CN118221712A - Lithium borate containing dimercapto and preparation method thereof - Google Patents
Lithium borate containing dimercapto and preparation method thereof Download PDFInfo
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- CN118221712A CN118221712A CN202410656913.2A CN202410656913A CN118221712A CN 118221712 A CN118221712 A CN 118221712A CN 202410656913 A CN202410656913 A CN 202410656913A CN 118221712 A CN118221712 A CN 118221712A
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- lithium
- dimercapto
- malonic acid
- mercaptoethyl
- propyl
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- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- ZDZVKPXKLLLOOA-UHFFFAOYSA-N Allylmalonic acid Chemical compound OC(=O)C(C(O)=O)CC=C ZDZVKPXKLLLOOA-UHFFFAOYSA-N 0.000 claims abstract description 13
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004327 boric acid Substances 0.000 claims abstract description 8
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 8
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 8
- DHBXNPKRAUYBTH-UHFFFAOYSA-N 1,1-ethanedithiol Chemical compound CC(S)S DHBXNPKRAUYBTH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims abstract 6
- 125000003396 thiol group Chemical group [H]S* 0.000 claims abstract 5
- KSJBMDCFYZKAFH-UHFFFAOYSA-N 2-(2-sulfanylethylsulfanyl)ethanethiol Chemical compound SCCSCCS KSJBMDCFYZKAFH-UHFFFAOYSA-N 0.000 claims description 24
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 24
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 17
- 229910052744 lithium Inorganic materials 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000005286 illumination Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- QMCLWCCRKCPMGG-UHFFFAOYSA-N boric acid;propanedioic acid Chemical compound OB(O)O.OC(=O)CC(O)=O QMCLWCCRKCPMGG-UHFFFAOYSA-N 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 150000001642 boronic acid derivatives Chemical class 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229910003002 lithium salt Inorganic materials 0.000 abstract description 19
- 159000000002 lithium salts Chemical class 0.000 abstract description 18
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 13
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 13
- 239000003792 electrolyte Substances 0.000 abstract description 10
- 238000012650 click reaction Methods 0.000 abstract description 3
- 238000001914 filtration Methods 0.000 abstract description 2
- 231100000331 toxic Toxicity 0.000 abstract description 2
- 230000002588 toxic effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 25
- 239000000047 product Substances 0.000 description 19
- 238000001819 mass spectrum Methods 0.000 description 10
- 238000001228 spectrum Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- -1 Lithium hexafluorophosphate Chemical compound 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- VYMPLPIFKRHAAC-UHFFFAOYSA-N 1,2-ethanedithiol Chemical compound SCCS VYMPLPIFKRHAAC-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 6
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 6
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 229910052796 boron Inorganic materials 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 230000005311 nuclear magnetism Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-L Malonate Chemical compound [O-]C(=O)CC([O-])=O OFOBLEOULBTSOW-UHFFFAOYSA-L 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 229910013870 LiPF 6 Inorganic materials 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 244000028419 Styrax benzoin Species 0.000 description 3
- 235000000126 Styrax benzoin Nutrition 0.000 description 3
- 235000008411 Sumatra benzointree Nutrition 0.000 description 3
- 229960002130 benzoin Drugs 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 235000019382 gum benzoic Nutrition 0.000 description 3
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000002390 rotary evaporation Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 3
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000005518 polymer electrolyte Substances 0.000 description 2
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000000694 effects Effects 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
- 230000008020 evaporation Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- OBCUTHMOOONNBS-UHFFFAOYSA-N phosphorus pentafluoride Chemical compound FP(F)(F)(F)F OBCUTHMOOONNBS-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Abstract
The invention discloses a lithium borate salt containing dimercapto and a preparation method thereof, comprising the following steps: (1) Carrying out sulfhydryl-alkene click reaction on allyl malonic acid and ethanedithiol; (2) purifying the malonic acid containing the mercapto group, and drying in vacuum; (3) Carrying out reaction on malonic acid and boric acid containing sulfhydryl and lithium carbonate in an organic solvent to obtain an organic solution containing dimercapto lithium salt; (4) And filtering, concentrating and drying the prepared organic solution of the lithium salt to obtain the lithium borate salt containing dimercapto. The lithium borate containing dimercapto synthesized by the method can improve the ionic conductivity of electrolyte and has wide application prospect in lithium ion batteries. The preparation method disclosed by the invention is simple, mild in reaction condition, convenient to operate, high in purity of the synthesized product, high in total yield, free of toxic and harmful product generation, and safe and environment-friendly in the whole reaction process.
Description
Technical Field
The invention relates to the field of chemical industry, in particular to a lithium borate salt containing dimercapto and a preparation method thereof.
Background
Lithium ion batteries are currently widely applied to the fields of consumer electronics, electric automobiles, large-scale energy storage and the like. In recent years, with the rapid development of smart phones, smart mobile devices, electric vehicles and hybrid vehicles, the requirements on the energy density, the cycle life and the safety performance of lithium batteries are increasingly high. The electrolyte is one of key components of the lithium ion battery and is a carrier for transferring lithium ions between the anode and the cathode. The composition of the lithium ion battery electrolyte comprises lithium salt, an organic solvent and various additives, and has great influence on the electrochemical performance, the working temperature range, the service life and the safety performance of the battery.
Electrolytes for commercial lithium ion batteries are typically made from lithium salts dissolved in mixed organic solvents in varying proportions. Lithium salts are the provider of lithium ions in the electrolyte and have a significant impact on the electrolyte and electrode performance. Lithium hexafluorophosphate (LiPF 6) is the most commonly used lithium salt for lithium ion batteries currently commercialized. However, lithium hexafluorophosphate has some limitations: poor thermal stability and is very sensitive to moisture. Lithium hexafluorophosphate is readily decomposed at high temperatures to form phosphorus pentafluoride (PF 5) and lithium fluoride (LiF), which react irreversibly with trace amounts of water to form HF. HF is corrosive to electrode materials, can easily react with organic matters on the surface of the electrode to generate LiF, and is deposited on the surface of the electrode, so that the impedance of the SEI film is increased, and the performance of the battery is reduced. Therefore, the replacement of LiPF 6 with a novel lithium salt electrolyte which is good in research stability, environment-friendly and low in cost is an important research direction of lithium ion battery electrolyte lithium salt. Lithium borate salts have unique properties such as excellent thermal stability, ionic conductivity, environmental friendliness, and good film forming properties, as compared with LiPF 6, and have attracted a wide range of attention.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a novel lithium borate salt containing dimercapto and a preparation method thereof.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
A lithium borate salt containing dimercapto is shown in a formula I:
the preparation method of the lithium borate salt containing dimercapto comprises the following steps:
Step 1: dissolving a photoinitiator into ethanedithiol and magnetically stirring; under the illumination of an ultraviolet lamp, dripping an organic solution of allyl malonic acid into ethanedithiol, performing mercapto-alkene clicking reaction, dripping the reacted solution into deionized water, layering the solution, collecting an upper layer solution, dripping a lower layer solution into deionized water again, collecting the layered upper layer solution, repeating the operation for 3-5 times, concentrating and vacuum drying to obtain 2- (3- ((2-mercaptoethyl) thioether) propyl) malonic acid;
Step 2: under the protection of inert gas, 2- (3- ((2-mercaptoethyl) thioether) propyl) malonic acid obtained in the step 1 reacts with boric acid and lithium carbonate in an organic solvent to obtain an organic solution of lithium borate containing mercapto, the organic solution of the lithium borate containing mercapto is concentrated, and the product lithium bis 2- (3- ((2-mercaptoethyl) thioether) propyl) malonic acid borate is obtained through vacuum drying.
The structural formula of the 2- (3- ((2-mercaptoethyl) thioether) propyl) malonic acid is shown as a formula (II):
Preferably, in the above preparation method of lithium salt containing dimercapto, the molar amount of ethanedithiol in step1 is 5 to 20 times that of allylmalonic acid.
Preferably, in the above preparation method of lithium salt containing dimercapto, the organic solution of allylmalonic acid in step 1 adopts any one of acetonitrile, dimethyl carbonate, diethyl carbonate, methylethyl carbonate, tetrahydrofuran, dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and acetone.
Preferably, in the preparation method of the lithium salt containing dimercapto, the concentration in the step 2 means spin evaporation at 30-80 ℃ until no obvious solvent exists; the drying refers to vacuum drying at 80-100 ℃ for 12-48 hours.
Preferably, in the above preparation method of the lithium salt containing dimercapto, in the step 2, the molar ratio of 2- (3- ((2-mercaptoethyl) thioether) propyl) malonic acid, boric acid and lithium carbonate is 4:2:1.
