CN117187593A - Device and method for separating and recovering lithium ions in waste lithium batteries by in-situ electroleaching coupling electric control membrane - Google Patents
Device and method for separating and recovering lithium ions in waste lithium batteries by in-situ electroleaching coupling electric control membrane Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 102
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 77
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 45
- 239000002699 waste material Substances 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 12
- 230000008878 coupling Effects 0.000 title claims description 10
- 238000010168 coupling process Methods 0.000 title claims description 10
- 238000005859 coupling reaction Methods 0.000 title claims description 10
- 238000011084 recovery Methods 0.000 claims abstract description 20
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 239000010405 anode material Substances 0.000 claims abstract description 7
- 238000011049 filling Methods 0.000 claims abstract description 5
- 239000003792 electrolyte Substances 0.000 claims description 14
- 238000004891 communication Methods 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 229910001220 stainless steel Inorganic materials 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 6
- 235000011152 sodium sulphate Nutrition 0.000 claims description 6
- 230000009471 action Effects 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 5
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 5
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 abstract description 7
- 238000007254 oxidation reaction Methods 0.000 abstract description 7
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 230000009467 reduction Effects 0.000 abstract description 6
- 230000007646 directional migration Effects 0.000 abstract description 3
- 230000033116 oxidation-reduction process Effects 0.000 abstract description 3
- 238000011161 development Methods 0.000 abstract description 2
- 230000000737 periodic effect Effects 0.000 abstract description 2
- 230000009466 transformation Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 18
- 230000005684 electric field Effects 0.000 description 15
- 238000004064 recycling Methods 0.000 description 11
- 230000008569 process Effects 0.000 description 8
- 238000002386 leaching Methods 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000008151 electrolyte solution Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000007731 hot pressing Methods 0.000 description 3
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 3
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
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- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
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- 239000012535 impurity Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
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- 239000012266 salt solution Substances 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
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- 239000007787 solid Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010926 waste battery Substances 0.000 description 1
Abstract
The invention belongs to the technical field of separation and recovery of lithium, and provides a device and a method for separating and recovering lithium ions in waste lithium batteries by in-situ electroleaching coupled electric control membranes, wherein the device comprises a consumption electrode, an electroactive permeable membrane electrode, an auxiliary electrode, an anode region, a cathode region and a rheostat; the consumption electrode is obtained by filling waste lithium battery anode materials into an anode electrode groove; the electroactive permeable membrane electrode has lithium ion selectivity. The electroactive permeable membrane electrode is communicated with the cathode/anode through periodic transformation to provide a pulse potential of oxidation-reduction potential, when the electroactive permeable membrane is at reduction potential, lithium ions are put into the electroactive permeable membrane from the anode region, and then the electroactive permeable membrane is changed to oxidation potential, the lithium ions in the electroactive permeable membrane are released to the cathode region again, so that selective directional migration of the lithium ions from the anode region to the cathode region is realized. The device and the method are environment-friendly, have high lithium ion recovery efficiency and low energy consumption, and have great development potential in the field of lithium battery resource recovery.
Description
Technical Field
The invention relates to the technical field of separation and recovery of lithium, in particular to a device and a method for separating and recovering lithium ions in waste lithium batteries by an in-situ electroleaching coupling electric control membrane.
Background
At present, the new sales of new energy automobiles continuously climb in proportion, and the quantity of power lithium batteries retired in the future is quite striking. If a large amount of waste batteries are improperly treated, the environment is polluted for a long time. On the other hand, lithium enriched in lithium battery is also an important raw material for producing lithium ion battery, and has great recovery value. Therefore, recycling lithium resources in waste lithium batteries has become an important issue in the environmental and energy fields.
The current methods for recycling and regenerating waste lithium batteries mainly comprise pyrometallurgy and hydrometallurgy. The fire recovery process is simple, but the recovery process is easy to cause the emission of dust and harmful gas, and the energy consumption is high; the wet metallurgy process has high recovery rate and high product purity, and is the main stream technology for recovering the current waste lithium ion batteries. Wet recovery typically employs strong acid leaching, after which the leached material is dissolved in an acid solution, and then the valuable metals such as cobalt, nickel, lithium, etc. are selectively recovered therefrom. The recovery method includes solvent extraction, precipitation, electrolysis, ion exchange, and salting out. However, the traditional methods have the defects of high energy consumption, large pollution and the like when used for recycling valuable metal resources in the waste lithium batteries. For example, the most widely used solvent extraction method at present requires that the positive electrode material of waste lithium batteries is first dissolved with high concentration acid, and then the metal ions therein are extracted stepwise with an organic solvent such as P-204 (di (2-ethylhexyl) phosphate) [ Jiangxi chemical industry, 2018, 06: 94-96 ]. The process can use a large amount of strong acid and toxic and harmful organic extractant in the operation process, and serious secondary pollution is generated. Patent application number CN201911411831.7 discloses a method for recovering lithium battery material, in which a large amount of sulfuric acid and lithium hydroxide are needed in the actual operation process, and the whole operation also needs to undergo complex separation and precipitation processes.
Therefore, the method for separating and recovering lithium ions from the waste lithium battery has the advantages of high lithium ion recovery efficiency, low energy consumption, environmental friendliness and no pollution, and has important value.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a device and a method for separating and recycling lithium ions in waste lithium batteries by in-situ electroleaching coupling electric control membranes. The device and the method can realize the efficient enrichment of lithium ions in the cathode region and directly form LiOH and Li 2 SO 4 The equal high-concentration lithium salt solution has the advantages of high metal recycling recovery efficiency, low energy consumption and no secondary pollution.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a device for recovering lithium ions in waste lithium batteries by in-situ electroleaching coupling electric control membrane separation, which comprises a consumption electrode, an electroactive permeable membrane electrode, an auxiliary electrode, an anode region, a cathode region and a rheostat;
the consumption electrode is obtained by filling waste lithium battery anode materials into an anode electrode groove;
the electroactive permeable membrane electrode has lithium ion selectivity, the auxiliary electrode is a cathode, and the consumable electrode is an anode.
Preferably, the electroactive permeable membrane electrode is positioned in the middle of the device, separating the anode and cathode regions.
Preferably, the electroactive permeable membrane electrode is in repeated alternating communication with the anode or the cathode, and the electroactive permeable membrane electrode is in communication with the anode or the cathode through a varistor.
Preferably, the preparation method of the electroactive permeable membrane electrode comprises the steps of constructing an electroactive layer on the surface of a conductive porous matrix; the electroactive layer is made of manganese dioxide, lithium manganate, lithium cobaltate or lithium iron phosphate; the conductive porous matrix is titanium mesh, nickel mesh or stainless steel mesh, and the mesh number of the conductive porous matrix is 2-500 mesh.
The invention also provides a method for separating and recycling lithium ions by the device, which comprises the following steps:
1) Connecting the electroactive permeable membrane electrode with the cathode, and accumulating H at the consuming electrode + Lithium ions are released into the electrolyte of the anode region under the action of the acidic microenvironment, and the released lithium ions migrate to the electroactive permeable membrane electrode and are put into the membrane;
2) The electroactive permeable membrane electrode is communicated with the anode, and lithium ions in the electroactive permeable membrane electrode migrate to the cathode region, so that enrichment and recovery of the lithium ions are realized;
repeating the steps 1) and 2) alternately, wherein the total time for communicating the electroactive permeable membrane electrode with the cathode and the anode is 8-10 h.
Preferably, the voltage between the cathode and the anode is 5 to 7V.
Preferably, in step 1) and step 2), the time of each communication with the cathode and the time of each communication with the anode are independently 12 to 18 minutes.
Preferably, in step 1), the consumable electrode accumulates H by the potential rejection effect and the electrolyzed water oxygen evolution reaction + The method comprises the steps of carrying out a first treatment on the surface of the The electrolyte in the anode region is sodium sulfate solution, and the concentration of the sodium sulfate solution is 0.05-0.15 mol/L.
Preferably, the electrolyte in the cathode region is a lithium sulfate solution, and the concentration of the lithium sulfate solution is 0.05-0.15 mol/L.
The beneficial effects of the invention include:
1) The invention uses electric energy as driving force, can be operated at normal temperature and normal pressure, and the electric energy is converted from renewable energy sources such as solar energy, wind energy and the like, thereby effectively reducing carbon emission generated in the traditional waste lithium battery recycling process; no corrosive reagents such as high-concentration acid and alkali and the like or toxic and harmful organic extractant are needed, and secondary pollution is avoided. The device and the method can efficiently recycle lithium ions in the waste lithium batteries, are environment-friendly and low in energy consumption, can improve resource shortage, avoid resource waste and have great development potential in the field of lithium battery resource recycling.
