CN116445941A - Preparation method of fluorine-containing sulfonate, electrolyte and electrochemical device thereof - Google Patents
Preparation method of fluorine-containing sulfonate, electrolyte and electrochemical device thereof Download PDFInfo
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- CN116445941A CN116445941A CN202310481017.2A CN202310481017A CN116445941A CN 116445941 A CN116445941 A CN 116445941A CN 202310481017 A CN202310481017 A CN 202310481017A CN 116445941 A CN116445941 A CN 116445941A
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 12
- 239000011737 fluorine Substances 0.000 title claims abstract description 12
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 title claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 10
- 239000011230 binding agent Substances 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 3
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 3
- 150000002367 halogens Chemical class 0.000 claims abstract description 3
- 125000001624 naphthyl group Chemical group 0.000 claims abstract description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- UQSQSQZYBQSBJZ-UHFFFAOYSA-M fluorosulfonate Chemical compound [O-]S(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-M 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- -1 fluorosulfonate ester Chemical class 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical class OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 12
- 229910001416 lithium ion Inorganic materials 0.000 description 12
- 238000012360 testing method Methods 0.000 description 5
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- WDXYVJKNSMILOQ-UHFFFAOYSA-N 1,3,2-dioxathiolane 2-oxide Chemical compound O=S1OCCO1 WDXYVJKNSMILOQ-UHFFFAOYSA-N 0.000 description 1
- AWFYPPSBLUWMFQ-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(1,4,6,7-tetrahydropyrazolo[4,3-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=C2 AWFYPPSBLUWMFQ-UHFFFAOYSA-N 0.000 description 1
- SJHAYVFVKRXMKG-UHFFFAOYSA-N 4-methyl-1,3,2-dioxathiolane 2-oxide Chemical compound CC1COS(=O)O1 SJHAYVFVKRXMKG-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000002000 Electrolyte additive Substances 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- NVJBFARDFTXOTO-UHFFFAOYSA-N diethyl sulfite Chemical compound CCOS(=O)OCC NVJBFARDFTXOTO-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/11—Halogen containing compounds
-
- 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
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/07—Oxygen containing compounds
-
- 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
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a preparation method of fluorine-containing sulfonate, electrolyte and an electrochemical device thereof, which comprise the following steps: mixing a compound of a formula (II), a compound of a formula (III), an acid binding agent and a solvent for reaction to obtain fluorine-containing sulfonate shown in the formula (I); wherein, the structures of the compounds shown in the formulas (I), (II) and (III) are as follows:wherein R is 1 And R is 2 Independently selected from H, halogen, C 1～6 Alkyl, C of (2) 1～6 Alkoxy, phenyl, naphthyl. The preparation method has high yield and mild conditions.
Description
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a preparation method of fluorine-containing sulfonate, electrolyte and an electrochemical device thereof.
Background
At present, commercial production of lithium ion power batteries becomes the focus of most attention, and the power lithium batteries not only bring substantial progress to the application of UPS (uninterrupted Power supply), mobile laser power supply, mobile illumination power supply, mobile communication equipment, military field and aerospace field, but also bring good news to the wish of replacing traditional energy sources with power supply in the automobile industry. The lithium manganate material is used as a positive electrode material of a power lithium ion battery, has the advantages of low price, high potential, environmental friendliness, high safety and the like, and is suitable for being applied to the field of energy storage batteries of electric tools, electric vehicles and the like; the lithium manganate and the ternary material can be mixed in a certain range; from the market share of the positive electrode material of the lithium battery, the market share of lithium manganate is in an increasing trend.
At present, in the charge and discharge process of commercial batteries, organic solvents react with electrode materials, so that electrolyte is reduced, the battery capacity is attenuated, and the service life of the batteries is greatly influenced. The electrolyte is an important component in the battery, and the performance of the battery can be improved by changing the composition of the electrolyte.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems existing in the prior art. Therefore, the first aspect of the invention provides a preparation method of fluorine-containing sulfonate, which has mild reaction conditions and higher yield of the prepared fluorine-containing sulfonate. When the lithium ion battery electrolyte is used as an electrode liquid additive, the cycle performance of the lithium ion battery can be effectively improved.
The second aspect of the invention also provides an electrolyte.
The third aspect of the present invention also provides an electrochemical device.
According to the preparation method of the fluorine-containing sulfonate provided by the embodiment of the first aspect of the invention, the preparation method comprises the following steps:
mixing a compound of a formula (II), a compound of a formula (III), an acid binding agent and a solvent for reaction to obtain fluorine-containing sulfonate shown in the formula (I);
wherein, the structures of the compounds shown in the formulas (I), (II) and (III) are as follows:
wherein R is 1 And R is 2 Independently selected from H, halogen, C 1～6 Alkyl, C of (2) 1～6 Alkoxy, phenyl, naphthyl.