Preferably, in the above preparation method of lithium salt containing dimercapto, the temperature of the reaction in step2 is 60 to 100 ℃ and the reaction time is 12 to 48 hours.
Compared with the prior art, the invention has the following beneficial effects:
The lithium bis 2- (3- ((2-mercaptoethyl) thioether) propyl) malonate synthesized by the invention is referred to as lithium borate containing dimercapto, the anion radius is large, the ionic conductivity of the electrolyte can be improved, the introduced mercapto can be subjected to mercapto-alkene click reaction with a compound or polymer with carbon-carbon double bonds, and a series of polymerized lithium borate or single-ion polymer electrolyte can be prepared, so that the lithium borate has wide application prospect in lithium ion batteries. The preparation method disclosed by the invention is simple, mild in reaction condition, convenient to operate, capable of obtaining the product without adopting complex equipment, high in purity of the synthesized product, high in total yield, free of toxic and harmful product generation in the reaction process, and safe and environment-friendly in the whole reaction process.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of 2- (3- ((2-mercaptoethyl) thioether) propyl) malonic acid obtained in example 1.
FIG. 2 is a high resolution mass spectrum of the lithium salt prepared in example 1.
FIG. 3 is a nuclear magnetic resonance boron spectrum of the lithium salt prepared in example 1.
FIG. 4 is a nuclear magnetic resonance hydrogen spectrum of the lithium salt prepared in example 1.
Detailed Description
The present invention will be further described with reference to examples, but the present invention is not limited to the following examples.
Example 1:
(1) Synthesis of 2- (3- ((2-mercaptoethyl) thioether) propyl) malonic acid
20 Mmol allyl malonic acid is dissolved in 12 mL acetonitrile, 0.05 g benzoin dimethyl ether is added into 100 mmol of 1, 2-ethanedithiol, magnetic stirring is carried out, 365 nm ultraviolet lamps are used for illumination, meanwhile, the allyl malonic acid solution is slowly dripped into the 1, 2-ethanedithiol, and illumination is continued for 20 minutes after dripping is finished. A pale yellow solution was obtained. The resulting solution was dropped into 150 mL deionized water, the solution was allowed to delaminate, the oily liquid was allowed to settle to the bottom, and the aqueous upper layer was collected. Then dripping the lower oil phase into 150 mL water, collecting the upper water solution, repeating for 2 times. Most of the solvent was removed by rotary evaporation at 70℃and dried in vacuo at 100℃for 6 hours to give 2- (3- ((2-mercaptoethyl) thioether) propyl) malonic acid 3.383 g as a white solid. The yield thereof was found to be 71%. And taking the dried product for nuclear magnetic testing, wherein a nuclear magnetic diagram is shown in figure 1, and the nuclear magnetic result proves that the target product is successfully obtained.
(2) Synthesis of lithium bis 2- (3- ((2-mercaptoethyl) thioether) propyl) malonate borate
3.383 G of 2- (3- ((2-mercaptoethyl) thio) propyl) malonic acid, 0.439 g boric acid, 0.255 g lithium carbonate and 60mL of acetonitrile are added into a three-neck flask, the reaction is carried out for 20 hours at 80 ℃ under the protection of nitrogen, the filtration is carried out after the reaction is finished, at least a quantity of viscous liquid is evaporated in a rotary way, and the filtrate is dried in vacuum for 12 hours at 80 ℃ to obtain the product of lithium bis 2- (3- ((2-mercaptoethyl) propyl) malonate 2.31 g. The yield thereof was found to be 66.3%. And taking the dried product to perform high-resolution mass spectrum and nuclear magnetism test, wherein a mass spectrum is shown in figure 2, a boron spectrum is shown in figure 3, a hydrogen spectrum is shown in figure 4, and the results of the high-resolution mass spectrum and the nuclear magnetism prove that the target product is successfully obtained.
