
This example is different from example 1 in that in step (1), the stirring rate after adding petroleum ether was adjusted to 70rpm, and the rest was exactly the same as in example 1.
Example 7
This example is different from example 1 in that in step (1), the stirring rate after adding petroleum ether was adjusted to 550rpm, and the rest was exactly the same as in example 1.
Comparative example 1
This comparative example differs from example 1 in that in step (1) no petroleum ether, i.e. no physical blowing agent, was added, the remainder being exactly the same as example 1.
Comparative example 2
The comparative example provides a method for preparing a carbon-coated lithium ion sieve, comprising the following steps:
(1) Weighing 1.0g of lithium iron phosphate and 0.3g of glucose, placing into a ball milling tank, performing wet ball milling for 2 hours by taking absolute ethyl alcohol as a dispersing agent, and drying at 80 ℃ for 12 hours;
(2) And (3) placing the dried solid product in a tube furnace, and calcining at 550 ℃ for 6 hours in a nitrogen atmosphere to obtain the carbon-coated lithium ion sieve.
Comparative example 3
The comparative example provides a method for preparing a carbon-coated lithium ion sieve, comprising the following steps:
(1) 1.0g of lithium iron phosphate, 0.3g of phenolic resin and 10mg of petroleum ether are weighed and placed in a ball milling tank, absolute ethyl alcohol is used as a dispersing agent for wet ball milling for 2 hours, and the mixture is dried for 12 hours at 80 ℃;
(2) And (3) placing the dried solid product in a tube furnace, and calcining at 550 ℃ for 6 hours in a nitrogen atmosphere to obtain the carbon-coated lithium ion sieve.
Comparative example 4
This comparative example differs from example 1 in that in step (1) petroleum ether was replaced with ammonium bicarbonate, and the remainder was exactly the same as example 1.
Application example 1
The application example provides a preparation method of an electrode, which comprises the following steps:
weighing a carbon-coated lithium ion sieve, acetylene black and polyvinylidene fluoride (PVDF) provided in example 1 according to a mass ratio of 8:1:1, adding the carbon-coated lithium ion sieve, the acetylene black and the polyvinylidene fluoride (PVDF) into N-methylpyrrolidone (NMP), fully stirring the mixture to form a slurry, uniformly coating the slurry on a titanium mesh current collector, and coating the slurry with a density of 200mg/cm 2 Then vacuum drying at 50 ℃ for 5 hours to obtain the electrode.
Application examples 2 to 7
The difference between this application example and application example 1 is that the carbon-coated lithium ion sieve provided in example 1 is replaced with the carbon-coated lithium ion sieve provided in example 2, example 3, example 4, example 5, example 6, and example 7, respectively, and the remainder are exactly the same as application example 1.
Comparative examples 1 to 4 were used
The difference between this application example and application example 1 is that the carbon-coated lithium ion sieves provided in example 1 were replaced with the carbon-coated lithium ion sieves provided in comparative examples 1, 2, 3 and 4, respectively, corresponding to application comparative examples 1, 2, 3 and 4, respectively, and the remainder was identical to application example 1.
Comparative example 5 was used
The application comparative example provides a preparation method of an electrode, which comprises the following steps:
weighing a lithium iron phosphate material and NaHCO according to the mass ratio of 8:1:1:1 3 Adding pore-forming agent, acetylene black and polyvinylidene fluoride (PVDF) into N-methyl pyrrolidone (NMP), stirring to form slurry, uniformly coating the slurry on titanium mesh current collector, wherein the coating density is 200mg/cm 2 Then, the electrode was obtained by vacuum drying at 50℃for 5 hours.
Performance testing
Lithium extraction experiments were performed on the electrodes provided in application examples 1 to 7 and application comparative examples 1 to 5 (i.e., lithium-rich electrodes): firstly, taking the prepared electrode as an anode, agCl electrode as a cathode, taking 0.05mol/L KCl solution as electrolyte, and carrying out lithium removal on the lithium-rich electrode under a constant voltage of 1.0V to obtain a lithium-poor electrode; then, the electrolysis device is divided into an anode chamber and a cathode chamber by an anion exchange membrane, a lithium-rich electrode and a lithium-poor electrode are respectively arranged in the anode chamber and the cathode chamber, brine (containing Li, na, mg, K, B and S elements) is injected into the cathode chamber, and NaCl solution is injected into the anode chamber.
(1) Lithium extraction efficiency test:
applying 0.3V voltage to the cathode and anode to extract lithium, detecting the concentration of anode lithium after 5h of lithium extraction, and testing the results as shown in Table 1;
wherein, the electrodes provided in application examples 1-3, application comparative examples 1-2 and application comparative example 5 were subjected to a lithium extraction efficiency test for 10 hours, and the lithium extraction effect within 10 hours is shown in fig. 1, and it can be seen from the graph that the lithium extraction rate of application examples 1-3 is much higher than that of application comparative examples 1-2.
