CN114517302B - Device and method for coupling lithium extraction and hydrogen production of electrically-assisted photocatalytic lithium iron phosphate waste - Google Patents
Device and method for coupling lithium extraction and hydrogen production of electrically-assisted photocatalytic lithium iron phosphate waste Download PDFInfo
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- CN114517302B CN114517302B CN202210198782.9A CN202210198782A CN114517302B CN 114517302 B CN114517302 B CN 114517302B CN 202210198782 A CN202210198782 A CN 202210198782A CN 114517302 B CN114517302 B CN 114517302B
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- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 54
- 239000002699 waste material Substances 0.000 title claims abstract description 54
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 40
- 239000001257 hydrogen Substances 0.000 title claims abstract description 37
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 37
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 31
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000000605 extraction Methods 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- 230000008878 coupling Effects 0.000 title claims abstract description 19
- 238000010168 coupling process Methods 0.000 title claims abstract description 19
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 19
- 239000011941 photocatalyst Substances 0.000 claims abstract description 20
- -1 hydrogen ions Chemical class 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 13
- 239000012528 membrane Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 9
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 30
- 239000000843 powder Substances 0.000 claims description 27
- 239000005955 Ferric phosphate Substances 0.000 claims description 26
- 229940032958 ferric phosphate Drugs 0.000 claims description 26
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 24
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 22
- 229910001416 lithium ion Inorganic materials 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 19
- 239000010802 sludge Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000002071 nanotube Substances 0.000 claims description 6
- 229910052724 xenon Inorganic materials 0.000 claims description 6
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 238000000975 co-precipitation Methods 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 238000007606 doctor blade method Methods 0.000 claims description 3
- 238000004070 electrodeposition Methods 0.000 claims description 3
- 230000001678 irradiating effect Effects 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 238000004528 spin coating Methods 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims 2
- 238000011084 recovery Methods 0.000 abstract description 9
- 239000003513 alkali Substances 0.000 abstract description 2
- 230000007797 corrosion Effects 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000007146 photocatalysis Methods 0.000 description 9
- 230000009471 action Effects 0.000 description 7
- 230000005484 gravity Effects 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 239000011888 foil Substances 0.000 description 5
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000005684 electric field Effects 0.000 description 4
- 229910000398 iron phosphate Inorganic materials 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 3
- 229910017771 LaFeO Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/14—Alkali metal compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/50—Processes
- C25B1/55—Photoelectrolysis
-
- 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 discloses an electrically assisted photocatalytic lithium iron phosphate waste lithium extraction and hydrogen production coupling device, which comprises an H-shaped reaction tank, wherein the H-shaped reaction tank comprises an anode tank and a cathode tank which are oppositely arranged, a transverse through pipe is arranged between the anode tank and the cathode tank, and a proton membrane which separates the anode tank from the cathode tank and only allows hydrogen ions to pass through is vertically arranged in the through pipe; the anode pool and the cathode pool are respectively provided with an electrode, and the surface of the electrode of the anode pool is loaded with a photocatalyst; the anode pool is made of light-transmitting materials, and a light source is arranged on the outer side of the anode pool; a direct current power supply is connected between the anode electrode and the cathode electrode through a lead; the invention also discloses a method for coupling the lithium extraction and the hydrogen production of the electrically assisted photocatalytic lithium iron phosphate waste, which is formed by combining a photocatalytic system and an electrocatalytic system, reduces the use of acid and alkali liquor in the recovery process of the lithium iron phosphate waste, saves the cost of raw materials, avoids equipment corrosion, has simple steps, high lithium extraction efficiency and is environment-friendly.
Description
Technical Field
The invention belongs to the technical field of waste recycling, relates to a device and a method for extracting lithium from lithium iron phosphate waste, and in particular relates to a device and a method for coupling lithium extraction and hydrogen production from lithium iron phosphate waste by electrically assisted photocatalysis.
Background
Because of various advantages, the lithium ion battery gradually replaces the traditional secondary power supply, is widely applied to portable electronic equipment, electric automobiles and the like since commercialization is realized, and the application of new energy automobiles in recent years shows good development prospect and value, so that a large amount of waste lithium iron phosphate batteries can be used, the retired batteries occupy a large amount of land space in the storage process, have certain pollution to the environment, and have potential safety hazards of electrolyte leakage and fire explosion. Therefore, how to effectively and reasonably treat the waste lithium iron phosphate batteries becomes a key.
