CN113293292B - Seawater lithium extraction system based on solar drive and preparation method thereof - Google Patents
Seawater lithium extraction system based on solar drive and preparation method thereof Download PDFInfo
- Publication number
- CN113293292B CN113293292B CN202110576559.9A CN202110576559A CN113293292B CN 113293292 B CN113293292 B CN 113293292B CN 202110576559 A CN202110576559 A CN 202110576559A CN 113293292 B CN113293292 B CN 113293292B
- Authority
- CN
- China
- Prior art keywords
- lithium
- seawater
- cathode
- substrate
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 149
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 144
- 239000013535 sea water Substances 0.000 title claims abstract description 124
- 238000000605 extraction Methods 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 43
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 39
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000000463 material Substances 0.000 claims abstract description 33
- 239000004065 semiconductor Substances 0.000 claims abstract description 22
- 238000005286 illumination Methods 0.000 claims abstract description 19
- 238000003860 storage Methods 0.000 claims abstract description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 77
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 73
- 239000000758 substrate Substances 0.000 claims description 62
- 229910052799 carbon Inorganic materials 0.000 claims description 43
- 239000003792 electrolyte Substances 0.000 claims description 40
- 239000011521 glass Substances 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 36
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 34
- 229910052760 oxygen Inorganic materials 0.000 claims description 34
- 239000001301 oxygen Substances 0.000 claims description 34
- 239000000243 solution Substances 0.000 claims description 33
- 239000004408 titanium dioxide Substances 0.000 claims description 33
- 229910052493 LiFePO4 Inorganic materials 0.000 claims description 32
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 32
- 229910052719 titanium Inorganic materials 0.000 claims description 32
- 239000010936 titanium Substances 0.000 claims description 32
- 239000004744 fabric Substances 0.000 claims description 31
- 238000001354 calcination Methods 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000008367 deionised water Substances 0.000 claims description 25
- 229910021641 deionized water Inorganic materials 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 24
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 24
- 229910052751 metal Inorganic materials 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- 239000011248 coating agent Substances 0.000 claims description 22
- 238000000576 coating method Methods 0.000 claims description 22
- 239000010406 cathode material Substances 0.000 claims description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 18
- 229910010710 LiFePO Inorganic materials 0.000 claims description 18
- 239000011230 binding agent Substances 0.000 claims description 18
- 239000006258 conductive agent Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 18
- 239000013078 crystal Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 17
- 239000004570 mortar (masonry) Substances 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 13
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 239000002033 PVDF binder Substances 0.000 claims description 12
- 239000012298 atmosphere Substances 0.000 claims description 12
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 12
- 238000004528 spin coating Methods 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 10
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 9
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 9
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 239000006229 carbon black Substances 0.000 claims description 9
- 239000004917 carbon fiber Substances 0.000 claims description 9
- 239000002041 carbon nanotube Substances 0.000 claims description 9
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 9
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 9
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 9
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 9
- 229910021389 graphene Inorganic materials 0.000 claims description 9
- 229910002804 graphite Inorganic materials 0.000 claims description 9
- 239000010439 graphite Substances 0.000 claims description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 9
- 230000008929 regeneration Effects 0.000 claims description 9
- 238000011069 regeneration method Methods 0.000 claims description 9
- 239000012266 salt solution Substances 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000002002 slurry Substances 0.000 claims description 9
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 9
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 230000010757 Reduction Activity Effects 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 125000004122 cyclic group Chemical group 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 6
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 229910052797 bismuth Inorganic materials 0.000 claims description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000007772 electrode material Substances 0.000 claims description 5
- 229910021645 metal ion Inorganic materials 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims description 5
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims description 4
- 238000003618 dip coating Methods 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- 230000005611 electricity Effects 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 230000010287 polarization Effects 0.000 claims description 4
- 229910005069 Li1−xMn2O4 Inorganic materials 0.000 claims description 3
- 229910016759 Ni0.5Mn1.5O4 Inorganic materials 0.000 claims description 3
- 229910015177 Ni1/3Co1/3Mn1/3 Inorganic materials 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 3
- 239000003575 carbonaceous material Substances 0.000 claims description 3
- 229910052681 coesite Inorganic materials 0.000 claims description 3
- 229910052906 cristobalite Inorganic materials 0.000 claims description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L magnesium chloride Substances [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 150000002825 nitriles Chemical class 0.000 claims description 3
- 230000002572 peristaltic effect Effects 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229910052682 stishovite Inorganic materials 0.000 claims description 3
- 229910052905 tridymite Inorganic materials 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 230000005284 excitation Effects 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000010405 anode material Substances 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 244000137852 Petrea volubilis Species 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- 238000002048 anodisation reaction Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000021148 sequestering of metal ion Effects 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910001868 water Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Hybrid Cells (AREA)
Abstract
The invention discloses a seawater lithium extraction system based on solar drive and a preparation method thereof. The N-type semiconductor is mainly used for generating photo-generated electron-hole pairs through light excitation during illumination, and providing electrons for the lithium extraction process. The lithium-rich material is mainly used for accepting electrons and providing storage sites for lithium ions; the embodiment of the invention can obtain a stable and reusable seawater lithium extraction system on the premise of ensuring simple process and environmental protection.
Description
Technical Field
The invention relates to the field of photoelectric conversion and energy, in particular to a solar-driven seawater lithium extraction system and a preparation method thereof.
Background
In recent years, the market size of lithium batteries has been greatly expanded due to the spread of electric vehicles and portable electronic devices. Under the premise that only the demand of lithium resources due to the growth of electric vehicles is considered, the consumption of the lithium resources in the next 30 years accounts for 1/3 of the worldwide exploitable lithium reserves, and the worldwide lithium resources are expected to be exhausted in 2080. Compared with the terrestrial lithium resources, the lithium reserve in seawater is 16000 times of that in the terrestrial lithium resources, and in consideration of the high reserve, research institutions of various countries develop technical development of seawater lithium extraction. However, the lithium concentration in seawater is only 0.17ppm, so the cost for extracting lithium from seawater is greatly different from the output. In addition, since the ion species in the seawater are rich, and Na and Mg ions with chemical properties similar to Li ions are not abundant, the lithium extraction process is accompanied with the carrying of other impurity ions. Therefore, how to reduce the cost of extracting lithium from seawater and improve the selection specificity of extracting lithium becomes the key of the development of the seawater lithium extraction technology.
Solar energy is used as an inexhaustible resource, which provides possibility for reducing energy output cost of extracting lithium from seawater. The Zhouhao cautious et al of Nanjing university propose a seawater lithium extraction system based on a lithium ion solid electrolyte film by taking a solar cell panel as the driving force of electric energy. Unfortunately, the solid electrolyte membrane is expensive to manufacture and the system needs to be sealed, which is not conducive to practical use in open ocean environments.
