CN115029734B - Integrated device for extracting lithium from salt lake and measuring lithium based on garnet type solid electrolyte - Google Patents
Integrated device for extracting lithium from salt lake and measuring lithium based on garnet type solid electrolyte Download PDFInfo
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 217
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 208
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 48
- 239000002223 garnet Substances 0.000 title claims description 14
- 239000012267 brine Substances 0.000 claims abstract description 42
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims abstract description 42
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000000605 extraction Methods 0.000 claims abstract description 39
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 38
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 239000002184 metal Substances 0.000 claims abstract description 24
- 238000007789 sealing Methods 0.000 claims abstract description 21
- 239000000126 substance Substances 0.000 claims abstract description 18
- 229920002545 silicone oil Polymers 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims description 34
- 238000005245 sintering Methods 0.000 claims description 22
- 235000015895 biscuits Nutrition 0.000 claims description 19
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- 238000009736 wetting Methods 0.000 claims description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 238000006138 lithiation reaction Methods 0.000 claims description 10
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 9
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 7
- 239000012528 membrane Substances 0.000 claims description 7
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 claims description 3
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims 1
- 230000008021 deposition Effects 0.000 abstract description 6
- 238000005259 measurement Methods 0.000 abstract description 5
- 238000011897 real-time detection Methods 0.000 abstract 1
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 27
- 238000000498 ball milling Methods 0.000 description 24
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 16
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 12
- 239000000919 ceramic Substances 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 10
- 230000005684 electric field Effects 0.000 description 7
- 239000000395 magnesium oxide Substances 0.000 description 6
- 229920002635 polyurethane Polymers 0.000 description 6
- 239000004814 polyurethane Substances 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 238000011049 filling Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 238000009616 inductively coupled plasma Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 229910001936 tantalum oxide Inorganic materials 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- -1 lithium ions Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 239000005486 organic electrolyte Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 2
- 206010063385 Intellectualisation Diseases 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- GUWKQWHKSFBVAC-UHFFFAOYSA-N [C].[Au] Chemical compound [C].[Au] GUWKQWHKSFBVAC-UHFFFAOYSA-N 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 1
- 238000009837 dry grinding Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910001195 gallium oxide Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- FZRNJOXQNWVMIH-UHFFFAOYSA-N lithium;hydrate Chemical compound [Li].O FZRNJOXQNWVMIH-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/02—Electrolytic production, recovery or refining of metals by electrolysis of solutions of light metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/04—Diaphragms; Spacing elements
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
- G01N27/626—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode using heat to ionise a gas
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical & Material Sciences (AREA)
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- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
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- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Engineering & Computer Science (AREA)
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- Biochemistry (AREA)
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Abstract
The invention relates to a salt lake lithium extraction and lithium measurement integrated device based on garnet-type solid electrolyte, which comprises an electrolytic cell, wherein a cathode region and an anode region are separated by garnet-type solid electrolyte (3), and the cathode region comprises prefabricated metallic lithium (2) and sealing silicone oil (1); the anode region comprises an anode (5) and salt lake brine (4), the anode is an inert electrode or a lithium-containing active electrode, the device also comprises an external power supply (7) and an electrochemical workstation (6) which are connected in parallel between the anode and the cathode, and switches S1 and S2 are respectively arranged on the two parallel circuits. Compared with the prior art, the device can directly deposit the simple substance of the metal lithium, can realize controllable lithium extraction rate by adjusting deposition current, obtain high-purity metal lithium, and can effectively avoid redundant steps of preparing the simple substance of the lithium in the prior art. Meanwhile, the device can also realize real-time detection of the lithium ion content in the salt lake.
Description
Technical Field
The invention belongs to the field of electrochemistry, relates to a new application of solid electrolyte, and in particular relates to a garnet-type solid electrolyte-based integrated device for extracting lithium from salt lakes and measuring lithium.
Background
Lithium is one of the most important resources in modern society, and lithium and its compounds are widely used in many fields including ceramic, glass, pharmaceutical and nuclear industries, and battery fields. In recent years, rapid developments in electric vehicles and portable electronic devices have led to a great expansion of the lithium battery market. However, lithium resources are limited in supply, and the price of lithium resources is also increasing. The lithium ion battery's rate in total global lithium consumption is gradually rising from 31% in 2010 to 43% in 2017, with the expectation that 2025 will reach 65%. By 2050, the total amount of lithium consumed is expected to be more than one third of the total land lithium reserves. Scientists predict that the remaining lithium resource reserves on land will be exhausted in 2080. Wherein, the lithium-rich brine is taken as an important raw material for producing lithium and compounds thereof, and occupies 66 percent of the total amount of the global lithium resource. In china, 86.8% of lithium brine resources are present in various salt lakes, and therefore, discussion of the extraction of lithium from salt lakes is of great importance to the development of the lithium battery industry.
