CN116656965A - Separation and recovery device and method for lithium ions in waste lithium batteries - Google Patents
Separation and recovery device and method for lithium ions in waste lithium batteries Download PDFInfo
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- CN116656965A CN116656965A CN202310578045.6A CN202310578045A CN116656965A CN 116656965 A CN116656965 A CN 116656965A CN 202310578045 A CN202310578045 A CN 202310578045A CN 116656965 A CN116656965 A CN 116656965A
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 43
- 238000000926 separation method Methods 0.000 title claims abstract description 41
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 37
- 238000011084 recovery Methods 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000002699 waste material Substances 0.000 title claims abstract description 28
- 238000005868 electrolysis reaction Methods 0.000 claims description 94
- 239000000243 solution Substances 0.000 claims description 90
- 239000002994 raw material Substances 0.000 claims description 60
- 239000007788 liquid Substances 0.000 claims description 57
- 239000002090 nanochannel Substances 0.000 claims description 47
- 239000012528 membrane Substances 0.000 claims description 45
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 239000012621 metal-organic framework Substances 0.000 claims description 18
- 239000000460 chlorine Substances 0.000 claims description 17
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- 239000003011 anion exchange membrane Substances 0.000 claims description 12
- 239000003446 ligand Substances 0.000 claims description 12
- 238000005530 etching Methods 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 229910021645 metal ion Inorganic materials 0.000 claims description 11
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 10
- 150000001768 cations Chemical class 0.000 claims description 10
- 229910052801 chlorine Inorganic materials 0.000 claims description 10
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 9
- 238000010521 absorption reaction Methods 0.000 claims description 9
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 9
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 8
- 229920002799 BoPET Polymers 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000010405 anode material Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 235000019253 formic acid Nutrition 0.000 claims description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 4
- 239000001103 potassium chloride Substances 0.000 claims description 4
- 235000011164 potassium chloride Nutrition 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000007599 discharging Methods 0.000 description 11
- 150000001450 anions Chemical class 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000012466 permeate Substances 0.000 description 7
- 238000012216 screening Methods 0.000 description 7
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 6
- 238000003487 electrochemical reaction Methods 0.000 description 6
- 230000009471 action Effects 0.000 description 5
- 238000000909 electrodialysis Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000005684 electric field Effects 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 239000004246 zinc acetate Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- -1 iron ions Chemical class 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000013148 Cu-BTC MOF Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000003090 exacerbative effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012527 feed solution Substances 0.000 description 1
- 238000000705 flame atomic absorption spectrometry Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000035772 mutation Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/44—Ion-selective electrodialysis
- B01D61/46—Apparatus therefor
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/02—Apparatus therefor
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/42—Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The invention relates to a separation and recovery device and a method for lithium ions in a waste lithium battery, belonging to the technical field of waste lithium battery recovery.
Description
Technical Field
The invention relates to the technical field of waste lithium batteries, in particular to a device and a method for separating and recovering lithium ions in waste lithium batteries.
Background
In the past few decades, industry development has consumed large amounts of fossil fuels and side-by-side large amounts of pollution, exacerbating global climate and environmental problems. At present, how to seek an efficient and environment-friendly energy production mode and reduce CO 2 The discharge becomes urgent. Lithium resources are used as novel metal resources, and the development of new energy automobiles, energy storage and other industries is greatly promoted due to the excellent energy storage property. However, there are two major problems in the lithium battery industry at present. On the one hand, limited by the current technology, the number of available lithium resources is not large. It is counted that land lithium resources are only 1400 ten thousand tons and would be expected to consume one third at 2050. On the other hand, a large number of new energy automobiles also generate a large number of retired lithium batteries, and if the batteries are discarded at will without disposal, serious environmental problems are caused. Therefore, the method has very important significance in recycling waste lithium batteries from the aspects of resource and environmental protection.