Disclosure of Invention
The invention aims to provide a preparation method of a seawater lithium extraction system based on solar drive aiming at extraction of lithium resources in the sea, and the seawater lithium extraction system takes sunlight as a unique energy input source, is environment-friendly, has low manufacturing cost and has feasible practicability.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the invention provides a preparation method of a seawater lithium extraction system based on solar drive, which comprises the following steps:
step 1: selection and preparation of cathode
Selection of a1 lithium-rich material: selecting an electrode material with lithium ion selectivity specificity as a cathode material;
preparation of a2 cathode: the preparation of the cathode adopts a spin coating or dip-coating pulling mode;
the spin coating specifically comprises the following steps: grinding the lithium-enriched material, a conductive agent and a binder for 10-30 minutes by using a mortar according to a mass ratio of 1-10: 0.1 under the action of a solvent; coating the uniformly ground slurry on a current collector, wherein the thickness of the coated film is 100 nm-1 dm, and the contained coordination crystal is 1mg/cm2～100mg/cm2And placing the cathode in an oven with the temperature of 50-100 ℃ for vacuum drying for 0.2-24 hours to obtain the cathode;
the dipping and pulling method specifically comprises the following steps: preparing a mixed aqueous solution of a Fe salt solution, a Li source salt solution and a P source inorganic salt, wherein the concentration of metallic Fe salt is 0.1-5 mmol/L; the concentration of the Li salt solution is 0.1 mmol/L-5 mmol/L; the concentration of the inorganic salt is 0.1-3 mol/L; selecting ammonia water to control the pH value of the solution to be less than 7, and magnetically stirring for 1-12 h; obtaining a yellow-green transparent solution; soaking the current collector in the above solution for 1-30min, and then soaking at a rate of 0.5-5cm/minCarrying out lifting at a speed; drying the impregnated current collector in an oven at the temperature of 40-100 ℃ for 0.2-24 h; then placing the mixture in a tube furnace at the temperature of 400-550 ℃ under N2Calcining for 2-4 h in the atmosphere, wherein the heating rate is 5-10 ℃/min; obtaining LiFePO with the thickness of 1nm-5 mu m on the surface of the substrate after calcination4The film is the cathode;
step 2: selection and preparation of photoanode
Selection of A1 photo-anode: an N-type semiconductor is selected as a photo-anode, namely, under the irradiation of sunlight, electron hole pairs can be generated, and the electron concentration is far greater than the hole concentration;
preparation of a2 photoanode: by coating or substrate growth
The coating specifically comprises the following steps: grinding N-type semiconductor powder, a conductive agent and a binder for 10-30 minutes by using a mortar according to a mass ratio of 1: 0.1-10 under the action of a solvent; coating the uniformly ground slurry on a current collector, wherein the thickness of the coated film is 100 nm-1 dm, and the N-type semiconductor powder is 1mg/cm2～100mg/cm2And placing the mixture in an oven at the temperature of between 50 and 100 ℃ for vacuum drying for 0.2 to 24 hours to obtain the photo-anode;
the substrate growth specifically comprises: FTO conductive glass with the purity range of 90-99% and the thickness of 0.05-10 mm is used as a substrate; putting the cut substrate into absolute ethyl alcohol, acetone and deionized water respectively, ultrasonically cleaning for 10-40 minutes, and then placing the substrate in a 60 ℃ drying oven for later use; adding 10-30ml of concentrated hydrochloric acid solution and equivalent deionized water into a reaction kettle, stirring for 10-15min, then adding 0.1-1ml of tetrabutyl titanate, and continuing stirring for 10-30 min; then measuring the conductive surface of the cleaned FTO conductive glass for later use by using a multimeter, obliquely placing the FTO conductive glass in a reaction kettle according to the rule that the conductive surface faces downwards, sealing the reaction kettle, and transferring the FTO conductive glass to a drying oven with the temperature of 160-220 ℃ for reaction for 5-48 hours; after the reaction is finished, cooling the reaction kettle to room temperature, and washing the substrate by deionized water; putting the substrate into an oven with the temperature of 40-100 ℃ for drying for 0.2-24 h; then calcining for 2-4 h in a muffle furnace at the temperature of 400-550 ℃ in the air atmosphere, wherein the temperature rise speed is 1 ℃/min; obtaining an FTO oxide film with the thickness of 1nm-1 mu m on the surface of the substrate after calcination, namely the photoanode;
and step 3: electrolyte is selected: selecting a real seawater solution with dissolved oxygen of more than or equal to 1ppm and lithium ion content of more than or equal to 0.15ppm as an electrolyte for providing metal ions required in the lithium enrichment process and balancing electrode polarization effect; the seawater is a seawater resource in the ocean that occupies about 70% of the earth;
and 4, step 4: preparation of oxygen reduction electrode
Selection of A1 oxygen reduction material: selecting a catalyst material with catalytic oxygen reduction activity;
preparation of a2 oxygen reduction electrode: adopting a spin coating mode;
the method specifically comprises the following steps: grinding the catalyst material, the conductive agent and the binder for 10-30 minutes by using a mortar according to the proportion under the action of a solvent, wherein the mass ratio is 1-10: 0.1; coating the uniformly ground slurry on a current collector, wherein the thickness of the coated film is 100 nm-1 dm, and the contained coordination crystal is 1mg/cm2～100mg/cm2And placing the mixture in an oven at 50-100 ℃ for vacuum drying for 0.2-24 hours to obtain the oxygen reduction electrode;
and 5: production of lithium extraction process by illuminating seawater
The cathode and the photo-anode are respectively placed in seawater electrolyte flowing through a peristaltic pump, the cathode and the photo-anode are connected through an external load, a semiconductor excites generated photo-generated electrons to flow into the cathode through an external current under the irradiation of sunlight, and the cathode material captures lithium ions from seawater to realize the enrichment of the lithium ions while receiving the photo-generated electrons and keeping neutral balance;
step 6: cyclic regeneration of delithiated and lithium-enriched cathodes
When the illumination stops, the illumination lithium extraction process stops due to the disconnection of the photo-generated electrons; at this time, the photoanode was turned off, and the lithium-rich electrode was taken out of the seawater and then connected to an oxygen reduction electrode, and placed at 100-2In solution; the lithium-enriched electrode releases lithium ions in the storage sites due to the oxidation process, and electrons are received by the manganese dioxide when flowing to the manganese dioxide electrode end through an external circuitElectrons, catalyzing the electrons to react with dissolved oxygen in seawater; thereby realizing the lithium removal and the cycle regeneration of the lithium-enriched cathode; and when the cathode-lithium enrichment material is illuminated again, the cathode-lithium enrichment material is communicated with the photoanode again, and the illumination lithium extraction process is continued.
Alternatively, an electrode material having a selectivity specific to lithium ions is selected as the cathode material. The crystal with the Li ion selection specific storage site is as follows: LiFePO4、LiMn2O4、Li1-xMn2O4、λ-MnO2、Ni1/3Co1/3Mn1/3O2、Ni0.5Mn1.5O4And coated by structural optimization, such as LiFePO4@TiO2、LiFePO4@SiO2、LiFePO4@ PDA, etc.
Optionally, in the step a2 of preparing the cathode by spin coating, the conductive agent comprises at least one of carbon black, conductive graphite, carbon fiber, carbon nanotube and graphene;
the binder is polyvinylidene fluoride, styrene butadiene rubber or carboxymethyl cellulose;
the solvent is N-methyl pyrrolidone, dimethylacetamide, N-dimethylformamide, triethyl phosphate or dimethyl sulfoxide;
the current collector is carbon cloth, metal titanium, metal copper or metal nickel.
Alternatively, in the preparation of the a2 cathode by dip-drawing, the metal sheet is: FTO or carbon cloth.
Optionally, in the step a2 of preparing the photoanode, the N-type semiconductor comprises at least one of titanium dioxide and bismuth vanadate;
the conductive agent comprises at least one of carbon black, conductive graphite, carbon fiber, carbon nanotube and graphene;
the binder is polyvinylidene fluoride, styrene butadiene rubber or carboxymethyl cellulose;
the solvent is N-methyl pyrrolidone, dimethylacetamide, N-dimethylformamide, or triethyl phosphate or dimethyl sulfoxide;
the current collector is carbon cloth, metal titanium, metal copper, metal nickel, ITO conductive glass or FTO conductive glass.
Optionally, in the step a2 of growing a substrate for preparing a photoanode, the metal sheet is: FTO or silicon wafer.
Optionally, in the selection of the oxygen reduction material in step a1, the catalyst with oxygen reduction activity is: MnO2Carbon material, Pt carbon, and polyvinyl nitrile carbon felt.
Optionally, in the step a2 of preparing the oxygen reduction electrode, the conductive agent includes at least one of carbon black, conductive graphite, carbon fiber, carbon nanotube and graphene;
the binder is polyvinylidene fluoride, styrene butadiene rubber or carboxymethyl cellulose;
the solvent is N-methyl pyrrolidone, dimethylacetamide, N-dimethylformamide, triethyl phosphate or dimethyl sulfoxide;
the current collector is a carbon felt, a carbon cloth or a titanium sheet.
Optionally, in step 5, in the generation of the process of extracting lithium from the illuminated seawater, the process of flowing out electrons through an external current is also a process of generating electricity.
Optionally, in step 6, in the generation of the light seawater lithium removal process, MgCl is added2The concentration of the solution is 0.1-0.5mol L-1。
According to another aspect of the invention, a seawater lithium extraction system based on solar drive is provided, and is prepared by any preparation method.