2) In the running process of the device, the external constant electric field promotes the electric leaching on one hand, and on the other hand, the electric field which is from left to right is provided for the two sides of the electrolytic cell to drive lithium ions to migrate to the cathode region. The middle electroactive permeable membrane electrode is communicated with the cathode/anode through periodic transformation to provide a pulse potential of oxidation-reduction potential, when the electroactive permeable membrane is at reduction potential, lithium ions are put into the electroactive permeable membrane from the anode region, and then when the electroactive permeable membrane is changed to oxidation potential, the lithium ions in the electroactive permeable membrane are released to the cathode region again, so that selective directional migration of the lithium ions from the anode region to the cathode region is realized, and finally enrichment and recovery of the lithium ions are realized.
Drawings
Fig. 1 is a device and a method for recovering lithium ions in waste lithium batteries by in-situ electroleaching coupling electric control membrane separation, wherein 1 is an anode region, 2 is a cathode region, 3 is a consumption electrode, 4 is an electroactive permeable membrane electrode, 5 is an auxiliary electrode, 6 is a regulated power supply, 7 is a rheostat, the left image is that the electroactive permeable membrane electrode is communicated with the cathode, and the right image is that the electroactive permeable membrane electrode is communicated with the anode.
Detailed Description
The invention provides a device for recovering lithium ions in waste lithium batteries by in-situ electroleaching coupling electric control membrane separation, which comprises a consumption electrode, an electroactive permeable membrane electrode, an auxiliary electrode, an anode region, a cathode region and a rheostat;
the consumption electrode is obtained by filling waste lithium battery anode materials into an anode electrode groove;
the electroactive permeable membrane electrode has lithium ion selectivity, the auxiliary electrode is a cathode, and the consumable electrode is an anode.
The device couples the electroleaching technology and the electric control membrane separation technology through three electrodes (a consumption electrode, an electroactive permeable membrane electrode and an auxiliary electrode), periodically communicates the electroactive permeable membrane electrode with an cathode (anode), and adjusts the membrane potential by using a rheostat to prevent hydrogen and oxygen evolution side reaction caused by high potential, so that lithium ions are separated and extracted in one step, and lithium ions in the waste lithium ion battery can be recovered cleanly and efficiently.
The device for separating and recovering lithium ions is of a one-cavity two-chamber structure, and the electroactive permeable membrane electrode is positioned in the middle of the device and separates an anode area from a cathode area.
In the present invention, the electroactive permeable membrane electrode is preferably in communication with the anode or the cathode repeatedly and alternately, and the electroactive permeable membrane electrode is in communication with the anode or the cathode through the varistor.
In the invention, the preparation method of the electroactive permeable membrane electrode is preferably to construct an electroactive layer on the surface of the conductive porous matrix; the material of the electroactive layer is preferably manganese dioxide, lithium manganate, lithium cobaltate or lithium iron phosphate; the electroactive layer realizes selective permeability of lithium ions under pulse potential; the electrically conductive porous substrate is preferably a titanium mesh, a nickel mesh or a stainless steel mesh, and the mesh number of the electrically conductive porous substrate is preferably 2 to 500 mesh, more preferably 10 to 400 mesh, and still more preferably 50 to 200 mesh.
In the invention, the waste lithium battery positive electrode material is preferably a waste lithium battery positive electrode sheet or a stripped positive electrode powder material, and is further preferably from a waste lithium iron phosphate battery, a waste lithium cobalt oxide battery, a waste lithium manganate battery or a waste ternary lithium battery.
In the present invention, the anode electrode groove is a porous electrode groove with adjustable thickness, the adjustable thickness is used for compacting the anode material to prevent the anode material from directly leaking into the electrolyte, the porous design provides a channel for lithium ion leaching, the mesh number of the electrode groove is preferably 2-500 meshes, more preferably 10-400 meshes, and even more preferably 50-200 meshes.
The invention also provides a method for separating and recycling lithium ions by the device, which comprises the following steps:
1) Connecting the electroactive permeable membrane electrode with the cathode, and accumulating H at the consuming electrode + Lithium ions are released into the electrolyte of the anode region under the action of the acidic microenvironment, and the released lithium ions migrate to the electroactive permeable membrane electrode and are put into the membrane;
2) The electroactive permeable membrane electrode is communicated with the anode, and lithium ions in the electroactive permeable membrane electrode migrate to the cathode region, so that enrichment and recovery of the lithium ions are realized;
repeating the steps 1) and 2) alternately, wherein the total time for communicating the electroactive permeable membrane electrode with the cathode and the anode is 8-10 h.
In the present invention, the voltage between the cathode and the anode is preferably 5 to 7V, and more preferably 6V.
In the steps 1) and 2) of the present invention, the time for each communication with the cathode and the time for each communication with the anode are independently preferably 12 to 18 minutes, more preferably 13 to 17 minutes, and still more preferably 14 to 15 minutes.
In the present invention, the total time for the electroactive permeable membrane electrode to communicate with the cathode and anode is preferably 8.5 to 9.5 hours, more preferably 9 hours.
In step 1) of the present invention, the consumable electrode accumulates H by the potential rejection effect and the electrolyzed water oxygen evolution reaction + The method comprises the steps of carrying out a first treatment on the surface of the The electrolyte in the anode region is preferably a sodium sulfate solution, and the concentration of the sodium sulfate solution is preferably 0.05 to 0.15mol/L, more preferably 0.08 to 0.12mol/L, and still more preferably 0.1mol/L.
In the present invention, the electrolyte in the cathode region is preferably a lithium sulfate solution, and the concentration of the lithium sulfate solution is preferably 0.05 to 0.15mol/L, more preferably 0.08 to 0.12mol/L, and still more preferably 0.1mol/L.
In the step 2), lithium ions in the electroactive permeable membrane electrode migrate to the cathode region under the drive of the repulsive potential and the externally applied electric field.
The invention provides pulse potential for periodically converting oxidation-reduction potential by periodically converting and connecting the electroactive permeable membrane electrode and the cathode (anode), thereby realizing selective placement and release of lithium ions; the electroactive permeable membrane electrode in step 1) is at a reduction potential, which places lithium ions from the anode region; in the step 2), the electroactive permeable membrane electrode becomes oxidation potential, and lithium ions in the electroactive permeable membrane are released to the cathode region, so that selective directional migration of the lithium ions from the anode region to the cathode region is realized, and finally the lithium ions are enriched and recovered.
The circuit is formed by coupling an external electric field and an internal electric field capable of periodically switching the electroactive permeable membrane to connect the cathode (anode), and the internal electric field is communicated with the cathode (anode) and the electroactive permeable membrane electrode through a rheostat. When lithium ions in the waste lithium battery are recovered, the electroactive permeable membrane electrode is communicated with the cathode to adsorb the lithium ions, and then is communicated with the anode to desorb the lithium ions.
The invention discloses a device and a method for recovering lithium ions in waste lithium batteries by in-situ electroleaching coupling electric control membrane separation, which are shown in figure 1, wherein 1 is an anode region, 2 is a cathode region, 3 is a consumption electrode, 4 is an electroactive permeable membrane electrode, 5 is an auxiliary electrode, 6 is a regulated power supply, and 7 is a rheostat. The device of the invention has a one-cavity two-chamber structure, and an electroactive permeable membrane with lithium ion selectivity is used in the middle to divide the whole device into a cathode area and an anode area. Filling waste lithium battery anode material into an anode electrode groove to serve as a consumption electrode, communicating an electroactive permeable membrane electrode with a cathode through a rheostat (left diagram in figure 1), and under the driving of electrolyte solution and oxidation potential, generating electrolysis water oxygen evolution reaction to accumulate H on the surface and the potential rejection effect of the consumption electrode + Under the action of the formed local acidic microenvironment, lithium ions are released into the electrolyte in the anode region. At the same time, lithium ions migrate under the drive of electric field force to the electroactive permeable membrane electrode to which a reduction potential is applied and become incorporated into the membrane. Then, the electrode of the switched electroactive permeable membrane is communicated with the anode through a rheostat (right diagram in fig. 1), and lithium ions which are previously put into the electroactive permeable membrane are released to the cathode area under the drive of the repulsive potential and the external electric field, so that the purpose of selectively enriching and recycling the lithium ions is realized.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
And placing the waste lithium cobaltate battery in a sodium chloride solution (the concentration is 0.2 mol/L), discharging for 48 hours, and then disassembling and separating the positive plate. Cutting the disassembled waste lithium cobaltate positive plate into a size of 5cm multiplied by 5cm, soaking the waste lithium cobaltate positive plate in absolute ethyl alcohol for 24 hours, and then soaking the waste lithium cobaltate positive plate in deionized water for 24 hours to remove organic electrolyte impurities in the waste lithium cobaltate positive plate. The treated positive plate is washed by deionized water and then is filled into a porous anode electrode groove (the thickness of the porous anode electrode groove is adjustable, the thickness is 0.1-5 mm, the mesh number is 100 mesh) and is clamped as a consumption electrode (anode), so that the effect of in-situ leaching is achieved.
lambda-MnO 2 lambda-MnO as electroactive component of permeable membranes 2 The conductive carbon and the organic polymer binder PVDF are mixed according to the mass ratio of 8:1:1, after uniformly mixing, adopting a vacuum filter pressing technology (the concentration of solid particles of suspension is 9%, the maximum relative vacuum degree of a vacuum pump is-88 kPa, and the operating pressure is 0.5 MPa) to press the suspension on a 400-mesh stainless steel wire net in situ, and then further stabilizing the structure by a hot pressing method, wherein the hot pressing method comprises the following specific processes: heating two smooth stainless steel plates to 120 ℃, applying pressure of 8.6MPa on the stainless steel plates, keeping the temperature and the pressure for 5min at constant temperature and constant pressure, and obtaining the electroactive permeable membrane electrode with high-efficiency selective permeability to lithium ions, wherein the thickness of the electroactive component is 200 mu m after hot pressing.
The graphite plate is used as an auxiliary electrode (cathode), and the electroactive permeable membrane electrode is used as a central membrane electrode to separate the anode region from the cathode region. Na of electrolyte solution of anode region of 0.1mol/L 2 SO 4 Solution, electrolyte solution in the cathode region was 0.1mol/L Li 2 SO 4 A solution. A voltage of 6V was applied between the cathode and the anode.
The electroactive permeable membrane electrode is communicated with the cathode, and the slide rheostat is adjusted to control the fixed resistance of the electroactive permeable membrane electrode from the generation of bubbles to the fact that no hydrogen evolution and oxygen evolution side reaction happens. Under the driving of electrolyte solution and oxidation potential, the consumption electrode accumulates H + Lithium ions are released into the electrolyte of the anode region under the action of the acidic microenvironment, migrate to the electroactive permeable membrane electrode to which the reduction potential is applied under the drive of the electric field force, and are placed in the membrane. And after the electroactive permeable membrane electrode is communicated with the cathode for 15min, the electroactive permeable membrane electrode is switched to be communicated with the anode, and lithium ions in the electroactive permeable membrane electrode are released and migrate to the cathode area under the drive of the oxidation potential and the external electric field. The electroactive permeable membrane electrode is communicated with the cathode or the anode every 15min. Finishing the wholeThe device is carried out at normal temperature and normal pressure, the total time for communicating the electroactive permeable membrane electrode with the cathode and the anode is 9 hours, and the enrichment and recovery of lithium ions are realized.
The concentration of lithium ions in the cathode region and anode region of this example was analyzed, and Li was calculated + The recovery rate of (2) was 80%.
Example 2
Changing the waste lithium cobalt oxide battery into a waste lithium iron phosphate battery, changing the mesh number of the porous anode electrode groove from 100 meshes into 200 meshes, and changing the electroactive component of the permeable membrane from lambda-MnO 2 Changing the stainless steel wire mesh of 400 meshes into a titanium mesh of 200 meshes; na (Na) 2 SO 4 Solution and Li 2 SO 4 The concentration of the solution is changed from 0.1mol/L to 0.08mol/L, and the voltage applied between the cathode and the anode is changed from 6V to 5V. The total time for the electroactive permeable membrane electrode to communicate with the cathode and anode was changed from 9h to 8h, otherwise the same conditions as in example 1.
The concentration of lithium ions in the cathode region and anode region of this example was analyzed, and Li was calculated + The recovery rate of (2) was 78%.