The method has the advantages that the problem of extracting lithium from the salt lake is solved, firstly, the concentration of lithium ions in the salt lake is very low (about 1/2000), secondly, most of salt lake brine in China is magnesium sulfate subtype, the Mg/Li ratio can be up to 500, in addition, the lithium extraction speed in the prior art is relatively slow, the concentrated lithium is still dissolved in water, and further treatment is needed to obtain metallic lithium or solid lithium compounds. Patent application CN201911297510.9 discloses a method for producing high-purity lithium hydroxide and synchronously preparing nano two-dimensional materials from salt lake brine, wherein the two-dimensional materials to be stripped are made into electrodes, and then stripping of the two-dimensional materials and preparation of the high-purity lithium hydroxide are synchronously realized through electrolysis in an organic environment isolated from air. And extracting lithium resources in the salt lake brine by adopting an electrochemical method. Lithium in the solid electrolyte enters the cathode by applying an electric field, and the organic electrolyte is adopted in the cathode region, so that a necessary condition is provided for obtaining a high-purity target product. And lithium ions in the anode enter the solid electrolyte to realize the recovery of lithium resources. The lithium hydroxide obtained by the method has high purity, can be continuously produced, and has the advantages of cleanness, environment friendliness, no pollution, low price, simple process and the like. However, the product obtained by the method is hydroxide, and further smelting and purification are still needed to obtain the metallic lithium; in addition, the cathode side of the method uses a large amount of organic electrolyte, so that the problems of cost increase, environmental pollution and the like are brought; meanwhile, the method does not have a lithium measuring function, cannot detect the concentration of lithium ions in brine in time, and is unfavorable for the intellectualization and continuity of the lithium extraction process.
The device for efficiently detecting the change of the concentration of lithium ions in brine and developing and evaluating the lithium extraction efficiency is lacking in the lithium extraction process, the current lithium extraction technology is possibly too slow, complex and low-efficiency to meet a large amount of requirements on the lithium metal in consideration of the wide application of the lithium metal in the future as the negative electrode materials of lithium sulfur batteries and lithium air batteries, and the defects of time consumption, high equipment requirement, high cost and the like in the lithium concentration detection cannot be simultaneously met, and the requirements of real-time monitoring, high selectivity, high sensitivity, simplicity and convenience in operation and the like can not be simultaneously met.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the integrated device for extracting and measuring lithium from the salt lake based on the garnet type solid electrolyte, which has the advantages of high lithium extraction speed, high purity, high selectivity and high sensitivity and can be used for detecting the concentration of lithium in real time.
The aim of the invention can be achieved by the following technical scheme: the integrated device for extracting lithium from salt lake based on garnet-type solid electrolyte comprises an electrolytic cell with a cathode area and an anode area separated by garnet-type solid electrolyte (LLZO), wherein the cathode area comprises prefabricated metal lithium and sealing silicone oil, and the sealing silicone oil and the solid electrolyte form a closed structure for protecting lithium; the anode region comprises an anode and salt lake brine, the anode is an inert electrode or a lithium-containing active electrode, the device further comprises an external power supply and an electrochemical workstation which are connected between the anode and the cathode in parallel, and two parallel circuits are respectively provided with a switch S1 and a switch S2, and the device is specifically: the negative electrode of the external power supply is connected with the cathode region, the positive electrode is connected with the anode region, the switch S1 is closed, the external power supply is started, and metal lithium is deposited on the cathode side. The device is changed from a lithium extraction mode to a lithium measurement mode by opening the switch S1 and closing the switch S2, and the lithium ion content in brine can be detected through real-time voltage recording of an electrochemical workstation.
The garnet-type solid electrolyte is used as a single ion permeable membrane of lithium ions.
The cathode region is obtained by the following method:
and (3) prefabricating lithium on one side of the garnet-type solid electrolyte by adopting a molten lithium wetting method, cooling to room temperature to obtain the pre-lithiated LLZO, sealing one side of the pre-lithiated LLZO, installing a lead wire and sealing, and realizing the isolation of an electronic path and gas on the cathode side.
Pre-lithiation on the cathode side achieves lithium wetting by melt coating metallic lithium with garnet-type solid electrolyte (LLZO), followed by cooling to room temperature;
the cathode side was sealed with silicone oil, and the metal lithium was protected by forming a closed space with silicone oil and garnet-type solid electrolyte (LLZO).
When the device carries out lithium extraction operation, the switch S1 is closed, and a metal lithium simple substance is obtained at one side of the cathode under the drive of an external power supply.
When extracting lithium element, the anode is an inert electrode, oxidation reaction occurs at one side of the anode, lithium ions pass through garnet type solid electrolyte and are directly deposited at one side of the cathode, and deposited lithium resources are lithium simple substances.
When the device is used for measuring lithium, the switch S1 is opened, the switch S2 is closed, meanwhile, the anode is switched from the inert electrode to the lithium-containing active electrode, and the lithium ion concentration at one side of brine is monitored by measuring the potential.
The garnet-type solid electrolyte can be prepared by adopting a method which is disclosed and reported in the prior art, for example, the garnet-type solid electrolyte is prepared by adopting a method disclosed in patent application CN 11380577A:
the materials are prepared according to the following weight percentages: 45-50% of lanthanum oxide, 15-20% of zirconium oxide, 10-15% of doping raw materials and 15-30% of lithium source; preferably, the lithium source may be in excess of-15% to 0% of its theoretical value, wherein a negative value indicates that the amount of lithium source is below the theoretical value, and when the lithium source is in excess, the remaining components are proportionally adjusted accordingly. Wherein the doping elements include, but are not limited to, ta, ga, ca, and the like.
Preparing a solid electrolyte stable to water: mixing lanthanum oxide, zirconium oxide, a lithium source and doping raw materials, grinding uniformly to obtain a mixture, pre-sintering the mixture, cooling the mixture to room temperature, heating the mixture to 850-1000 ℃ in a sintering system of 5 ℃/min, secondarily grinding the pre-sintered mixture to obtain mother powder, tabletting the mother powder to obtain a biscuit, secondarily sintering the biscuit, heating the sintering system to 1250-1350 ℃ in a sintering system of 5-10 ℃/min, and preserving heat for 10-30min to obtain the garnet type solid electrolyte. The above grinding methods all adopt dry grinding.
Subsequently, the pre-lithiation was achieved by pre-wetting metallic lithium on the LLZO side using a molten lithium wetting method, followed by cooling to room temperature. And a lead is arranged on one side of the cathode, and silicone oil is used for sealing, so that the sealing of the cathode side and the protection of metallic lithium are realized. Filling lithium-containing brine at one side of an anode, using an inert electrode as the anode, closing a switch S1, under the drive of an external electric field, obtaining a metal lithium simple substance at one side of a cathode, opening the switch S1, closing a switch S2, switching the inert electrode into a lithium-containing active electrode, measuring the potential by using an electrochemical workstation, and detecting the lithium ion concentration at one side of the brine.
Preferably, during the pre-lithiation of the cathode side, metallic lithium can be melt coated on one side of the LLZO with a melting temperature in the range of 200-500 ℃ and then cooled to room temperature. Wherein, graphite, aluminum, silver and other materials with the mass ratio of 10-50% can be added into the metal lithium to improve the wettability of the molten lithium.
Preferably, in the lithium extraction mode, an inert electrode is used as the electrode on one side of the anode, wherein the inert electrode comprises a platinum electrode or a carbon electrode and the like.
Preferably, in the lithium measurement mode, the inert electrode is switched to a lithium-containing active electrode, wherein the lithium-containing active electrode comprises a lithium iron phosphate electrode, a lithium cobalt oxide electrode, a lithium manganate electrode or the like.
The invention relates to a salt lake brine lithium extraction and measurement method based on garnet solid electrolyte, which comprises the following steps: the invention separates the anode region and the cathode region by using the film with high selective permeability to lithium ions, uses LLZO with high stability to lithium and water, and realizes the structure that salt lake brine in the anode region is used as electrolyte and lithium is directly deposited in the cathode region. 1) When the lithium extraction mode is used, cations including lithium ions, sodium ions, magnesium ions and the like in brine in an anode region directionally move to the cathode region under the action of external current, only lithium ions can pass through and diffuse to a negative electrode of the cathode region under the action of selective permeability of a garnet type solid electrolyte membrane separating the cathode region from the anode region, other ions are blocked in the anode region, the lithium ions obtain electrons at one side of the cathode region and are reduced to form metallic lithium, and in the anode region, hydroxide ions are discharged on the surface of the electrode to generate oxygen evolution reaction. 2) When the lithium measuring mode is used, the electrolytic cell mode is changed into the primary cell mode, one side of the pre-lithiation is used as the negative electrode of the primary cell, and the counter electrode is switched into the lithium iron phosphate or other lithium-containing positive electrode.
Compared with the prior art, the invention has the following advantages:
1. lithium extraction-electrochemical efficient extraction of metallic lithium, using lithium-water stable LLZO as the permselective membrane for lithium ions. Because the contact interface of the solid electrolyte and the metal lithium has the characteristics of chemical stability and electrochemical stability, the metal lithium can be directly extracted from the salt lake brine in a manner of over-electrolysis.
2. Lithium measurement-the device can be used as a solid lithium concentration detector: the developed LLZO stable to water is used as a lithium ion selective permeability membrane, and metal lithium is used as a reference electrode, so that the concentration of lithium ions on the other side of the membrane can be converted into voltage signals to be output, the sensor has several times of resolution and a wide working concentration range, and the concentration of lithium ions in salt lake brine can be dynamically monitored.
3. According to the invention, the stability of the garnet type solid electrolyte is improved by using a dry method, a single ion permeable membrane stable to lithium and brine is obtained, metallic lithium can be directly deposited on one side of a cathode, the subsequent metal smelting process flow is avoided, the lithium extraction speed is in direct proportion to the current deposition size, and the lithium extraction speed is controllable; because garnet-type solid electrolyte can only realize the permeation of lithium ions, high-purity metallic lithium can be obtained; the device can also detect the change of the concentration of lithium ions in brine, and realizes the integration of lithium extraction and lithium measurement. The device can realize the functions of extracting metal lithium from salt lake brine and detecting lithium concentration.
Drawings
FIG. 1 is a schematic diagram of a garnet-based solid electrolyte salt lake lithium extraction and measurement device according to the invention;
FIG. 2 is a scanning electron micrograph of a cross section of a lithium stabilized garnet-type solid electrolyte of the present invention;
FIG. 3 is a scanning electron micrograph of lithium metal deposited on the surface of a garnet-type solid electrolyte;
FIG. 4 is a graph of XPS data for lithium metal deposited on the cathode side;
fig. 5 is a graph of the voltage profile of deposited lithium at a current density of 50 ua.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings and examples. It should be noted that variations and modifications could be made by those skilled in the art without departing from the spirit of the invention. These are all within the scope of the present invention.
Example 1
As shown in fig. 1, the integrated device for extracting lithium and measuring lithium based on garnet type solid electrolyte salt lake comprises an electrolytic cell with a cathode area and an anode area separated by a garnet type solid electrolyte 3, wherein the cathode area comprises prefabricated metal lithium 2 and sealing silicone oil 1; the anode region comprises an anode 5 and salt lake brine 4, the anode is an inert electrode or a lithium-containing active electrode, the device also comprises an external power supply 7 and an electrochemical workstation 6 which are connected in parallel between the anode and the cathode, and switches S1 and S2 are respectively arranged on the two parallel circuits. Wherein the negative electrode of the external power supply 7 is connected with the cathode region, the positive electrode is connected with the anode region, a switch S1 is arranged on a circuit formed by the external power supply 7 and the electrolytic cell, and a switch S2 is arranged on a circuit formed by the electrochemical workstation 6 and the electrolytic cell.
Wherein the garnet-type solid electrolyte 3 is prepared by the following method:
lithium hydroxide, lanthanum oxide, zirconium oxide and tantalum oxide were weighed in the order of 15%,50%,20% and 15% by mass, respectively, and dry ball-milled for 2 hours at 175r/min using zirconia balls and a polyurethane ball-milling pot, followed by separation of balls and powder using a sieve. Transferring the powder into an alumina crucible for presintering, wherein the sintering system is that the temperature is raised to 950 ℃ at 5 ℃ per minute, the temperature is kept for 3 hours, then the powder is cooled to room temperature along with a furnace, secondary dry ball milling is carried out at the rotating speed of 175r/min, a zirconia ball and polyurethane ball milling tank is used, the ball milling time is 2 hours, and after ball milling, the ball material is separated to obtain the mother powder. 1g of mother powder is weighed, and the pressure is maintained for 1min under 500MPa to obtain a biscuit with the diameter of 12mm. Transferring the ceramic wafer biscuit into a magnesia crucible with the inner diameter of 13mm, carrying out secondary sintering without adding any buried powder, heating the ceramic wafer biscuit to 1320 ℃ at a sintering system of 5 ℃/min, preserving heat for 10min, and cooling along with a furnace to obtain LLZO.
Subsequently, the pre-lithiation was achieved by heating lithium to 350 ℃ using a molten lithium wetting method, and adding 10wt% graphite, pre-wetting metallic lithium on the LLZO side, followed by cooling to room temperature. And a lead is arranged on one side of the cathode, and silicone oil is used for sealing, so that the sealing of the cathode side and the protection of metallic lithium are realized. When the lithium extraction mode is used, lithium-containing brine is filled at one side of the anode, an inert platinum electrode is used as the anode, the switch S1 is closed, a metal lithium simple substance can be obtained at one side of the cathode under the drive of an external electric field 7, the lithium extraction speed is in direct proportion to the current, and the lithium extraction speed is controllable. In this example, when the current density was 0.386mA/cm 2 At the time of extraction, the extraction rate of the metallic lithium was 100. Mu.g/cm 2 The purity of the simple substance lithium is 98.2%, and the balance is impurities of the purified metallic lithium which react with the outside air.
When the lithium measuring mode is used, the switch S1 is opened, the switch S2 is closed, the inert electrode is switched into the lithium cobalt oxide electrode, and the electrochemical workstation is used for measuring the potential, so that the lithium ion concentration at one side of brine can be detected. Lithium ion concentration was 97ppm and electrochemical workstation potential was 3.825V as measured using inductively coupled plasma analysis (ICP-MS).
Example 2
Lithium hydroxide, lanthanum oxide, zirconium oxide and gallium oxide were weighed in the order of mass fraction of 30%,45%,15% and 10%, respectively, and ball-milled dry for 0.5 hours using zirconia balls and polyurethane ball-milling pot at a rotational speed of 300r/min, followed by separation of balls and powder using a sieve. Transferring the powder into an alumina crucible for presintering, wherein the sintering system is that the temperature is raised to 900 ℃ at 5 ℃ per minute, the temperature is kept for 3 hours, then the powder is cooled to room temperature along with a furnace, secondary dry ball milling is carried out at the rotating speed of 300r/min, a zirconia ball and polyurethane ball milling tank is used, the ball milling time is 0.5 hour, and the ball material is separated after ball milling, so that the mother powder is obtained. Weighing 0.5g of mother powder, and maintaining the pressure at 100MPa for 1min to obtain a biscuit with the diameter of 12mm. Transferring the ceramic wafer biscuit into a magnesia crucible with the inner diameter of 14mm, carrying out secondary sintering without adding any buried powder, heating the ceramic wafer biscuit to 1320 ℃ at a sintering system of 5 ℃/min, preserving heat for 30min, and cooling along with a furnace to obtain LLZO.
Subsequently, the lithium was heated to 200 degrees by a molten lithium wetting method, and 25% aluminum was added, and the metallic lithium was pre-wetted on the LLZO side, followed by cooling to room temperature to achieve pre-lithiation. And a lead is arranged on one side of the cathode, and silicone oil is used for sealing, so that the sealing of the cathode side and the protection of metallic lithium are realized. Filling lithium-containing brine at one side of an anode, using an inert carbon gold electrode as the anode, closing a switch S1, obtaining a metal lithium simple substance at one side of a cathode under the drive of an external electric field, opening the switch S1, closing a switch S2, switching the inert electrode into a lithium iron phosphate electrode, measuring the potential by using an electrochemical workstation, and detecting the lithium ion concentration at one side of the brine. Fig. 2 is a scanning electron micrograph of a cross section of a garnet-type solid electrolyte stabilized against lithium according to the present embodiment, and it can be seen from the figure that the LLZO cross section exhibits a mixed crystal-penetrating and crystal-along fracture mode, and has high compactness and almost no pores, which can ensure that the LLZO has a sufficient isolation effect against brine. The lithium extraction speed of the device is in direct proportion to the current, and the lithium extraction speed is controllable; in this example, when the current density is 0.193mA cm -2 The extraction efficiency of the metallic lithium was 50. Mu.g cm -2 The purity of the simple substance lithium is 98.3 percent, and the rest is impurities of the purified metal lithium which react with the outside air.
When the lithium measuring mode is used, the switch S1 is opened, the switch S2 is closed, the inert electrode is switched into the lithium iron phosphate electrode, and the electrochemical workstation is used for measuring the potential, so that the lithium ion concentration at one side of brine can be detected. Lithium ion concentration was measured to be 152ppm using inductively coupled plasma analysis (ICP-MS) and electrochemical workstation potential was 3.525V.
Example 3
Lithium hydroxide, lanthanum oxide, zirconium oxide and calcium oxide were weighed in the mass fractions of 15%,50%,20% and 15%, respectively, and dry ball milled for 2.5 hours using tungsten carbide balls and nylon ball milling pot at a rotational speed of 250r/min, followed by separation of balls and powder using a sieve. Transferring the powder into an alumina crucible for presintering, wherein the sintering system is that the temperature is raised to 850 ℃ at 5 ℃ per minute, the temperature is kept for 6 hours, then the powder is cooled to room temperature along with a furnace, secondary dry ball milling is carried out at the rotating speed of 175r/min, a tungsten carbide ball and nylon ball milling tank is used, the ball milling time is 2 hours, and after ball milling, the ball material is separated to obtain the mother powder. 2g of mother powder is weighed, and the pressure is maintained for 1min under the pressure of 1000MPa to obtain a biscuit with the diameter of 12mm. Transferring the ceramic wafer biscuit into a magnesia crucible with the inner diameter of 15mm, carrying out secondary sintering without adding any buried powder, heating the ceramic wafer biscuit to 1320 ℃ at a sintering system of 10 ℃/min, preserving heat for 10min, and cooling along with a furnace to obtain LLZO.
Subsequently, the lithium was heated to 500 degrees by a molten lithium wetting method, and 45% silver powder was added, and the metallic lithium was pre-wetted on the LLZO side, followed by cooling to room temperature to achieve pre-lithiation. And a lead is arranged on one side of the cathode, and silicone oil is used for sealing, so that the sealing of the cathode side and the protection of metallic lithium are realized. Filling lithium-containing brine at one side of an anode, using an inert platinum electrode as the anode, closing a switch S1, obtaining a metal lithium simple substance at one side of a cathode under the drive of an external electric field, opening the switch S1, closing a switch S2, switching the inert electrode into a lithium manganate electrode, measuring the potential by using an electrochemical workstation, and detecting the lithium ion concentration at one side of the brine. Fig. 3 is a scanning electron micrograph of lithium metal deposited on the surface of a garnet-type solid electrolyte in a lithium extraction mode, and it can be seen from the figure that lithium extracted from brine is precipitated in the form of lithium metal, and the lithium metal layer is dense and well contacted with LLZO, so that the device can directly extract lithium metal from brine. The lithium extraction speed of the device is in direct proportion to the current deposition size, and the lithium extraction speed is controllable; in this example, when the current density was 0.212mA/cm 2 The extraction efficiency of the metal lithium was 55. Mu.g/cm 2 The purity of the simple substance lithium is 97.3%, and the rest is impurities of the purified metallic lithium which react with the outside air.
When the lithium measuring mode is used, the switch S1 is opened, the switch S2 is closed, the inert electrode is switched into the lithium manganate electrode, and the electrochemical workstation is used for measuring the potential, so that the lithium ion concentration at one side of brine can be detected. The lithium ion concentration was measured to be 252ppm using inductively coupled plasma analysis (ICP-MS) and the electrochemical workstation potential was 3.846V.
Example 4
Lithium hydroxide, lanthanum oxide, zirconium oxide and tantalum oxide were weighed in the order of 15%,50%,20% and 15% by mass respectively, dry ball milling was performed for 2.5 hours using zirconia balls and a polyurethane ball milling tank at a rotation speed of 250r/min, followed by separation of balls and powder using a sieve. Transferring the powder into a platinum crucible for presintering, wherein the sintering system is that the temperature is raised to 850 ℃ at 5 ℃ per minute, the temperature is kept for 6 hours, then the powder is cooled to room temperature along with a furnace, secondary dry ball milling is carried out at the rotating speed of 175r/min, a zirconia ball and polyurethane ball milling tank is used, the ball milling time is 3 hours, and after ball milling, the ball material is separated to obtain the mother powder. 2g of mother powder is weighed, and the pressure is maintained for 10s under the pressure of 1000MPa to obtain a biscuit with the diameter of 12mm. Transferring the ceramic wafer biscuit into a magnesia crucible with the inner diameter of 15mm, carrying out secondary sintering without adding any buried powder, heating the ceramic wafer biscuit to 1320 ℃ at a sintering system of 10 ℃/min, preserving heat for 10min, and cooling along with a furnace to obtain LLZO.
Subsequently, the pre-lithiation was achieved by heating the lithium to 450 degrees by molten lithium wetting, adding 50% graphite, pre-wetting the metallic lithium on the LLZO side, and then cooling to room temperature. And a lead is arranged on one side of the cathode, and silicone oil is used for sealing, so that the sealing of the cathode side and the protection of metallic lithium are realized. Filling lithium-containing brine at one side of an anode, using an inert platinum electrode as the anode, closing a switch S1, obtaining a metal lithium simple substance at one side of a cathode under the drive of an external electric field, opening the switch S1, closing a switch S2, switching the inert electrode into a lithium manganate electrode, measuring the potential by using an electrochemical workstation, and detecting the lithium ion concentration at one side of the brine. FIG. 4 is a XPS data spectrum of lithium metal deposited on the cathode side in the lithium extraction mode, from which it can be seen that the precipitated lithium metal is elemental lithium, and thus the device can extract lithium metal from salt lake brine, instead of lithium hydroxide or carbonAnd (3) lithium acid. The lithium extraction speed of the device is in direct proportion to the current deposition size, and the lithium extraction speed is controllable; in this example, when the current density was 0.4mA/cm 2 The extraction efficiency of the metallic lithium was 103.6. Mu.g/cm 2 The purity of the simple substance lithium is 98.3 percent, and the rest is impurities of the purified metal lithium which react with the outside air.
When the lithium measuring mode is used, the switch S1 is opened, the switch S2 is closed, the inert electrode is switched into the lithium iron phosphate electrode, and the electrochemical workstation is used for measuring the potential, so that the lithium ion concentration at one side of brine can be detected. Lithium ion concentration was measured to be 174ppm using inductively coupled plasma analysis (ICP-MS) and electrochemical workstation potential was 3.535V.
Example 5
Lithium hydroxide, lanthanum oxide, zirconium oxide and tantalum oxide were weighed in the order of 15%,50%,20% and 15% by mass, respectively, and dry ball milled for 5 hours using agate balls and a zirconia pot at a rotational speed of 100r/min, followed by separation of balls and powder using a sieve. Transferring the powder into a magnesia crucible for presintering, wherein the sintering system is that the temperature is raised to 850 ℃ at 5 ℃ per minute, the temperature is kept for 6 hours, then the powder is cooled to room temperature along with a furnace, secondary dry ball milling is carried out at the rotating speed of 100r/min, agate balls and a zirconia pot are used, the ball milling time is 5 hours, and after ball milling, ball materials are separated to obtain mother powder. 2g of mother powder is weighed, and the pressure is maintained for 1min under the pressure of 1000MPa to obtain a biscuit with the diameter of 12mm. Transferring the ceramic wafer biscuit into a magnesia crucible with the inner diameter of 15mm, carrying out secondary sintering without adding any buried powder, heating the ceramic wafer biscuit to 1320 ℃ at a sintering system of 10 ℃/min, preserving heat for 10min, and cooling along with a furnace to obtain LLZO.
Subsequently, the pre-lithiation was achieved by heating the lithium to 350 degrees by molten lithium wetting, adding 25% graphite, pre-wetting the metallic lithium on the LLZO side, and then cooling to room temperature. And a lead is arranged on one side of the cathode, and silicone oil is used for sealing, so that the sealing of the cathode side and the protection of metallic lithium are realized. Filling lithium-containing brine at one side of the anode, using an inert carbon electrode as the anode, closing the switch S1, obtaining a metal lithium simple substance at one side of the cathode under the drive of an external electric field, opening the switch S1, closing the switch S2,the inert electrode is switched into a lithium manganate electrode, and the electrochemical workstation is used for measuring the potential, so that the lithium ion concentration at one side of brine can be detected. Fig. 5 is a graph of the voltage profile of lithium deposition at a current density of 50 ua in this example. As can be seen, the device in this example deposited lithium at a current density of 5 ua at an overpotential of approximately 4.5V. The lithium extraction speed of the device is in direct proportion to the current deposition size, and the lithium extraction speed is controllable; in this example, when the current density was 0.3mA/cm 2 The extraction efficiency of the metallic lithium was 77.7. Mu.g/cm 2 The purity of the elemental lithium was 96.7%, and the balance was impurities of the purified metallic lithium reacted with the outside air.
When the lithium measuring mode is used, the switch S1 is opened, the switch S2 is closed, the inert electrode is switched into the lithium iron phosphate electrode, and the electrochemical workstation is used for measuring the potential, so that the lithium ion concentration at one side of brine can be detected. The lithium ion concentration was 243ppm and the electrochemical workstation potential was 3.665V using inductively coupled plasma analysis (ICP-MS).
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (6)
1. The integrated device for extracting lithium from salt lakes and measuring lithium based on garnet-type solid electrolyte is characterized by comprising an electrolytic cell with a cathode area and an anode area separated by garnet-type solid electrolyte (3), wherein the cathode area comprises prefabricated metallic lithium (2) and sealing silicone oil (1); the anode region comprises an anode (5) and salt lake brine (4), the anode is an inert electrode or a lithium-containing active electrode, the device also comprises an external power supply (7) and an electrochemical workstation (6) which are connected in parallel between the anode and the cathode, and switches S1 and S2 are respectively arranged on the two parallel circuits; the cathode region is obtained by the following method:
prefabricating lithium on one side of a garnet type solid electrolyte (3) by adopting a molten lithium wetting method, cooling to room temperature to obtain a pre-lithiated LLZO, sealing one side of the pre-lithiated LLZO, installing a wire and sealing, and isolating an electronic passage on the cathode side from gas;
when the device carries out lithium extraction operation, a switch S1 is closed, and a metal lithium simple substance is obtained at one side of a cathode under the drive of an external power supply (7); when extracting lithium elements, the anode (5) is an inert electrode, oxidation reaction occurs at one side of the anode, lithium ions are directly deposited at one side of the cathode through the garnet type solid electrolyte (3), and deposited lithium resources are lithium simple substances;
when the device is used for measuring lithium, the switch S1 is opened, the switch S2 is closed, the anode (5) is switched from the inert electrode to the lithium-containing active electrode, and the lithium ion concentration at one side of brine is monitored by measuring the potential.
2. The integrated device for extracting and measuring lithium from salt lakes based on garnet-type solid electrolyte according to claim 1, wherein the garnet-type solid electrolyte (3) is used as a single ion permeable membrane for lithium ions.
3. The integrated device for extracting and measuring lithium from salt lakes based on garnet-type solid electrolytes according to claim 1, characterized in that the pre-lithiation on the cathode side achieves lithium wetting by means of melt-coating the garnet-type solid electrolyte (3) with metallic lithium, followed by cooling to room temperature;
the cathode side is sealed by silicone oil, and a closed space is formed by the silicone oil and the garnet-type solid electrolyte (3) to protect the metal lithium.
4. The integrated device for extracting and measuring lithium from salt lakes based on garnet-type solid electrolyte according to claim 1, characterized in that the garnet-type solid electrolyte (3) is prepared by the following method:
the materials are prepared according to the following weight percentages: 45-50% of lanthanum oxide, 15-20% of zirconium oxide, 10-15% of doping raw materials and 15-30% of lithium source;
mixing lanthanum oxide, zirconium oxide, a lithium source and doping raw materials, grinding uniformly to obtain a mixture, pre-sintering the mixture, cooling to room temperature, grinding the pre-sintered mixture for the second time to obtain mother powder, tabletting the mother powder to obtain a biscuit, and sintering the biscuit for the second time to obtain the garnet type solid electrolyte.
5. The integrated device for extracting and measuring lithium from a salt lake based on a garnet-type solid electrolyte according to claim 4, wherein the doping raw material is a substance containing Ta, ga, or Ca element.
6. The integrated device for extracting and measuring lithium from salt lakes based on garnet-type solid electrolyte according to claim 1, wherein the inert electrode comprises a platinum electrode or a carbon electrode; the lithium-containing active electrode includes a lithium iron phosphate electrode, a lithium cobalt oxide electrode, or a lithium manganate electrode.
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| CN109609977A (en) * | 2019-02-20 | 2019-04-12 | 长江师范学院 | The electrode structure and its manufacturing method of extraction lithium and application |
| CN109778218A (en) * | 2019-02-01 | 2019-05-21 | 南京大学 | A kind of electrochemistry hydrogen manufacturing and the device and method for proposing lithium coproduction |
| CN110923739A (en) * | 2019-12-17 | 2020-03-27 | 中南大学 | Method for stripping two-dimensional material and synchronously producing high-purity lithium hydroxide by using salt lake brine |
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| CN109778218A (en) * | 2019-02-01 | 2019-05-21 | 南京大学 | A kind of electrochemistry hydrogen manufacturing and the device and method for proposing lithium coproduction |
| CN109609977A (en) * | 2019-02-20 | 2019-04-12 | 长江师范学院 | The electrode structure and its manufacturing method of extraction lithium and application |
| CN110923739A (en) * | 2019-12-17 | 2020-03-27 | 中南大学 | Method for stripping two-dimensional material and synchronously producing high-purity lithium hydroxide by using salt lake brine |
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