CN111341980A - Sodium perfluorosulfonate ion battery electrolyte membrane and preparation method and application thereof - Google Patents
Sodium perfluorosulfonate ion battery electrolyte membrane and preparation method and application thereof Download PDFInfo
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- CN111341980A CN111341980A CN202010112671.2A CN202010112671A CN111341980A CN 111341980 A CN111341980 A CN 111341980A CN 202010112671 A CN202010112671 A CN 202010112671A CN 111341980 A CN111341980 A CN 111341980A
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- sodium
- calcium
- ion battery
- electrolyte membrane
- perfluorosulfonate
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- 239000011734 sodium Substances 0.000 title claims abstract description 54
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 46
- -1 Sodium perfluorosulfonate ion Chemical class 0.000 title claims abstract description 37
- 239000003792 electrolyte Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000012528 membrane Substances 0.000 title claims description 24
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000011575 calcium Substances 0.000 claims abstract description 38
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 38
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000011593 sulfur Substances 0.000 claims abstract description 25
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 25
- 238000005245 sintering Methods 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 16
- 239000003518 caustics Substances 0.000 claims abstract description 9
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 159000000007 calcium salts Chemical class 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 150000003463 sulfur Chemical class 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 239000000243 solution Substances 0.000 claims description 37
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- 239000003292 glue Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 19
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 16
- 239000002002 slurry Substances 0.000 claims description 16
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 11
- 239000011248 coating agent Substances 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 229910001424 calcium ion Inorganic materials 0.000 claims description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 5
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910001416 lithium ion Inorganic materials 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- VEUACKUBDLVUAC-UHFFFAOYSA-N [Na].[Ca] Chemical compound [Na].[Ca] VEUACKUBDLVUAC-UHFFFAOYSA-N 0.000 abstract description 22
- 239000002808 molecular sieve Substances 0.000 abstract description 21
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 abstract description 21
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 14
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 13
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 8
- 239000011244 liquid electrolyte Substances 0.000 abstract description 7
- 210000001787 dendrite Anatomy 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 239000007784 solid electrolyte Substances 0.000 abstract description 3
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 239000000843 powder Substances 0.000 abstract description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- 235000011121 sodium hydroxide Nutrition 0.000 description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- PPQREHKVAOVYBT-UHFFFAOYSA-H dialuminum;tricarbonate Chemical compound [Al+3].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O PPQREHKVAOVYBT-UHFFFAOYSA-H 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 239000007772 electrode material Substances 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- JBJWASZNUJCEKT-UHFFFAOYSA-M sodium;hydroxide;hydrate Chemical compound O.[OH-].[Na+] JBJWASZNUJCEKT-UHFFFAOYSA-M 0.000 description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- 229940118662 aluminum carbonate Drugs 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000002238 attenuated effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- AWRQDLAZGAQUNZ-UHFFFAOYSA-K sodium;iron(2+);phosphate Chemical compound [Na+].[Fe+2].[O-]P([O-])([O-])=O AWRQDLAZGAQUNZ-UHFFFAOYSA-K 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the technical field of solid electrolyte materials of sodium ion batteries, and particularly relates to a sodium perfluorosulfonate ion battery electrolyte diaphragm and a preparation method and application thereof. The preparation method takes calcium salt, aluminum salt and sulfur salt with specific proportion as raw materials, and prepares calcium sulfoaluminate through high-temperature sintering; then caustic alkali and the calcium sulphoaluminate are subjected to low-temperature hydrothermal reaction to prepare a sodium calcium sulphoaluminate molecular sieve; and finally, preparing the sulfur-containing calcium sodium aluminate molecular sieve and PFSA-Li powder into a sodium ion solid electrolyte diaphragm. The finished product prepared by the preparation method can reduce or avoid the use of liquid electrolyte, remarkably inhibit the generation of dendrite of a metal sodium negative electrode, has higher strength, can be directly used for assembling a battery as a sodium ion secondary battery diaphragm, and can remarkably enhance the conductivity of sodium ions and the cycle stability of a large-current charge-discharge battery.
Description
Technical Field
The invention belongs to the technical field of solid electrolyte materials of sodium ion batteries, and particularly relates to a sodium perfluorosulfonate ion battery electrolyte diaphragm and a preparation method and application thereof.
Background
Among many energy storage systems, lithium ion batteries have been rapidly developed in portable devices due to their advantages of high energy density, high power density, high discharge voltage, low self-discharge rate, and the like. However, lithium resources are a relatively scarce resource, and their large use leads to an increase in the price of lithium products. Although the energy density of the sodium ion battery is lower than that of the lithium ion battery, the sodium ion battery has good application prospect in the field with low requirement on the energy density because the sodium resource is abundant and easy to obtain.
However, sodium ion batteries mostly adopt organic liquid electrolytes, and the electrolytes and electrode materials can damage electrode materials during charging and discharging processes and cause irreversible attenuation of battery capacity; meanwhile, in the long-term service process of the battery, the organic liquid electrolyte can volatilize, dry, leak and the like, and the service life of the battery is seriously influenced. On the other hand, due to factors such as the current density on the surface of the electrode and the uneven distribution of sodium ions, the desorption and the intercalation of ions in the battery circulation of the sodium ion battery can cause the occurrence of side reactions of electrode materials to generate decomposition products and the desorbed electrode materials, and the dissolution and the deposition of the electrode materials can form uneven holes and dendrites. The dendrite can pierce through the diaphragm to contact the positive electrode, and a series of potential safety hazards such as battery short circuit, thermal runaway, ignition and explosion are caused.
Disclosure of Invention
The invention provides a preparation method of an electrolyte diaphragm of a sodium perfluorosulfonate ion battery, aiming at the problems that the battery capacity is attenuated and potential safety hazards can be caused by dendritic crystals due to side reactions of a liquid electrolyte and an electrode.
The invention also provides a sodium perfluorosulfonate ion battery electrolyte diaphragm.
The invention also provides application of the sodium perfluorosulfonate ion battery electrolyte membrane in preparation of a lithium ion battery.
In order to achieve the purpose of the invention, the embodiment of the invention adopts the following technical scheme:
a preparation method of an electrolyte diaphragm of a sodium perfluorosulfonate ion battery specifically comprises the following steps:
s1, mixing the calcium salt, the sulfate and the aluminum salt, and sintering at 1300-1600 ℃ to obtain porous layered calcium sulphoaluminate; in the calcium salt, the sulfur salt and the aluminum salt, the molar ratio of calcium to aluminum is 1: 1.2-2, and the molar ratio of calcium to sulfur is 4-10: 1;
s2, placing the porous layered calcium sulphoaluminate into a caustic alkali solution, and reacting at the temperature of 110-160 ℃; the molar weight of alkali metal ions in the caustic solution is 4-10 times of that of calcium ions in the porous layered calcium sulphoaluminate;
and S3, preparing a glue solution from the product obtained in S2, polyethylene oxide (PEO), lithium perfluorosulfonate (PFSA-Li) and an organic solvent, blade-coating, and drying to obtain the polyethylene terephthalate.
According to the preparation method, firstly, calcium salt, aluminum salt and sulfur salt with limited proportion of calcium element, aluminum element and sulfur element are used as raw materials in S1, and porous layered calcium sulphoaluminate can be prepared by high-temperature sintering at a specific temperature.
Then in S2, the porous calcium sulphoaluminate prepared in S1 and alkali metal in caustic soda undergo ion exchange through low-temperature hydrothermal reaction at a specific temperature, so that the sodium sulphoaluminate molecular sieve with uniform pore diameter and complete crystal form is prepared. The molecular sieve can selectively filter decomposition products of electrode side reactions and electrode falling objects, prevent the decomposition products from passing through and can remarkably inhibit the generation of dendritic crystals of the metal sodium cathode.
And finally, carrying out ion exchange reaction on the sulfur-containing calcium sodium aluminate molecular sieve and water-soluble PFSA-Li in glue solution in S3 to obtain calcium sodium sulphoaluminate molecular sieve modified PFSA-Na composite powder, and carrying out blade coating and drying to form a solid sulfur-containing PFSA-Na composite diaphragm, namely the sodium perfluorosulfonate ion battery electrolyte diaphragm. PFSA-Li is water soluble and has relaxed requirement on production environment, and low temperature film forming is performed, so that S3 has no need of high temperature and long reaction time. The framework structure of the molecular sieve obtained from S2 can also enhance the strength of the electrolyte membrane.
Compared with other polymer electrolyte diaphragms, the sodium perfluorosulfonate ion battery electrolyte diaphragm obtained by the invention can be directly used for assembling batteries without additionally adding liquid electrolyte, has good conductivity, does not have the conditions of collapse, melting and the like caused by the reaction of the liquid electrolyte and electrodes, and reduces the battery capacity attenuation caused by the use of the liquid electrolyte. Meanwhile, the obtained diaphragm can filter decomposition products of electrode side reaction and electrode falling objects, and can inhibit generation of dendritic crystals. The electrolyte diaphragm is used as a diaphragm of a sodium ion secondary battery, and can obviously enhance the conductivity of sodium ions and the cycle stability of a large-current charge-discharge battery.
The process flow diagram of the preparation method of the invention is shown in figure 1.
Preferably, the mixing is to treat the calcium salt, the sulfate and the aluminum salt together with the absolute ethyl alcohol in a ball mill until the materials are mixed uniformly.
Preferably, the sintering is carried out for 10-15 min at 1550-1600 ℃, and then the temperature is reduced to 1300-1400 ℃ for 2-10 h.
Preferably, the caustic is sodium hydroxide.
Preferably, the concentration of the sodium hydroxide solution is 10-80 g/L. At the concentration, the reaction time is preferably 6-24 h.
Preferably, the caustic alkali solution further contains carbonate of alkali metal, wherein the molar amount of the carbonate in the carbonate is 1/6-1/3 of the molar amount of the calcium element. The carbonate can remove part of calcium in the calcium sulphoaluminate, and can further form pores on the calcium sulphoaluminate.
Preferably, the organic solvent is Dimethylformamide (DMF).
Preferably, the method for preparing the glue solution comprises the following steps: and (3) preparing the product obtained in the step (S2), the polyoxyethylene, the lithium perfluorosulfonate and the organic solvent into slurry, and dispersing the slurry to form uniform glue solution at the temperature of 45-65 ℃.
Preferably, the dispersion is on a magnetic stirrer. Under magnetic stirring, the positive charge of the molecular sieve is close to the magnetic field of the negative electrode, so that the molecular sieve with one-way permeability is obtained, and the passing of substances has selectivity.
Preferably, the drying temperature is 80-100 ℃.
Preferably, the thickness of the blade coating is 30-40 μm.
The embodiment of the invention also provides a sodium perfluorosulfonate ion battery electrolyte diaphragm, which is prepared by the preparation method of the sodium perfluorosulfonate ion battery electrolyte diaphragm.
The embodiment of the invention also provides application of the sodium perfluorosulfonate ion battery electrolyte membrane in preparation of a lithium ion battery. The sodium ion battery prepared by using the sodium perfluorosulfonate ion battery electrolyte membrane can keep stable structure after repeated cyclic charge and discharge, the battery capacity is not obviously attenuated, and the dendritic crystal can be effectively inhibited. And the battery assembled by the separator has good conductivity and good performance even at relatively high working temperature.
Drawings
FIG. 1 is a schematic process flow diagram of the present invention;
FIG. 2 is a micro-morphology of calcium sulfoaluminate produced at S1 in example 2 of the present invention;
FIG. 3 shows the microstructure of S2 of the sodium calcium aluminate containing sulfur prepared in example 2 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
The embodiment provides a sodium perfluorosulfonate ion battery electrolyte membrane, and the preparation method comprises the following steps:
s1, taking calcium carbonate, aluminum sulfate and aluminum hydroxide as raw materials, mixing and mixing according to the molar ratio of calcium element to aluminum element to sulfur element of 10:17:2, putting the mixed material and absolute ethyl alcohol into a high-energy ball mill for treatment for 12 hours, then making the treated material into a cake shape, putting the cake shape into a high-temperature sintering furnace for sintering at 1600 ℃ for 10 minutes, cooling to 1350 ℃ and preserving heat for 6 hours to obtain the porous layered calcium sulphoaluminate.
S2, putting the porous layer calcium sulphoaluminate prepared in the S1 into a hydrothermal kettle containing 25g/L of NaOH aqueous solution for carrying out sodium treatment and pore-forming treatment, wherein the molar weight of NaOH is 6 times of that of calcium ions in the porous layer calcium sulphoaluminate, the hydrothermal temperature is 135 ℃, and the hydrothermal time is 8 hours, so that the sodium calcium sulphoaluminate molecular sieve with uniform pore diameter and complete crystal form is prepared.
S3, preparing the sodium calcium aluminate containing sulfur prepared in the S2, PEO, PFSA-Li and DMF into slurry, and uniformly dispersing the slurry on a magnetic stirrer at the temperature of 55 ℃ in the dispersing process for 12 hours to form uniform glue solution. And finally, carrying out blade coating on the obtained glue solution (the thickness is 35 mu m), and drying at 90 ℃ for 8h to obtain the sulfur-containing PFSA-Na compound diaphragm modified by the sodium calcium sulphoaluminate molecular sieve.
Example 2
The embodiment provides a sodium perfluorosulfonate ion battery electrolyte membrane, and the preparation method comprises the following steps:
s1, taking calcium carbonate, aluminum sulfate and aluminum hydroxide as raw materials, mixing and mixing according to the molar ratio of calcium element to aluminum element to sulfur element of 10:17:2, putting the mixed material and absolute ethyl alcohol into a high-energy ball mill for treatment for 12 hours, then making the treated material into a cake shape, putting the cake shape into a high-temperature sintering furnace for sintering at 1600 ℃ for 10 minutes, cooling to 1350 ℃ and preserving heat for 6 hours to obtain the porous layered calcium sulfoaluminate, wherein the microscopic appearance of the porous layered calcium sulfoaluminate is shown in figure 2.
S2, placing the porous calcium sulphoaluminate prepared in S1 into a solution containing 25g/L NaOH water solution and 4.1g/L Na2CO3Carrying out sodium treatment and pore-forming treatment in a hydrothermal kettle of aqueous solution, wherein the molar weight of NaOH is 4 times of that of calcium ions in the porous calcium sulphoaluminate, the hydrothermal temperature is 135 ℃, the hydrothermal time is 8h, and the prepared sulphoaluminate-containing acid with uniform aperture and complete crystal formThe micro-topography of the calcium sodium molecular sieve is shown in figure 3.
S3, preparing the sodium calcium aluminate containing sulfur prepared in the S2, PEO, PFSA-Li and DMF into slurry, and uniformly dispersing the slurry on a magnetic stirrer at the temperature of 55 ℃ in the dispersing process for 12 hours to form uniform glue solution. And finally, carrying out blade coating on the obtained glue solution (the thickness is 35 mu m), and drying at 90 ℃ for 8h to obtain the sulfur-containing PFSA-Na compound diaphragm modified by the sodium calcium sulphoaluminate molecular sieve.
Example 3
The embodiment provides a sodium perfluorosulfonate ion battery electrolyte membrane, and the preparation method comprises the following steps:
s1, taking calcium hydroxide, aluminum sulfate and aluminum carbonate as raw materials, mixing and mixing according to the molar ratio of calcium element to aluminum element to sulfur element of 10:15:2, putting the mixed material and absolute ethyl alcohol into a high-energy ball mill for treatment for 12 hours, then making the treated material into a cake shape, putting the cake shape into a high-temperature sintering furnace for sintering at 1550 ℃ for 15 minutes, and cooling to 1320 ℃ for heat preservation for 4 hours to obtain the porous layered calcium sulfoaluminate.
S2, placing the porous calcium sulfoaluminate prepared in S1 into a solution containing 10g/L NaOH water solution and 0.4g/L Na2CO3Carrying out sodium treatment and pore-forming treatment in a hydrothermal kettle of the aqueous solution, wherein the molar weight of NaOH is 10 times of that of calcium ions in the porous calcium sulphoaluminate, the hydrothermal temperature is 160 ℃, and the hydrothermal time is 6 hours, so as to prepare the sodium calcium sulphoaluminate molecular sieve with uniform aperture and complete crystal form.
S3, preparing the sodium calcium aluminate containing sulfur prepared in the S2, PEO, PFSA-Li and DMF into slurry, and uniformly dispersing the slurry on a magnetic stirrer at the temperature of 45 ℃ in the dispersing process for 12 hours to form uniform glue solution. And finally, carrying out blade coating on the obtained glue solution (the thickness is 35 mu m), and drying at 80 ℃ for 9h to obtain the sulfur-containing PFSA-Na compound diaphragm modified by the sodium calcium sulphoaluminate molecular sieve.
Example 4
The embodiment provides a sodium perfluorosulfonate ion battery electrolyte membrane, and the preparation method comprises the following steps:
s1, taking calcium sulfate, calcium hydroxide and aluminum carbonate as raw materials, mixing and mixing according to the molar ratio of calcium element to aluminum element to sulfur element of 10:16:2, putting the mixed material and absolute ethyl alcohol into a high-energy ball mill for treatment for 12 hours, then making the treated material into a cake shape, putting the cake shape into a high-temperature sintering furnace for sintering at 1600 ℃ for 12 minutes, cooling to 1300 ℃ and preserving heat for 8 hours to obtain the porous layered calcium sulfoaluminate.
S2, placing the porous calcium sulfoaluminate prepared in S1 into a solution containing 30g/L NaOH water solution and 2.5g/L Na2CO3Carrying out sodium treatment and pore-forming treatment in a hydrothermal kettle of the aqueous solution, wherein the molar weight of NaOH is 8 times of that of calcium ions in the porous calcium sulphoaluminate, the hydrothermal temperature is 145 ℃, and the hydrothermal time is 10h, so as to prepare the sodium calcium sulphoaluminate molecular sieve with uniform aperture and complete crystal form.
S3, preparing the sodium calcium aluminate containing sulfur prepared in the S2, PEO, PFSA-Li and DMF into slurry, and uniformly dispersing the slurry on a magnetic stirrer at the temperature of 50 ℃ in the dispersing process for 12 hours to form uniform glue solution. Finally, the obtained glue solution is subjected to blade coating (the thickness is 40 mu m), and then is dried for 7 hours at the temperature of 100 ℃, so as to prepare the sulfur-containing PFSA-Na composite diaphragm modified by the calcium sulphoaluminate sodium molecular sieve.
Example 5
The embodiment provides a sodium perfluorosulfonate ion battery electrolyte membrane, and the preparation method comprises the following steps:
s1, taking calcium hydroxide, aluminum sulfate and aluminum hydroxide as raw materials, mixing and mixing according to the molar ratio of calcium element to aluminum element to sulfur element of 10:12:2.5, putting the mixed material and absolute ethyl alcohol into a high-energy ball mill for treatment for 12 hours, then making the treated material into a cake shape, putting the cake shape into a high-temperature sintering furnace for sintering at 1570 ℃ for 13 minutes, cooling to 1350 ℃ and preserving heat for 8 hours to obtain the porous layered calcium sulphoaluminate.
S2, placing the porous calcium sulfoaluminate prepared in S1 into a solution containing 45g/L NaOH water solution and 4.8g/L Na2CO3Carrying out sodium treatment and pore-forming treatment in a hydrothermal kettle of the aqueous solution, wherein the molar weight of NaOH is 5 times of that of calcium ions in the porous calcium sulphoaluminate, the hydrothermal temperature is 125 ℃, and the hydrothermal time is 18h, so as to prepare the sodium calcium sulphoaluminate molecular sieve with uniform aperture and complete crystal form.
S3, preparing the sodium calcium aluminate containing sulfur prepared in the S2, PEO, PFSA-Li and DMF into slurry, and uniformly dispersing the slurry on a magnetic stirrer at the temperature of 55 ℃ in the dispersing process for 12 hours to form uniform glue solution. And finally, carrying out blade coating on the obtained glue solution (the thickness is 35 mu m), and drying at 95 ℃ for 8h to obtain the sulfur-containing PFSA-Na compound diaphragm modified by the sodium calcium sulphoaluminate molecular sieve.
Example 6
The embodiment provides a sodium perfluorosulfonate ion battery electrolyte membrane, and the preparation method comprises the following steps:
s1, taking calcium sulfate, calcium carbonate and aluminum carbonate as raw materials, mixing and mixing according to the molar ratio of calcium element to aluminum element to sulfur element of 10:20:1, putting the mixed material and absolute ethyl alcohol into a high-energy ball mill for treatment for 12 hours, then making the treated material into a cake shape, putting the cake shape into a high-temperature sintering furnace for sintering at 1520 ℃ for 15 minutes, and cooling to 1400 ℃ for heat preservation for 2 hours to obtain the porous layered calcium sulfoaluminate.
S2, placing the porous calcium sulfoaluminate prepared in S1 into a solution containing 80g/L NaOH aqueous solution and 17.7g/L Na2CO3Carrying out sodium treatment and pore-forming treatment in a hydrothermal kettle of the aqueous solution, wherein the molar weight of NaOH is 4 times of that of calcium ions in the porous calcium sulphoaluminate, the hydrothermal temperature is 110 ℃, and the hydrothermal time is 24 hours, so as to prepare the sodium calcium sulphoaluminate molecular sieve with uniform aperture and complete crystal form.
S3, preparing the sodium calcium aluminate containing sulfur prepared in the S2, PEO, PFSA-Li and DMF into slurry, and uniformly dispersing the slurry on a magnetic stirrer at the temperature of 65 ℃ in the dispersing process for 12 hours to form uniform glue solution. And finally, carrying out blade coating on the obtained glue solution (the thickness is 30 mu m), and drying at 85 ℃ for 9h to obtain the sulfur-containing PFSA-Na compound diaphragm modified by the sodium calcium sulphoaluminate molecular sieve.
Example 7
The embodiment provides application of an electrolyte membrane of a sodium perfluorosulfonate ion battery in preparation of a sodium ion battery.
And assembling the CR2032 button cell by using sodium iron phosphate as a positive electrode, metal sodium as a negative electrode and the finished product obtained in the example 2 as a diaphragm, wherein the test voltage range is 1.2-3.6V. The specific discharge capacity of the first ring of the battery reaches 128 mAh.g-1The battery has excellent performance, the contact ratio of charge and discharge curves after 100, 500 and 1000 cycles of circulation is higher, the capacity retention rates are respectively 99.32%, 98.75% and 96.58%, and the polarization is smaller, which indicates that the battery has good reversibility in the circulation process. Meanwhile, the conductivity of the assembled battery measured at the working temperature of 40-50 ℃ is close to 10-3S/cm, which shows that the performance is good.
After 1000 cycles of circulation, the assembled battery is disassembled, no obvious sodium dendrite is generated on the sodium metal cathode close to one side of the diaphragm, and trace 10-35 nm small particles are attached to the diaphragm close to one side of the anode material, which shows that the diaphragm can effectively inhibit the generation of dendrite.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents or improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A preparation method of an electrolyte diaphragm of a sodium perfluorosulfonate ion battery is characterized by comprising the following steps:
s1, mixing the calcium salt, the sulfate and the aluminum salt, and sintering at 1300-1600 ℃ to obtain porous layered calcium sulphoaluminate; in the calcium salt, the sulfur salt and the aluminum salt, the molar ratio of calcium to aluminum is 1: 1.2-2, and the molar ratio of calcium to sulfur is 4-10: 1;
s2, placing the porous layered calcium sulphoaluminate into a caustic alkali solution, and reacting at the temperature of 110-160 ℃; the molar weight of alkali metal ions in the caustic solution is 4-10 times of that of calcium ions in the porous layered calcium sulphoaluminate;
and S3, preparing a glue solution from the product obtained in the step S2, polyoxyethylene, lithium perfluorosulfonate and an organic solvent, blade-coating, and drying to obtain the lithium perfluorosulfonate-containing aqueous solution.
2. The method for preparing the electrolyte membrane of the sodium perfluorosulfonate ion battery according to claim 1, wherein the mixing is performed by treating the calcium salt, the sulfate and the aluminum salt together with absolute ethyl alcohol in a ball mill until the materials are uniformly mixed.
3. The method for preparing the electrolyte membrane of the sodium perfluorosulfonate ion battery according to claim 1, wherein the sintering step comprises the steps of maintaining the temperature at 1550-1600 ℃ for 10-15 min, and then cooling to 1300-1400 ℃ for 2-10 h.
4. The method of making a sodium perfluorosulfonate ion battery electrolyte membrane according to claim 1, wherein the caustic is sodium hydroxide; and/or
The caustic alkali solution also contains carbonate of alkali metal, and the molar quantity of the carbonate in the carbonate is 1/6-1/3 of the molar quantity of the calcium element.
5. The method for preparing the sodium perfluorosulfonate ion battery electrolyte membrane according to claim 4, wherein the concentration of the sodium hydroxide solution is 10-80 g/L.
6. The method of preparing a sodium perfluorosulfonate ion battery electrolyte membrane according to claim 1, wherein the organic solvent is dimethylformamide; and/or
The method for preparing the glue solution comprises the following steps: and (3) preparing the product obtained in the step (S2), the polyoxyethylene, the lithium perfluorosulfonate and the dimethylformamide into slurry, and dispersing the slurry to form uniform glue solution at the temperature of 45-65 ℃.
7. The method of preparing a sodium perfluorosulfonate ion battery electrolyte membrane according to claim 6, wherein the dispersing is dispersing on a magnetic stirrer.
8. The method for preparing the sodium perfluorosulfonate ion battery electrolyte membrane according to claim 1, wherein the drying temperature is 80-100 ℃; and/or
The thickness of the blade coating is 30-40 mu m.
9. A sodium perfluorosulfonate ion battery electrolyte membrane is characterized in that the sodium perfluorosulfonate ion battery electrolyte membrane is prepared by the preparation method of the sodium perfluorosulfonate ion battery electrolyte membrane according to any one of claims 1 to 8.
10. Use of the sodium perfluorosulfonate ion battery electrolyte membrane of claim 9 in the preparation of a lithium ion battery.
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