In the lithium ion recovery process, the recovery technology at the present stage is mostly concentrated on the traditional wet chemical recovery, and the recovery rate is low, the cost is high and the environmental risk is high. The patent with publication number CN 109742473A discloses a metal recovery process in waste lithium ion batteries, which comprises the steps of coarsely crushing the waste lithium ion batteries, screening coarse crushed materials, and magnetically separating magnetic substances remained in the screened materials; refining the material subjected to magnetic separation, secondarily screening the refined material, and performing acid leaching treatment on the secondarily screened material to obtain the lithium-containing material + 、Co 2+ Is a solution of (a); li-containing material to be obtained + 、Co 2+ The solution of (2) is subjected to saponification treatment,then using extractant and Li in solution + 、Co 2+ Extracting, washing the extracted material, and separating and purifying Li by back extraction + 、Co 2+ . The whole separation process is complex, the recovery cost is high, the recovery efficiency is low, and the recovery rate is low.
How to realize efficient, economical and rapid recovery of lithium ions in waste lithium batteries becomes an important point of current research.
Disclosure of Invention
In order to solve the technical problems, the invention provides a separation and recovery device and a separation and recovery method for lithium ions in waste lithium batteries, which are characterized in that a nano channel membrane capable of separating single and polyvalent metal cations is designed and applied to an electrodialysis device, anions can be driven to pass through an anion exchange membrane to realize separation and enrichment of the anions, and monovalent lithium ions can permeate the nano channel membrane to realize screening and enrichment.
In order to achieve the above purpose, the technical scheme adopted by the invention for solving the technical problems is as follows: the separation and recovery device for lithium ions in the waste lithium batteries comprises a raw material liquid electrolysis chamber, an anode electrolysis chamber and a cathode electrolysis chamber, wherein the raw material liquid electrolysis chamber is connected with the cathode electrolysis chamber through a nano channel membrane to separate single and multivalent metal cations, and the raw material liquid electrolysis chamber is connected with the anode electrolysis chamber through an anion exchange membrane.
The nanochannel membrane comprises a PET membrane with a nanochannel formed by surface etching, and MOFs are filled in the nanochannels.
The bottom of the raw material liquid electrolysis chamber is connected with the top of the raw material liquid electrolysis chamber sequentially through a raw material liquid pool and a raw material liquid pump, and lithium iron phosphate solution obtained by dissolving waste lithium battery anode material powder is contained in the raw material liquid pool.
Inert electrodes are arranged in the anode electrolysis chamber and the cathode electrolysis chamber, and an adjustable power supply is connected between the two inert electrodes.
The bottom of the anode electrolysis chamber is connected with the top of the anode electrolysis chamber sequentially through an anode pool and an anode water pump, and saturated sodium chloride solution is contained in the anode pool; the top of the anode electrolytic chamber is connected with a chlorine gas absorption tank through a pipeline, and the solution contained in the chlorine gas absorption tank comprises dichloromethane solution or sodium hydroxide solution.
The bottom of the cathode electrolysis chamber is connected with the top of the cathode electrolysis chamber through a cathode pool and a cathode water pump in sequence.
A method for separating and recovering lithium ions in waste lithium batteries, which uses the separation and recovery device, comprises the following steps:
step 1: introducing saturated sodium chloride solution into the anode electrolysis chamber, and introducing lithium iron phosphate solution obtained by dissolving waste lithium battery anode material powder into the raw material solution electrolysis chamber;
step 2: electrifying electrodes in the anode electrolysis chamber and the cathode electrolysis chamber;
step 3: chlorine generated in the anode electrolysis chamber is recovered through a chlorine absorption tank, lithium ions in the raw material liquid electrolysis chamber enter the cathode electrolysis chamber through a nano channel membrane and are recycled through the cathode tank.
The preparation method of the nano-channel membrane used in the separation and recovery device comprises the following steps:
step 1: carrying out electrochemical etching on the PET membrane to form a nano channel;
step 2: filling of MOFs is performed within the formed nanochannels.
The specific operation method of the step 1 is as follows:
1) Sealing and fixing the PET film between two electrolytic tanks added with NaOH solution;
2) Placing inert electrodes in the two electrolytic tanks, and connecting an adjustable power supply and a picoampere meter between the two inert electrodes;
3) Heating two electrolytic tanks in water bath at 30-50 deg.c and applying voltage of 1-2 v;
4) When the current is suddenly changed to 0.1 to 1nA, a mixed solution of formic acid and potassium chloride is added into the electrolytic cell to terminate etching.
The specific operation method of the step 2 is as follows:
1) Vertically immersing the etched PET membrane in a metal ion solution for 1-5 min, taking out, drying in air for 3-5 min, washing in absolute ethyl alcohol or absolute methanol for multiple times, and drying in air for 3-5 min;
2) Immersing the PET membrane into the ligand solution for 1-10 min, taking out, drying in the air for 3-5 min, washing in absolute ethyl alcohol or absolute methyl alcohol for multiple times, and drying in the air for 3-5 min;
3) And (3) circularly operating for 30-100 times according to the method of the step 1) and the step 2), so that metal ions and ligand solutions are continuously combined in the nanochannel to grow into compact MOFs.
Wherein the metal ion solution comprises a copper nitrate solution and a zinc acetate solution, and the ligand solution comprises a trimesic acid solution and a 2-methylimidazole solution.
The beneficial effects of the invention are as follows:
according to the invention, the nano channel membrane filled by MOFs is designed and connected between the raw material liquid electrolysis chamber and the cathode electrolysis chamber in the electrodialysis device, the raw material liquid electrolysis chamber is connected with the anode electrolysis chamber through the anion exchange membrane, the electrodialysis system can drive anions to pass through the anion exchange membrane to realize separation and enrichment of anions, the nano channel membrane can enable monovalent lithium ions to permeate and prevent polyvalent metal cations from permeating, screening and enrichment of lithium ions are realized, the separation efficiency of lithium ions is improved, the separation process is simple, the separation cost is low, and the separation process is safe and reliable.
Drawings
The contents of the drawings and the marks in the drawings of the present specification are briefly described as follows:
FIG. 1 is a schematic structural view of a device for separating and recovering lithium ions in waste lithium batteries;
FIG. 2 is an exploded view of the connection structure of the feed solution electrolysis chamber, the anode electrolysis chamber and the cathode electrolysis chamber of the present invention;
the labels in the above figures are: 1. the system comprises a raw material liquid electrolysis chamber 11, a raw material liquid feeding channel 12, a raw material liquid discharging channel 2, an anode electrolysis chamber 21, an anode feeding channel 22, an anode discharging channel 23, a chlorine collecting channel 3, a cathode electrolysis chamber 31, a cathode feeding channel 32, a cathode discharging channel 4, a nano channel membrane 5, an anion exchange membrane 6, a raw material liquid pool 7, a raw material liquid pump 8, an inert electrode 9, an adjustable power supply 10, an anode pool 11, an anode water pump 12, a chlorine absorbing pool 13, a cathode pool 14 and a cathode water pump.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments will be clearly and completely described with reference to the accompanying drawings in the embodiments of the present invention, and the following embodiments are used to illustrate the present invention, but are not intended to limit the scope of the present invention.
In the description of the present invention, it should be noted that the directions or positional relationships indicated by the terms "upper", "lower", "front", "rear", "left", "right", "vertical", "inner", "outer", etc. are based on the directions or positional relationships shown in the drawings, are merely for convenience of describing the present invention and simplifying the description, and do not indicate or imply that the devices or elements referred to must have a specific orientation, be configured and operated in a specific orientation, and thus should not be construed as limiting the present invention.
In the description of the present invention, it should be noted that, unless explicitly specified and limited otherwise, the terms "mounted," "connected," and "connected" are to be construed broadly, and may be either fixedly connected, detachably connected, or integrally connected, for example; can be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium. The specific meaning of the above terms in the present invention will be understood in specific cases by those of ordinary skill in the art.
