CN111364054B - Bipolar membrane and method for preparing high-purity lithium hydroxide by using bipolar membrane - Google Patents
Bipolar membrane and method for preparing high-purity lithium hydroxide by using bipolar membrane Download PDFInfo
- Publication number
- CN111364054B CN111364054B CN202010339712.1A CN202010339712A CN111364054B CN 111364054 B CN111364054 B CN 111364054B CN 202010339712 A CN202010339712 A CN 202010339712A CN 111364054 B CN111364054 B CN 111364054B
- Authority
- CN
- China
- Prior art keywords
- membrane
- polyvinyl alcohol
- bipolar membrane
- bipolar
- layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/14—Alkali metal compounds
- C25B1/16—Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B13/00—Diaphragms; Spacing elements
- C25B13/02—Diaphragms; Spacing elements characterised by shape or form
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B13/00—Diaphragms; Spacing elements
- C25B13/04—Diaphragms; Spacing elements characterised by the material
- C25B13/08—Diaphragms; Spacing elements characterised by the material based on organic materials
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention relates to a preparation method of a bipolar membrane, which comprises the following steps: 1) spraying or casting a film solution of polyvinyl alcohol, polypyrrolidone and lithium salt to obtain an intermediate film layer; 2) spraying or casting membrane liquid mixed with sulfonated polyvinyl alcohol and sulfonated polyether ether ketone on the intermediate membrane layer, and drying to obtain an anion exchange membrane layer; 3) spraying or casting membrane liquid mixed with the ammonium polyvinyl alcohol and the ammonium polyether-ether-ketone to the other side of the middle membrane layer, drying to obtain a cation exchange membrane layer, and obtaining an initial bipolar membrane basement membrane; 4) immersing the bipolar membrane basement membrane obtained in the step 3) in a solution containing aldehyde compounds, carrying out chemical crosslinking, taking out, and carrying out heat treatment to obtain the bipolar membrane; the preparation method is simple, easy to operate, energy-saving and environment-friendly, and the prepared bipolar membrane material has high interception performance on lithium ions, is not easy to delaminate, and has high ion exchange capacity and ion exchange rate.
Description
[ technical field ]
The invention relates to the technical field of bipolar membrane preparation, in particular to a bipolar membrane and a method for preparing high-purity lithium hydroxide by using the bipolar membrane.
[ background art ]
The bipolar membrane is a novel composite ion exchange membrane and generally consists of an anion exchange layer, a middle interface layer and an anion exchange layer; under the action of direct current, water in the middle interface layer is dissociated under the action of high electric field intensity to obtain hydroxyl ions and hydrogen ions, and the hydroxyl ions and the hydrogen ions are respectively migrated to two sides of the bipolar membrane under the action of an electric field. The bipolar membrane system comprises a bipolar membrane, an anion exchange membrane and a cation exchange membrane, and can disassemble and convert salts into corresponding alkali and acid without entering other compounds. Acid and alkali can be generated under the condition of not generating hydrogen and oxygen, and the energy consumption of electrode polarization in the traditional electrolysis process is reduced. Provides a new idea and solution for the technical problems in the fields of environment, resources, energy and the like.
The preparation method of the bipolar membrane generally comprises the following steps: hot pressing the anion-cation exchange membrane, adhering the anion-cation exchange membrane, casting the membrane, introducing anion-cation exchange groups to both sides of the base membrane, etc. The hot-pressing forming method of the anion-cation exchange membrane layer comprises the following specific steps: laminating the dried anion-cation exchange membranes and the dried anion-cation exchange membranes, and heating and pressing the bipolar membranes; the bipolar membrane prepared by the method has the advantages that the cation-anion exchange membrane layer and the anion-cation exchange membrane layer are mutually permeated, the electrostatic action of active groups is strong, the resistance of a middle interface layer is higher, and the working voltage of the bipolar membrane is higher. The adhesive for the bonding forming method adopts an ion permeable adhesive, so that the resistance and the working voltage of the intermediate interface layer can be reduced. The tape casting method is to cast a layer of anion exchange membrane liquid on a cation exchange membrane serving as a substrate, and obtain the bipolar membrane after drying and cooling, wherein the bipolar membrane is easy to delaminate after the membrane layer runs for a long time. In addition, the bipolar membrane can be obtained by respectively introducing the anion-cation exchange membrane layer and the cation-anion exchange membrane layer through chemical reactions on two sides of the basement membrane, but the reaction control requirement is higher. The preparation of bipolar membranes and related research in China are started late, and the bipolar membranes have been developed rapidly in recent years, so that the application fields of the bipolar membranes are greatly widened, such as the preparation of organic acid and alkali, zero discharge of industrial wastewater and the like.
Lithium hydroxide is a strong base and has wide application in metallurgy, atomic energy, chemical reagents, aerospace and defense industries. The high-purity lithium hydroxide plays an important role in the field of energy sources, and can be used as an additive to increase the storage capacity of the alkaline storage battery and prolong the service life of the battery. In the nickel cobalt lithium manganate (NCM811) and nickel cobalt lithium aluminate (NCA) type ternary electrode materials, lithium hydroxide is the only lithium source of the nickel cathode material, and has greater advantages in sintering temperature and product performance compared with battery-grade lithium carbonate, and meanwhile, the purity of the lithium hydroxide also meets the requirement of battery grade.
At present, the preparation method of lithium hydroxide comprises a causticization method, limestone calcination, soda leaching and an electrolysis method. The causticizing method, the limestone calcining method and the soda leaching method all introduce new compounds, the purity of the lithium hydroxide is low, and the purification steps are complicated; the two-stage membrane electrolysis method can effectively prepare lithium hydroxide, and the existing bipolar membrane has low lithium ion rejection rate, so that lithium loss is caused; and the purity of the lithium hydroxide is low, and other purification steps are required to be introduced if the high-purity lithium hydroxide is to be obtained, so that the process is complex and the energy consumption is high. CN10957160A discloses a preparation method of a bipolar membrane with high lithium ion retention, which comprises the steps of activating on a polyether-ether-ketone membrane, obtaining the bipolar membrane with high lithium ion retention performance through modes of electrolytic catalysis, alkali liquor soaking and the like, and having high retention rate of lithium ions. CN106040013A discloses a preparation method of a bipolar membrane, which adopts sulfonated polyphenyl ether and ammonium polyphenyl ether to coat a substrate to obtain the bipolar membrane which is not easy to separate. CN109516479A discloses a preparation method of battery-grade lithium hydroxide, which adopts a method of alkali liquor sedimentation and multiple evaporation crystallization.
[ summary of the invention ]
The invention aims to solve the defects and provide a preparation method of a bipolar membrane, which is simple in preparation method, easy to operate, energy-saving and environment-friendly, and the prepared bipolar membrane material has high lithium ion interception performance, is not easy to delaminate, and has high ion exchange capacity and ion exchange rate.
In order to achieve the purpose, the preparation method of the bipolar membrane comprises the following steps: 1) spraying or casting a film solution of polyvinyl alcohol, polypyrrolidone and lithium salt to obtain an intermediate film layer; 2) spraying or casting membrane liquid mixed with sulfonated polyvinyl alcohol and sulfonated polyether ether ketone on the intermediate membrane layer obtained in the step 1), and drying to obtain an anion exchange membrane layer; 3) spraying or casting a membrane liquid mixed with the aminated polyvinyl alcohol and the aminated polyether-ether-ketone to the other side of the intermediate membrane layer obtained in the step 1), drying to obtain a cation exchange membrane layer, and obtaining an initial bipolar membrane basement membrane; 4) immersing the bipolar membrane basement membrane obtained in the step 3) in a solution containing aldehyde compounds, carrying out chemical crosslinking, taking out, and carrying out heat treatment to obtain the bipolar membrane.
Further, in the step 1), the mass ratio of the polyvinyl alcohol to the polyvinylpyrrolidone is 0.01-10, the lithium salt accounts for 0.1-10% of the total mass of the polyvinyl alcohol and the polyvinylpyrrolidone, and the thickness of the intermediate film layer is 1-20 microns.
Further, the mass ratio of the sulfonated polyvinyl alcohol to the sulfonated polyether ether ketone is 0.01-1, and the mass ratio of the aminated polyvinyl alcohol to the aminated polyether ether ketone is 0.01-1.
Further, the thicknesses of the anion exchange membrane layer and the cation exchange membrane layer are both 20-200 microns.
Further, the solvent of the intermediate membrane layer is one or more of water, methanol and ethanol, and the solvent of the anion exchange membrane solution and the cation exchange membrane solution is one or more of NN-dimethylacetamide, NN-dimethylformamide, dimethyl sulfoxide and 1, 4-dioxane.
Further, in the step 4), the aldehyde in the solution containing the aldehyde compound contains two or more aldehyde groups, the mass ratio of the aldehyde compound is 0.01-10%, and the solvent is one or a mixture of water, methanol, ethanol and acetone.
Further, in the step 4), the heat treatment mode is hot air blowing, and the heat treatment temperature is 30-90 ℃.
The invention also provides application of the bipolar membrane prepared by the preparation method in preparation of high-purity lithium hydroxide, and the method for preparing high-purity lithium hydroxide by adopting the bipolar membrane comprises the following steps: and (3) matching the bipolar membrane with a commercial anion membrane and a commercial cation membrane to build a bipolar membrane device, and electrolyzing the lithium salt solution to obtain the high-purity lithium hydroxide solution.
Further, the lithium salt solution is one or a mixture of several of lithium sulfate, lithium nitrate, lithium chloride and lithium phosphate as a raw material, and the purity of lithium hydroxide obtained by electrolysis is 90-99.9%.
Compared with the prior art, the bipolar membrane prepared by the preparation method has the advantages that the membrane material has higher interception performance on lithium ions, is not easy to stratify, has higher ion exchange capacity and ion exchange rate, and is simple in preparation method, easy to operate, energy-saving and environment-friendly. In addition, based on the bipolar membrane, the invention also provides a preparation method of high-purity lithium hydroxide, the membrane material is adopted, and a commercialized cation exchange membrane and an anion exchange membrane are combined to carry out lithium salt electrolysis, so that the high-purity lithium hydroxide can be prepared.
[ description of the drawings ]
FIG. 1 is a schematic flow diagram of a bipolar membrane preparation process of the present invention;
FIG. 2 is a schematic diagram of the present invention for preparing high purity lithium hydroxide.
[ detailed description of the invention ]
The invention provides a preparation method of a bipolar membrane, which comprises the following steps: 1) spraying or casting a film solution of polyvinyl alcohol, polypyrrolidone and lithium salt to obtain an intermediate film layer; 2) spraying or casting membrane liquid mixed with sulfonated polyvinyl alcohol and sulfonated polyether ether ketone on the intermediate membrane layer obtained in the step 1), and drying to obtain an anion exchange membrane layer; 3) spraying or casting a membrane liquid mixed with the aminated polyvinyl alcohol and the aminated polyether-ether-ketone to the other side of the intermediate membrane layer obtained in the step 1), drying to obtain a cation exchange membrane layer, and obtaining an initial bipolar membrane basement membrane; 4) immersing the bipolar membrane basement membrane obtained in the step 3) in a solution containing aldehyde compounds, carrying out chemical crosslinking, taking out, and carrying out heat treatment to obtain the bipolar membrane.
Wherein, the mass ratio of the polyvinyl alcohol to the polyvinylpyrrolidone is 0.01-10, the lithium salt accounts for 0.1-10% of the total mass of the polyvinyl alcohol and the polyvinylpyrrolidone, and the thickness of the middle film layer is 1-20 microns. The mass ratio of the sulfonated polyvinyl alcohol to the sulfonated polyether ether ketone is 0.01-1, the mass ratio of the aminated polyvinyl alcohol to the aminated polyether ether ketone is 0.01-1, and the thicknesses of the anion exchange membrane layer and the cation exchange membrane layer are both 20-200 microns. The solvent of the intermediate membrane layer is one or more of water, methanol and ethanol, and the solvent of the anion exchange membrane solution and the cation exchange membrane solution is one or more of NN-dimethylacetamide, NN-dimethylformamide, dimethyl sulfoxide and 1, 4-dioxane. In the step 4), the aldehyde in the solution containing the aldehyde compound is two or more than two aldehyde groups, the mass ratio of the aldehyde compound is 0.01-10%, and the solvent is one or a mixture of water, methanol, ethanol and acetone; and 4) adopting hot air blowing in the heat treatment mode in the step 4), wherein the heat treatment temperature is 30-90 ℃.
The bipolar membrane prepared by the preparation method can be used for preparing high-purity lithium hydroxide, and the method for preparing the high-purity lithium hydroxide comprises the following steps: and (3) matching the bipolar membrane with a commercial anion membrane and a commercial cation membrane to build a bipolar membrane device, and electrolyzing the lithium salt solution to obtain the high-purity lithium hydroxide solution. In the method for preparing high-purity lithium hydroxide by adopting the bipolar membrane, one or more of lithium sulfate, lithium nitrate, lithium chloride and lithium phosphate solution are adopted as the lithium salt solution and mixed as the raw material, and the purity of lithium hydroxide obtained by electrolysis is 90-99.9%.
To sum up: the invention provides a preparation method of a bipolar membrane and application of the bipolar membrane in high-purity lithium hydroxide, wherein the preparation method of the bipolar membrane comprises the following steps: firstly, preparing a film intermediate film layer of polyvinyl alcohol, polypyrrolidone and lithium salt; spraying or casting membrane liquid mixed with sulfonated polyvinyl alcohol and sulfonated polyether ether ketone on the intermediate membrane layer to obtain a negative membrane layer; spraying or casting membrane liquid mixed with the aminated polyvinyl alcohol and the aminated polyether-ether-ketone to the other side of the middle membrane layer to obtain an initial bipolar membrane; and immersing the initial membrane in a solution containing polyaldehyde, carrying out chemical crosslinking, taking out, and carrying out heat treatment to obtain the bipolar membrane material. The membrane material has high interception performance to lithium ions, is not easy to delaminate, and has high ion exchange capacity and ion exchange rate. Based on the bipolar membrane. The invention also provides a preparation method of the high-purity lithium hydroxide, and the high-purity lithium hydroxide can be prepared by adopting the membrane material of the invention and combining with a commercialized cation exchange membrane and an anion exchange membrane to electrolyze lithium salt; has the advantages of high lithium recovery rate, simple process, safety, environmental protection, easy industrial production and the like.
The invention is further illustrated below with reference to specific examples:
example 1
The bipolar membrane is prepared by the following steps:
(1) preparing a film liquid of polyvinyl alcohol, polyvinylpyrrolidone and lithium salt, wherein the mass ratio of the polyvinyl alcohol to the polyvinylpyrrolidone is 0.01, lithium chloride accounts for 8% of the total mass of the polyvinyl alcohol and the polyvinylpyrrolidone, and water is used as a solvent, and spraying to prepare an intermediate film layer with the thickness of 2 microns;
(2) casting membrane liquid mixed with sulfonated polyvinyl alcohol and sulfonated polyether ether ketone onto the intermediate membrane layer, wherein the mass ratio of the sulfonated polyvinyl alcohol to the sulfonated polyether ether ketone is 1, the solvent is mixed solution of NN-dimethylacetamide and 1.4 dioxane, and drying to obtain an anion exchange membrane layer, and the thickness of the membrane layer is 20 micrometers;
(3) casting membrane liquid mixed with the aminated polyvinyl alcohol and the aminated polyether-ether-ketone to the other side of the intermediate membrane layer, wherein the mass ratio of the aminated polyvinyl alcohol to the aminated polyether-ether-ketone is 0.1, the solvent is NN-dimethylformamide, and drying to obtain a cation exchange membrane layer, wherein the thickness of the membrane layer is 200 microns, so that the initial bipolar membrane basement membrane is obtained;
(4) immersing the bipolar membrane base membrane in an aqueous solution containing 0.05% of glutaraldehyde for 1 hour, taking out, and then carrying out 50-degree hot air blowing to obtain the bipolar membrane.
The bipolar membrane is matched with a commercial anion membrane and a commercial cation membrane to build a bipolar membrane device, an electrolysis experiment is carried out on lithium sulfate, the transmembrane voltage is 2V, a lithium hydroxide solution is obtained, and the purity can reach 99.9%.
Example 2
The bipolar membrane is prepared by the following steps:
(1) preparing a film liquid of polyvinyl alcohol, polyvinylpyrrolidone and lithium salt, wherein the mass ratio of the polyvinyl alcohol to the polyvinylpyrrolidone is 8, the lithium chloride accounts for 0.2 percent of the total mass of the polyvinyl alcohol and the polyvinylpyrrolidone, and water is used as a solvent, and spraying to prepare an intermediate film layer with the thickness of 20 microns;
(2) casting membrane liquid mixed with sulfonated polyvinyl alcohol and sulfonated polyether ether ketone onto the intermediate membrane layer, wherein the mass ratio of the sulfonated polyvinyl alcohol to the sulfonated polyether ether ketone is 0.05, the solvent is 1.4 dioxane solution, and drying to obtain an anion exchange membrane layer, wherein the thickness of the membrane layer is 20 microns;
(3) spraying membrane liquid mixed with the aminated polyvinyl alcohol and the aminated polyether-ether-ketone on the other surface of the intermediate membrane layer, wherein the mass ratio of the aminated polyvinyl alcohol to the aminated polyether-ether-ketone is 0.5, the solvent is dimethyl sulfoxide, and drying to obtain a cation exchange membrane layer, wherein the thickness of the membrane layer is 180 microns, so as to obtain the initial bipolar membrane-based membrane;
(4) immersing the bipolar membrane base membrane in an aqueous solution containing 5% of glutaraldehyde for 20 minutes, taking out, and then carrying out 90-degree hot air blowing to obtain the bipolar membrane.
Matching the bipolar membrane with a commercial anion membrane and a commercial cation membrane, building a bipolar membrane device with a sequence of bipolar membrane-anion exchange membrane-cation exchange membrane repeatedly arranged, and carrying out an electrolysis experiment on lithium chloride, wherein the transmembrane voltage is 1.8V, so as to obtain a lithium hydroxide solution; wherein the purity of the lithium hydroxide can reach 99.5%.
Example 3
The bipolar membrane is prepared by the following steps:
(1) preparing a film liquid of polyvinyl alcohol, polyvinylpyrrolidone and lithium salt, wherein the mass ratio of the polyvinyl alcohol to the polyvinylpyrrolidone is 2, the lithium chloride accounts for 4% of the total mass of the polyvinyl alcohol and the polyvinylpyrrolidone, and water is used as a solvent, and spraying to prepare an intermediate film layer with the thickness of 10 microns;
(2) casting membrane liquid mixed with sulfonated polyvinyl alcohol and sulfonated polyether ether ketone onto the intermediate membrane layer, wherein the mass ratio of the sulfonated polyvinyl alcohol to the sulfonated polyether ether ketone is 0.8, the solvent is NN-dimethylacetamide solution, and drying to obtain an anion exchange membrane layer, wherein the thickness of the membrane layer is 195 micrometers;
(3) casting membrane liquid mixed with the aminated polyvinyl alcohol and the aminated polyether-ether-ketone to the other surface of the intermediate membrane layer, wherein the mass ratio of the aminated polyvinyl alcohol to the aminated polyether-ether-ketone is 0.5, the solvent is NN-dimethylformamide, and drying to obtain a cation exchange membrane layer, wherein the thickness of the membrane layer is 30 microns; namely obtaining an initial bipolar membrane basement membrane;
(4) immersing the bipolar membrane base membrane in an acetone solution containing 5% of glutaraldehyde for 20 minutes, taking out, and performing 90-degree hot air blowing to obtain the bipolar membrane.
Matching the bipolar membrane with a commercial anion membrane and a commercial cation membrane, building a bipolar membrane device with a sequence of bipolar membrane-anion exchange membrane-cation exchange membrane repeatedly arranged, and carrying out an electrolysis experiment on lithium nitrate, wherein the transmembrane voltage is 1.8V, so as to obtain a lithium hydroxide solution; wherein the purity of the lithium hydroxide can reach 98 percent.
Example 4
The bipolar membrane is prepared by the following steps:
(1) preparing a film liquid of polyvinyl alcohol, polyvinylpyrrolidone and lithium salt, wherein the mass ratio of the polyvinyl alcohol to the polyvinylpyrrolidone is 6, the lithium chloride accounts for 0.15 percent of the total mass of the polyvinyl alcohol and the polyvinylpyrrolidone, and water is used as a solvent, and spraying to prepare an intermediate film layer with the thickness of 5 microns;
(2) casting membrane liquid mixed with sulfonated polyvinyl alcohol and sulfonated polyether ether ketone onto the intermediate membrane layer, wherein the mass ratio of the sulfonated polyvinyl alcohol to the sulfonated polyether ether ketone is 0.9, the solvent is a mixed solution of NN-dimethylacetamide and 1.4 dioxane, and drying to obtain an anion exchange membrane layer, wherein the thickness of the membrane layer is 60 micrometers;
(3) casting membrane liquid mixed with the aminated polyvinyl alcohol and the aminated polyether-ether-ketone to the other side of the intermediate membrane layer, wherein the mass ratio of the aminated polyvinyl alcohol to the aminated polyether-ether-ketone is 0.5, the solvent is NN-dimethylformamide, and drying to obtain a cation exchange membrane layer, wherein the thickness of the membrane layer is 30 microns, so that the initial bipolar membrane basement membrane is obtained;
(4) immersing the bipolar membrane base membrane in an acetone solution containing 5% of glutaraldehyde for 20 minutes, taking out, and performing hot air blowing at 30 degrees to obtain the bipolar membrane.
Matching the bipolar membrane with a commercial anion membrane and a commercial cation membrane, building a bipolar membrane device with a sequence of bipolar membrane-anion exchange membrane-cation exchange membrane repeatedly arranged, and carrying out an electrolysis experiment on a solution of lithium nitrate and lithium chloride, wherein the transmembrane voltage is 1.5V, so as to obtain a lithium hydroxide solution; wherein the purity of the lithium hydroxide can reach 99%.
Example 5
The bipolar membrane is prepared by the following steps:
(1) preparing a film liquid of polyvinyl alcohol, polyvinylpyrrolidone and lithium salt, wherein the mass ratio of the polyvinyl alcohol to the polyvinylpyrrolidone is 0.01, lithium chloride accounts for 10% of the total mass of the polyvinyl alcohol and the polyvinylpyrrolidone, and water is used as a solvent, and spraying to prepare an intermediate film layer with the thickness of 1 micron;
(2) casting membrane liquid mixed with sulfonated polyvinyl alcohol and sulfonated polyether ether ketone onto the intermediate membrane layer, wherein the mass ratio of the sulfonated polyvinyl alcohol to the sulfonated polyether ether ketone is 1, the solvent is mixed solution of NN-dimethylacetamide and 1.4 dioxane, and drying to obtain an anion exchange membrane layer, and the thickness of the membrane layer is 200 micrometers;
(3) casting membrane liquid mixed with the aminated polyvinyl alcohol and the aminated polyether-ether-ketone to the other side of the intermediate membrane layer, wherein the mass ratio of the aminated polyvinyl alcohol to the aminated polyether-ether-ketone is 0.01, the solvent is NN-dimethylformamide, and drying to obtain a cation exchange membrane layer, wherein the thickness of the membrane layer is 200 microns, so that the initial bipolar membrane basement membrane is obtained;
(4) immersing the bipolar membrane base membrane in an aqueous solution containing 0.05% of glutaraldehyde for 1 hour, taking out, and then carrying out 50-degree hot air blowing to obtain the bipolar membrane.
The bipolar membrane is matched with a commercial anion membrane and a commercial cation membrane to build a bipolar membrane device, an electrolysis experiment is carried out on lithium sulfate, the transmembrane voltage is 2V, a lithium hydroxide solution is obtained, and the purity can reach 99.9%.
Example 6
The bipolar membrane is prepared by the following steps:
(1) preparing a film liquid of polyvinyl alcohol, polyvinylpyrrolidone and lithium salt, wherein the mass ratio of the polyvinyl alcohol to the polyvinylpyrrolidone is 10, the lithium chloride accounts for 0.1 percent of the total mass of the polyvinyl alcohol and the polyvinylpyrrolidone, and water is used as a solvent, and spraying to prepare an intermediate film layer with the thickness of 20 microns;
(2) casting membrane liquid mixed with sulfonated polyvinyl alcohol and sulfonated polyether ether ketone onto the intermediate membrane layer, wherein the mass ratio of the sulfonated polyvinyl alcohol to the sulfonated polyether ether ketone is 0.01, the solvent is 1.4 dioxane solution, and drying to obtain an anion exchange membrane layer, wherein the thickness of the membrane layer is 20 microns;
(3) spraying membrane liquid mixed with the aminated polyvinyl alcohol and the aminated polyether-ether-ketone on the other surface of the intermediate membrane layer, wherein the mass ratio of the aminated polyvinyl alcohol to the aminated polyether-ether-ketone is 0.5, the solvent is dimethyl sulfoxide, and drying to obtain a cation exchange membrane layer, wherein the thickness of the membrane layer is 20 microns, so that the initial bipolar membrane basement membrane is obtained;
(4) immersing the bipolar membrane base membrane in an aqueous solution containing 5% of glutaraldehyde for 20 minutes, taking out, and then carrying out 90-degree hot air blowing to obtain the bipolar membrane.
The bipolar membrane is matched with commercial anion membranes and cation membranes to build a bipolar membrane device with the sequence of bipolar membrane-anion exchange membrane-cation exchange membrane repeatedly arranged, lithium chloride is subjected to an electrolysis experiment, the transmembrane voltage is 1.8V, a lithium hydroxide solution is obtained, and the purity can reach 99.5%.
The present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents and are included in the scope of the present invention.
Claims (6)
1. A preparation method of the bipolar membrane is characterized by comprising the following steps:
1) spraying or casting a film solution of polyvinyl alcohol, polypyrrolidone and lithium salt to obtain an intermediate film layer;
2) spraying or casting membrane liquid mixed with sulfonated polyvinyl alcohol and sulfonated polyether ether ketone on the intermediate membrane layer obtained in the step 1), and drying to obtain an anion exchange membrane layer;
3) spraying or casting a membrane liquid mixed with the aminated polyvinyl alcohol and the aminated polyether-ether-ketone to the other side of the intermediate membrane layer obtained in the step 1), drying to obtain a cation exchange membrane layer, and obtaining an initial bipolar membrane basement membrane;
4) immersing the bipolar membrane basement membrane obtained in the step 3) in a solution containing aldehyde compounds, carrying out chemical crosslinking, taking out, and carrying out heat treatment to obtain the bipolar membrane;
in the step 1), the mass ratio of the polyvinyl alcohol to the polyvinylpyrrolidone is 0.01-10, the lithium salt accounts for 0.1-10% of the total mass of the polyvinyl alcohol and the polyvinylpyrrolidone, and the thickness of the intermediate film layer is 1-20 microns;
in the step 2), the mass ratio of the sulfonated polyvinyl alcohol to the sulfonated polyether-ether-ketone is 0.01-1, and the mass ratio of the aminated polyvinyl alcohol to the aminated polyether-ether-ketone is 0.01-1;
the solvent of the intermediate membrane layer is one or more of water, methanol and ethanol, and the solvent of the anion exchange membrane layer and the solvent of the cation exchange membrane layer are one or more of NN-dimethylacetamide, NN-dimethylformamide, dimethyl sulfoxide and 1, 4-dioxane;
in the step 4), the solution containing the aldehyde compound is an aqueous solution of glutaraldehyde.
2. The method for producing a bipolar membrane according to claim 1, wherein: the thicknesses of the anion exchange membrane layer and the cation exchange membrane layer are both 20-200 microns.
3. The method for producing a bipolar membrane according to claim 1, wherein: in the step 4), the heat treatment mode is that hot air blowing is adopted, and the heat treatment temperature is 30-90 ℃.
4. Use of a bipolar membrane prepared by the preparation method according to any one of claims 1 to 3 in the preparation of high-purity lithium hydroxide.
5. A method for preparing high-purity lithium hydroxide from the bipolar membrane prepared by the preparation method of any one of claims 1 to 3, comprising the steps of: and (3) matching the bipolar membrane with a commercial anion membrane and a commercial cation membrane to build a bipolar membrane device, and electrolyzing the lithium salt solution to obtain the high-purity lithium hydroxide solution.
6. The method of claim 5, wherein: the lithium salt solution is one or a mixture of more of lithium sulfate, lithium nitrate, lithium chloride and lithium phosphate as a raw material, and the purity of lithium hydroxide obtained by electrolysis is 90-99.9%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010339712.1A CN111364054B (en) | 2020-04-26 | 2020-04-26 | Bipolar membrane and method for preparing high-purity lithium hydroxide by using bipolar membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010339712.1A CN111364054B (en) | 2020-04-26 | 2020-04-26 | Bipolar membrane and method for preparing high-purity lithium hydroxide by using bipolar membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111364054A CN111364054A (en) | 2020-07-03 |
| CN111364054B true CN111364054B (en) | 2022-01-28 |
Family
ID=71205671
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010339712.1A Active CN111364054B (en) | 2020-04-26 | 2020-04-26 | Bipolar membrane and method for preparing high-purity lithium hydroxide by using bipolar membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111364054B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104593819A (en) * | 2015-01-06 | 2015-05-06 | 山东天维膜技术有限公司 | Bipolar membrane and preparation method thereof |
| CN106040013A (en) * | 2016-06-24 | 2016-10-26 | 盐城师范学院 | Bipolar membrane and preparation method thereof |
| CN109574160A (en) * | 2018-12-07 | 2019-04-05 | 杭州水处理技术研究开发中心有限公司 | A kind of preparation method of the Bipolar Membrane of the high rejection of lithium ion |
| CN110917881A (en) * | 2019-12-13 | 2020-03-27 | 陕西易莱德新材料科技有限公司 | Preparation method of bipolar membrane |
-
2020
- 2020-04-26 CN CN202010339712.1A patent/CN111364054B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104593819A (en) * | 2015-01-06 | 2015-05-06 | 山东天维膜技术有限公司 | Bipolar membrane and preparation method thereof |
| CN106040013A (en) * | 2016-06-24 | 2016-10-26 | 盐城师范学院 | Bipolar membrane and preparation method thereof |
| CN109574160A (en) * | 2018-12-07 | 2019-04-05 | 杭州水处理技术研究开发中心有限公司 | A kind of preparation method of the Bipolar Membrane of the high rejection of lithium ion |
| CN110917881A (en) * | 2019-12-13 | 2020-03-27 | 陕西易莱德新材料科技有限公司 | Preparation method of bipolar membrane |
Non-Patent Citations (1)
| Title |
|---|
| "均相荷电膜技术在氢氧化锂制备中的应用";连文玉等;《盐科学与化工》;20191215;第48卷(第12期);第7-10页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111364054A (en) | 2020-07-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102941026B (en) | Ion exchange composite film with selectivity on single cation | |
| CN109574092B (en) | Preparation method of full-concentration gradient nickel-cobalt-aluminum ternary precursor | |
| CN108997141A (en) | A kind of preparation method of 1,5- pentanediamine | |
| CN103055895A (en) | Method for preparing core-shell type nano-porous platinum alloy catalyst | |
| CN108134046B (en) | Clean production method of coprecipitation method anode material carbonate precursor | |
| CN105622435A (en) | Bipolar membrane device for preparing amino-1-propanol | |
| CN113680326A (en) | Sulfonic acid COFs membrane and preparation method and application thereof | |
| CN104681780A (en) | Method for preparing thin thermal battery positive electrode-electrolyte-negative electrode combined pole piece based on slurry coating method | |
| CN111364054B (en) | Bipolar membrane and method for preparing high-purity lithium hydroxide by using bipolar membrane | |
| CN109134317B (en) | Method for preparing L-10-camphorsulfonic acid by bipolar membrane electrodialysis | |
| CN109574160B (en) | Preparation method of bipolar membrane with high lithium ion rejection rate | |
| CN208667866U (en) | A kind of bipolar membrane device suitable for preparing lithium hydroxide using lithium carbonate as raw material | |
| CN112126355B (en) | Preparation method of coating solution for ion exchange membrane | |
| CN205676398U (en) | A kind of bipolar membrane device preparing aminopropanol | |
| CN111188064B (en) | Enhanced perfluorinated sulfonic acid ion exchange membrane for alkali chloride electrolysis and preparation method thereof | |
| CN111101152B (en) | Perfluorocarboxylic acid ion exchange membrane with rough coating and preparation method thereof | |
| CN111020630B (en) | Ultrathin perfluorocarboxylic acid ion exchange membrane with bubble-dispelling function and preparation method thereof | |
| CN112850682B (en) | Inorganic membrane material and preparation method and application thereof | |
| CN112588327A (en) | Preparation method and application of organic solvent-resistant cation exchange membrane | |
| CN111188061A (en) | Perfluorosulfonic acid ion exchange membrane and preparation method thereof | |
| CN112481657B (en) | Fluoride ion exchange membrane for alkali chloride electrolysis having impurity tolerance | |
| CN111074298B (en) | Perfluorosulfonic acid ion exchange membrane for chloride electrolysis and preparation method thereof | |
| CN110004457A (en) | A kind of bipolar membrane device suitable for preparing lithium hydroxide using lithium carbonate as raw material | |
| CN114220984B (en) | SPEEK/modified bentonite composite ion exchange membrane and preparation method thereof | |
| CN111074299B (en) | Ultrathin perfluorinated sulfonic acid ion exchange membrane for alkali metal chloride electrolysis and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |