CN117586295A - Preparation method of sodium tetra (pentafluorophenol) borate and application of sodium tetra (pentafluorophenol) borate in sodium electricity - Google Patents
Preparation method of sodium tetra (pentafluorophenol) borate and application of sodium tetra (pentafluorophenol) borate in sodium electricity Download PDFInfo
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- CN117586295A CN117586295A CN202410069286.2A CN202410069286A CN117586295A CN 117586295 A CN117586295 A CN 117586295A CN 202410069286 A CN202410069286 A CN 202410069286A CN 117586295 A CN117586295 A CN 117586295A
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- pentafluorophenol
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- -1 sodium tetra (pentafluorophenol) borate Chemical compound 0.000 title claims abstract description 98
- 239000011734 sodium Substances 0.000 title claims abstract description 30
- 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 title claims abstract description 23
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 23
- 230000005611 electricity Effects 0.000 title claims abstract description 5
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000003792 electrolyte Substances 0.000 claims abstract description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- XBNGYFFABRKICK-UHFFFAOYSA-N 2,3,4,5,6-pentafluorophenol Chemical compound OC1=C(F)C(F)=C(F)C(F)=C1F XBNGYFFABRKICK-UHFFFAOYSA-N 0.000 claims abstract description 17
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachloro-phenol Natural products OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 11
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 10
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 abstract description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052731 fluorine Inorganic materials 0.000 abstract description 3
- 239000011737 fluorine Substances 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 2
- 235000019441 ethanol Nutrition 0.000 abstract 1
- 238000001953 recrystallisation Methods 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 238000001228 spectrum Methods 0.000 description 24
- 238000005481 NMR spectroscopy Methods 0.000 description 19
- 230000014759 maintenance of location Effects 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 239000000654 additive Substances 0.000 description 8
- 230000000996 additive effect Effects 0.000 description 7
- 229910021385 hard carbon Inorganic materials 0.000 description 7
- VQQHOCOBXJTWDY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ylperoxyboronic acid Chemical compound B(O)(O)OOC(C(F)(F)F)C(F)(F)F VQQHOCOBXJTWDY-UHFFFAOYSA-N 0.000 description 6
- XGKVVMPYYAOOTQ-UHFFFAOYSA-N C(C)O.FC1=C(C(=C(C(=C1O)F)F)F)F Chemical compound C(C)O.FC1=C(C(=C(C(=C1O)F)F)F)F XGKVVMPYYAOOTQ-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 159000000000 sodium salts Chemical class 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
- C07F5/02—Boron compounds
- C07F5/022—Boron compounds without C-boron linkages
-
- 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
Abstract
The invention discloses a preparation method of sodium tetra (pentafluorophenol) borate and application thereof in sodium electricity, and relates to the technical field of sodium ion batteries. Dissolving pentafluorophenol solid in ethanol, and adding sodium borohydride to react by heating to obtain a sodium tetra (pentafluorophenol) borate solution. Filtering the solution to obtain a sodium tetra (pentafluorophenol) borate solid, washing the solid with absolute ethyl alcohol, and drying in vacuum to obtain sodium tetra (pentafluorophenol) borate. The sodium tetra (pentafluorophenol) borate can be obtained by the one-step method, the process route is simple, and the method has environmental protection. And the product can be obtained by filtration without separation steps of recrystallization. The obtained sodium tetrakis (pentafluorophenol) borate has a plurality of fluorine-containing benzene ring structures, and thus has high stability and high hydrophobicity. The sodium tetrakis (pentafluorophenol) borate is used as electrolyte of sodium battery electrolyte, and has more excellent performance than the common sodium hexafluorophosphate.
Description
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to a preparation method of sodium tetra (pentafluorophenol) borate and application thereof in sodium electricity.
Background
A sodium battery is a battery using sodium ions as charge carriers and operates on a principle and structure similar to that of a lithium battery, but uses sodium ions instead of lithium ions. Sodium batteries are considered to be important competitors to future battery technology because of their higher ionic conductivity and lower manufacturing costs. The sodium battery can be used as an energy storage device for adjusting the load of a power grid, so that the stability of a power system is improved. In the field of renewable energy sources such as wind energy, solar energy and the like, the sodium battery can be used as an energy storage system to provide stable power output.