The invention is illustrated by the following examples.
Example 1
As shown in fig. 1 and 2, the invention provides a separation and recovery device for lithium ions in waste lithium batteries, which comprises a raw material liquid electrolysis chamber 1, an anode electrolysis chamber 2 and a cathode electrolysis chamber 3, wherein the raw material liquid electrolysis chamber 1 and the cathode electrolysis chamber 3 are connected through a nano channel membrane 4 to separate single and multivalent metal cations (namely, the surface of the raw material liquid electrolysis chamber 1, which is contacted with the cathode electrolysis chamber 3, is provided with a hollow structure, the nano channel membrane 4 is hermetically connected at the hollow structure), the raw material liquid electrolysis chamber 1 and the anode electrolysis chamber 2 are connected through an anion exchange membrane 5 to separate anions and cations (namely, the surface of the raw material liquid electrolysis chamber 1, which is contacted with the anode electrolysis chamber 2, is provided with the hollow structure, and the hollow structure is hermetically connected with the anion exchange membrane 5). The whole electrodialysis system can drive anions to pass through the anion exchange membrane 5 to realize separation and enrichment of the anions, the nano channel membrane 4 can enable monovalent lithium ions to permeate and block multivalent metal cations to permeate, screening and enrichment of the lithium ions are realized, and the separation efficiency of the lithium ions is improved, the separation process is simple, the separation cost is low, and the separation process is safe and reliable.
Specifically, the nanochannel membrane 4 comprises a PET membrane with a nanochannel formed by surface etching, MOFs (metal organic framework compounds) are filled in the nanochannels, and the MOFs have the function of size screening, so that multi-valence metal cations cannot permeate, monovalent metal cations can permeate, and the selective separation of single and multivalent ions is realized.
Specifically, the anode electrolysis chamber 2 and the cathode electrolysis chamber 3 are respectively provided with an inert electrode 8, the inert electrodes 8 can be graphite carbon rods or platinum electrodes and the like, the inert electrodes 8 do not participate in oxidation-reduction reaction, only play a role in transferring electrons, an adjustable power supply 9 is connected between the two inert electrodes 8, the positive electrode of the adjustable power supply 9 is connected with the inert electrodes 8 in the anode electrolysis chamber 2, and the negative electrode of the adjustable power supply 9 is connected with the inert electrodes 8 in the cathode electrolysis chamber 3. The voltage of the adjustable power supply 9 can be set to be about 2v according to the operation parameters and specific conditions, and good concentration rate, ion migration rate and membrane operation effect can be ensured.
Specifically, a raw material liquid feeding channel 11 is arranged at the top of a raw material liquid electrolysis chamber 1, a raw material liquid discharging channel 12 is arranged at the bottom of the raw material liquid electrolysis chamber 1, the raw material liquid discharging channel 12 is connected with the raw material liquid feeding channel 11 sequentially through a raw material liquid pond 6 and a raw material liquid pump 7, lithium iron phosphate solution obtained by dissolving waste lithium battery anode material powder is contained in the raw material liquid pond 6, and the lithium iron phosphate solution in the raw material liquid pond 6 can be injected under the action of the raw material liquid pump 7And the solution is filled into the raw material liquid electrolysis chamber 1, an exhaust valve is arranged in the raw material liquid discharging channel 12, and the solution in the raw material liquid electrolysis chamber 1 can be discharged into the raw material liquid pool 6 according to the requirement. The raw material liquid electrolytic chamber 1 has a membrane mass transfer process, namely: the medium-low concentration lithium iron phosphate solution in the raw material liquid pool 6 flows into the raw material liquid electrolysis chamber 1 under the action of the raw material liquid pump 7, and Li + Driven by electric field force, passes through the MOFs-filled nanochannel membrane 4; phosphate ions are subjected to charge repulsion and iron ions with larger size are subjected to size sieving effect of the nano-channel film 4, and cannot penetrate through the nano-channel film 4, so that Li is realized + Is selected from the group consisting of a nitrogen source, and a nitrogen source.
Specifically, an anode discharging channel 22 is arranged at the bottom of the anode electrolysis chamber 2, an anode feeding channel 21 is arranged at the top of the anode electrolysis chamber 2, the anode discharging channel 22 is connected with the anode feeding channel 21 sequentially through an anode pool 10 and an anode water pump 11, a saturated sodium chloride solution is contained in the anode pool 10, and under the action of the anode water pump 11, the saturated sodium chloride solution in the anode pool 10 is injected into the anode electrolysis chamber 2; the top of the anode electrolytic chamber 2 is also provided with a chlorine gas collecting channel 23, the chlorine gas collecting channel 23 is connected with the chlorine gas absorbing tank 12 through a pipeline, and the solution contained in the chlorine gas absorbing tank 12 comprises a solution capable of absorbing chlorine gas, such as a dichloromethane solution or a sodium hydroxide solution; an exhaust valve is arranged in the anode discharging channel 22, and the solution in the anode electrolysis chamber 2 can be discharged into the anode pool 10 according to the requirement.
The electrochemical reaction process exists in the anode electrolysis chamber 2, namely: the saturated NaCl solution in the anode cell 10 flows into the anode electrolytic chamber 2 through the anode feed passage 21 under the action of the anode water pump 11, and electrochemical reaction occurs in the anode electrolytic chamber 2: cl - -2e＝Cl 2 ↑，Cl 2 Enters the chlorine absorption tank 12 to be absorbed, and the saturated sodium chloride solution in the anode tank 10 can prevent Cl generated by the electrode 2 Redissolved in solution to facilitate the reaction to Cl 2 Recycling and protecting the anion exchange membrane 5; cl of the solution in the anode electrolytic chamber 2 - The concentration is reduced, a concentration difference is generated around the anion exchange membrane 5, and the PO4 in the raw material liquid electrolysis chamber 1 is promoted by the electric field force 3- Through anion exchangeThe membrane 5 is replenished into the anolyte compartment 2, maintaining the saturation state of the system anions.
Specifically, a cathode feeding channel 31 is arranged at the top of the cathode electrolysis chamber 3, a cathode discharging channel 32 is arranged at the bottom of the cathode electrolysis chamber 3, and the cathode discharging channel 32 is connected with the cathode feeding channel 31 sequentially through a cathode pool 13 and a cathode water pump 14. The concentration of lithium ions in the cathode electrolytic chamber 3 is continuously increased, the continuously increased solution flows into the cathode pool 13, the solution flows back into the cathode electrolytic chamber 3 through the cathode water pump 14 until the concentration of lithium ions in the cathode pool 13 reaches a certain value, a recovery pipeline is arranged on the cathode pool 13, a switch valve is arranged in the recovery pipeline, and the switch valve is opened, so that the lithium-rich solution can be recovered and transferred into other recovery devices. The solution in the cathode pool 13 can be sampled at fixed time, and the concentration of lithium ions in the solution can be measured by the existing method (such as flame atomic absorption spectrometry, inductively coupled plasma mass spectrometry, ion selective electrode method and the like); of course, an on-line monitoring method can also be adopted, for example, the German Metrele group has a LITHIUM ion selective electrode DX207 LITHIUM ISE, so that the on-line monitoring of LITHIUM ions in solution can be realized, and the on-line detection cost is higher. When the concentration of lithium ions reaches a certain value, the switch valve is opened to recover and transfer the lithium-rich solution in the cathode pool 13.
The electrochemical reaction process exists in the cathode electrolysis chamber 3, namely: lithium ions continuously enter the cathode electrolysis chamber 3 and are enriched in the electrolysis chamber. At the same time, electrochemical reactions take place in the catholyte compartment 3: h 2 O+2e - ＝H 2 ↑+2OH - Further promote Li + Is a migration of (a). The lithium ion concentration in the cathode electrolytic chamber 3 is continuously increased, the continuously increased solution flows into the cathode pool 13, the solution is returned into the cathode electrolytic chamber 3 through the cathode water pump 14 until the lithium ion concentration in the cathode pool 13 reaches a certain value, and the lithium-rich solution in the cathode pool 13 is recovered and turned out.
A method for separating and recovering lithium ions in waste lithium batteries, which uses the separation and recovery device, comprises the following steps:
step 1: introducing saturated sodium chloride solution into the anode electrolysis chamber 2, and introducing lithium iron phosphate solution obtained by dissolving waste lithium battery anode material powder into the raw material solution electrolysis chamber 1;
step 2: electrifying the electrodes in the anode electrolysis chamber 2 and the cathode electrolysis chamber 3;
step 3: chlorine generated in the anode electrolytic chamber 2 is recovered through a chlorine absorption tank 12, lithium ions in the raw material liquid electrolytic chamber 1 enter the cathode electrolytic chamber 3 through a nano channel membrane 4, and are recycled through a cathode tank 13.
Electrochemical reaction occurs in the anolyte compartment 2: cl - -2e＝Cl 2 ↑，Cl 2 Enters a chlorine absorption tank 12 to be absorbed, and Cl in the solution in the anode electrolysis chamber 2 - The concentration is reduced, a concentration difference is generated around the anion exchange membrane 5, and the PO4 in the raw material liquid electrolysis chamber 1 is promoted by the electric field force 3- The negative ions pass through the negative ion exchange membrane 5 to be supplemented into the anode electrolysis chamber 2, and the saturation state of the negative ions of the system is maintained.
The membrane mass transfer process occurs in the raw material liquid electrolysis chamber 1: the lithium iron phosphate solution in the raw material liquid pool 6 flows into the raw material liquid electrolysis chamber 1 under the action of the raw material liquid pump 7, and Li + Driven by electric field force, passes through the MOFs-filled nanochannel membrane 4; phosphate ions are subjected to charge repulsion and iron ions with larger size are subjected to size sieving effect of the nano-channel film 4, and cannot penetrate through the nano-channel film 4, so that Li is realized + Is selected from the group consisting of a nitrogen source, and a nitrogen source.
Electrochemical reaction occurs in the cathode electrolytic chamber 3: h 2 O+2e - ＝H 2 ↑+2OH - Further promote Li + The lithium ion concentration in the cathode electrolytic chamber 3 is continuously increased, the continuously increased solution flows into the cathode pool 13, the solution is returned into the cathode electrolytic chamber 3 through the cathode water pump 14 until the lithium ion concentration in the cathode pool 13 reaches a certain value, and the lithium-rich solution in the cathode pool 13 is recovered and turned out.
Example two
The preparation method of the nano-channel membrane used in the separation and recovery device comprises the following steps:
step 1: the PET membrane is electrochemically etched to form nanochannels.
The specific operation method comprises the following steps:
1) Sealing and fixing the PET membrane between two electrolytic tanks added with NaOH solution, wherein the two electrolytic tanks can utilize a raw material liquid electrolytic chamber 1 and a cathode electrolytic chamber 3 in a separation and recovery device, and the concentration of the NaOH solution is 2mol/L;
2) Placing inert electrodes 8 in the two electrolytic tanks, connecting an adjustable power supply 9 and a picoammeter between the two inert electrodes 8, wherein the voltage of the adjustable power supply 9 can be used for detecting the current in a circuit connected with the two electrodes according to the operation parameters and specific conditions;
3) Heating two electrolytic tanks in water bath at 30-50 ℃, applying voltage of 1-2 v, and performing electrochemical etching on the PET membrane, wherein in the etching process, naOH solution corrodes the PET membrane to break lipid bonds in the PET membrane material and expose carboxyl and hydroxyl functional groups, so that a nano channel with the aperture of 200-300 nm is formed;
4) When the current monitored by the Pian meter in real time has a mutation of 0.1-1 nA, adding a mixed solution of formic acid and potassium chloride with the concentration ratio of 1:1 into the electrolytic tank to stop etching. The equation for the termination reaction principle is: HCOOH+NaOH- & gtHCOONa+H 2 O, potassium chloride therein acts to stabilize the film surface and co-stop etching with formic acid solution.
Step 2: filling of MOFs is performed within the formed nanochannels.
The specific operation method comprises the following steps:
1) Vertically immersing the etched PET film into Cu (NO) with the concentration of 1mol/L 3 Extracting metal ion solution for 5min, drying in air for 3min, washing in absolute ethanol solution for 2 times (3 min each time), and drying in air for 3min;
2) Immersing PET membrane in 1mol/L trimesic acid ligand solution for 10min, taking out, and air drying for 3min, cu (NO) 3 The equation for reaction with trimesic acid ligand is: 3Cu (NO) 3 ) 2 +3C 6 H 3 (COOH) 3 +18H 2 O→Cu 3 (C 6 H 3 (COO) 3 ) 2 ·xH 2 O+6HNO 3 Obtaining a connector HKUST-1, washing the obtained PET film containing the connector in an absolute ethanol solution for 2 times (3 min each time), and then drying in air for 3min;
3) And (3) circularly operating for 100 times according to the method of the step 1) and the step 2), and continuously combining metal ions and ligand solution in the nano channel to grow into compact MOFs small particles, wherein the diameters of the MOFs small particles are 100-200nm.
Example III
The difference from example two is that when filling MOFs in the formed nanochannels, the metal ion solution employed was zinc acetate solution and the ligand solution was 2-methylimidazole solution. The specific method comprises the following steps:
1) Vertically immersing the etched PET film in a zinc acetate metal ion solution with the concentration of 0.572mol/L for 1min, taking out, drying in air for 3min, washing in an anhydrous methanol solution for 2 times (1 min each time), and then drying in air for 3min;
2) Immersing the PET membrane into 2-methylimidazole ligand solution with the concentration of 2.56mol/L for 1min, taking out, drying in air for 3min, and reacting the metal ion solution with the ligand solution according to the equation: zn (zinc) 2+ +2MeIm→Zn(MeIm) 2 Obtaining a linker Zn (Meim) 2 Washing the obtained PET film containing the connector in an anhydrous methanol solution with the concentration for 2 times (1 min each time), and then drying in air for 3min;
3) And (3) circularly operating for 30 times according to the method of the step 1) and the step 2), and continuously combining metal ions and ligand solution in the nano channel to grow into compact MOFs small particles, wherein the diameters of the MOFs small particles are 100-200nm.
In summary, the nano-channel membrane capable of separating the single and multivalent metal cations is designed and applied to the electrodialysis device, so that the monovalent lithium ions permeate the nano-channel membrane to realize screening enrichment, the lithium ion separation efficiency is improved, the separation process is simple, the separation cost is low, and the separation process is safe and reliable.
The foregoing is provided by way of illustration of the principles of the present invention, and is not intended to be limited to the specific constructions and applications illustrated herein, but rather to all modifications and equivalents which may be utilized as fall within the scope of the invention as defined in the claims.
Claims (10)
1. The device is characterized by comprising a raw material liquid electrolysis chamber, an anode electrolysis chamber and a cathode electrolysis chamber, wherein the raw material liquid electrolysis chamber is connected with the cathode electrolysis chamber through a nano channel membrane to separate single and multivalent metal cations, and the raw material liquid electrolysis chamber is connected with the anode electrolysis chamber through an anion exchange membrane.
2. The separation and recovery device for lithium ions in waste lithium batteries according to claim 1, wherein the separation and recovery device is characterized in that: the nanochannel membrane comprises a PET membrane with a nanochannel formed by surface etching, and MOFs are filled in the nanochannels.
3. The separation and recovery device for lithium ions in waste lithium batteries according to claim 1, wherein the separation and recovery device is characterized in that: the bottom of the raw material liquid electrolysis chamber is connected with the top of the raw material liquid electrolysis chamber sequentially through a raw material liquid pool and a raw material liquid pump, and lithium iron phosphate solution obtained by dissolving waste lithium battery anode material powder is contained in the raw material liquid pool.
4. The separation and recovery device for lithium ions in waste lithium batteries according to claim 1, wherein the separation and recovery device is characterized in that: inert electrodes are arranged in the anode electrolysis chamber and the cathode electrolysis chamber, and an adjustable power supply is connected between the two inert electrodes.
5. The separation and recovery device for lithium ions in waste lithium batteries according to claim 1, wherein the separation and recovery device is characterized in that: the bottom of the anode electrolysis chamber is connected with the top of the anode electrolysis chamber sequentially through an anode pool and an anode water pump, and saturated sodium chloride solution is contained in the anode pool; the top of the anode electrolytic chamber is connected with a chlorine gas absorption tank through a pipeline, and the solution contained in the chlorine gas absorption tank comprises dichloromethane solution or sodium hydroxide solution.
6. The separation and recovery device for lithium ions in waste lithium batteries according to claim 5, wherein the separation and recovery device is characterized in that: the bottom of the cathode electrolysis chamber is connected with the top of the cathode electrolysis chamber through a cathode pool and a cathode water pump in sequence.
7. A method for separating and recovering lithium ions in waste lithium batteries by using the separation and recovery device as claimed in any one of claims 1 to 6, which is characterized by comprising the following steps:
step 1: introducing saturated sodium chloride solution into the anode electrolysis chamber, and introducing lithium iron phosphate solution obtained by dissolving waste lithium battery anode material powder into the raw material solution electrolysis chamber;
step 2: electrifying electrodes in the anode electrolysis chamber and the cathode electrolysis chamber;
step 3: chlorine generated in the anode electrolysis chamber is recovered through a chlorine absorption tank, lithium ions in the raw material liquid electrolysis chamber enter the cathode electrolysis chamber through a nano channel membrane and are recycled through the cathode tank.
8. A method for producing a nanochannel membrane for use in a separation and recovery device as claimed in any one of claims 1 to 6, comprising the steps of:
step 1: carrying out electrochemical etching on the PET membrane to form a nano channel;
step 2: filling of MOFs is performed within the formed nanochannels.
9. The method for preparing a nanochannel membrane according to claim 8, wherein: the specific operation method of the step 1 is as follows:
1) Sealing and fixing the PET film between two electrolytic tanks added with NaOH solution;
2) Placing inert electrodes in the two electrolytic tanks, and connecting an adjustable power supply and a picoampere meter between the two inert electrodes;
3) Heating two electrolytic tanks in water bath at 30-50 deg.c and applying voltage of 1-2 v;
4) When the current is suddenly changed to 0.1 to 1nA, a mixed solution of formic acid and potassium chloride is added into the electrolytic cell to terminate etching.
10. The method for preparing a nanochannel membrane according to claim 8, wherein: the specific operation method of the step 2 is as follows:
1) Vertically immersing the etched PET membrane in a metal ion solution for 1-5 min, taking out, drying in air for 3-5 min, washing in absolute ethyl alcohol or absolute methanol solution for multiple times, and drying in air for 3-5 min;
2) Immersing the PET membrane into the ligand solution for 1-10 min, taking out, drying in the air for 3-5 min, washing in absolute ethyl alcohol or absolute methyl alcohol for multiple times, and drying in the air for 3-5 min;
3) And (3) circularly operating for 30-100 times according to the method of the step 1) and the step 2), so that metal ions and ligand solutions are continuously combined in the nanochannel to grow into compact MOFs.
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