(2) And (3) testing the cycle performance:
applying 0.3V voltage to the cathode and anode, extracting lithium for 5 hours, and testing to obtain the initial adsorption capacity of the electrode, wherein the initial adsorption capacity is the 1 st cycle; then exchanging the anode electrode with the cathode electrode, and extracting lithium, namely, the 2 nd cycle; repeating the above steps, repeating the steps for 100 circles, testing the adsorption capacity of the electrode, and calculating to obtain the capacity retention rate of the electrode, wherein the test result is shown in table 1.
TABLE 1
| Anode lithium concentration (g/L) | Capacity retention (%) | |
| Application example 1 | 2.99 | 90 |
| Application example 2 | 2.99 | 91 |
| Application example 3 | 3 | 89 |
| Application example 4 | 2.88 | 88 |
| Application example 5 | 2.89 | 86 |
| Application example 6 | 2.83 | 87 |
| Application example 7 | 2.87 | 88 |
| Comparative example 1 was used | 2.61 | 85 |
| Comparative example 2 was used | 2.82 | 86 |
| Comparative example 3 was used | 2.71 | 84 |
| Comparative example 4 was used | 2.69 | 83 |
| Comparative example 5 was used | 2.84 | 84 |
Analysis:
from the results of application examples 1 to 3, it is apparent that the electrode prepared by using the carbon-coated lithium ion sieve provided in examples 1 to 3 exhibits higher lithium extraction efficiency and capacity retention rate because the phenolic compound and the aldehyde compound are combined with the physical foaming agent, and the physical foaming agent can foam during the phenolic polycondensation process to generate pores and can effectively control the size of the pores, thereby forming a loose carbon coating layer with larger pore size on the surface of the electrode active material. The electrode active material particles can be communicated with each other through the air holes of the carbon coating layer, so that a solution mass transfer channel is formed, the solution mass transfer is facilitated, and the adsorption and separation efficiency of lithium ions is improved; and the formed foam net structure is compact, and can prevent the hole wall from tearing, so that the circulation stability of the material can be improved.
As can be seen from the results of application examples 1, 4 and 5, in the process of preparing the carbon-coated lithium ion sieve, if the mass fraction of the physical foaming agent is small, the foaming degree is small, the foam density is high, the pore diameter of the coating layer is small, and the lithium extraction efficiency is affected; if the mass fraction of the physical foaming agent is large, the foam body has large pores, the strength of the coating layer is low, and the circulation stability is reduced.
As is clear from the results of application examples 1, 6 and 7, in the process of preparing the carbon-coated lithium ion sieve, if the stirring rate is too low during the reaction, the reactant contact is insufficient, the reaction rate is slow, and a uniform coating layer cannot be formed on the surface of the electrode active material particles, thereby reducing the lithium extraction efficiency and the capacity retention rate; if the rate is too high, the micelle nucleation probability is reduced, the reaction center is reduced, the polymerization reaction rate is reduced, the porous coating layer is reduced, the mass transfer of the solution is hindered, and the lithium extraction efficiency and the capacity retention rate are reduced.
As is apparent from the results of application example 1 and application comparative example 1, in the process of preparing the carbon-coated lithium ion sieve, if the phenolic compound and the aldehyde compound are directly used for carbon coating of the electrode active material, a dense carbon coating layer is formed on the surface of the electrode active material without adding a physical foaming agent, and a mass transfer channel cannot be formed among particles, so that the lithium extraction efficiency of the electrode is low.
As is apparent from the results of application example 1 and application comparative example 2, the lithium extraction efficiency and capacity retention rate of the electrode provided by application comparative example 2 are low, because the carbon-coated lithium ion sieve used in comparative example 2 is prepared by directly mixing and carbonizing an electrode active material with a carbon source, coating carbon on the surface of the electrode active material, that is, cracking the carbon source on the surface of particles during high-temperature calcination to form multiple pores, but mainly improving the surface infiltration of the particles, and mass transfer channels cannot be formed, and the carbon coating layer shields active sites on the surface of the electrode material, thereby reducing the lithium extraction efficiency and capacity retention rate.
As is apparent from the results of application example 1 and application comparative example 3, the lithium extraction efficiency and capacity retention rate of the electrode provided by application comparative example 3 are low, since the application of comparative example 3 directly uses phenolic resin as a carbon source, foaming during the polymerization of monomers is impossible, and thus the cells generated are not uniform, thereby reducing the lithium extraction efficiency and capacity retention rate.
As is clear from the results of application example 1 and application comparative example 4, if a chemical foaming agent (ammonium bicarbonate) is used in the carbon coating process, foaming is insufficient, the size is not uniform, and lithium extraction efficiency is low.
As is apparent from the results of application example 1 and application comparative example 5, the lithium extraction efficiency and capacity retention rate of the electrode provided by application comparative example 5 are low, because the application comparative example 5 is to add a pore-forming agent in the preparation process of the electrode, and decompose the pore-forming agent to generate multiple pores in the drying process, but the pores generated by the pore-forming agent are uncontrollable, poor in connectivity, low in solution mass transfer efficiency and unable to be quickly transferred to an active site for reaction, thereby resulting in low lithium extraction efficiency and capacity retention rate.