Example 2:
(1) Synthesis of 2- (3- ((2-mercaptoethyl) thioether) propyl) malonic acid
10 Mmol allyl malonic acid is dissolved in 8mL acetonitrile, 0.05 g benzoin dimethyl ether is added into 100 mmol of 1, 2-ethanedithiol, magnetic stirring is carried out, 365 nm ultraviolet lamps are used for illumination, meanwhile, the allyl malonic acid solution is slowly dripped into the 1, 2-ethanedithiol, and illumination is continued for 20 minutes after dripping is finished. A pale yellow solution was obtained. The resulting solution was dropped into 150 mL deionized water, the solution was allowed to delaminate, the oily liquid was allowed to settle to the bottom, and the aqueous upper layer was collected. Then dripping the lower oil phase into 150 mL water, collecting the upper water solution, repeating for 3 times. Most of the solvent was removed by rotary evaporation at 80℃and dried in vacuo at 100℃for 12 hours to give 2.02g of 2- (3- ((2-mercaptoethyl) thioether) propyl) malonic acid as a white solid in a yield of 84.8%. And taking the dried product for nuclear magnetic testing, wherein the nuclear magnetic diagram is basically consistent with that of fig. 1, and the nuclear magnetic result proves that the target product is successfully obtained.
(2) Synthesis of lithium bis 2- (3- ((2-mercaptoethyl) thioether) propyl) malonate borate
2.02 G of 2- (3- ((2-mercaptoethyl) thio) propyl) malonic acid, 0.262 g of boric acid, 0.157 g of lithium carbonate and 30mL of dimethyl carbonate are added into a three-neck flask, the mixture is reacted for 24 hours at 80 ℃ under the protection of nitrogen, the mixture is filtered after the reaction is finished, at least a viscous liquid is distilled off from the filtrate, the mixture is dried in vacuum for 12 hours at 80 ℃ to obtain the product of lithium bis 2- (3- ((2-mercaptoethyl) thio) propyl) malonate 1.28 and g, and the yield is 61.5%. And taking the dried product to carry out high-resolution mass spectrum and nuclear magnetism test, wherein the mass spectrum is basically consistent with the figure 2, the boron spectrum is basically consistent with the figure 3, the hydrogen spectrum is basically consistent with the figure 4, and the results of the high-resolution mass spectrum and the nuclear magnetism prove that the target product is successfully obtained.
Example 3:
(1) Synthesis of 2- (3- ((2-mercaptoethyl) thioether) propyl) malonic acid
20 Mmol allyl malonic acid is dissolved in 15 mL tetrahydrofuran, 0.1 g benzoin dimethyl ether is added into 200 mmol of 1, 2-ethanedithiol, magnetic stirring is carried out, 365 nm ultraviolet lamps are used for illumination, meanwhile, the allyl malonic acid solution is slowly dripped into the 1, 2-ethanedithiol, and illumination is continued for 20 minutes after dripping is finished. A pale yellow solution was obtained. The resulting solution was dropped into 150 mL deionized water, the solution was allowed to delaminate, the oily liquid was allowed to settle to the bottom, and the aqueous upper layer was collected. Then dripping the lower oil phase into 150 mL water, collecting the upper water solution, repeating for 3 times. Most of the solvent was removed by rotary evaporation at 70℃and dried in vacuo at 100℃for 12 hours to give 3.22g of 2- (3- ((2-mercaptoethyl) thioether) propyl) malonic acid as a white solid. The yield thereof was found to be 67.7%. And taking the dried product for nuclear magnetic testing, wherein the nuclear magnetic diagram is basically consistent with that of fig. 1, and the nuclear magnetic result proves that the target product is successfully obtained.
(2) Synthesis of lithium bis 2- (3- ((2-mercaptoethyl) thioether) propyl) malonate borate
3.22 G of 2- (3- ((2-mercaptoethyl) thio) propyl) malonic acid, 0.418 g boric acid, 0.25 g lithium carbonate and 50mL of acetonitrile are added into a three-neck flask, the mixture is reacted for 20 hours at 80 ℃ under the protection of nitrogen, the mixture is filtered after the reaction is finished, at least a quantity of viscous liquid is distilled off from the filtrate, the mixture is dried in vacuum for 6 hours at 80 ℃ to obtain the product of lithium bis 2- (3- ((2-mercaptoethyl) thio) propyl) malonate 2.24 g, and the yield is 67.8 percent. And taking the dried product to carry out high-resolution mass spectrum and nuclear magnetism test, wherein the mass spectrum is basically consistent with the figure 2, the boron spectrum is basically consistent with the figure 3, the hydrogen spectrum is basically consistent with the figure 4, and the results of the high-resolution mass spectrum and the nuclear magnetism prove that the target product is successfully obtained.
Example 4: ion conductivity test
Lithium bis 2- (3- ((2-mercaptoethyl) sulfide) propyl) malonate synthesized in example 1 was dissolved in ethylene carbonate/dimethyl carbonate (1/1, v/v), propylene carbonate/methylethyl carbonate (1/1, v/v), 1, 3-dioxolane/ethylene glycol dimethyl ether (1/1, v/v), tetraethyl glycol dimethyl ether, and triethyl phosphate, respectively, in a glove box to prepare 1 mol/L of lithium salt solution. And (3) dripping the prepared solution on a glass fiber diaphragm to assemble the steel sheet/diaphragm/steel sheet blocking battery. Ac impedance testing was performed on an electrochemical workstation at a frequency range of 100 kHz-1 Hz. The ionic conductivity is calculated by the formula σ=l/(R b S), where σ is the ionic conductivity, l is the thickness of the separator, R b is the bulk impedance of the electrolyte, and S is the contact area of the steel sheet with the separator. The results of the ion conductivity test are shown in table 1.
The boron atom in the lithium bis 2- (3- ((2-mercaptoethyl) thioether) propyl) malonate is connected with four carboxyl groups with strong electron-withdrawing effect, and the oxygen atom in the carboxyl groups disperses the negative charge of the boron atom through conjugation, so that the acting force of lithium ions and lithium salt anions is weakened, and the dissociation of the lithium ions is facilitated. At 30 ℃, the ionic conductivity of lithium bis (2- (3- ((2-mercaptoethyl) thioether) propyl) malonate in the above 5 solvents is basically more than 10 -4 S/cm, so that the practical application requirement is met, wherein the 1, 3-dioxolane/ethylene glycol dimethyl ether and triethyl phosphate are used as solvents, and have higher ionic conductivity, which indicates that the two solvents can better dissociate lithium salt and form a solvation structure with lithium ions.
The lithium bis 2- (3- ((2-mercaptoethyl) thioether) propyl) malonate has great expansibility, can be used for carrying out mercapto-alkene click reaction with a plurality of compounds or polymers with carbon-carbon double bonds to obtain a single-ion polymer electrolyte, can be applied to solid-state lithium batteries, and has great application prospect.
Claims (7)
1. A lithium borate salt containing dimercapto is shown in a formula I:
。
2. a process for the preparation of the lithium dimercapto-containing borate salt according to claim 1, comprising the steps of:
Step 1: dissolving a photoinitiator into ethanedithiol and magnetically stirring; under the illumination of an ultraviolet lamp, dripping an organic solution of allyl malonic acid into ethanedithiol, performing mercapto-alkene clicking reaction, dripping the reacted solution into deionized water, layering the solution, collecting an upper layer solution, dripping a lower layer solution into deionized water again, collecting the layered upper layer solution, repeating the operation for 3-5 times, concentrating and vacuum drying to obtain 2- (3- ((2-mercaptoethyl) thioether) propyl) malonic acid;
Step 2: under the protection of inert gas, 2- (3- ((2-mercaptoethyl) thioether) propyl) malonic acid obtained in the step 1 reacts with boric acid and lithium carbonate in an organic solvent to obtain an organic solution of lithium borate containing mercapto, the organic solution of the lithium borate containing mercapto is concentrated, and the product lithium bis 2- (3- ((2-mercaptoethyl) thioether) propyl) malonic acid borate is obtained through vacuum drying.
3. The method for producing a lithium dimercapto-containing borate salt according to claim 2, wherein in step 1, the molar amount of said ethanedithiol is 5 to 20 times that of allylmalonic acid.
4. The method for preparing lithium borate containing dimercapto according to claim 2, wherein in step1, the organic solution of allylmalonic acid adopts any one of acetonitrile, dimethyl carbonate, diethyl carbonate, methylethyl carbonate, tetrahydrofuran, dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and acetone.
5. The method for preparing lithium borate containing dimercapto according to claim 2, wherein in step 2, the concentration means spin-evaporation at 30-80 ℃ until no obvious solvent is present; the drying refers to vacuum drying at 80-100deg.C for 12-48 hr.
6. The method for preparing lithium borate salt containing double mercapto groups according to claim 2, wherein in the step 2, the feeding mole ratio of 2- (3- ((2-mercaptoethyl) thioether) propyl) malonic acid, boric acid and lithium carbonate is 4:2:1.
7. The method for preparing lithium borate containing dimercapto according to claim 2, wherein in the step 2, the reaction temperature is 60-100 ℃ and the reaction time is 12-48 hours.
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