CN117098861A - Electrode and preparation method thereof, salt lake lithium extraction device and salt lake lithium extraction method - Google Patents
Electrode and preparation method thereof, salt lake lithium extraction device and salt lake lithium extraction method Download PDFInfo
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- CN117098861A CN117098861A CN202380009564.9A CN202380009564A CN117098861A CN 117098861 A CN117098861 A CN 117098861A CN 202380009564 A CN202380009564 A CN 202380009564A CN 117098861 A CN117098861 A CN 117098861A
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 126
- 238000000605 extraction Methods 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229920000359 diblock copolymer Polymers 0.000 claims abstract description 54
- 239000011248 coating agent Substances 0.000 claims abstract description 37
- 238000000576 coating method Methods 0.000 claims abstract description 37
- 239000011247 coating layer Substances 0.000 claims abstract description 29
- 239000011159 matrix material Substances 0.000 claims abstract description 27
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims description 40
- 238000001035 drying Methods 0.000 claims description 34
- 239000000243 solution Substances 0.000 claims description 28
- 229920001577 copolymer Polymers 0.000 claims description 23
- 239000006185 dispersion Substances 0.000 claims description 23
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 18
- -1 polyoxyethylene Polymers 0.000 claims description 18
- 239000002002 slurry Substances 0.000 claims description 18
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 17
- 239000011230 binding agent Substances 0.000 claims description 17
- 239000012267 brine Substances 0.000 claims description 17
- 239000003792 electrolyte Substances 0.000 claims description 17
- 238000002791 soaking Methods 0.000 claims description 17
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 17
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 14
- 239000002033 PVDF binder Substances 0.000 claims description 13
- 239000004793 Polystyrene Substances 0.000 claims description 13
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 13
- 229920002223 polystyrene Polymers 0.000 claims description 12
- 239000003011 anion exchange membrane Substances 0.000 claims description 11
- 239000006258 conductive agent Substances 0.000 claims description 11
- 239000007774 positive electrode material Substances 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- 239000011780 sodium chloride Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000004743 Polypropylene Substances 0.000 claims description 8
- 239000006230 acetylene black Substances 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 239000011888 foil Substances 0.000 claims description 8
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 8
- 229920001155 polypropylene Polymers 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 239000001103 potassium chloride Substances 0.000 claims description 7
- 235000011164 potassium chloride Nutrition 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 229920001451 polypropylene glycol Polymers 0.000 claims description 6
- 239000004952 Polyamide Substances 0.000 claims description 5
- 229920002647 polyamide Polymers 0.000 claims description 5
- 239000005062 Polybutadiene Substances 0.000 claims description 4
- 229920002125 Sokalan® Polymers 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 229920002857 polybutadiene Polymers 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- 230000002950 deficient Effects 0.000 claims description 2
- 229910003002 lithium salt Inorganic materials 0.000 claims 2
- 159000000002 lithium salts Chemical class 0.000 claims 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 12
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 12
- 150000003839 salts Chemical class 0.000 abstract description 8
- 238000005868 electrolysis reaction Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000004220 aggregation Methods 0.000 description 6
- 230000002776 aggregation Effects 0.000 description 6
- 229910010710 LiFePO Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000010410 layer Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 3
- 239000005543 nano-size silicon particle Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229920000361 Poly(styrene)-block-poly(ethylene glycol) Polymers 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000007614 solvation Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 1
- 229910003251 Na K Inorganic materials 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000012612 commercial material Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The disclosure belongs to the technical field of lithium extraction in salt lakes, and particularly relates to an electrode and a preparation method thereof, a lithium extraction device in salt lakes and a lithium extraction method in salt lakes. The surface of the electrode matrix is modified by the amphiphilic diblock copolymer to form a diblock copolymer coating layer, and the amphiphilic diblock copolymer simultaneously contains a hydrophilic segment and a hydrophobic segment, so that the hydrophobic segment is easy to adsorb on the surface of the electrode matrix to form a stable coating; the hydrophilic section can not only increase the hydrophilicity of the electrode, but also complex lithium ions on the surface of the electrode, thereby improving the lithium extraction efficiency.
Description
Technical Field
The disclosure belongs to the technical field of lithium extraction in salt lakes, and particularly relates to an electrode and a preparation method thereof, a lithium extraction device in salt lakes and a lithium extraction method in salt lakes.
Background
In recent years, with the rapid development of new energy automobiles and chemical energy storage, the global demand for lithium resources continues to increase. Lithium resources in nature are mainly present in salt lake brine, seawater and ores, wherein the salt lake lithium resources account for about 70%. Therefore, the lithium extraction technology of salt lakes is more and more paid attention to. In recent years, researchers have widely explored and studied new lithium extraction processes, and the developed electrochemical lithium extraction technology has good use value and application prospect.
The principle of electrochemical lithium extraction is that lithium ions are extracted from a working electrode by charging the working electrode in an electrolyte solution to form a lithium-removing electrode, a lithium-rich electrode and the lithium-removing electrode are respectively used as an anode and a cathode, the anode is added with the electrolyte solution without impurities, and the cathode is added with salt lake brine; under the drive of external potential, li in brine is selectively inserted into the lithium-removing electrode, and simultaneously the lithium-rich electrode releases Li into the solution to form the lithium-removing electrode, and selective enrichment of lithium is realized through electrode exchange and cyclic operation.
Although the electrochemical lithium extraction has good application prospect in the lithium extraction of salt lakes, the electrochemical deintercalation method has the problem of lower lithium extraction efficiency due to the fact that the impurities in brine are more and the concentration of lithium is low. And the binder PVDF used in the preparation process of the electrode slurry has extremely strong hydrophobicity, so that the wettability of brine can be reduced, the mass transfer of a solution is hindered, and the lithium extraction efficiency can be influenced.
In view of this, the present disclosure is presented.
Disclosure of Invention
The purpose of the present disclosure includes providing an electrode and a preparation method thereof, a salt lake lithium extraction device and a salt lake lithium extraction method, aiming at significantly improving the lithium extraction efficiency of salt lake lithium extraction.
In order to achieve the above object of the present disclosure, the following technical solutions may be adopted:
in a first aspect, the present disclosure provides an electrode comprising an electrode substrate and an amphiphilic diblock copolymer coating coated on the surface of the electrode substrate, the electrode substrate comprising a current collector and a positive active coating attached to the current collector;
wherein the amphiphilic diblock copolymer coating layer comprises a hydrophilic segment and a hydrophobic segment.
In some embodiments of the present disclosure, the hydrophilic segment is selected from at least one of polyoxyethylene, polyethylene glycol, and polyacrylic acid.
In some embodiments of the present disclosure, the hydrophobic segment is selected from at least one of polystyrene, polybutadiene, and polyoxypropylene.
In some embodiments of the present disclosure, the hydrophilic segment is polyoxyethylene and the hydrophobic segment is polystyrene.
In some embodiments of the present disclosure, the amphiphilic diblock copolymer coating is present in the electrode at a mass ratio of from 0.1% to 5%.
In some embodiments of the present disclosure, the amphiphilic diblock copolymer employed to form the amphiphilic diblock copolymer coating has a molecular weight of 5000-50000Da and a mass ratio of hydrophilic segments to hydrophobic segments of 1 (1.6-4).
In some embodiments of the present disclosure, a positive electrode active material is contained in the positive electrode active coating layer, and the positive electrode active material is selected from at least one of lithium iron phosphate, lithium manganate, and lithium nickel cobalt manganate.
In some embodiments of the present disclosure, the positive electrode active coating further comprises a conductive agent and a binder, wherein the mass ratio of the positive electrode active material, the conductive agent and the binder is 100 (10-20): 10-15.
In some embodiments of the present disclosure, the current collector is selected from at least one of aluminum foil, titanium mesh, and carbon fiber cloth.
In some embodiments of the present disclosure, the conductive agent is selected from at least one of acetylene black and conductive carbon black.
In some embodiments of the present disclosure, the binder is selected from at least one of polyvinylidene fluoride and polypropylene.
In some embodiments of the present disclosure, the current collector has a thickness of 10 μm to 15 μm and the positive electrode active coating has a thickness of 100 μm to 300 μm.
In a second aspect, the present disclosure provides a method for preparing an electrode, including: an amphiphilic diblock copolymer coating is formed on the electrode substrate.
In some embodiments of the present disclosure, the method of making comprises: the amphiphilic diblock copolymer is dispersed to obtain a copolymer dispersion, and an amphiphilic diblock copolymer coating layer is formed on the surface of the electrode base by using the copolymer dispersion.
In some embodiments of the present disclosure, the process of forming the amphiphilic diblock copolymer coating comprises: and soaking the electrode matrix in the copolymer dispersion liquid, and taking out and drying after the soaking is finished.
In some embodiments of the present disclosure, the mass fraction of the amphiphilic diblock copolymer in the copolymer dispersion is from 2% to 5%.
In some embodiments of the present disclosure, the soaking time is 4h-12h and the soaking temperature is 15-30 ℃.
In some embodiments of the present disclosure, the drying temperature is 60 ℃ to 80 ℃ and the drying time is 4h to 6h.
In some embodiments of the present disclosure, the electrode matrix is prepared by a process comprising: coating the positive electrode active slurry on a current collector, and drying to form a positive electrode active coating;
the preparation process of the positive electrode active slurry comprises the following steps: the positive electrode active material, the conductive agent, and the binder are mixed and homogenized using a dispersant.
In some embodiments of the present disclosure, the drying temperature is controlled to be 100-120 ℃ and the drying time is controlled to be 10-20 h during the formation of the positive electrode active coating.
In a third aspect, the present disclosure provides a solution further comprising a salt lake lithium extraction device comprising a lithium-rich electrode and a lithium-poor electrode;
the lithium-rich state electrode is the electrode in any embodiment or the electrode prepared by the preparation method in any embodiment.
In some embodiments of the present disclosure, the lithium-deficient electrode is prepared by delithiating the lithium-rich electrode of the above embodiments.
In some embodiments of the present disclosure, an electrolysis device is further included, wherein an anion exchange membrane is disposed to divide the electrolysis device into an anode chamber and a cathode chamber.
In some embodiments of the present disclosure, the anion exchange membrane is made of at least one material selected from the group consisting of polystyrene, polypropylene, and polyamide.
In a fourth aspect, the present disclosure provides a method for extracting lithium from a salt lake, including: and extracting lithium by using the salt lake lithium extraction device in any embodiment.
In some embodiments of the present disclosure, there is provided: and respectively placing the lithium-rich electrode and the lithium-poor electrode in an anode chamber and a cathode chamber, injecting brine into the cathode chamber, injecting electrolyte into the anode chamber, and then electrifying.
In some embodiments of the present disclosure, the electrolyte injected into the anode chamber is selected from at least one of a potassium chloride solution and a sodium chloride solution, and the concentration of the electrolyte is 0.05mol/L to 0.10mol/L.
In some embodiments of the present disclosure, the energizing voltage is 0.3V-1.2V.
Modifying the surface of the electrode matrix by using an amphiphilic diblock copolymer to form a diblock copolymer coating, wherein the amphiphilic diblock copolymer contains a hydrophilic segment and a hydrophobic segment, and the hydrophobic segment is easy to adsorb on the surface of the electrode matrix to form a stable coating; the function of the hydrophilic segment is mainly expressed in two aspects: on one hand, the hydrophilic section can increase the wettability of brine to the electrode, and the hydrophilic section and the solution can form a stable solvation layer so as to further obstruct the aggregation of colloid and particles in the solution and prevent the aggregation from entering the electrode to cause the blockage of a mass transfer channel; on the other hand, the hydrophilic section also has excellent capability of complexing lithium ions, and in the positive ion aggregation layer on the surface of the electrode, the lithium ions can be specifically complexed, so that the lithium ion current distribution on the interface is more uniform, the lithium ions are promoted to enter the interior of the electrode, and the lithium extraction efficiency is improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present disclosure, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present disclosure and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person of ordinary skill in the art.
FIG. 1 is a process diagram of the preparation of an electrode provided by the present disclosure;
fig. 2 is a diagram of an overall manufacturing process of an electrode for extracting lithium from a salt lake provided by the present disclosure;
fig. 3 is a graph showing the time-dependent trend of the anode lithium concentration.
Detailed Description
Embodiments of the present disclosure will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are merely illustrative of the present disclosure and should not be construed as limiting the scope of the present disclosure. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The endpoints of the ranges and any values disclosed in this disclosure are not limited to the precise range or value, and such range or value should be understood to encompass values approaching those range or value. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The solution provided in the embodiments of the present disclosure includes a method for preparing an electrode, referring to fig. 1, an amphiphilic diblock copolymer coating layer is formed on an electrode substrate, and the electrode substrate is modified by using the amphiphilic diblock copolymer.
It is noted that, because the amphiphilic diblock copolymer contains both hydrophilic segments and hydrophobic segments, the hydrophobic segments are easily adsorbed on the surface of the electrode matrix to form a stable coating; the function of the hydrophilic segment is mainly expressed in two aspects: on one hand, the hydrophilic section can increase the wettability of brine to the electrode, and the hydrophilic section and the solution can form a stable solvation layer so as to further obstruct the aggregation of colloid and particles in the solution and prevent the aggregation from entering the electrode to cause the blockage of a mass transfer channel; on the other hand, the hydrophilic section also has excellent capability of complexing lithium ions, and in the positive ion aggregation layer on the surface of the electrode, the lithium ions can be specifically complexed, so that the lithium ion current distribution on the interface is more uniform, the lithium ions are promoted to enter the interior of the electrode, and the lithium extraction efficiency is improved.
Specifically, referring to fig. 2, a method for preparing an electrode according to an embodiment of the disclosure includes the following steps:
s1, preparing positive electrode active slurry
The preparation process of the positive electrode active slurry comprises the following steps: and mixing the positive electrode active material, the conductive agent and the binder, homogenizing by using a dispersing agent, and fully and uniformly stirring and mixing to form the electrode slurry.
In some embodiments, the positive electrode active material is at least one selected from lithium iron phosphate, lithium manganate and lithium nickel cobalt manganate, and may be any one or several of the above, and common positive electrode active materials are suitable for the examples of the present disclosure. Specifically, the proportion of nickel cobalt manganese in the lithium nickel cobalt manganese oxide is not limited, and may be commercially available materials such as NCM811, NCM622, and the like.
In some embodiments, the conductive agent is at least one selected from acetylene black and conductive carbon black, and may be any one or more of the above; the binder is at least one selected from polyvinylidene fluoride (PVDF) and polypropylene (PP), and can be any one or more of the above, preferably PVDF.
In some embodiments, the mass ratio of positive electrode active material, conductive agent, and binder is 100 (10-20): (10-15), such as may be 100:10:10, 100:12:11, 100:15:13, 100:17:14, 100:20:15, etc.
The type and amount of dispersant is not limited, and may be, but not limited to, N-methylpyrrolidone (NMP) capable of forming a uniform slurry, and volatilized and removed at the time of subsequent drying.
S2, preparing an electrode matrix
And coating the positive electrode active slurry on a current collector, and drying to form a positive electrode active coating to obtain the electrode matrix.
In some embodiments, the current collector is at least one selected from aluminum foil, titanium mesh and carbon fiber cloth, and can be any one or more of the above materials, and screening is performed according to different application scenarios. The thickness of the current collector is 10 μm to 15 μm, and the thickness may be adjusted as required, for example, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, or the like.
In some embodiments, the thickness of the dried positive electrode active coating layer is controlled to be 100 μm to 300 μm by controlling the coating thickness to ensure electrochemical performance of the electrode substrate.
In some embodiments, the drying temperature is controlled to be 100-120 ℃ and the drying time is controlled to be 10-20 hours during the formation of the positive electrode active coating to form a tightly-bonded coating. Specifically, the drying temperature may be 100 ℃, 110 ℃,120 ℃, etc., and the drying time may be 10 hours, 15 hours, 20 hours, etc.
S3, forming an amphoteric diblock copolymer coating layer
The method for preparing the coating layer of the amphiphilic diblock copolymer on the electrode substrate is not limited, and various methods are available and are not specifically mentioned herein.
In some embodiments, the process of forming the coating includes: the amphiphilic diblock copolymer is dispersed to obtain a copolymer dispersion, and an amphiphilic diblock copolymer coating layer is formed on the surface of the electrode base by using the copolymer dispersion. In practice, the electrode substrate may be immersed in the copolymer dispersion, and after the completion of the immersing, taken out and dried to form a uniform coating.
The amphiphilic diblock copolymer is a commercially available material and contains a hydrophilic segment and a hydrophobic segment, wherein the hydrophilic segment is at least one of Polyoxyethylene (PEO), polyethylene glycol (PEG) or polyacrylic acid (PAA), the hydrophobic segment is at least one of Polystyrene (PS), polybutadiene (PBD) and polyoxypropylene (PPO), the hydrophilic segment and the hydrophobic segment can be selected from any one or more of the above, and the amphiphilic diblock copolymer is prepared in a copolymerization mode. Preferably, the hydrophilic segment is polyoxyethylene, the hydrophobic segment is polystyrene, namely the amphiphilic diblock copolymer is polyoxyethylene-polystyrene copolymer (PEO-PS), and the modified PEO-PS is a commercial material, so that the lithium extraction efficiency can be further improved.
In some embodiments, the amphiphilic diblock copolymer used to form the amphiphilic diblock copolymer coating has a molecular weight of 5000-50000Da and a mass ratio of hydrophilic to hydrophobic segments of 1 (1.6-4). The lithium extraction efficiency is further improved by controlling specific parameters of the amphiphilic diblock copolymer. Specifically, the mass ratio of hydrophilic segment to hydrophobic segment may be 1:1.6, 1:2.0, 1:3.0, 1:4.0, etc.
In some embodiments, the preparation of the copolymer dispersion comprises: the amphiphilic diblock copolymer is mixed with a solvent, which may be, but is not limited to, water, the mass fraction of amphiphilic diblock in the copolymer dispersion being 2% to 5%, such as 2%, 3%, 4%, 5%, etc.
In some embodiments, the soaking time is 4-12 h, the soaking temperature is 15-30 ℃, i.e. the soaking can be performed under room temperature condition, and the operation is convenient. Specifically, the soaking time can be 4 hours, 6 hours, 8 hours, 10 hours, 12 hours, etc.; the soaking temperature can be 15 deg.C, 20 deg.C, 25 deg.C, 30 deg.C, etc.
In some embodiments, the drying temperature is controlled to be 60-80 ℃ and the drying time is controlled to be 4-6 h in the process of taking out and drying after soaking is finished, so that water is removed, and the amphoteric diblock copolymer is uniformly dispersed on the surface of the electrode matrix. Specifically, the drying temperature may be 60 ℃, 70 ℃, 80 ℃ and the like, and the drying time may be 4 hours, 5 hours, 6 hours and the like.
The embodiment of the disclosure also provides an electrode, which comprises an electrode matrix and an amphoteric diblock copolymer coating layer coated on the surface of the electrode matrix, wherein the electrode matrix comprises a current collector and an anode active coating attached to the current collector; wherein the amphiphilic diblock copolymer coating layer comprises a hydrophilic segment and a hydrophobic segment.
The electrode matrix is modified by an amphoteric diblock copolymer containing both hydrophilic segments and hydrophobic segments, and the hydrophilic segments can not only increase the hydrophilicity of the electrode, but also complex lithium ions on the surface of the electrode, thereby improving the lithium extraction efficiency.
In some embodiments, the mass ratio of the amphiphilic diblock copolymer coating layer in the electrode is 0.1% -5% (such as 0.1%, 1.0%, 2.0%, 3.0%, 4.0%, 5.0%, etc.), and the mass of the amphiphilic diblock copolymer coating layer is preferably controlled within the above range, so as to further improve the lithium extraction efficiency of the lithium-rich electrode.
In some embodiments, the lithium-rich electrode may be used for lithium removal to obtain a lithium-poor electrode, and the specific operation process of lithium removal is not limited, and an existing lithium removal method may be used.
In some embodiments, the delithiating process comprises: and taking the lithium-rich electrode as a positive electrode, placing the positive electrode and the negative electrode in electrolyte, electrifying the positive electrode and the negative electrode, and removing lithium from the lithium-rich electrode under constant voltage to obtain the lithium-poor electrode. The voltage of the power supply may be 0.5V-2V, such as 0.5V, 1.0V, 1.5V, 2.0V, etc.
In some embodiments, the negative electrode is selected from at least one of silver chloride electrode and foam nickel, and any one of the above electrodes can be used as the negative electrode, so that the lithium removal process can be completed.
In some embodiments, the electrolyte is selected from at least one of potassium chloride solution and sodium chloride solution, and can be any one or more of the above, and the concentration of the electrolyte is 0.05mol/L to 0.10mol/L, such as 0.05mol/L, 0.06mol/L, 0.07mol/L, 0.08mol/L, 0.09mol/L, 0.10mol/L, and the like.
The embodiment of the disclosure also provides a lithium extraction device for a salt lake, which comprises the lithium-rich electrode and the lithium-poor electrode, and can also comprise an electrolysis device, wherein an anion exchange membrane is arranged on the electrolysis device so as to divide the electrolysis device into an anode chamber and a cathode chamber.
In some embodiments, the anion exchange membrane is at least one selected from polystyrene, polypropylene and polyamide, and may be any one or more of the above.
The embodiment of the disclosure also provides a method for extracting lithium from a salt lake, which comprises the following steps: the lithium extraction device for the salt lake has the advantage of high lithium extraction efficiency.
In the actual operation process, the lithium-rich electrode and the lithium-poor electrode are respectively arranged in an anode chamber and a cathode chamber, brine is injected into the cathode chamber, electrolyte is injected into the anode chamber, then the anode chamber is electrified, lithium extraction is carried out under constant voltage, and lithium is selectively enriched in the lithium-poor electrode. The energizing voltage may be 0.3V-1.2V, such as 0.3V, 0.5V, 0.8V, 1.0V, 1.2V, etc.
In some embodiments, the electrolyte injected into the anode chamber is at least one selected from potassium chloride solution and sodium chloride solution, and can be any one or more of the above, and the concentration of the electrolyte is 0.05mol/L to 0.10mol/L, such as 0.05mol/L, 0.06mol/L, 0.07mol/L, 0.08mol/L, 0.09mol/L, 0.10mol/L, and the like.
The features and capabilities of the present disclosure are described in further detail below in connection with the examples.
The compositions of the brines used in the following examples and comparative examples are shown in table 1.
Table 1 composition of brine
| Component (A) | Li | Na | K | Mg | B | CO 3 2 - | SO 4 2 - |
| Content g/L | 0.68 | 99.24 | 20.12 | 0.148 | 2.25 | 20.11 | 20.26 |
Example 1
The embodiment provides a method for extracting lithium from a salt lake, which comprises the following specific steps:
preparing a lithium-rich electrode:
(1) 100g of lithium iron phosphate (LiFePO) 4 ) 10g of acetylene black and 10g of binder PVDF are added into 180g of NMP, and the mixture is fully stirred and uniformly mixed to form positive electrode active slurry.
(2) The positive electrode active slurry was coated on a current collector (aluminum foil with a thickness of 10 μm), and dried at 100℃for 15 hours to obtain an electrode substrate. Wherein the thickness of the positive electrode active coating layer formed after drying was 100 μm.
(3) Polyoxypropylene-polyoxyethylene copolymer (PPO-PEO, available from Rexi organism, molecular weight 12000 Da) was dissolved in water and stirred to prepare a copolymer dispersion having a mass fraction of 2%.
(4) Soaking the electrode matrix prepared in the step (2) in the copolymer dispersion liquid prepared in the step (3) for 8 hours, taking out, and drying at 60 ℃ for 6 hours to obtain the lithium-rich electrode with the amphiphilic diblock copolymer coating layer.
Preparing a lithium-poor electrode:
taking the lithium-rich electrode prepared in the step (4) as an anode, agCl electrode as a cathode, and 0.05mol/L NaCl solution as electrolyte, carrying out lithium removal on the lithium-rich electrode under a constant voltage of 1.0V, and when the current is lower than 0.5A/m 2 When the power is stopped, the lean state is obtainedA lithium state electrode.
Extracting lithium from salt lake:
the electrolysis device is divided into an anode chamber and a cathode chamber by an anion exchange membrane (polystyrene), a lithium-rich electrode and a lithium-poor electrode are respectively arranged in the anode chamber and the cathode chamber, brine is injected into the cathode chamber, 0.05mol/L KCl solution is injected into the anode chamber, a constant voltage of 0.3V is applied to the anode and the cathode, and lithium is extracted by electrolysis for 8 hours at 25 ℃.
Example 2
The embodiment provides a method for extracting lithium from a salt lake, which comprises the following specific steps:
preparing a lithium-rich electrode:
(1) 100g of lithium iron phosphate (LiFePO) 4 ) 20g of acetylene black and 15g of binder PVDF are added into 150g of NMP, and the mixture is fully stirred and uniformly mixed to form positive electrode active slurry.
(2) And (3) coating the positive electrode active slurry obtained in the step (1) on a current collector (aluminum foil with the thickness of 15 mu m), and drying at 120 ℃ for 10 hours to obtain an electrode matrix. Wherein the thickness of the positive electrode active coating layer formed after drying was 200 μm.
(3) Polyoxyethylene-polystyrene copolymer (PEO-PS, available from the Siam Azithro organism, molecular weight 25500 Da) was dissolved in water and stirred to prepare a copolymer dispersion having a mass fraction of 3%.
(4) Soaking the electrode matrix prepared in the step (2) in the copolymer dispersion liquid prepared in the step (3) for 6 hours, taking out, and drying at 80 ℃ for 4 hours to obtain the lithium-rich electrode with the amphiphilic diblock copolymer coating layer.
Preparing a lithium-poor electrode:
taking the lithium-rich electrode prepared in the step (4) as an anode, agCl electrode as a cathode, and 0.05mol/L NaCl solution as electrolyte, carrying out lithium removal on the lithium-rich electrode under a constant voltage of 1.0V, and when the current is lower than 0.5A/m 2 And stopping electrifying to obtain the lithium-poor electrode.
Extracting lithium from salt lake:
the electrolysis device is divided into an anode chamber and a cathode chamber by an anion exchange membrane (polypropylene), a lithium-rich electrode and a lithium-poor electrode are respectively arranged in the anode chamber and the cathode chamber, brine is injected into the cathode chamber, 0.05mol/LKCl solution is injected into the anode chamber, a constant voltage of 0.3V is applied to the anode and the cathode, and lithium is extracted by electrolysis for 8 hours at 25 ℃.
Example 3
The embodiment provides a method for extracting lithium from a salt lake, which comprises the following specific steps:
preparing a lithium-rich electrode:
(1) 100g of lithium iron phosphate (LiFePO) 4 ) 15g of acetylene black and 12g of binder PVDF are added into 200g of NMP, and the mixture is fully stirred and uniformly mixed to form positive electrode active slurry.
(2) And (3) coating the positive electrode active slurry obtained in the step (1) on a current collector (aluminum foil with the thickness of 12 mu m) to obtain an electrode, and drying at 100 ℃ for 15 hours to obtain an electrode matrix. Wherein the thickness of the positive electrode active coating layer formed after drying was 250 μm.
(3) Polyoxyethylene-polyoxypropylene copolymer (PEO-PPO, available from Ruixi Bio, molecular weight 12000 Da) was dissolved in water and stirred to prepare a copolymer dispersion having a mass fraction of 2%.
(4) Soaking the electrode matrix prepared in the step (2) in the copolymer dispersion liquid prepared in the step (3) for 10 hours, taking out, and drying at 80 ℃ for 4 hours to obtain the lithium-rich electrode with the amphiphilic diblock copolymer coating layer.
Preparing a lithium-poor electrode:
taking the lithium-rich electrode prepared in the step (4) as an anode, agCl electrode as a cathode, and 0.05mol/L NaCl solution as electrolyte, carrying out lithium removal on the lithium-rich electrode under a constant voltage of 1.0V, and when the current is lower than 0.5A/m 2 And stopping electrifying to obtain the lithium-poor electrode.
Extracting lithium from salt lake:
the electrolysis device is divided into an anode chamber and a cathode chamber by an anion exchange membrane (polyamide), a lithium-rich electrode and a lithium-poor electrode are respectively arranged in the anode chamber and the cathode chamber, brine is injected into the cathode chamber, 0.05mol/LKCl solution is injected into the anode chamber, a constant voltage of 0.3V is applied to the anode and the cathode, and lithium is extracted by electrolysis for 8 hours at 25 ℃.
Example 4
The only difference from example 1 is that: the polyoxypropylene-polyoxyethylene copolymer (PPO-PEO) in step (3) was replaced with polystyrene-polyacrylic acid (PS-PAA) (ruixi organism, molecular weight 6000 Da).
Example 5
The only difference from example 1 is that: the polyoxypropylene-polyoxyethylene copolymer (PPO-PEO) in step (3) was replaced with polystyrene-polyethylene glycol (PS-PEG) (Hangzhou New Qiao organism, molecular weight 10000 Da).
Example 6
The only difference from example 1 is that: the polyoxypropylene-polyoxyethylene copolymer (PPO-PEO) in step (3) was replaced with polybutadiene-polyoxyethylene (PBD-PEO) (Raschi Bio, molecular weight 9000 Da).
Example 7
The only difference from example 1 is that: the mass fraction of the copolymer dispersion in the step (3) was 1%.
Example 8
The only difference from example 1 is that: and (3) the mass fraction of the copolymer dispersion in the step (3) is 0.2%.
Example 9
The only difference from example 1 is that: and (3) the mass fraction of the copolymer dispersion in the step (3) is 6%.
Example 10
The only difference from example 1 is that: immersing the electrode matrix in the step (4) in the copolymer dispersion liquid for 1h.
Comparative example 1
This comparative example provides a method for extracting lithium from a salt lake, which differs from example 1 only in that: the method does not form an amphoteric diblock copolymer coating layer on the electrode matrix, and comprises the following specific steps:
(1) 100g of lithium iron phosphate (LiFePO) 4 ) 10g of acetylene black and 10g of binder PVDF are added into 180g of NMP, and the mixture is fully stirred and uniformly mixed to form positive electrode active slurry.
(2) And (3) coating the positive electrode active slurry obtained in the step (1) on a current collector (aluminum foil with the thickness of 10 mu m), and drying at 100 ℃ for 15 hours to obtain a finished electrode. Wherein the thickness of the positive electrode active coating layer formed after drying was 100 μm.
(3) Taking the electrode in the step (2) as an anode, agCl electrode as a cathode and 0.05mol/L NaCl solution as electrolyte, carrying out lithium removal on the lithium-rich electrode under a constant voltage of 1.0V, and when the current is lower than 0.5A/m 2 And stopping electrifying to obtain the lithium-poor electrode.
(4) The electrolysis device is divided into an anode chamber and a cathode chamber by an anion exchange membrane (polystyrene), the electrode obtained in the step (2) and the lithium-poor electrode obtained in the step (3) are respectively placed in the anode chamber and the cathode chamber, brine is injected into the cathode chamber, 0.05mol/L KCl solution is injected into the anode chamber, a constant voltage of 0.3V is applied to the cathode and anode, and lithium is extracted by electrolysis for 8 hours at 25 ℃.
Comparative example 2
This comparative example provides a method for extracting lithium from a salt lake, which differs from comparative example 1 only in that: in the step (1), nano silicon dioxide is introduced, and the hydrophilic performance of PVDF can be enhanced by blending modification of PVDF due to the large specific surface area of the nano silicon dioxide and the hydroxyl groups on the surface.
The method comprises the following specific steps:
(1) 100g of lithium iron phosphate (LiFePO) 4 ) 10g of acetylene black, 5g of nano silicon dioxide (particle size of 50 nm) and 10g of binder PVDF are added into 180g of NMP, and the mixture is fully stirred and uniformly mixed to form positive electrode active slurry.
(2) And (3) coating the positive electrode active slurry obtained in the step (1) on a current collector (aluminum foil with the thickness of 10 mu m), and drying at 100 ℃ for 15 hours to obtain a finished electrode.
(3) Taking the electrode in the step (2) as an anode, agCl electrode as a cathode, 0.05mol/L NaCl solution as electrolyte, and carrying out lithium removal on the lithium-rich electrode under a constant voltage of 1.0V, wherein the electrifying time is when the current is lower than 0.5A/m 2 And stopping electrifying to obtain the lithium-poor electrode.
(4) The electrolysis device is divided into an anode chamber and a cathode chamber by an anion exchange membrane (polyamide), a lithium-rich electrode and a lithium-poor electrode are respectively arranged in the anode chamber and the cathode chamber, brine is injected into the cathode chamber, 0.05mol/L KCl solution is injected into the anode chamber, a constant voltage of 0.3V is applied to the anode and the cathode, and lithium is extracted by electrolysis for 8 hours at 25 ℃.
Comparative example 3
This comparative example provides a method for extracting lithium from a salt lake, which differs from example 1 only in that: the hydrophobic group is not introduced in the step (3), namely, the polyoxypropylene-polyoxyethylene copolymer (PPO-PEO) in the step (3) is replaced by Polyoxyethylene (PEO), and the molecular weight is 10000Da.
Comparative example 4
This comparative example provides a method for extracting lithium from a salt lake, which differs from example 1 only in that: no hydrophilic group is introduced in step (3), i.e. the polyoxypropylene-polyoxyethylene copolymer (PPO-PEO) in step (3) is replaced by polyoxypropylene (PPO) with a molecular weight of 20000Da.
Test example 1
The change in lithium ion concentration of brine before and after the lithium extraction reaction, the lithium concentration of anolyte after the end of lithium extraction, and the capacity retention rate of the electrode after 100 times of lithium extraction were detected in examples and comparative examples, and the results are shown in table 2 and fig. 3.
Table 2 test results of lithium extraction effect of the salt lake lithium extraction method provided in examples and comparative examples
It can be seen that after the lithium-rich electrode and the lithium-poor electrode prepared in the embodiment are used for extracting lithium from a salt lake, the lithium extraction efficiency is higher, and the better capacity is still maintained after the cycle is performed for 100 times.
Industrial applicability
The surface of the electrode matrix is modified by the amphiphilic diblock copolymer to form the diblock copolymer coating layer, and the amphiphilic diblock copolymer simultaneously contains the hydrophilic segment and the hydrophobic segment, so that the stable coating layer can be formed on the surface of the electrode matrix, and meanwhile, the lithium extraction efficiency can be improved. The process of forming the diblock copolymer coating is convenient to operate and has very good industrial applicability.
Claims (28)
1. An electrode, characterized by comprising an electrode matrix and an amphoteric diblock copolymer coating layer coated on the surface of the electrode matrix, wherein the electrode matrix comprises a current collector and a positive electrode active coating attached to the current collector;
wherein the amphiphilic diblock copolymer coating layer contains a hydrophilic segment and a hydrophobic segment.
2. The electrode of claim 1, wherein the hydrophilic segment is selected from at least one of polyoxyethylene, polyethylene glycol, and polyacrylic acid.
3. The electrode according to claim 1 or 2, wherein the hydrophobic segment is selected from at least one of polystyrene, polybutadiene and polyoxypropylene.
4. An electrode according to any one of claims 1 to 3, wherein the hydrophilic segment is polyoxyethylene and the hydrophobic segment is polystyrene.
5. The electrode according to any one of claims 1 to 4, wherein the amphiphilic diblock copolymer coating layer has a mass ratio of 0.1 to 5% in the electrode.
6. The electrode of any one of claims 1-5, wherein the amphiphilic diblock copolymer used to form the amphiphilic diblock copolymer coating has a molecular weight of 5000-50000Da and the mass ratio of the hydrophilic segments to the hydrophobic segments is 1 (1.6-4).
7. The electrode according to any one of claims 1 to 6, wherein a positive electrode active material selected from at least one of lithium iron phosphate, lithium manganate, and lithium nickel cobalt manganate is contained in the positive electrode active coating layer.
8. The electrode according to claim 7, wherein a conductive agent and a binder are further contained in the positive electrode active coating layer, and the mass ratio of the positive electrode active material, the conductive agent and the binder is 100 (10-20): 10-15.
9. The electrode of claim 8, wherein the current collector is selected from at least one of aluminum foil, titanium mesh, and carbon fiber cloth.
10. The electrode according to claim 8 or 9, wherein the conductive agent is selected from at least one of acetylene black and conductive carbon black.
11. The electrode according to any one of claims 8-10, wherein the binder is selected from at least one of polyvinylidene fluoride and polypropylene.
12. The electrode according to any one of claims 9 to 11, wherein the thickness of the current collector is 10 μm to 15 μm and the thickness of the positive electrode active coating is 100 μm to 300 μm.
13. A method of preparing an electrode according to any one of claims 1 to 12, comprising: the amphiphilic diblock copolymer coating is formed on the electrode substrate.
14. The method of manufacturing according to claim 13, comprising: and dispersing the amphiphilic diblock copolymer to obtain a copolymer dispersion, and forming the amphiphilic diblock copolymer coating layer on the surface of the electrode substrate by using the copolymer dispersion.
15. The method of claim 14, wherein forming the amphiphilic diblock copolymer coating comprises: and soaking the electrode matrix in the copolymer dispersion liquid, and taking out and drying after the soaking is finished.
16. The method of claim 15, wherein the mass fraction of the amphiphilic diblock copolymer in the copolymer dispersion is from 2% to 5%.
17. The method of claim 15 or 16, wherein the soaking time is 4h-12h and the soaking temperature is 15 ℃ -30 ℃.
18. The method of any one of claims 15 to 17, wherein the drying temperature is 60 ℃ to 80 ℃ and the drying time is 4 hours to 6 hours.
19. The method of any one of claims 13-18, wherein the electrode substrate is prepared by a process comprising: coating positive electrode active slurry on a current collector, and drying to form the positive electrode active coating;
the preparation process of the positive electrode active slurry comprises the following steps: the positive electrode active material, the conductive agent, and the binder are mixed and homogenized using a dispersant.
20. The method of claim 19, wherein the drying temperature is controlled to be 100-120 ℃ and the drying time is controlled to be 10-20 h during the formation of the positive electrode active coating.
21. The device for extracting lithium from the salt lake is characterized by comprising a lithium-rich electrode and a lithium-poor electrode;
wherein the lithium-rich electrode is an electrode according to any one of claims 1 to 12 or an electrode prepared by the preparation method according to any one of claims 13 to 20.
22. The lithium extraction device of claim 21, wherein the lithium-deficient electrode is prepared by delithiating the lithium-rich electrode.
23. The lithium salt lake device of claim 21 further comprising an electrolyzer having an anion exchange membrane disposed therein to divide the electrolyzer into an anode compartment and a cathode compartment.
24. The lithium salt lake device of claim 23 wherein the anion exchange membrane is at least one member selected from the group consisting of polystyrene, polypropylene and polyamide.
25. A method for extracting lithium from a salt lake, comprising the steps of: lithium extraction using a salt lake lithium extraction device according to any one of claims 21 to 24.
26. The method for extracting lithium from a salt lake of claim 25, comprising: and respectively placing the lithium-rich electrode and the lithium-poor electrode in an anode chamber and a cathode chamber, injecting brine into the cathode chamber, injecting electrolyte into the anode chamber, and then electrifying.
27. The method for extracting lithium from a salt lake of claim 26, wherein the electrolyte injected into the anode chamber is selected from at least one of a potassium chloride solution and a sodium chloride solution, and the concentration of the electrolyte is 0.05mol/L to 0.10mol/L.
28. The method for extracting lithium from a salt lake of claim 26 or 27 wherein the energizing voltage is 0.3V to 1.2V.
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