Claims (16)
1. A method of preparing a carbon-coated lithium ion sieve, the method comprising:
and mixing the electrode active material, the phenolic compound, the aldehyde compound, the physical foaming agent and the solvent, separating after reaction, and carbonizing the separated solid to obtain the carbon-coated lithium ion sieve.
2. The production method according to claim 1, wherein the electrode active material comprises a positive electrode active material;
the positive electrode active material includes at least one of lithium iron phosphate, lithium manganese iron phosphate, lithium manganate, lithium cobaltate and lithium nickel cobalt manganate.
3. The production method according to claim 1 or 2, wherein the phenolic compound comprises at least one of resorcinol, phenol, cresol, and xylenol.
4. A production method according to any one of claims 1 to 3, wherein the aldehyde compound comprises at least one of formaldehyde, furfural and acrolein.
5. The method of any one of claims 1-4, wherein the physical blowing agent comprises at least one of n-pentane, isopentane, cyclopentane, dichloromethane, and petroleum ether.
6. The method of preparation according to claims 1-5, wherein the solvent comprises water and/or ethanol.
7. The production method according to claim 1, wherein the mixed raw material further comprises a catalyst;
the catalyst comprises a basic catalyst or an acidic catalyst.
8. The preparation method according to claim 7, wherein the basic catalyst comprises ammonia water and/or sodium hydroxide;
the acidic catalyst comprises hydrochloric acid and/or oxalic acid.
9. The production method according to any one of claims 1 to 8, wherein the mass fraction of the electrode active material is 70 to 80% based on the total mass of the electrode active material, the phenolic compound, the aldehyde compound and the physical blowing agent;
optionally, the mass fraction of the phenolic compound is 15-25% based on the total mass of the electrode active material, the phenolic compound, the aldehyde compound and the physical blowing agent;
optionally, the mass fraction of the aldehyde compound is 6-10% based on the total mass of the electrode active material, the phenol compound, the aldehyde compound and the physical foaming agent;
alternatively, the physical blowing agent has a mass fraction of 1 to 5% based on the total mass of the electrode active material, the phenolic compound, the aldehyde compound, and the physical blowing agent.
10. The production method according to any one of claims 1 to 9, wherein the mixing of the electrode active material, the phenolic compound, the aldehyde compound, the physical blowing agent, and the solvent comprises the steps of:
(1) Mixing the electrode active material with a solvent to obtain a first mixture;
(2) Mixing the first mixture with a phenolic compound to obtain a second mixture;
(3) Mixing the second mixture with an aldehyde compound, a catalyst and a physical foaming agent;
optionally, the mixing of step (1) is accompanied by sonication;
optionally, the ultrasonic treatment is carried out for 20-50min;
optionally, the mixing of step (2) is accompanied by stirring;
optionally, during the mixing in the step (2), the stirring speed is 100-500rpm, and the stirring time is 0.5-1.5h.
11. The production method according to any one of claims 1 to 10, wherein the temperature of the reaction is room temperature;
optionally, the reaction time is 10-15 hours;
optionally, stirring is carried out during the reaction, and the stirring speed is 100-500rpm.
12. The production method according to any one of claims 1 to 11, wherein the production method further comprises: a step of drying between the steps of separating and carbonizing;
optionally, the drying temperature is 60-100 ℃;
optionally, the drying time is 10-15 hours.
13. The production method according to any one of claims 1 to 12, wherein the temperature rise rate of the carbonization is 3 to 8 ℃/min;
optionally, the carbonization temperature is 400-800 ℃;
optionally, the carbonization time is 4-10h;
optionally, the carbonization atmosphere is an inert atmosphere.
14. The preparation method according to any one of claims 1 to 13, wherein the preparation method comprises the steps of:
ultrasonically treating an electrode active material and a solvent for 20-50min to obtain a first mixture, stirring the first mixture and a phenolic compound at a speed of 100-500rpm for 0.5-1.5h to obtain a second mixture, mixing the second mixture with an aldehyde compound, a catalyst and a physical foaming agent, and reacting at room temperature for 10-15h to obtain a reaction product;
and (II) separating the reaction product, drying the separated solid for 10-15 hours at 60-100 ℃, and carbonizing for 4-10 hours at 400-800 ℃ to obtain the carbon-coated lithium ion sieve.
15. A carbon-coated lithium ion sieve prepared by the preparation method of any one of claims 1-14;
optionally, the carbon-coated lithium ion sieve comprises an electrode active material inner core and a carbon coating layer coated on the surface of the inner core;
optionally, the average particle size of the carbon-coated lithium ion sieve is 0.5-20 μm.
16. Use of the carbon-coated lithium ion sieve of claim 15 in electrochemical lithium extraction.
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