Example 3
Changing the waste lithium cobalt oxide battery into a waste lithium manganate battery, changing the mesh number of the porous anode electrode groove from 100 meshes into 400 meshes, and changing the electroactive component of the permeable membrane from lambda-MnO 2 The stainless steel wire mesh with 400 meshes is changed into a nickel mesh with 100 meshes; na (Na) 2 SO 4 Solution and Li 2 SO 4 The concentration of the solution is changed from 0.1mol/L to 0.12mol/L, and the voltage applied between the cathode and the anode is changed from 6V to 7V. The total time for the electroactive permeable membrane electrode to communicate with the cathode and anode was changed from 9h to 10h, otherwise the same conditions were as in example 1.
The concentration of lithium ions in the cathode region and anode region of this example was analyzed, and Li was calculated + The recovery rate of (2) was 82%.
The invention fills the anode electrode material of the waste lithium battery into the anode electrode groove as the consumption electrode, and under the driving of electrolyte solution and oxidation potential, the consumption electrode accumulates H under the potential repulsive effect and the electrolytic water oxygen evolution reaction of the surface + Formed local acidic microenvironmentUnder the condition of using the lithium ion electrolyte, lithium ions are released to enter the electrolyte of the anode region, so that the purpose of electric leaching is achieved. At the same time, lithium ions migrate under the drive of electric field force to the electroactive permeable membrane electrode to which a reduction potential is applied and become incorporated into the membrane. Then, the electroactive permeable membrane electrode is switched to be communicated with the anode, at the moment, lithium ions which are previously put into the membrane are released to the cathode area under the drive of the repulsive potential and the externally applied electric field, so that the purpose of selectively enriching and recycling the lithium ions is realized. When the device is operated, the external constant electric field promotes the electric leaching on one hand, and on the other hand, the electric field with the direction from left to right is provided for the two sides of the electrolytic cell, and the directional electric field can drive lithium ions in the anode region to directionally migrate to the cathode region.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (9)
1. The device for recovering lithium ions in the waste lithium battery through in-situ electroleaching coupling electric control membrane separation is characterized by comprising a consumption electrode, an electroactive permeable membrane electrode, an auxiliary electrode, an anode region, a cathode region and a rheostat;
the consumption electrode is obtained by filling waste lithium battery anode materials into an anode electrode groove;
the electroactive permeable membrane electrode has lithium ion selectivity, the auxiliary electrode is a cathode, and the consumable electrode is an anode.
2. The device of claim 1, wherein the electroactive permeable membrane electrode is positioned intermediate the device separating the anode and cathode regions.
3. The device of claim 1 or 2, wherein the electroactive permeable membrane electrode is in repeated alternating communication with the anode or the cathode, and the electroactive permeable membrane electrode is in communication with the anode or the cathode through a varistor.
4. The device according to claim 3, wherein the electroactive permeable membrane electrode is prepared by constructing an electroactive layer on the surface of the conductive porous substrate; the electroactive layer is made of manganese dioxide, lithium manganate, lithium cobaltate or lithium iron phosphate; the conductive porous matrix is titanium mesh, nickel mesh or stainless steel mesh, and the mesh number of the conductive porous matrix is 2-500 mesh.
5. The method for separating and recovering lithium ions by using the device according to any one of claims 1 to 4, comprising the steps of:
1) Connecting the electroactive permeable membrane electrode with the cathode, and accumulating H at the consuming electrode + Lithium ions are released into the electrolyte of the anode region under the action of the acidic microenvironment, and the released lithium ions migrate to the electroactive permeable membrane electrode and are put into the membrane;
2) The electroactive permeable membrane electrode is communicated with the anode, and lithium ions in the electroactive permeable membrane electrode migrate to the cathode region, so that enrichment and recovery of the lithium ions are realized;
repeating the steps 1) and 2) alternately, wherein the total time for communicating the electroactive permeable membrane electrode with the cathode and the anode is 8-10 h.
6. The method of claim 5, wherein the voltage between the cathode and the anode is between 5 and 7V.
7. The method according to claim 5 or 6, wherein in step 1) and step 2), the time of each communication with the cathode and the time of each communication with the anode are independently 12 to 18 minutes.
8. The method according to claim 7, wherein in step 1), the consumable electrode accumulates H by the potential rejection effect and the electrolyzed water oxygen evolution reaction + The method comprises the steps of carrying out a first treatment on the surface of the The electrolyte in the anode region is sodium sulfate solution, and the concentration of the sodium sulfate solution is 0.05-0.15 mol/L.
9. The method of claim 8, wherein the electrolyte in the cathode region is a lithium sulfate solution having a concentration of 0.05 to 0.15mol/L.
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