The preparation method provided by the embodiment of the invention has at least the following beneficial effects:
the fluorine-containing sulfonate shown in the formula (I) is obtained by mixing and reacting the compound shown in the formula (II), the compound shown in the formula (III), the acid binding agent and the solvent. On the other hand, when the electrolyte additive is used in a lithium ion battery electrolyte, the cycle performance of the battery can be effectively improved.
According to some embodiments of the invention, the acid binding agent is selected from at least one of triethylamine, pyridine, sodium hydroxide, sodium acetate, or potassium carbonate. Thereby, the yield thereof is further improved.
According to some embodiments of the invention, the solvent is selected from at least one of ethyl acetate, DMF, dichloromethane, or chloroform. According to some embodiments of the invention, the solvent is selected from ethyl acetate, which can further promote yield improvement.
According to some embodiments of the invention, the temperature of the reaction is-10 ℃ to 30 ℃.
According to some embodiments of the invention, the temperature of the reaction is-5 ℃ to 10 ℃. Thereby, the yield thereof is further improved.
According to some embodiments of the invention, the reaction time is 2 to 6 hours.
According to some embodiments of the invention, the molar ratio of the compound of formula (iii), the compound of formula (ii) and the acid-binding agent is 1: (1.5-3): (4-6).
According to some embodiments of the invention, the compound of formula (ii) may be prepared commercially or according to known literature methods.
According to some embodiments of the invention, the compound of formula (iii) may be prepared commercially or according to known literature methods.
According to a second aspect of the present invention there is provided an electrolyte comprising a fluorosulfonate ester prepared by the preparation method as described above.
According to some embodiments of the invention, the electrolyte further comprises an electrolyte and an organic solvent.
According to some embodiments of the present invention, the fluorosulfonate represented by formula (i) is contained in an amount of 0.1 to 10 parts by weight relative to 100 parts by weight of the organic solvent; the electrolyte content is 1-20 parts by weight.
According to some embodiments of the invention, the electrolyte is selected from LiPF 6 、LiBF 4 、LiClO 4 、LiAsF 6 、LiCF 3 SO 3 、LiN(CF 3 SO 2 ) 2 、LiN(C 2 F 5 SO 2 ) 2 、LiC(CF 3 SO 2 ) 3 And LiB (C) 2 O 4 ) 2 At least one of them.
According to some embodiments of the invention, the organic solvent is selected from at least one of methyl ethyl carbonate, dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, butylene carbonate, ethylene sulfite, propylene sulfite, diethyl sulfite, gamma-butyrolactone, dimethyl sulfoxide, ethyl acetate, and methyl acetate.
According to some embodiments of the invention, the fluorosulfonate represented by formula (I) is present in an amount of 0.1 to 1 part by weight relative to 100 parts by weight of the organic solvent.
A third aspect of the present invention provides an electrochemical device comprising the electrolyte as described above.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Detailed Description
The following are specific embodiments of the present invention, and the technical solutions of the present invention will be further described with reference to the embodiments, but the present invention is not limited to these embodiments.
The reagents, methods and apparatus employed in the present invention, unless otherwise specified, are all conventional in the art.
The yield was calculated as: yield= (actual yield/theoretical yield) ×100%.
Example 1
Example 1 provides a method for preparing fluorosulfonate ester, the reaction equation and steps are as follows:
dissolving a compound (1 mmol) shown in a formula (III) and triethylamine (4 mmol) in 10mL of ethyl acetate, dropwise adding the compound (2 mmol) shown in a formula (II) into a reaction bottle at 0 ℃ for reaction for 3h at 25 ℃; washing with water, drying the organic phase, concentrating, and gradient eluting with petroleum ether and ethyl acetate in volume of 3:1 to obtain fluorosulfonate (2 mg, 93.02% yield) represented by formula (I).
Examples 2 to 5
Examples 2 to 5 provide a series of fluorosulfonate ester preparation methods, which are the same as example 1, except that the acid-binding agent is specifically shown in table 1.
TABLE 1
| Acid binding agent | Yield% | |
| Example 2 | Pyridine compound | 85.1 |
| Example 3 | Sodium hydroxide | 86.5 |
| Example 4 | Acetic acid sodium salt | 60.4 |
| Example 5 | Potassium carbonate | 65.6 |
Examples 6 to 9
Examples 6-9 provide a series of fluorosulfonate ester preparation methods, which are the same as example 1, except that the reaction temperature is different, specifically as shown in Table 2.
TABLE 2
| Reaction temperature (DEG C) | Yield% | |
| Example 6 | -10℃ | 40 |
| Example 7 | 15 | 60 |
| Example 8 | 30 | 79％ |
Performance testing
Test example 1
(1) Preparing an electrolyte:
cyclic carbonate (ethylene carbonate), linear carbonate (diethyl carbonate) were prepared in an argon glove box according to 3:7 weight ratio to obtain the organic solvent. The organic solvent was mixed with an electrolyte lithium salt (lithium hexafluorophosphate) so that the lithium salt concentration was 1.1mol/L. Then, the mixture was mixed with the fluorosulfonate prepared in example 1, wherein the content of the electrolyte lithium salt (lithium hexafluorophosphate) was 12 parts by weight and the content of the fluorosulfonate was 0.5 part by weight, relative to 100 parts by weight of the organic solvent (ethylene carbonate and diethyl carbonate). Stirring until all solid substances are completely dissolved, and obtaining the lithium ion battery electrolyte of the embodiment.
(2) Preparing a lithium ion battery:
NCM523 (LiNi) 0.5 Co 0.2 Mn 0.3 O 2 ) Uniformly mixing acetylene black and polyvinylidene fluoride according to the weight ratio of 90:5:5, and pressing the mixture on an aluminum foil to obtain a positive plate; taking a graphite sheet as a negative plate; taking a conventional PE or PP or composite membrane as an ion exchange membrane; the lithium ion battery electrolyte of this example was used to produce the lithium ion battery S1 of this example by a method conventional in the art.
Comparative example 1
Comparative example 1 provides a lithium ion battery prepared in the same manner as in test example 1, except that the fluorosulfonate prepared in example 1 is not contained.
The cycle performance test was performed as follows.
And (3) testing the cycle performance: the prepared lithium ion battery is charged to 4.5V at normal temperature with a constant current and constant voltage of 1C multiplying power, the charge cut-off current is 0.05mA, then the lithium ion battery is discharged to 2.8V with a constant current of 0.5mA, the first charge capacity and the discharge capacity are recorded, after the charge and discharge cycle is repeated for 100 times, the discharge capacity of the 100 th cycle is recorded, and the capacity retention rate after the cycle is calculated, wherein the capacity retention rate (%) = the discharge capacity of the 100 th cycle/the first discharge capacity multiplied by 100%; the cut-off voltage was 4.5V. The test results are shown in Table 3.
TABLE 3 Table 3
The present invention has been described in detail with reference to the above embodiments, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the spirit of the present invention.
Claims (10)
1. The preparation method of the fluorine-containing sulfonate is characterized by comprising the following steps:
mixing a compound of a formula (II), a compound of a formula (III), an acid binding agent and a solvent for reaction to obtain fluorine-containing sulfonate shown in the formula (I);
wherein, the structures of the compounds shown in the formulas (I), (II) and (III) are as follows:
wherein R is 1 And R is 2 Independently selected from H, halogen, C 1～6 Alkyl, C of (2) 1～6 Alkoxy, phenyl, naphthyl.
2. The method for producing a fluorosulfonate according to claim 1, wherein said acid-binding agent is at least one selected from the group consisting of triethylamine, pyridine, sodium hydroxide, sodium acetate and potassium carbonate.
3. The method for producing a fluorosulfonate according to claim 1, wherein said solvent is at least one selected from the group consisting of ethyl acetate, DMF, dichloromethane and chloroform.
4. The method for producing a fluorosulfonate according to claim 1, wherein the reaction temperature is-10 ℃ to 30 ℃.
5. The method for producing a fluorosulfonate according to claim 4, wherein the reaction temperature is 15 ℃ to 25 ℃.
6. The method for producing a fluorosulfonate according to claim 1, wherein the reaction time is 2 to 6 hours.
7. The process for the preparation of fluorosulfonic acid esters according to claim 1, wherein the molar ratio of the compound of formula (iii), the compound of formula (ii) and the acid-binding agent is 1: (1.5-3): (4-6).
8. An electrolyte comprising the fluorosulfonate ester produced by the production method according to any one of claims 1 to 7; preferably, the electrolyte further comprises an organic solvent and an electrolyte.
9. The electrolyte according to claim 8, wherein the content of the fluorosulfonate represented by formula (i) is 0.1 to 10 parts by weight with respect to 100 parts by weight of the organic solvent; the electrolyte content is 1-20 parts by weight.
10. An electrochemical device comprising the electrolyte of claim 8 or 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310481017.2A CN116445941A (en) | 2023-04-28 | 2023-04-28 | Preparation method of fluorine-containing sulfonate, electrolyte and electrochemical device thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310481017.2A CN116445941A (en) | 2023-04-28 | 2023-04-28 | Preparation method of fluorine-containing sulfonate, electrolyte and electrochemical device thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116445941A true CN116445941A (en) | 2023-07-18 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310481017.2A Pending CN116445941A (en) | 2023-04-28 | 2023-04-28 | Preparation method of fluorine-containing sulfonate, electrolyte and electrochemical device thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116445941A (en) |
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2023
- 2023-04-28 CN CN202310481017.2A patent/CN116445941A/en active Pending
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