Has the advantages that:
the embodiment of the invention takes sunlight as the only energy input source, has simple scientific principle, safety and stability, full environmental friendliness, low manufacturing cost, feasible practicability and easy popularization in an open real seawater environment. The N-type semiconductor is mainly used for generating photo-generated electron-hole pairs through light excitation during illumination, and providing electrons for the lithium extraction process. The lithium-rich material is mainly used for accepting electrons and providing storage sites for lithium ions; the embodiment of the invention can obtain a stable and reusable seawater lithium extraction system on the premise of ensuring simple process and environmental protection.
The embodiment of the invention adopts an N-type semiconductor which can be excited by light in water to generate electron-hole pairs as a photoanode region and is used for providing electron and hole sources; the lithium-enriched material which mainly has high selectivity specificity to lithium ions is used as a cathode region for providing storage sites for photo-generated electrons and lithium ions in seawater at the same time, and has the characteristic of reversible intercalation and deintercalation of the lithium ions; real seawater solution with lithium ion content of at least 0.15ppm is used as electrolyte.
According to the method, when illumination occurs, photo-generated electrons generated by the photoelectrode flow into the cathode end through the external circuit, and in order to keep the self-neutral balance, the cathode material can capture lithium ions from seawater, so that the enrichment of the lithium ions is realized. By changing the ion selection specificity of the cathode material, the method can realize enrichment and extraction of other metal ions in the seawater.
Drawings
Fig. 1 is a schematic structural diagram of a seawater lithium extraction system based on solar drive according to an embodiment of the present invention;
fig. 2 is a schematic structural diagram of a lithium removal process, i.e., a cyclic regeneration structure, of a lithium-enriched material of a solar-driven seawater lithium extraction system according to embodiment 1 of the present invention;
FIG. 3 is a lithium extraction constant current lithium extraction curve for a solar powered seawater lithium extraction system made in accordance with example 1 of the present invention;
FIG. 4 is a lithium extraction constant current lithium extraction curve for a solar powered seawater lithium extraction system made in example 2 of the present invention;
FIG. 5 is a lithium extraction constant current lithium extraction curve for a solar powered seawater lithium extraction system made in accordance with example 3 of the present invention;
fig. 6 is a lithium extraction constant current lithium extraction curve of a solar-powered seawater lithium extraction system prepared in example 4 of the present invention.
Reference numerals:
1FTO conductive glass; 2, sunlight; 3 titanium dioxide; 4, loading; 5, conductive carbon cloth; 6 a lithium rich material; 7, seawater electrolyte; 8 carbon felt; 9 manganese dioxide; 10MgCl2The electrolyte of (1).
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The inventors of the present invention have developed a set of open ocean lithium extraction systems based on ocean solar energy. The inventor finds that spinel-type LiMn2O4The electrode material has a unique chemical structure (space group Fd3m) and high Li+Adsorption capacity, separation of lithium from other coexisting ions (Na)+，K+，Ca2+，Mg2+Etc.). Therefore, the lithium ion selective specific material is an ideal cathode material for seawater lithium enrichment, and provides possibility for manufacturing an environment-friendly, low-cost and efficient seawater lithium extraction technology.
The embodiment of the invention provides a preparation method of a seawater lithium extraction system based on solar drive, which comprises the following specific steps:
step 1: selection and preparation of cathode
A1: selection of lithium-rich materials
An electrode material having a selectivity specific to lithium ions is selected as a cathode material.
The crystal with the Li ion selection specific storage site is as follows: LiFePO4、LiMn2O4、Li1-xMn2O4、λ-MnO2、Ni1/3Co1/3Mn1/3O2、Ni0.5Mn1.5O4And coated by structural optimization, such as LiFePO4@TiO2、LiFePO4@SiO2、LiFePO4@ PDA, etc.
A2: preparation of the cathode
The preparation of the cathode adopts a spin coating or dip-coating pulling mode;
i) coating: grinding the lithium-enriched material, a conductive agent and a binder for 10-30 minutes by using a mortar according to a mass ratio of 1-10: 0.1 under the action of a solvent; coating the uniformly ground slurry on a current collector, wherein the thickness of the coated film is 100 nm-1 dm, and the contained coordination crystal is 1mg/cm2～100mg/cm2And placing the cathode in an oven with the temperature of 50-100 ℃ for vacuum drying for 0.2-24 hours to obtain the cathode; wherein,
the conductive agent is one or a mixture of a plurality of carbon black, conductive graphite, carbon fiber, carbon nano tube and graphene;
the binder is polyvinylidene fluoride, styrene butadiene rubber or carboxymethyl cellulose;
the solvent is N-methyl pyrrolidone, dimethylacetamide, N-dimethylformamide, triethyl phosphate or dimethyl sulfoxide;
the current collector is carbon cloth, metal titanium, metal copper or metal nickel;
ii) dip-drawing: preparing a mixed aqueous solution of an Fe salt solution, a Li source salt solution and a P source inorganic salt, wherein the concentration of metallic Fe salt is 0.1-5 mmol/L; the concentration of the Li salt solution is 0.1 mmol/L-5 mmol/L; the concentration of the inorganic salt is 0.1-3 mol/L; selecting ammonia water to control the pH value of the solution to be less than 7, and magnetically stirring for 1-12 h; a yellow-green transparent solution was obtained. And soaking the current collector in the gold plate solution for 10min, and then burning at the speed of 0.5cm/min for lifting. Drying the impregnated current collector in an oven at the temperature of 40-100 ℃ for 0.2-24 h; then the tube furnace is in N at 400-550 DEG C2Calcining for 2-4 h in the atmosphere, wherein the heating rate is 5 ℃/min; obtaining LiFePO with the thickness of 1nm-5 mu m on the surface of the substrate after calcination4The film is the cathode; wherein,
the metal sheet is: FTO or carbon cloth;
step 2: selection and preparation of photoanode
A1: selection of photo-anode
The method comprises the following steps of selecting an N-type semiconductor such as titanium dioxide or bismuth vanadate as a photo-anode, namely, under the irradiation of sunlight, electron-hole pairs can be generated, and the electron concentration is far greater than the hole concentration;
a2: preparation of photo-anode
The preparation of the photo-anode material adopts a coating or substrate growth mode
i) Coating: grinding N-type semiconductor powder, a conductive agent and a binder for 10-30 minutes by using a mortar according to a mass ratio of 1: 0.1-10 under the action of a solvent; coating the uniformly ground slurry on a current collector, wherein the thickness of the coated film is 100 nm-1 dm, and the N-type semiconductor powder is 1mg/cm2～100mg/cm2And placing the mixture in an oven at the temperature of between 50 and 100 ℃ for vacuum drying for 0.2 to 24 hours to obtain the photo-anode; wherein,
the N-type semiconductor is one or a mixture of more than one of titanium dioxide and bismuth vanadate;
the conductive agent is one or a mixture of more than one of carbon black, conductive graphite, carbon fiber, carbon nano tube and graphene;
the binder is polyvinylidene fluoride, styrene butadiene rubber or carboxymethyl cellulose;
the solvent is N-methyl pyrrolidone, dimethylacetamide, N-dimethylformamide, triethyl phosphate or dimethyl sulfoxide;
the current collector is carbon cloth, metal titanium, metal copper, metal nickel, ITO conductive glass or FTO conductive glass; ii) substrate growth: FTO conductive glass with the purity range of 90-99% and the thickness of 0.05-10 mm is used as a substrate; and (3) putting the cut substrate into absolute ethyl alcohol, acetone and deionized water respectively, ultrasonically cleaning for 10-40 minutes, and then putting the substrate into an oven at 60-100 ℃ for drying for later use. Adding 10-30ml of concentrated hydrochloric acid solution and equivalent deionized water into a reaction kettle, stirring for 10-15min, then adding 0.1-1ml of tetrabutyl titanate, and continuing stirring for 10-30 min; then measuring the conductive surface of the cleaned FTO for later use by using a multimeter, obliquely placing the FTO in a reaction kettle according to the criterion that the conductive surface faces downwards, sealing the reaction kettle, and transferring the FTO into a drying oven with the temperature of 160-220 ℃ for reaction for 5-48 hours; after the reaction is finished, cooling the reaction kettle to room temperature, and washing the substrate by deionized water; putting the substrate into an oven with the temperature of 40-100 ℃ for drying for 0.2-24 h; then calcining for 2-4 h in a muffle furnace at 400-550 ℃ in the air atmosphere, wherein the temperature rise speed is 1-10 ℃/min; obtaining an FTO oxide film with the thickness of 1nm-1 mu m on the surface of the substrate after calcination, namely the photoanode; wherein,
the metal sheet is: FTO or silicon wafer;
and step 3: electrolyte solution
Selecting a real seawater solution with dissolved oxygen of more than or equal to 1ppm and lithium ion content of more than or equal to 0.15ppm as an electrolyte for providing metal ions required in the lithium enrichment process and balancing electrode polarization effect; the seawater is a seawater resource in the ocean that occupies about 70% of the earth; the seawater is used as electrolyte for providing metal ions required in the lithium enrichment process and balancing electrode polarization effect; the seawater is a seawater resource in the ocean that occupies about 70% of the earth;
and 4, step 4: preparation of oxygen reduction electrode
A1: selection of oxygen-reducing materials
A catalyst material having catalytic oxygen reduction activity is selected. The catalyst with oxygen reduction activity is as follows: MnO2Carbon material, Pt carbon, and polyvinyl nitrile carbon felt;
a2: preparation of oxygen reduction electrode
The preparation of the oxygen reduction electrode adopts a spin coating mode;
grinding the oxygen reduction catalyst, the conductive agent and the binder for 10-30 minutes by using a mortar according to the proportion under the action of a solvent, wherein the mass ratio is 1-10: 0.1; coating the uniformly ground slurry on a current collector, wherein the thickness of the coated film is 100 nm-1 dm, and the contained coordination crystal is 1mg/cm2～100mg/cm2And placing the mixture in an oven at 50-100 ℃ for vacuum drying for 0.2-24 hours to obtain the oxygen reduction electrode; wherein,
the conductive agent is one or a mixture of a plurality of carbon black, conductive graphite, carbon fiber, carbon nano tube and graphene;
the binder is polyvinylidene fluoride, styrene butadiene rubber or carboxymethyl cellulose;
the solvent is N-methyl pyrrolidone, dimethylacetamide, N-dimethylformamide, triethyl phosphate or dimethyl sulfoxide;
the current collector is a carbon felt, a carbon cloth and a titanium sheet;
and 5: production of lithium extraction process by illuminating seawater
The cathode and the photo-anode are respectively placed in seawater electrolyte flowing through a peristaltic pump, the cathode and the photo-anode are connected through an external load, a semiconductor excites generated photo-generated electrons to flow into the cathode through an external current under the irradiation of sunlight, and the cathode material captures lithium ions from seawater to realize the enrichment of the lithium ions in order to keep neutral balance of electricity while receiving the photo-generated electrons. During the process of extracting lithium from seawater by illumination, the method is characterized in that the process of flowing out electrons by external current is also the process of generating electricity.
Step 6: cyclic regeneration of delithiated and lithium-enriched cathodes
When the illumination stops, the illumination lithium extraction process stops due to the disconnection of the photo-generated electrons; at this point the photoanode was switched off and placed in MgCl at 100ml-1000 by taking the lithium rich electrode out of the seawater and then switching on with the oxygen reduction electrode2In solution, wherein MgCl2The concentration of the solution is 0.1-0.5mol L-1. The lithium enrichment electrode releases lithium ions in the storage site due to the oxidation process, and meanwhile, when electrons flow to the manganese dioxide electrode end through an external circuit, the manganese dioxide receives the electrons to catalyze the electrons to react with dissolved oxygen in seawater; thereby realizing the lithium removal and the cycle regeneration of the lithium-enriched cathode; when the light is radiated again, the cathode-lithium rich base material is communicated with the photo-anode again, and the process of light lithium extraction is continued.
Referring to fig. 1, a schematic structural diagram of a solar-powered seawater lithium extraction system according to an embodiment of the present invention is shown in the figure, in which a conductive carbon cloth 5 coated with a lithium-ion-selective specific lithium-rich material 6 is connected to a cathode of a load 4 by a copper wire lead-out; the FTO conductive glass 1 with the titanium dioxide 3 is led out by a copper wire to be connected with a photo-anode of a load 4. And then the connected conductive carbon cloth 5 and the FTO conductive glass 1 are put into a beaker filled with seawater electrolyte 7 together to form the solar-driven seawater lithium extraction system. When sunlight 2 irradiates on the titanium dioxide 3, the lithium ion can be enriched in the cathode from the seawater.
Referring to fig. 2, a schematic diagram of a lithium removal process, i.e., a cyclic regeneration structure, of the lithium-enriched material of the solar-driven seawater lithium extraction system according to the embodiment of the present invention. When the illumination is removed or the metal ion storage sites in the lithium-rich material 6 coated on the conductive carbon cloth 5 are fully occupied, the illumination lithium extraction process is stopped. Disconnecting the photo-anode and the cathode, taking out the cathode end, and leading out the conductive carbon cloth 5 of the lithium-enriched material 6 after enriching the lithium ions to be connected with the load 4 by using a copper wire; the carbon felt 8 coated with manganese dioxide 9 catalyst with oxygen reduction activity is led out by a copper wire to be connected with the redox electrode of the load 4, and then the connected conductive carbon cloth 5 and the carbon felt 8 are put into a container with 0.5mol L-1MgCl2The lithium-rich material 6 can be oxidized by using dissolved oxygen under the catalytic action of manganese dioxide in the beaker of the electrolyte 10, so that the lithium-rich material 6 loses electrons and releases lithium ions which are captured from seawater and stored in a storage site, thereby realizing lithium extraction and electrode cyclic regeneration.
The following are specific examples
Example 1
Spin coating + substrate growth
The cathode material selected in this example is LiFePO4(ii) a The photo-anode material is a titanium dioxide N-type semiconductor with a molecular formula of TiO2(ii) a The electrolyte is natural seawater.
Step 1: LiFePO4Preparation of lithium-rich cathode materials
Equal amount of FeCl (0.05)2H2O、LiCO3And H3PO4Adding the Fe source, the Li source and the P source into 200ml of absolute ethyl alcohol in sequence, carrying out ultrasonic dispersion, stirring at room temperature (25 ℃), standing at room temperature for 12 hours after the sol is completely changed into gray gel, transferring the product into an air-blast drying oven at 80 ℃, and drying for 12 hours. And then grinding the dried product in an agate mortar to powder, transferring the powder into a porcelain boat, and calcining the powder for 10 hours at 500 ℃ at the temperature rise speed of 5 ℃/min under the protection of the nitrogen atmosphere of a tube furnace. To obtainThe obtained gray black product is the obtained LiFePO4。
Step 2: preparation of solar-driven cathode of seawater lithium extraction system
Taking 70mg of LiFePO in the step 14The powder and 20mg of conductive carbon powder, 10mg of polyvinylidene fluoride were placed in a mortar, 2ml of N-methylpyrrolidone was added, and manually ground for 15 minutes. The uniformly ground mixture was coated on a conductive carbon cloth having a size of 3cm × 4cm with a blade. And placing the mixture in an oven at 100 ℃ for vacuum drying for 12 hours, wherein the vacuum degree is less than 0.1 Pa. The obtained electrode can be used as a cathode of a solar-driven seawater lithium extraction system;
and step 3: and (3) preparing a photoanode of a solar-driven seawater lithium extraction system.