The sodium electroelectrolyte is a carrier for transmitting sodium ions and consists of electrolyte, solvent and additive. The ideal electrolyte salt has the following conditions: (1) the ionic conductivity of the solution is high; (2) The electrochemical stability is good, and a wider electrochemical window is provided; (3) The chemical stability is good, the reaction with the solvent and the electrode material is avoided, and the thermal stability is good; (4) So that the ion embedding quantity in the anode and cathode materials is high, the reversibility is good, and the like. Sodium ion batteries use sodium salts as solutes, which can be classified as fluorine-containing sodium salts (NaPF 6 NaOTF, naFSI, naTFSI, etc.), and other sodium salts (NaClO) 4 Etc.). The Stokes radius and desolvation energy of sodium ions are smaller than those of lithium ions, and the sodium salt electrolyte with low concentration has higher ionic conductivity. Currently, sodium ion battery electrolytes typically employ NaPF 6 As the sodium salt. However, sodium hexafluorophosphate is very sensitive to water, and highly corrosive hydrofluoric acid (HF) is easily generated to react with alkaline components of the SEI film, generating harmful gases to weaken the rigid SEI film. And sodium hexafluorophosphate has poor stability in air. Therefore, a novel sodium ion electrolyte salt is designed, so that the sodium ion electrolyte salt has high hydrophobicity and high stability, and has wide application prospect.
The Chinese patent document with publication number CN116162102A discloses a preparation method of sodium borate salt. But the preparation process is complex; in addition, the purification process adopts a precipitant, which not only increases the cost, but also has low purity of the product.
Disclosure of Invention
The invention aims to provide a preparation method of sodium tetra (pentafluorophenol) borate, which has the advantages of simple and convenient process route, environmental protection, stable product to air and water, high yield, high purity and high conductivity. The invention also evaluates sodium tetra (pentafluorophenol) borate as sodium electrolyte, and the result shows that the sodium tetra (pentafluorophenol) borate synthesized by the invention has better performance than the sodium hexafluorophosphate commonly used at present.
The preparation method of the sodium tetra (pentafluorophenol) borate comprises the following steps:
(1) Dissolving pentafluorophenol solid in absolute ethyl alcohol, and then adding sodium borohydride to react by heating to obtain sodium tetra (pentafluorophenol) borate. The step of dissolving the pentafluorophenol comprises the steps of adding the pentafluorophenol solid into absolute ethyl alcohol for dissolution; the proportion of the pentafluorophenol to the absolute ethyl alcohol is 1mol:30-50ml; the molar ratio of the pentafluorophenol to the sodium borohydride is 3.6-4.4:1, a step of; the reaction equation is as follows:
(2) Filtering the solution obtained in the step (1), washing the precipitate with absolute ethyl alcohol for 3 times, and vacuum drying to obtain sodium tetrakis (pentafluorophenol) borate crystals.
Preferably, in the step (1), the reaction temperature is 50-80 ℃ and the reaction time is 12-20h.
More preferably, in the step (1), the reaction temperature is 60-70 ℃ and the reaction time is 14-18h.
Preferably, in the step (2), the temperature of the vacuum drying is 60-80 ℃ and the time is 16-24 hours.
It is another object of the present invention to provide the use of sodium tetrakis (pentafluorophenol) borate prepared by the above method for use in an electrolyte in a sodium battery electrolyte.
The sodium tetra (pentafluorophenol) borate can be obtained by the one-step method, the reaction process route is simple and environment-friendly, and the purification step is not needed. The obtained sodium tetrakis (pentafluorophenol) borate has high purity (> 99.9%) and low impurity content (free acid <30ppm, moisture <40ppm, chloride <4ppm, sulfate <5 ppm). And because the sodium tetra (pentafluorophenol) borate contains a large amount of fluorine-containing benzene rings, the sodium tetra (pentafluorophenol) borate has high stability and high hydrophobicity. The sodium tetra (pentafluorophenol) borate is used as a sodium battery electrolyte solute, has more excellent performance (cycle performance, conductivity and low-temperature performance are obviously better than those of sodium hexafluorophosphate) than the common sodium hexafluorophosphate, and has wide industrialization prospect.
Drawings
FIG. 1 is an H-nuclear magnetic resonance spectrum of sodium tetrakis (pentafluorophenol) borate of example 1 of the present invention;
FIG. 2 is a B-nuclear magnetic resonance spectrum of sodium tetrakis (pentafluorophenol) borate of example 1 of the present invention;
FIG. 3 is an F-nuclear magnetic resonance spectrum of sodium tetrakis (pentafluorophenol) borate of example 1 of the present invention.
Detailed Description
The technical scheme of the present invention will be clearly and completely described in the following in conjunction with the accompanying drawings and examples. Those skilled in the art will appreciate that the embodiments described below are some, but not all, embodiments of the present invention and are intended to be illustrative of the present invention only and should not be construed as limiting the scope of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
4mol of pentafluorophenol was added to 160ml of absolute ethanol and stirred at 40℃for 1 hour. 1mol of sodium borohydride is added into the pentafluorophenol ethanol solution to react for 16 hours at 65 ℃ to obtain a sodium tetra (pentafluorophenol) borate solution.
The sodium tetrakis (pentafluorophenol) borate solution was filtered and the precipitate was washed 3 times with absolute ethanol and dried in vacuo at 70 ℃ for 20h to give sodium tetrakis (pentafluorophenol) borate crystals.
Performing H spectrum nuclear magnetic resonance, B spectrum nuclear magnetic resonance test and F spectrum nuclear magnetic resonance test on sodium tetra (pentafluorophenol) borate; sodium tetrakis (pentafluorophenol) borate was taken at 3.3V Na 0.83 Li 0.25 Mn 0.75 O 2 The hard carbon soft package battery system is subjected to cycle stability, low-temperature discharge capacity retention rate and conductivity test, wherein the sodium-electricity electrolyte solvent is 30wt% DMC+25wt% DEC, the electrolyte is sodium tetra (hexafluoroisopropoxy) borate, the content is 30wt% -40wt%, and the balance is a well-known common additive. And compared with commercially available sodium hexafluorophosphate.
Example 2
3.6mol of pentafluorophenol are added to 120ml of absolute ethanol and stirred for 1h at 40 ℃.1mol of sodium borohydride is added into the pentafluorophenol ethanol solution to react for 12 hours at 50 ℃ to obtain a sodium tetra (pentafluorophenol) borate solution.
The sodium tetrakis (pentafluorophenol) borate solution was filtered and the precipitate was washed 3 times with absolute ethanol and dried under vacuum at 60 ℃ for 16h to give sodium tetrakis (pentafluorophenol) borate crystals.
Performing H spectrum nuclear magnetic resonance, B spectrum nuclear magnetic resonance test and F spectrum nuclear magnetic resonance test on sodium tetra (pentafluorophenol) borate; sodium tetrakis (pentafluorophenol) borate was taken at 3.3V Na 0.83 Li 0.25 Mn 0.75 O 2 The hard carbon soft package battery system is subjected to cycle stability, low-temperature discharge capacity retention rate and conductivity test, wherein the sodium-electricity electrolyte solvent is 30wt% DMC+25wt% DEC, the electrolyte is sodium tetra (hexafluoroisopropoxy) borate, the content is 30wt% -40wt%, and the balance is a well-known common additive. And compared with commercially available sodium hexafluorophosphate.
Example 3
4.4mol of pentafluorophenol are added to 200ml of absolute ethanol and stirred for 1h at 40 ℃.1mol of sodium borohydride is added into the pentafluorophenol ethanol solution to react for 20 hours at 80 ℃ to obtain a sodium tetra (pentafluorophenol) borate solution.
The sodium tetra (pentafluorophenol) borate solution was filtered and the precipitate was rinsed 3 times with absolute ethanol and dried under vacuum at 80 ℃ for 24h to give sodium tetra (pentafluorophenol) borate crystals.
Performing H spectrum nuclear magnetic resonance, B spectrum nuclear magnetic resonance test and F spectrum nuclear magnetic resonance test on sodium tetra (pentafluorophenol) borate; sodium tetrakis (pentafluorophenol) borate was taken at 3.3V Na 0.83 Li 0.25 Mn 0.75 O 2 The hard carbon soft package battery system is subjected to cycle stability, low-temperature discharge capacity retention rate and conductivity test, wherein the sodium-electricity electrolyte solvent is 30wt% DMC+25wt% DEC, the electrolyte is sodium tetra (hexafluoroisopropoxy) borate, the content is 30wt% -40wt%, and the balance is a well-known common additive. And compared with commercially available sodium hexafluorophosphate.
Example 4
4.1mol of pentafluorophenol are added to 150ml of absolute ethanol and stirred for 1h at 40 ℃. 1.1mol of sodium borohydride was added to the pentafluorophenol ethanol solution and reacted at 60℃for 14 hours to obtain a sodium tetrakis (pentafluorophenol) borate solution.
The sodium tetra (pentafluorophenol) borate solution was filtered and the precipitate was rinsed 3 times with absolute ethanol and dried in vacuo at 65 ℃ for 18h to give sodium tetra (pentafluorophenol) borate crystals.
Performing H spectrum nuclear magnetic resonance, B spectrum nuclear magnetic resonance test and F spectrum nuclear magnetic resonance test on sodium tetra (pentafluorophenol) borate; sodium tetrakis (pentafluorophenol) borate was taken at 3.3V Na 0.83 Li 0.25 Mn 0.75 O 2 The hard carbon soft package battery system is subjected to cycle stability, low-temperature discharge capacity retention rate and conductivity test, wherein the sodium-electricity electrolyte solvent is 30wt% DMC+25wt% DEC, the electrolyte is sodium tetra (hexafluoroisopropoxy) borate, the content is 30wt% -40wt%, and the balance is a well-known common additive. And compared with commercially available sodium hexafluorophosphate.
Example 5
3.8mol of pentafluorophenol were added to 170ml of absolute ethanol and stirred at 40℃for 1 hour. 0.9mol of sodium borohydride is added into the pentafluorophenol ethanol solution to react for 18 hours at 70 ℃ to obtain a sodium tetrakis (pentafluorophenol) borate solution.
The sodium tetrakis (pentafluorophenol) borate solution was filtered and the precipitate was rinsed 3 times with absolute ethanol and dried under vacuum at 75 ℃ for 24h to give sodium tetrakis (pentafluorophenol) borate crystals.
Performing H spectrum nuclear magnetic resonance, B spectrum nuclear magnetic resonance test and F spectrum nuclear magnetic resonance test on sodium tetra (pentafluorophenol) borate; sodium tetrakis (pentafluorophenol) borate was taken at 3.3V Na 0.83 Li 0.25 Mn 0.75 O 2 The hard carbon soft package battery system is subjected to cycle stability, low-temperature discharge capacity retention rate and conductivity test, wherein the sodium-electricity electrolyte solvent is 30wt% DMC+25wt% DEC, the electrolyte is sodium tetra (hexafluoroisopropoxy) borate, the content is 30wt% -40wt%, and the balance is a well-known common additive. And compared with commercially available sodium hexafluorophosphate.
Example 6
4.2mol of pentafluorophenol are added to 140ml of absolute ethanol and stirred for 1h at 40 ℃. 0.9mol of sodium borohydride is added into the pentafluorophenol ethanol solution to react for 18 hours at 75 ℃ to obtain a sodium tetrakis (pentafluorophenol) borate solution.
The sodium tetrakis (pentafluorophenol) borate solution was filtered and the precipitate was washed 3 times with absolute ethanol and dried in vacuo at 70 ℃ for 19h to give sodium tetrakis (pentafluorophenol) borate crystals.
Performing H spectrum nuclear magnetic resonance, B spectrum nuclear magnetic resonance test and F spectrum nuclear magnetic resonance test on sodium tetra (pentafluorophenol) borate; sodium tetrakis (pentafluorophenol) borate was taken at 3.3V Na 0.83 Li 0.25 Mn 0.75 O 2 The hard carbon soft package battery system is subjected to cycle stability, low-temperature discharge capacity retention rate and conductivity test, wherein the sodium-electricity electrolyte solvent is 30wt% DMC+25wt% DEC, the electrolyte is sodium tetra (hexafluoroisopropoxy) borate, the content is 30wt% -40wt%, and the balance is a well-known common additive. And compared with commercially available sodium hexafluorophosphate.
Comparative example 1
The sodium hexafluorophosphate of the comparative example is obtained by market purchase, and the manufacturer is mikrin with the purity of 99.9% and the brand number of 21324-39-0. Similarly, at 3.3V Na 0.83 Li 0.25 Mn 0.75 O 2 And (3) carrying out cycle stability, low-temperature discharge capacity retention rate and conductivity test on the hard carbon soft package battery system. The sodium electroelectrolyte solvent is 30wt% DMC+25wt% DEC, the electrolyte is sodium hexafluorophosphate, the content is 30wt% -40wt%, and the rest is common additives.
EXAMPLE 1 sodium tetrakis (pentafluorophenol) borate stability experiment
The sodium tetrakis (pentafluorophenol) borate of example 1 was exposed to air for 9 days, and the change in its composition was detected by nuclear magnetism, to thereby judge the stability of the sodium tetrakis (pentafluorophenol) borate.
EXAMPLE 1 sodium tetrakis (pentafluorophenol) borate hydrophobicity experiments
The hydrophobicity of sodium tetrakis (pentafluorophenol) borate was determined by mixing 1mol of sodium tetrakis (pentafluorophenol) borate of example 1 with 10mol of water for 4 days, and detecting the change in the composition by nuclear magnetism.
As can be seen from Table 1, the obtained sodium tetrakis (pentafluorophenol) borate had a high purity (> 99.9%) and a low impurity content (free acid <30ppm, moisture <40ppm, chloride <4ppm, sulfate <5 ppm)).
As can be seen from Table 2, the sodium tetrakis (pentafluorophenol) borate of example 1 was immersed in water for 4 days, and the H spectrum, F spectrum and B spectrum showed little change in peak positions, indicating that the sodium tetrakis (pentafluorophenol) borate of the present invention had very strong hydrophobicity; the sodium tetrakis (pentafluorophenol) borate of example 1 was subjected to nuclear magnetic resonance test by exposing it to air for 9 days, and the changes in the peak positions of the H spectrum, F spectrum and B spectrum were still small, indicating that the sodium tetrakis (pentafluorophenol) borate of the present invention has high stability.
As can be seen from Table 3, the sodium tetrakis (pentafluorophenol) borate of the present invention has significantly higher conductivity than the comparative example, with the highest example 1 being up to 14.6mS/cm, while the sodium hexafluorophosphate of the comparative example is only 4.7mS/cm; the sodium tetrakis (pentafluorophenol) borate of example 1 was cycled 500 times at 25 c to 92.5% capacity retention, while the comparative sodium hexafluorophosphate was only 74.9%; the 0.5C-20 ℃ discharge capacity retention rate of the sodium tetrakis (pentafluorophenol) borate of example 1 reached 81.6%, while the comparative example sodium hexafluorophosphate was only 57.4%, indicating that the sodium tetrakis (pentafluorophenol) borate of the present invention has better performance as a sodium electroelectrolyte than sodium hexafluorophosphate.
Claims (5)
1. A method for preparing sodium tetrakis (pentafluorophenol) borate, comprising the steps of:
(1) Dissolving pentafluorophenol solid in absolute ethyl alcohol, and then adding sodium borohydride to perform heating reaction to obtain sodium tetra (pentafluorophenol) borate; the step of dissolving the pentafluorophenol comprises the steps of adding the pentafluorophenol solid into absolute ethyl alcohol for dissolution; the proportion of the pentafluorophenol to the absolute ethyl alcohol is 1mol:30-50ml; the molar ratio of the pentafluorophenol to the sodium borohydride is 3.6-4.4:1, a step of;
(2) Filtering the solution obtained in the step (1), washing the precipitate with absolute ethyl alcohol, and drying in vacuum to obtain sodium tetra (pentafluorophenol) borate crystals.
2. The method for preparing sodium tetrakis (pentafluorophenol) borate according to claim 1, wherein in the step (1), the reaction temperature is 50 to 80 ℃ and the reaction time is 12 to 20 hours.
3. The method for preparing sodium tetrakis (pentafluorophenol) borate according to claim 2, wherein in the step (1), the reaction temperature is 60 to 70 ℃ and the reaction time is 14 to 18 hours.
4. The method for producing sodium tetrakis (pentafluorophenol) borate according to claim 1, wherein: in the step (2), the temperature of vacuum drying is 60-80 ℃ and the time is 16-24h.
5. Use of sodium tetrakis (pentafluorophenol) borate as claimed in any of claims 1 to 4 in sodium electricity, wherein said sodium tetrakis (pentafluorophenol) borate is used as electrolyte in a sodium battery electrolyte.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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