At present, most of recovery researches of waste lithium iron phosphate batteries are carried out on positive electrode black powder, the main methods include gradient utilization, pyrogenic recovery, wet recovery, high-temperature solid phase repair and the like, and the wet recovery with various advantages is a technology mainly adopted by domestic lithium battery recovery enterprises, however, the wet recovery has poor economy, and acid wastewater and waste residues can be generated.
When the photon energy is higher than the absorption threshold of the photocatalyst, the valence band electrons of the photocatalyst generate interband transition from the valence band to the conduction band, so that photo-generated electrons (e-) and holes (h+), wherein the photo-generated electrons have strong reducing capability, and the photo-generated holes have strong oxidizing capability. Oxygen (O) dissolved in water adsorbed on the catalyst surface at this time 2 ) Trapping electrons (e-) to form superoxide anion (O) 2- ) While the holes (h+) adsorb hydroxide ions (OH-) and water (H) on the surface of the catalyst 2 O) is oxidized into hydroxyl radical (OH. Cndot.), superoxide anion (O) 2 (-) and hydroxyl radicals (OH.) have a very strong oxidizing property. Can degrade organic matters or metal oxide ions in a non-selective way.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the device and the method for coupling the lithium extraction and the hydrogen production of the electrically-assisted photocatalytic lithium iron phosphate waste, which reduce the use of acid liquor and alkali liquor in the recycling process of the lithium iron phosphate waste, save the cost of raw materials, avoid equipment corrosion, have simple steps, high lithium extraction efficiency and are environment-friendly.
In order to achieve the above purpose, the invention is realized by adopting the following technical scheme:
the device comprises an H-shaped reaction tank, wherein the H-shaped reaction tank comprises an anode tank and a cathode tank which are oppositely arranged, a transverse through pipe is arranged between the anode tank and the cathode tank, a proton membrane which separates the anode tank from the cathode tank is vertically arranged in the through pipe, and only hydrogen ions are allowed to pass through by the proton membrane;
an anode electrode is arranged in the anode pool, and the surface of the anode electrode is loaded with a photocatalyst;
the anode pool is made of light-transmitting materials, and a light source for irradiating the photocatalyst loaded on the anode electrode is arranged on the outer side of the anode pool;
a cathode electrode is arranged in the cathode pool;
and a direct current power supply is connected between the anode electrode and the cathode electrode through a lead.
The invention also has the following technical characteristics:
preferably, the upper part of the anode tank is provided with a liquid outlet, the lower part of the anode tank is provided with a feed inlet, the bottom of the anode tank is provided with a sludge outlet, and the sludge outlet is provided with a pump.
Preferably, the anode electrode is TiO 2 A nanotube sheet, FTO sheet or ITO sheet;
the cathode electrode is Pt, au, pb, ag or Ti.
Preferably, the photocatalyst comprises MOF-based catalyst, tiO 2 、Fe 2 O 3 、WO 3 、Cd x Zn 1-x S、LaFeO 3 Or BiVO 4 One or more materials of the following materials.
Preferably, the photocatalyst is supported on the surface of the anode electrode by means of electrodeposition, spin coating, doctor blade coating, hydrothermal or coprecipitation.
Preferably, the light source comprises sunlight, an ultraviolet lamp and a xenon lamp light source.
Preferably, the voltage of the direct current power supply is between 0.01 and 2.5 v.
The invention also protects a method for realizing coupling of lithium extraction and hydrogen production of the electrically assisted photocatalytic lithium iron phosphate waste by adopting the device, which comprises the following steps:
step one: introducing the water mixed solution of the positive black powder of the crushed waste lithium iron phosphate battery into an anode pool through a feed inlet, wherein the solid-liquid ratio of the water mixed solution of the positive black powder is 0.1-10 g/ml;
step two: injecting dilute acid solution with the hydrogen ion concentration of 0.1-1 mol/L into the cathode pool;
step three: turning on a direct current power supply, turning on a light source to irradiate the photocatalyst loaded on the anode electrode, and generating hydrogen on the cathode electrode of the cathode pool;
step four: lithium ions can automatically overflow along with the solution from a liquid outlet at the upper part of the anode pool, and the residual substances in the anode black powder are extracted and recovered from a sludge outlet at the bottom of the anode pool in the form of ferric phosphate precipitation.
Preferably, the granularity of the positive black powder of the waste lithium iron phosphate battery is less than or equal to 1.0mm.
Preferably, the dilute acid in the cathode pool is one or a mixed solution of a plurality of dilute sulfuric acid, dilute hydrochloric acid or dilute nitric acid.
Compared with the prior art, the invention has the following technical effects:
the invention is formed by combining a photocatalysis system and an electrocatalytic system, and based on that the photocatalyst can generate hydroxyl free radical (OH) with oxidizing capability under the condition of illumination, the hydroxyl free radical (OH) can replace oxidant (H) in the traditional wet method recovery 2 O 2 ) The ferrous iron in the positive lithium iron phosphate in the waste lithium ion battery is oxidized into ferric iron, so that lithium ions are released, and the purpose of recovering lithium is achieved; meanwhile, an external electric field environment is formed by providing an external bias voltage for the photocatalysis system, and the simple recombination of photo-generated electrons and photo-generated holes can be prevented by forming the external electric field environment so as to improve the photon efficiency, thereby improving the oxidation effect on lithium iron phosphate;
according to the method for recycling the waste lithium iron phosphate battery by utilizing the electro-assisted photocatalysis, the lithium element in the positive electrode of the waste lithium iron phosphate battery is extracted in the form of lithium ion solution, and the lithium iron phosphate is converted into the form of ferric phosphate precipitation to be recycled, so that the recycling of the lithium element in the waste lithium iron phosphate battery is realized, the treatment efficiency of the method is high, the effect is obvious compared with that of the traditional method, and the steps are simple;
the invention adopts an electric auxiliary photocatalysis mode to replace the traditional combination of inorganic acid/organic acid and hydrogen peroxide recovered by a wet method, thereby avoiding the use of chemical reagents with higher cost such as inorganic acid/organic acid and the like;
the invention avoids the problem of large amount of waste liquid generated by traditional wet recovery, and does not need to spend extra cost for treating the subsequent waste liquid;
according to the invention, the co-production hydrogen production is realized while the lithium in the waste lithium iron phosphate battery is recovered, so that the economic benefit is improved;
the photocatalyst can be reused, so that the cost is greatly saved, the step of frequently replacing acid liquor is omitted, the steps are simplified, and the industrial application is easier;
the electro-assisted photocatalysis lithium extraction process has mild reaction conditions, inhibits the dissolution and release of impurity ions, improves the quality of lithium products, and has the advantages of environmental protection, high lithium extraction efficiency and the like compared with the traditional acid leaching process.
Drawings
FIG. 1 is a schematic diagram of an electrically assisted photocatalytic lithium iron phosphate waste lithium extraction and hydrogen production coupling device according to the present invention;
FIG. 2 is an X-ray diffraction pattern (XRD) of the iron phosphate of example 1;
the meaning of the numbers in the figures is: the device comprises a 1-anode tank, a 2-cathode tank, a 3-through pipe, a 4-proton membrane, a 5-anode electrode, a 6-cathode electrode, a 7-lead, an 8-direct current power supply, a 9-liquid outlet, a 10-feed inlet and a 11-sludge inlet.
Detailed Description
The following examples illustrate the invention in further detail.
As shown in fig. 1, this embodiment provides a device for coupling lithium extraction and hydrogen production by electrically assisting photocatalytic lithium iron phosphate waste, which comprises an H-shaped reaction tank, wherein the H-shaped reaction tank comprises an anode tank 1 and a cathode tank 2 which are oppositely arranged, a transverse through pipe 3 is arranged between the anode tank 1 and the cathode tank 2, a proton membrane 4 for separating the anode tank 1 and the cathode tank 2 is vertically arranged in the through pipe 3, and the proton membrane 4 only allows hydrogen ions to pass through;
an anode electrode 5 is arranged in the anode pool 1, and a photocatalyst is loaded on the surface of the anode electrode 5;
the anode pool 1 is made of light-transmitting materials, and a light source for irradiating a photocatalyst loaded on the anode electrode 5 is arranged on the outer side of the anode pool 1;
a cathode electrode 6 is arranged in the cathode pool 2;
a direct current power supply 8 is connected between the anode electrode 5 and the cathode electrode 6 through a lead 7. The anode electrode 5 is connected with the positive end of the direct current power supply 8 through a wire, and the cathode electrode 6 is connected with the negative end of the direct current power supply 8 through a wire.
The photocatalyst carried on the anode electrode 5 of the anode cell 1 generates electrons and holes under the irradiation of a suitable light source, and the electrons are transmitted to the cathode electrode 6 of the other cathode cell 2 through the anode electrode 5 and the lead 7 under the action of an external direct current power supply 8.
The upper part of the anode tank 1 is provided with a liquid outlet 9, the lower part is provided with a feed inlet 10, the bottom is provided with a sludge inlet 11, and the sludge inlet 11 is provided with a pump. The liquid outlet 9 is used for discharging a solution containing lithium ions, and the feed inlet 10 is used for circularly feeding; the pump of the sludge port 11 is used for pumping out and recovering the residual substances in the positive black powder from the bottom of the anode pool 1 in the form of ferric phosphate precipitation.
The anode electrode 5 is TiO 2 A nanotube sheet, FTO sheet or ITO sheet;
the cathode electrode 6 is Pt, au, pb, ag or Ti.
The photocatalyst comprises MOF-based catalyst and TiO 2 、Fe 2 O 3 、WO 3 、Cd x Zn 1-x S、LaFeO 3 Or BiVO 4 One or more materials of the following materials.
The photocatalyst is supported on the surface of the anode electrode 5 by electrodeposition, spin coating, doctor blade coating, hydrothermal or coprecipitation.
The light source comprises sunlight, an ultraviolet lamp and a xenon lamp light source. Wherein, the sunlight is convenient to obtain, clean and safe; the ultraviolet lamp is mainly used for exciting a catalyst with wider band gap; xenon lamps can simulate sunlight to provide uninterrupted light source supply.
The voltage of the DC power supply 8 is between 0.01 and 2.5 v.
When the device of the invention works, the principle is as follows:
the holes generated by the catalyst loaded on the anode electrode 5 of the anode pool 1 under the irradiation of the light source can lead hydroxyl ions (OH-) and water (H) in the solid-liquid mixture system of the anode pool 1 2 O) oxidizing into an oxidation intermediate state such as hydroxyl free radical (OH), superoxide free radical, singlet oxygen and the like with strong oxidizing property;
photo-generated holes, hydroxyl radicals (OH), superoxide radicals and singlet oxygen oxidize ferrous iron in lithium iron phosphate in a solid-liquid mixture system into ferric iron to generate ferric iron phosphate solid and lithium ions;
the ferric phosphate can sink to the bottom of the anode pool 1 under the action of gravity, lithium ions can automatically overflow along with the solution from a liquid outlet 9 at the upper part of the anode pool 1, after the ferric phosphate is deposited at the bottom of the anode pool 1 to a certain thickness, a pump at a sludge port 11 is turned on, a part of ferric phosphate sludge is pumped away, the purpose of separating lithium is achieved, finally lithium elements in the product are recovered in the form of lithium ion solution, and the remaining substances in the positive black powder are recovered in the form of ferric phosphate deposition;
the reaction occurring on the cathode electrode 6 of the cathode cell 2 without illumination is 2H++2e- →H 2 ↑；
The flow direction of electrons in the whole system is as follows: the catalyst generates electrons, the electrons flow to a direct current power supply 8 along the electrode of the anode pool 1 and a lead 7, the electrons of the direct current power supply 8 flow to a cathode electrode 6 of the cathode pool 2 through the lead 7, and hydrogen ions in the cathode pool 2 are reduced on the surface of the cathode electrode 6 to generate hydrogen gas to be separated out;
meanwhile, the direct current power supply 8 provides an external bias voltage for the photocatalytic system to form an external electric field environment, and the external electric field environment can prevent the photo-generated electrons and the photo-generated holes from being simply compounded to improve the photon efficiency, so that the oxidation effect on the lithium iron phosphate is improved.
Examples of the method of the invention for coupling lithium extraction and hydrogen production from electrically assisted photocatalytic lithium iron phosphate waste are given below:
example 1:
the electro-assisted photo-catalytic system of the embodiment comprises an H-shaped electro-catalytic cell with a proton membrane and a photo-catalytic system, and TiO is prepared by 2 Nano-material as photocatalytic material is electrodeposited onto the TiO of the anode electrode 5 2 On the nanotube sheet; introducing water mixed solution of the positive black powder of the crushed waste lithium iron phosphate battery with the solid-to-liquid ratio of 10g/ml into the anode tank 1 through a feed inlet 10 of the anode tank, wherein the granularity of the positive black powder of the waste lithium iron phosphate battery is 0.3mm; the cathode pool 2 is filled with dilute sulfuric acid with the hydrogen ion concentration of 0.1 mol/L;
turning on an ultraviolet lamp with the power of 40w, and turning on a direct-current voltage of 1.5v of an externally-applied direct-current power supply 8; under the irradiation of ultraviolet light, waste lithium iron phosphate battery black powder in the anode tank 1 reacts to obtain ferric phosphate precipitate and lithium ions are released in the solution, the ferric phosphate slowly deposits at the bottom of the anode tank 1 under the action of gravity, and the solution containing the lithium ions is discharged from a liquid outlet 9 at the upper end of the anode tank 1; after the iron phosphate at the bottom of the anode tank 1 was deposited to a thickness of 10cm, the pump of the bottom sludge port 11 was turned on, and after the iron phosphate deposited at the bottom of the anode tank 1 was pumped away by about 6cm, the pump was turned off. The Pt foil of the cathode electrode 6 of the cathode pool 1 is provided with continuous hydrogen generation, and the hydrogen generation rate is 99.1%;
the separated precipitate was washed 3 times with deionized water and then dried at 60 ℃ for 12 hours, and the dried product was confirmed to be iron phosphate by XRD pattern as shown in fig. 2.
Example 2:
the electro-assisted photocatalytic system of the embodiment comprises an H-shaped electro-catalytic cell with a proton membrane and a photocatalytic system, and LaFeO is adopted 3 The nano material is used as a photocatalysis material and is coated on the FTO sheet of the anode electrode 5 in a rotary coating mode; introducing water mixed solution of the positive black powder of the crushed waste lithium iron phosphate battery with the solid-to-liquid ratio of 8g/ml into the anode tank 1 through a feed inlet 10 of the anode tank 1, wherein the granularity of the positive black powder of the waste lithium iron phosphate battery is 1.0mm; the cathode pool 2 is filled with dilute hydrochloric acid with the hydrogen ion concentration of 0.2 mol/L;
turning on a xenon lamp with the power of 150w, and turning on an external direct current power supply 8 to be a direct current voltage of 0.5 v; under the irradiation of a light source, waste lithium iron phosphate battery black powder in the anode tank 1 reacts to obtain ferric phosphate precipitate and lithium ions are released in solution, ferric phosphate slowly deposits at the bottom of the anode tank under the action of gravity, and the solution containing lithium ions is discharged from a liquid outlet 9 at the upper end of the anode tank 1; after the ferric phosphate at the bottom of the anode pool 1 is deposited to the thickness of 10cm, a pump of a sludge port 11 at the bottom is started, and after the ferric phosphate deposited at the bottom of the anode pool 1 is pumped away by about 6cm, the pump is closed; the Au foil of the cathode electrode 6 of the cathode pool 2 is continuously provided with hydrogen, and the hydrogen production rate is 99.3 percent.
Example 3:
the electro-assisted photocatalytic system of the embodiment comprises an H-shaped electro-catalytic cell with a proton membrane and a photocatalytic system, and the MOF-based catalyst UIO-66-NH 2 The material is coated on the ITO sheet of the anode electrode 5 in a scraper coating mode; introducing water mixed solution of the positive black powder of the crushed waste lithium iron phosphate battery with the solid-to-liquid ratio of 1g/ml into the anode tank 1 through a feed inlet 10 of the anode tank 1, wherein the granularity of the positive black powder of the waste lithium iron phosphate battery is 0.8mm; the cathode pool 2 is filled with dilute hydrochloric acid with the hydrogen ion concentration of 0.5 mol/L;
using sunlight as a light source, and turning on an external direct current power supply 8 to obtain a direct current voltage of 0.01 v; under the irradiation of a light source, waste lithium iron phosphate battery black powder in the anode tank 1 reacts to obtain ferric phosphate precipitate and lithium ions are released in solution, the ferric phosphate slowly deposits at the bottom of the anode tank 1 under the action of gravity, and the solution containing the lithium ions is discharged from a liquid outlet 9 at the upper end of the anode tank 1; after the ferric phosphate at the bottom of the anode pool 1 is deposited to the thickness of 10cm, a pump of a sludge port 11 at the bottom is started, and after the ferric phosphate deposited at the bottom of the anode pool 1 is pumped away by about 6cm, the pump is closed; the Pb foil of the cathode electrode 6 of the cathode pool 2 is continuously provided with hydrogen, and the hydrogen production rate is 99.3 percent.
Example 4:
the electro-assisted photocatalytic system of the embodiment comprises an H-shaped electro-catalytic cell with a proton membrane and a photocatalytic system, and is disclosed in WO 3 TiO coated on anode electrode 5 by hydrothermal method with nano material as photocatalysis material 2 On the nanotube sheet; introducing water mixed solution of the positive black powder of the crushed waste lithium iron phosphate battery with the solid-to-liquid ratio of 0.1g/ml into the anode tank 1 through a feed inlet 10 of the anode tank 1, wherein the granularity of the positive black powder of the waste lithium iron phosphate battery is 0.2mm; the cathode pool 2 is filled with dilute hydrochloric acid with the hydrogen ion concentration of 0.8 mol/L;
turning on a xenon lamp with the power of 100w, and turning on an externally applied direct current power supply 8 to be a direct current voltage of 1.0 v; under the irradiation of a light source, waste lithium iron phosphate battery black powder in the anode tank 1 reacts to obtain ferric phosphate precipitate and lithium ions are released in solution, the ferric phosphate slowly deposits at the bottom of the anode tank 1 under the action of gravity, and the solution containing the lithium ions is discharged from a liquid outlet 9 at the upper end of the anode tank 1; after the ferric phosphate at the bottom of the anode pool 1 is deposited to the thickness of 10cm, a pump of a sludge port 11 at the bottom is started, and after the ferric phosphate deposited at the bottom of the anode pool 1 is pumped away by about 6cm, the pump is closed; the water mixed solution of the positive black powder of the waste lithium iron phosphate battery is continuously or intermittently introduced into the anode tank 1 through the feed inlet 10 of the anode tank 1 to form a circulating system, and the Ag foil of the cathode electrode 6 of the cathode tank 2 is continuously and continuously subjected to hydrogen generation, so that the hydrogen generation rate is 99.5%.
Example 5:
the electro-assisted photocatalytic system of the embodiment comprises an H-shaped electro-catalytic cell with a proton membrane and a photocatalytic system, and BiVO is carried out 4 /TiO 2 TiO coated on anode electrode 5 by coprecipitation method by using composite material as photocatalysis material 2 On the nanotube sheet; introducing water mixed solution of the positive black powder of the crushed waste lithium iron phosphate battery with the solid-to-liquid ratio of 5g/ml into the anode tank 1 through a feed inlet 10 of the anode tank 1, wherein the granularity of the positive black powder of the waste lithium iron phosphate battery is 0.4mm; the cathode pool 2 is filled with dilute nitric acid with the hydrogen ion concentration of 1 mol/L;
turning on an ultraviolet lamp with the power of 100w, and turning on a direct-current voltage of 2.5v of an externally-applied direct-current power supply 8; under the irradiation of a light source, waste lithium iron phosphate battery black powder in the anode tank 1 reacts to obtain ferric phosphate precipitate and lithium ions are released in solution, the ferric phosphate slowly deposits at the bottom of the anode tank 1 under the action of gravity, and the solution containing the lithium ions is discharged from a liquid outlet 9 at the upper end of the anode tank 1; after the ferric phosphate at the bottom of the anode pool 1 is deposited to the thickness of 10cm, a pump of a sludge port 11 at the bottom is started, and after the ferric phosphate deposited at the bottom of the anode pool 1 is pumped away by about 6cm, the pump is closed; the Ti foil of the cathode electrode 6 of the cathode cell 2 is provided with continuous hydrogen generation, and the hydrogen generation rate is 99.3 percent.
It should be noted that the foregoing is merely a further detailed description of the present invention, and it should not be construed that the specific embodiments of the present invention are limited thereto, and the catalyst may be any one or a combination of several other catalysts given in the technical solution of the present invention, and in addition, it should be understood that, to those skilled in the art to which the present invention pertains, several simple deductions or substitutions may be made without departing from the spirit of the present invention, which is defined by the appended claims.
Claims (8)
1. The method for coupling the lithium extraction and the hydrogen production of the electric-assisted photocatalytic lithium iron phosphate waste is characterized by adopting a device for coupling the lithium extraction and the hydrogen production of the electric-assisted photocatalytic lithium iron phosphate waste, wherein the device comprises an H-shaped reaction tank, the H-shaped reaction tank comprises an anode tank (1) and a cathode tank (2) which are oppositely arranged, a transverse through pipe (3) is arranged between the anode tank (1) and the cathode tank (2), a proton membrane (4) for separating the anode tank (1) and the cathode tank (2) is vertically arranged in the through pipe (3), and the proton membrane (4) only allows hydrogen ions to pass through;
an anode electrode (5) is arranged in the anode pool (1), and a photocatalyst is loaded on the surface of the anode electrode (5);
the anode pool (1) is made of light-transmitting materials, and a light source for irradiating the photocatalyst loaded on the anode electrode (5) is arranged on the outer side of the anode pool (1);
a cathode electrode (6) is arranged in the cathode pool (2);
a direct current power supply (8) is connected between the anode electrode (5) and the cathode electrode (6) through a lead (7);
the upper part of the anode pool (1) is provided with a liquid outlet (9), the lower part is provided with a feed inlet (10), the bottom is provided with a sludge port (11), and the sludge port (11) is provided with a pump;
the method comprises the following steps:
step one: injecting water mixed solution of the positive black powder of the crushed waste lithium iron phosphate battery into an anode tank (1) through a feed inlet (10), wherein the solid-to-liquid ratio of the water mixed solution of the positive black powder is 0.1-10 g/ml;
step two: injecting dilute acid solution with the hydrogen ion concentration of 0.1-1 mol/L into the cathode pool (2);
step three: turning on a direct current power supply (8), turning on a light source to irradiate a photocatalyst loaded on an anode electrode (5), and generating hydrogen on a cathode electrode (6) of a cathode pool (1);
step four: lithium ions can automatically overflow along with the solution from a liquid outlet (9) at the upper part of the anode tank (1), and the residual substances in the anode black powder are extracted and recovered from a sludge outlet (11) at the bottom of the anode tank (1) in the form of ferric phosphate precipitation.
2. The method for coupling lithium extraction and hydrogen production by using the electrically assisted photocatalytic lithium iron phosphate waste material as claimed in claim 1, wherein the granularity of positive black powder of the waste lithium iron phosphate battery is less than or equal to 1.0mm.
3. The method for coupling lithium extraction and hydrogen production by using the electrically assisted photocatalytic lithium iron phosphate waste material as claimed in claim 1, wherein the dilute acid in the cathode pool (2) is one or a mixed solution of a plurality of dilute sulfuric acid, dilute hydrochloric acid or dilute nitric acid.
4. The method for coupling lithium extraction and hydrogen production of the electrically assisted photocatalytic lithium iron phosphate waste according to claim 1, wherein the anode electrode (5) is a TiO2 nanotube sheet, an FTO sheet or an ITO sheet;
the cathode electrode (6) is Pt, au, pb, ag or Ti.
5. The method for coupling lithium extraction and hydrogen production from electrically assisted photocatalytic lithium iron phosphate waste according to claim 1, wherein the photocatalyst comprises one or more of a MOF-based catalyst, tiO2, fe2O3, WO3, cdxZn1-xS, laFeO3, or BiVO 4.
6. The method for coupling lithium extraction and hydrogen production of the electrically assisted photocatalytic lithium iron phosphate waste according to claim 1, wherein the photocatalyst is supported on the surface of the anode electrode (5) in a manner of electrodeposition, spin coating, doctor blade coating, hydrothermal or coprecipitation.
7. The method for coupling lithium extraction and hydrogen production from electrically assisted photocatalytic lithium iron phosphate waste according to claim 1, wherein the light source comprises a solar light source, an ultraviolet lamp and a xenon lamp light source.
8. The method for coupling lithium extraction and hydrogen production by using the electrically assisted photocatalytic lithium iron phosphate waste material as claimed in claim 1, wherein the voltage of the direct current power supply (8) is 0.01-2.5 v.
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| CN112981433A (en) * | 2021-02-04 | 2021-06-18 | 中南大学 | Method for recycling waste lithium iron phosphate anode material by electrolyzing cation membrane pulp and recycled lithium hydroxide |
| CN113430571A (en) * | 2021-06-16 | 2021-09-24 | 华中师范大学 | Method for recovering metal lithium in photo-assisted waste lithium iron phosphate battery |
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| CN106910959A (en) * | 2017-05-04 | 2017-06-30 | 北京科技大学 | A kind of method of selective recovery lithium in waste material from LiFePO4 |
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| CN112981433A (en) * | 2021-02-04 | 2021-06-18 | 中南大学 | Method for recycling waste lithium iron phosphate anode material by electrolyzing cation membrane pulp and recycled lithium hydroxide |
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