Using conductive glass with the resistance of 10 omega, the size of 2.5cm multiplied by 4m and the thickness of 0.1mm as a substrate; respectively putting the substrate into 18% acetone, absolute ethyl alcohol and deionized water, ultrasonically cleaning for 10 minutes, vertically and obliquely putting the substrate into a reaction kettle, and putting the substrate with the conductive surface facing downwards; adding 25ml of hydrochloric acid solution with the concentration of 18% into a 50ml reaction kettle; then sealing the reaction kettle, and transferring the reaction kettle to an oven with the temperature of 200 ℃ for reaction for 12 hours; after the reaction is finished, cooling the reaction kettle to room temperature, and washing the substrate by deionized water; putting the substrate into an oven at 100 ℃ for drying for 24 hours; soaking the dried substrate sheet in a titanium tetrachloride solution with the concentration of 0.5mol/L in an oven at 80 ℃ for 30min, then washing the substrate sheet with absolute ethyl alcohol, and drying the substrate sheet in the oven at 70 ℃ for 2 h; finally calcining for 3h in a muffle furnace at 550 ℃ in the air atmosphere, wherein the heating rate is 5 ℃/min; obtaining a white oxide film with the thickness of 10nm on the conductive surface of the substrate after calcination, and obtaining the photoanode of the solar-driven seawater lithium extraction system.
And 4, step 4: assembly of solar-driven seawater lithium extraction system
Coating the LiFePO obtained in the step 24And (3) respectively placing the conductive carbon cloth and the conductive glass electrode plate with the titanium dioxide electric film grown thereon obtained in the step (3) in seawater electrolyte which can flow mutually, and connecting the conductive carbon cloth and the conductive glass electrode plate with the titanium dioxide electric film grown thereon by using a lead to obtain the solar-driven seawater lithium extraction system.
FIG. 3 shows the solar-powered seawater of this embodimentThe lithium extraction system adopts a lithium extraction constant current lithium extraction curve under the test condition that the coating obtained in the step 2 is coated with LiFePO4And (3) respectively placing the conductive carbon cloth and the conductive glass electrode plate with the titanium dioxide electric film obtained in the step (3) into 500mL of seawater electrolyte which can flow mutually, and placing the seawater electrolyte into a 1000mL quartz electrolytic cell. The titanium dioxide electrode is connected to a counter electrode and a reference electrode of an electrochemical workstation and is coated with LiFePO4The conductive carbon cloth is connected to a working electrode of an electrochemical workstation, and a 100W xenon lamp is used as a simulated solar light source for irradiation in a voltage-time mode, so that a voltage-time relation graph shown in figure 3 can be obtained;
in the embodiment, the prepared cathode and the photo-anode are connected and respectively put into seawater electrolyte with the salinity of more than or equal to 0.1 percent, and during illumination, titanium dioxide can generate electron-hole pairs under the excitation of sunlight, so that LiFePO is obtained4The crystal has the ability to accept electrons, so that photogenerated electrons flow to the cathode through an external circuit to form current, and simultaneously, to maintain electroneutrality, LiFePO4The crystal will take one lithium ion from the seawater. The whole process is simple and easy to implement, and is green and pollution-free to the seawater environment.
Example 2
Spin coating + anodization process
The cathode material selected in this example is LiFePO4(ii) a The photo-anode material is a titanium dioxide N-type semiconductor with a molecular formula of TiO2(ii) a The electrolyte is natural seawater.
Step 1: LiFePO4Preparation of lithium-rich cathode materials
Equal amount of FeCl (0.05)2H2O、LiCO3And H3PO4Adding the Fe source, the Li source and the P source into 200ml of absolute ethyl alcohol in sequence, carrying out ultrasonic dispersion, stirring at room temperature (25 ℃), standing at room temperature for 12 hours after the sol is completely changed into gray gel, transferring the product into an air-blast drying oven at 80 ℃, and drying for 12 hours. Then grinding the dried product in an agate mortar to powder, transferring the powder to a porcelain boat, and heating at a speed of 5 ℃/min at 500 ℃ in a tube furnace under the protection of nitrogen atmosphereAnd calcining for 10 hours. The obtained gray black product is the obtained LiFePO4。
Step 2: preparation of solar-driven cathode of seawater lithium extraction system
Taking 70mg of LiFePO in the step 14The powder and 20mg of conductive carbon powder, 10mg of polyvinylidene fluoride were placed in a mortar, 2ml of N-methylpyrrolidone was added, and manually ground for 15 minutes. The uniformly ground mixture was coated on a conductive carbon cloth having a size of 3cm × 4cm with a blade. And placing the mixture in an oven at 100 ℃ for vacuum drying for 12 hours, wherein the vacuum degree is less than 0.1 Pa. The obtained electrode can be used as a cathode of a solar-driven seawater lithium extraction system;
and step 3: and (3) preparing a photoanode of a solar-driven seawater lithium extraction system.
And (3) pretreating the titanium sheet, namely polishing and grinding the titanium sheet with the size of 4cm multiplied by 3cm and the thickness of 0.3mm by adopting 1000-mesh sand paper and aluminum oxide nano particles so as to remove scratches in the processing process. After polishing, the glass is washed by deionized water and naturally dried. Configuring HF (40.0%), HNO3(65-68%) and deionized water at a volume ratio of 1: 4: 5. And soaking the polished titanium sheet in the mixed solution for 30s for etching to remove the oxide layer. And ultrasonically cleaning the etched titanium sheet by using deionized water, ethanol and acetone respectively, and naturally airing for later use. And preparing electrolyte, wherein the concentration of the electrolyte is 1 mol/L. And (3) placing the beaker filled with the electrolyte on a magnetic stirrer, setting the rotating speed of the stirrer to be 100r/min, adjusting the rotating speed to be 400r/min after uniformly stirring, adopting a pretreated titanium sheet as a working electrode and a platinum sheet electrode as a double-electrode system of a counter electrode, and adjusting a direct-current power supply to work for 30min under the voltage of 30V. And after the reaction is finished, taking out the titanium sheet, washing the titanium sheet by using deionized water and ethanol, and naturally airing the titanium sheet. Then calcining for 3h in a muffle furnace at 550 ℃ in the air atmosphere, wherein the heating rate is 5 ℃/min; calcining to obtain a titanium dioxide film with the thickness of 0.5 mu m, which grows on the surface of the titanium sheet substrate and is the photo-anode;
and 4, step 4: assembly of solar-driven seawater lithium extraction system
Coating the LiFePO obtained in the step 24Conductive carbon cloth and step 3The obtained titanium sheets on which the titanium dioxide electric film grows are respectively placed in seawater electrolyte which can be mutually circulated and then connected by a lead, and the solar-driven seawater lithium extraction system can be obtained.
FIG. 4 is a lithium extraction constant current lithium extraction curve of the solar-powered seawater lithium extraction system of the present embodiment, under the test conditions that the coated LiFePO obtained in step 2 is obtained4And (3) respectively placing the conductive carbon cloth and the titanium sheet with the titanium dioxide electric film grown thereon obtained in the step (3) into 500mL of seawater electrolyte which can be circulated mutually, and placing the seawater electrolyte into a 1000mL quartz electrolytic cell. The titanium dioxide electrode is connected to a counter electrode and a reference electrode of an electrochemical workstation and is coated with LiFePO4The conductive carbon cloth is connected to a working electrode of an electrochemical workstation, and a 100W xenon lamp is used as a simulated solar light source for irradiation in a voltage-time mode, so that a voltage-time relation graph shown in figure 4 can be obtained;
in the embodiment, the prepared cathode and the photo-anode are connected and respectively put into seawater electrolyte with the salinity of more than or equal to 0.1 percent, and during illumination, titanium dioxide can generate electron-hole pairs under the excitation of sunlight, so that LiFePO is obtained4The crystal has the ability to accept electrons, so that photogenerated electrons flow to the cathode through an external circuit to form current, and simultaneously, to maintain electroneutrality, LiFePO4The crystal will take one lithium ion from the seawater. The whole process is simple and easy to implement, and is green and pollution-free to the seawater environment.
Example 3
Dip lift + substrate growth
The cathode material selected in this example is LiFePO4(ii) a The photo-anode material is a titanium dioxide N-type semiconductor with a molecular formula of TiO2(ii) a The electrolyte is natural seawater.
Step 1: LiFePO4Preparation of lithium-rich cathode materials
Using conductive glass with the resistance of 10 omega, the size of 2.5cm multiplied by 4m and the thickness of 0.1mm as a substrate; and respectively putting the substrate into 18% acetone, absolute ethyl alcohol and deionized water, ultrasonically cleaning for 10 minutes, and drying for later use. Equal amount (0.005mol) of FeCl2H2O、LiCO3Adding Fe source and Li source into 100ml deionized water in sequence, ultrasonically dispersing, stirring at room temperature (25 ℃), adding 50% citric acid solution dropwise, stirring, and adding 0.005molH3PO4As a P source, and simultaneously adjusting the pH value to 5.5 by using ammonia water; after magnetic stirring for 1h, the sol was completely converted into a yellow-green transparent solution. Taking clean FTO conductive glass for standby, measuring a conductive surface by using a universal meter, coating a non-conductive surface by using a high-temperature glass adhesive tape, vertically placing the FTO conductive glass in a dipping solution for soaking for 10min, then carrying out lifting at the speed of 0.5cm/min, and drying the dipped FTO conductive glass in an oven at the temperature of 80 ℃ for 12 h; then tube furnace at 500 ℃ N2Calcining for 3h in the atmosphere, wherein the heating rate is 5 ℃/min; after calcination, LiFePO with the thickness of 2 mu m is obtained on the surface of the substrate4The film is the cathode;
step 2: preparation of solar-driven cathode of seawater lithium extraction system
Taking 70mg of LiFePO in the step 14The powder and 20mg of conductive carbon powder, 10mg of polyvinylidene fluoride were placed in a mortar, 2ml of N-methylpyrrolidone was added, and manually ground for 15 minutes. The uniformly ground mixture was coated on a conductive carbon cloth having a size of 3cm × 4cm with a blade. And placing the mixture in an oven at 100 ℃ for vacuum drying for 12 hours, wherein the vacuum degree is less than 0.1 Pa. The obtained electrode can be used as a cathode of a solar-driven seawater lithium extraction system;
and step 3: and (3) preparing a photoanode of a solar-driven seawater lithium extraction system.
Growing a substrate: using conductive glass with the resistance of 10 omega, the size of 2.5cm multiplied by 4m and the thickness of 0.1mm as a substrate; respectively putting the substrate into 18% acetone, absolute ethyl alcohol and deionized water, ultrasonically cleaning for 10 minutes, vertically and obliquely putting the substrate into a reaction kettle, and putting the substrate with the conductive surface facing downwards; adding 25ml of hydrochloric acid solution with the concentration of 18% into a 50ml reaction kettle; then sealing the reaction kettle, and transferring the reaction kettle to an oven with the temperature of 200 ℃ for reaction for 12 hours; after the reaction is finished, cooling the reaction kettle to room temperature, and washing the substrate by deionized water; putting the substrate into an oven at 100 ℃ for drying for 24 hours; soaking the dried substrate sheet in a titanium tetrachloride solution with the concentration of 0.5mol/L in an oven at 80 ℃ for 30min, then washing the substrate sheet with absolute ethyl alcohol, and drying the substrate sheet in the oven at 70 ℃ for 2 h; finally calcining for 3h in a muffle furnace at 550 ℃ in the air atmosphere, wherein the heating rate is 5 ℃/min; obtaining a white oxide film with the thickness of 10nm on the conductive surface of the substrate after calcination, and obtaining the photoanode of the solar-driven seawater lithium extraction system.
And 4, step 4: assembly of solar-driven seawater lithium extraction system
Coating the LiFePO obtained in the step 14And (3) respectively placing the conductive carbon cloth and the conductive glass electrode plate with the titanium dioxide electric film grown thereon obtained in the step (3) in seawater electrolyte which can flow mutually, and connecting the conductive carbon cloth and the conductive glass electrode plate with the titanium dioxide electric film grown thereon by using a lead to obtain the solar-driven seawater lithium extraction system.
Fig. 4 is a lithium extraction constant current lithium extraction curve of the solar-powered seawater lithium extraction system of the present embodiment, under the test conditions that the immersion extraction obtained in step 1 is performed with LiFePO4And (3) respectively placing the FTO conductive glass and the conductive glass electrode plate with the titanium dioxide electric film obtained in the step (2) into 500mL of seawater electrolyte which can be mutually circulated, and placing the seawater electrolyte into a 1000mL quartz electrolytic cell. Connecting the titanium dioxide electrode to a counter electrode and a reference electrode of an electrochemical workstation, and pulling the impregnated and drawn LiFePO obtained in the step 14The FTO conductive glass is connected to a working electrode of an electrochemical workstation, and a 100W xenon lamp is used as a simulated solar light source for irradiation in a voltage-time mode, so that a voltage-time relation graph shown in figure 3 can be obtained;
in the embodiment, the prepared cathode and the photo-anode are connected and respectively put into seawater electrolyte with the salinity of more than or equal to 0.1 percent, and during illumination, titanium dioxide can generate electron-hole pairs under the excitation of sunlight, so that LiFePO is obtained4The crystal has the ability to accept electrons, so that photogenerated electrons flow to the cathode through an external circuit to form current, and simultaneously, to maintain electroneutrality, LiFePO4The crystal will take one lithium ion from the seawater. The whole process is simple and easy to implement, and is green and pollution-free to the seawater environment.
Example 4
Dipping and pulling and anodic oxidation method
In this embodiment, theThe selected cathode material has a molecular formula of LiFePO4(ii) a The photo-anode material is a titanium dioxide N-type semiconductor with a molecular formula of TiO2(ii) a The electrolyte is natural seawater.
Step 1: LiFePO4Preparation of lithium-rich cathode materials
Using conductive glass with the resistance of 10 omega, the size of 2.5cm multiplied by 4m and the thickness of 0.1mm as a substrate; and respectively putting the substrate into 18% acetone, absolute ethyl alcohol and deionized water, ultrasonically cleaning for 10 minutes, and drying for later use. Equal amount (0.005mol) of FeCl2H2O、LiCO3Adding Fe source and Li source into 100ml deionized water in sequence, ultrasonically dispersing, stirring at room temperature (25 ℃), adding 50% citric acid solution dropwise, stirring, and adding 0.005molH3PO4As a P source, and simultaneously adjusting the pH value to 5.5 by using ammonia water; after magnetic stirring for 1h, the sol was completely converted into a yellow-green transparent solution. Taking clean FTO conductive glass for standby, measuring a conductive surface by using a universal meter, coating a non-conductive surface by using a high-temperature glass adhesive tape, vertically placing the FTO conductive glass in a dipping solution for soaking for 10min, then carrying out lifting at the speed of 0.5cm/min, and drying the dipped FTO conductive glass in an oven at the temperature of 80 ℃ for 12 h; then tube furnace at 500 ℃ N2Calcining for 3h in the atmosphere, wherein the heating rate is 5 ℃/min; after calcination, LiFePO with the thickness of 2 mu m is obtained on the surface of the substrate4The film is the cathode;
step 2: and (3) preparing a photoanode of a solar-driven seawater lithium extraction system.
And (3) pretreating the titanium sheet, namely polishing and grinding the titanium sheet with the size of 4cm multiplied by 3cm and the thickness of 0.3mm by adopting 1000-mesh sand paper and aluminum oxide nano particles so as to remove scratches in the processing process. After polishing, the glass is washed by deionized water and naturally dried. Configuring HF (40.0%), HNO3(65-68%) and deionized water at a volume ratio of 1: 4: 5. And soaking the polished titanium sheet in the mixed solution for 30s for etching to remove the oxide layer. And ultrasonically cleaning the etched titanium sheet by using deionized water, ethanol and acetone respectively, and naturally airing for later use. And preparing electrolyte, wherein the concentration of the electrolyte is 1 mol/L. Will be charged with electricityAnd placing the beaker of the electrolyte on magnetic stirring, setting the rotating speed of a stirrer to be 100r/min, adjusting the rotating speed to be 400r/min after uniform stirring, adopting a pretreated titanium sheet as a working electrode and a platinum sheet electrode as a double-electrode system of a counter electrode, and adjusting a direct-current power supply to enable the beaker to work for 30min under the voltage of 30V. And after the reaction is finished, taking out the titanium sheet, washing the titanium sheet by using deionized water and ethanol, and naturally airing the titanium sheet. Then calcining for 3h in a muffle furnace at 550 ℃ in the air atmosphere, wherein the heating rate is 5 ℃/min; calcining to obtain a titanium dioxide film with the thickness of 0.5 mu m, which grows on the surface of the titanium sheet substrate and is the photo-anode;
and step 3: assembly of solar-driven seawater lithium extraction system
The impregnation obtained in step 1 is pulled up with LiFePO4And (3) respectively placing the FTO conductive glass and the titanium sheet with the titanium dioxide electric film grown obtained in the step (2) in seawater electrolyte which can flow mutually, and connecting the FTO conductive glass and the titanium sheet with the titanium dioxide electric film grown in the step (2) by using a lead wire to obtain the solar-driven seawater lithium extraction system.
Fig. 5 is a lithium extraction constant current lithium extraction curve of the solar-powered seawater lithium extraction system of the present embodiment, under the test conditions that LiFePO is extracted by dipping obtained in step 14And (3) respectively placing the FTO conductive glass and the titanium sheet obtained in the step (2) on which the titanium dioxide electric film grows into 500mL of seawater electrolyte which can be mutually circulated, and placing the seawater electrolyte into a 1000mL quartz electrolytic cell. The titanium dioxide electrode is connected to a counter electrode and a reference electrode of an electrochemical workstation and is coated with LiFePO4The conductive carbon cloth is connected to a working electrode of an electrochemical workstation, and a 100W xenon lamp is used as a simulated solar light source for irradiation in a voltage-time mode, so that a voltage-time relation graph shown in figure 4 can be obtained;
in the embodiment, the prepared cathode and the photo-anode are connected and respectively put into seawater electrolyte with the salinity of more than or equal to 0.1 percent, and during illumination, titanium dioxide can generate electron-hole pairs under the excitation of sunlight, so that LiFePO is obtained4The crystal has the ability to accept electrons, so that photogenerated electrons flow to the cathode through an external circuit to form current, and simultaneously, to maintain electroneutrality, LiFePO4The crystal will take one lithium ion from the seawater. The whole processSimple and easy to operate, and has no pollution to the seawater environment.
Although the embodiments of the present invention have been described in the specification, these embodiments are merely provided as a hint, and should not limit the scope of the present invention. Various omissions, substitutions, and changes may be made without departing from the spirit of the invention and are intended to be within the scope of the invention.
Claims (9)
1. A preparation method of a seawater lithium extraction system based on solar drive is characterized by comprising the following steps:
step 1: selection and preparation of cathode
Selection of a1 lithium-rich material: selecting an electrode material with lithium ion selectivity specificity as a cathode material;
the cathode material selects a crystal with a lithium ion selection specific storage site, and specifically comprises the following components: LiFePO4、LiMn2O4、Li1-xMn2O4、λ-MnO2、Ni1/3Co1/3Mn1/3O2、Ni0.5Mn1.5O4And coated LiFePO4@TiO2、LiFePO4@SiO2、LiFePO4@PDA；
Preparation of a2 cathode: the preparation of the cathode adopts a spin coating or dip-coating pulling mode;
the spin coating specifically comprises the following steps: grinding the lithium-enriched material, a conductive agent and a binder for 10-30 minutes by using a mortar according to a certain proportion under the action of a solvent, wherein the mass ratio is 1-10: 0.1; coating the uniformly ground slurry on a current collector, wherein the thickness of the coated film is 100 nm-1 dm, and the contained coordination crystal is 1mg/cm2～100mg/cm2And placing the cathode in an oven with the temperature of 50-100 ℃ for vacuum drying for 0.2-24 hours to obtain the cathode;
the dipping and pulling method specifically comprises the following steps: preparing a mixed aqueous solution of a Fe salt solution, a Li source salt solution and a P source inorganic salt, wherein the concentration of metallic Fe salt is 0.1-5 mmol/L; the concentration of the Li salt solution is 0.1 mmol/L-5 mmol/L; inorganic salt concentration of 0.1mol/L to E3 mol/L; and selecting ammonia water to control the pH value of the solution<7, magnetically stirring for 1-12 h; obtaining a yellow-green transparent solution; soaking the current collector in the solution for 1-30min, and then pulling at the speed of 0.5-5 cm/min; drying the impregnated current collector in an oven at the temperature of 40-100 ℃ for 0.2-24 h; then placing the mixture in a tube furnace at 400-550 ℃ in N2Calcining for 2-4 h in the atmosphere, wherein the heating rate is 5-10 ℃/min; obtaining LiFePO with the thickness of 1nm-5 mu m on the surface of the substrate after calcination4The film is the cathode;
step 2: selection and preparation of photoanode
Selection of A1 photo-anode: selecting a titanium dioxide or bismuth vanadate N-type semiconductor as a photo-anode;
preparation of a2 photoanode: by coating or substrate growth
The coating specifically comprises the following steps: grinding N-type semiconductor powder, a conductive agent and a binder for 10-30 minutes by using a mortar according to a certain proportion under the action of a solvent, wherein the mass ratio is 1: 0.1-10; coating the uniformly ground slurry on a current collector, wherein the thickness of the coated film is 100 nm-1 dm, and the N-type semiconductor powder is 1mg/cm2～100mg/cm2And placing the mixture in an oven at the temperature of between 50 and 100 ℃ for vacuum drying for 0.2 to 24 hours to obtain the photo-anode;
the substrate growth specifically comprises: FTO conductive glass with the purity range of 90% -99% and the thickness of 0.05mm-10mm is used as a substrate; putting the cut substrate into absolute ethyl alcohol, acetone and deionized water respectively, ultrasonically cleaning for 10-40 minutes, and then putting the substrate into an oven at 60-100 ℃ for drying for later use; adding 10-30ml of concentrated hydrochloric acid solution and equivalent deionized water into a reaction kettle, stirring for 10-15min, then adding 0.1-1ml of tetrabutyl titanate, and continuing stirring for 10-30 min; then measuring the conductive surface of the cleaned substrate by using a multimeter, obliquely placing the cleaned substrate in a reaction kettle according to the rule that the conductive surface faces downwards, sealing the reaction kettle, and transferring the reaction kettle to a drying oven with the temperature of 160-220 ℃ for reaction for 5-48 hours; after the reaction is finished, cooling the reaction kettle to room temperature, and washing the substrate by deionized water; putting the substrate into an oven at the temperature of 40-100 ℃ for drying for 0.2-24 h; then calcining for 2-4 h in a muffle furnace at the temperature of 400-550 ℃ in the air atmosphere, wherein the temperature rise speed is 1-10 ℃/min; obtaining an FTO oxide film with the thickness of 1nm-1 mu m on the surface of the substrate after calcination, namely the photoanode;
and step 3: selection of electrolyte
Selecting a real seawater solution with dissolved oxygen of more than or equal to 1ppm and lithium ion content of more than or equal to 0.15ppm as an electrolyte for providing metal ions required in the lithium enrichment process and balancing electrode polarization effect;
and 4, step 4: preparation of oxygen reduction electrode
Selection of A1 oxygen reduction material: selecting a catalyst material with oxygen reduction activity;
preparation of a2 oxygen reduction electrode: adopting a spin coating mode;
the method specifically comprises the following steps: grinding the catalyst material, the conductive agent and the binder for 10-30 minutes by using a mortar according to a certain proportion under the action of a solvent, wherein the mass ratio is 1-10: 0.1; coating the uniformly ground slurry on a current collector, wherein the thickness of the coated film is 100 nm-1 dm, and the contained coordination crystal is 1mg/cm2～100mg/cm2And placing the mixture in an oven at 50-100 ℃ for vacuum drying for 0.2-24 hours to obtain the oxygen reduction electrode;
and 5: production of lithium extraction process by illuminating seawater
The cathode and the photo-anode are respectively placed in seawater electrolyte flowing through a peristaltic pump, the cathode and the photo-anode are connected through an external load, a semiconductor excites generated photo-generated electrons to flow into the cathode through an external current under the irradiation of sunlight, and the cathode material captures lithium ions from seawater to realize the enrichment of the lithium ions while receiving the photo-generated electrons and keeping neutral balance;
step 6: cyclic regeneration of delithiated and lithium-enriched cathodes
When the illumination stops, the illumination lithium extraction process stops due to the disconnection of the photo-generated electrons; at this time, the photoanode is turned off, and the lithium-rich electrode is taken out of the seawater and then put in contact with an oxygen reduction electrode, and placed in a container of 100-500ml MgCl2In solution; the lithium-rich electrode releases lithium ions in the storage sites due to the oxidation process, while electrons flow through an external circuit to the storage sitesWhen the manganese dioxide electrode is terminated, electrons are received through the manganese dioxide, and the electrons are catalyzed to react with dissolved oxygen in seawater; thereby realizing the lithium removal and the cycle regeneration of the lithium-enriched cathode; and when the cathode-lithium enrichment material is illuminated again, the cathode-lithium enrichment material is communicated with the photoanode again, and the illumination lithium extraction process is continued.
2. The method according to claim 1, wherein in the preparation spin coating of the cathode in step a2, the conductive agent comprises at least one of carbon black, conductive graphite, carbon fiber, carbon nanotube and graphene;
the binder is polyvinylidene fluoride, styrene butadiene rubber or carboxymethyl cellulose;
the solvent is N-methyl pyrrolidone, dimethylacetamide, N-dimethylformamide, triethyl phosphate or dimethyl sulfoxide;
the current collector is carbon cloth, metal titanium, metal copper or metal nickel.
3. The method of claim 1, wherein in the preparation of a2 cathode by dip-coating, the metal sheet is: FTO or carbon cloth.
4. The method according to claim 1, wherein in the step a2, the N-type semiconductor comprises at least one of titanium dioxide and bismuth vanadate;
the conductive agent comprises at least one of carbon black, conductive graphite, carbon fiber, carbon nanotube and graphene;
the binder is polyvinylidene fluoride, styrene butadiene rubber or carboxymethyl cellulose;
the solvent is N-methyl pyrrolidone, dimethylacetamide, N-dimethylformamide, or triethyl phosphate or dimethyl sulfoxide;
the current collector is carbon cloth, metal titanium, metal copper, metal nickel, ITO conductive glass or FTO conductive glass.
5. The method according to claim 1, wherein in the step a2 of growing a substrate for preparing the photoanode, the metal sheet is: FTO or silicon wafer.
6. The method according to claim 1, wherein in the selection of the oxygen reduction material in step a1, the catalyst having oxygen reduction activity is: MnO2Carbon material, Pt carbon, and polyvinyl nitrile carbon felt.
7. The production method according to claim 1, wherein in the production of the oxygen reduction electrode of step a2, the conductive agent includes at least one of carbon black, conductive graphite, carbon fiber, carbon nanotube, and graphene;
the binder is polyvinylidene fluoride, styrene butadiene rubber or carboxymethyl cellulose;
the solvent is N-methyl pyrrolidone, dimethylacetamide, N-dimethylformamide, triethyl phosphate or dimethyl sulfoxide;
the current collector is a carbon felt, a carbon cloth or a titanium sheet.
8. The production method according to claim 1,
in the step 5, in the process of lithium extraction by illuminating seawater, the process of electron outflow through external current is also the process of electricity generation;
in step 6, MgCl is generated in the process of removing lithium from seawater by illumination2The concentration of the solution is 0.1-0.5mol L-1。
9. A seawater lithium extraction system based on solar drive, which is characterized by being prepared by the preparation method of any one of claims 1 to 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110576559.9A CN113293292B (en) | 2021-05-25 | 2021-05-25 | Seawater lithium extraction system based on solar drive and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110576559.9A CN113293292B (en) | 2021-05-25 | 2021-05-25 | Seawater lithium extraction system based on solar drive and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113293292A CN113293292A (en) | 2021-08-24 |
| CN113293292B true CN113293292B (en) | 2022-02-15 |
Family
ID=77325107
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110576559.9A Active CN113293292B (en) | 2021-05-25 | 2021-05-25 | Seawater lithium extraction system based on solar drive and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113293292B (en) |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105506310B (en) * | 2016-01-07 | 2017-12-08 | 李震祺 | A kind of method that lithium is extracted from bittern containing lithium |
| WO2019028174A2 (en) * | 2017-08-02 | 2019-02-07 | Lilac Solutions, Inc. | Ion exchange system for lithium extraction |
| JP7379351B2 (en) * | 2018-02-17 | 2023-11-14 | ライラック ソリューションズ，インク． | Integrated system for lithium extraction and conversion |
| CN109097791B (en) * | 2018-07-23 | 2021-03-19 | 南京大学 | Seawater lithium extraction method and device based on lithium ion solid electrolyte |
| CN109616674B (en) * | 2018-11-03 | 2021-10-12 | 华东师范大学 | Hybrid battery based on seawater solute and preparation method |
| CN109637813B (en) * | 2018-11-12 | 2020-08-04 | 华东师范大学 | Sunlight sea water assisting battery and preparation method thereof |
| CN111816890B (en) * | 2020-07-17 | 2023-06-09 | 华东师范大学 | Fluid seawater battery and preparation method thereof |
| CN112086289A (en) * | 2020-08-12 | 2020-12-15 | 华东师范大学 | Sunlight-driven electricity-oxygen co-production seawater battery and preparation method thereof |
| CN112795940B (en) * | 2020-12-28 | 2022-06-28 | 北京化工大学 | Method for inhibiting coexistence cation interference by electrochemical lithium extraction of brine |
-
2021
- 2021-05-25 CN CN202110576559.9A patent/CN113293292B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN113293292A (en) | 2021-08-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109637813B (en) | Sunlight sea water assisting battery and preparation method thereof | |
| CN112436118A (en) | VO2(B) Carbon cloth self-supporting material and preparation method and application thereof | |
| CN106856241B (en) | Multiphase composite nano-structure cathode material and preparation method thereof | |
| CN109148877A (en) | Rechargeable zinc-manganese battery and preparation method thereof | |
| CN109616674B (en) | Hybrid battery based on seawater solute and preparation method | |
| CN112582610A (en) | Flexible zinc ion battery based on conductive MOFs (metal-organic frameworks) based nano material | |
| CN113506881B (en) | Carbon felt-based iron/magnesium/zirconium/nitrogen doped carbon catalytic electrode and preparation process and application thereof | |
| CN112086289A (en) | Sunlight-driven electricity-oxygen co-production seawater battery and preparation method thereof | |
| CN108987688B (en) | Carbon-based composite material, preparation method and sodium ion battery | |
| CN108364792B (en) | Preparation method and application of nickel-cobalt-selenium hollow spherical multilevel structure material | |
| CN112582658A (en) | Microbial fuel cell constructed by Fe-MOF-GO film anode | |
| CN115621454A (en) | Cathode material and preparation method and application thereof | |
| CN103515611A (en) | Lithium ion positive electrode material cladded by nanometer alumina membrane and preparation method thereof | |
| CN106981650B (en) | Preparation method of nanoscale elemental bismuth | |
| CN113903910A (en) | Carbon cloth/cobaltosic oxide nanowire composite material and preparation method and application thereof | |
| CN116177556B (en) | Sodium-electricity positive electrode material, precursor thereof, preparation method and application | |
| CN113299873A (en) | Preparation method of composite cathode material of water-based zinc ion battery | |
| CN113293292B (en) | Seawater lithium extraction system based on solar drive and preparation method thereof | |
| CN110600710B (en) | Iron sulfide-carbon composite material and preparation method thereof, lithium ion battery negative electrode material, lithium ion battery negative electrode piece and lithium ion battery | |
| CN110098398B (en) | Preparation method and application of honeycomb-like sulfur-doped carbon material | |
| CN106531966A (en) | Preparation method for nanometer Cu@CuO material and application of nanometer Cu@CuO material to lithium ion battery | |
| CN114369942B (en) | Carbon fiber/titanium dioxide photoelectric composite material and preparation method and application thereof | |
| WO2022188503A1 (en) | Photogenerated anti-corrosion electrode material and preparation method and application thereof | |
| CN114014330A (en) | Energy storage electrode material K3Nb3Si2O13Preparation method and application of | |
| CN110644017B (en) | Dendritic silver-iron oxide composite photoelectrode and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |