CN102432474B - Preparation method of high-purity alkylammonium tetrafluoroborate for super capacitor - Google Patents
Preparation method of high-purity alkylammonium tetrafluoroborate for super capacitor Download PDFInfo
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Abstract
The invention discloses a preparation method of high-purity alkylammonium tetrafluoroborate for a super capacitor, characterized by reacting tertiary amine with tetrafluoroborate alcoxylonium salt at a certain temperature to obtain corresponding alkylammonium tetrafluoroborate, and purifying to obtain the high-purity alkylammonium tetrafluoroborate. The method has the advantages of simple operation steps, good selectivity, high conversion rate, high product purity, and no halogen ions, and can satisfy the requirements of a high performance super capacitor. The use of the prepared alkylammonium tetrafluoroborate as an electrolyte in the super capacitor can achieve the advantages of high product capacity, low internal resistance, and reduced capacity fade at a high temperature.
Description
Technical field
The invention belongs to the synthetic method field of ultracapacitor organic electrolyte, relate in particular to a kind of method of preparing high purity tetrafluoroborate.
Background technology
Ultracapacitor (double layer capacitor) is a kind of high-energy power storage element that development in recent years is got up, there is high power density, high cycle life, the advantage such as impulse electricity and environmentally safe fast, be widely used in the backup power source of regulex, sensor, computer memory, clear energy sources systems such as the starter gear of Motor vehicles, wind-power electricity generation and solar power systems, thereby receive publicity.Quaternary amine, as the nonaqueous electrolyte of ultracapacitor, can be used as the chemical cell of energy storages device or the supporting electrolyte of high-energy electrical condenser.
As high purity tetrafluoroborate synthetic method, at patent (JP11-310555, JP11-315055, CN101131897) in, described by carbonic acid mono-methyl triethyl methyl ammonium salt and Tetrafluoroboric acid or ammonium tetrafluoroborate, or anhydrous hydrogen fluoride and boron trifluoride, prepare the method for Tetrafluoroboric acid triethyl methyl ammonium salt.In addition, in patent (US2008033209, WO2006021304), described by dimethyl sulfite and tertiary amine effect and obtained sulfurous acid mono-methyl alkyl quaternary ammonium salts, then reacted with Tetrafluoroboric acid, prepared the method for tetrafluoroborate.Fluoroboric acid used in aforesaid method, hydrogen fluoride etc. are serious to equipment corrosion, are difficult to operation, obtain product foreign matter content high, cause ultracapacitor internal resistance increase, inflatable, thereby cause chemical property and safety performance greatly to reduce.
In patent (EP1505057), a kind of triethyl ammonium methyl hydrochloride and boric acid and anhydrous hydrogen fluoride of passing through described, prepare the method for Tetrafluoroboric acid triethyl methyl ammonium salt.Patent (CN1762979, JP2001348388) has been described by tetraethyl ammonium hydrochloride and fluoborate aqueous solution, the method for under reduced pressure deviating from preparation of hydrogen chloride tetraethylammonium tetrafluoroborate salt.These class methods fail to avoid from raw material source the introducing of halide-ions.
Summary of the invention
The present invention is intended to overcome the deficiencies in the prior art part and provides a kind of easy and simple to handle, and selectivity is good, is suitable for the synthetic method of high purity tetrafluoroborate for the ultracapacitor organic electrolyte of large-scale production.
For achieving the above object, the present invention is achieved in that
The preparation method of high-purity alkylammonium tetrafluoroborate for super capacitor, it carries out single step reaction by tertiary amine and Tetrafluoroboric acid alcoxyl salt, obtains corresponding tetrafluoroborate, more obtains object product after purified.
As a kind of preferred version, tertiary amine of the present invention is for having a kind of in formula (A) chain-like structure, formula (B) ring texture, formula (C) ring texture and formula (D) ring texture;
Wherein: R
1, R
2, R
3for alkyl, containing thiazolinyl, alkynyl, alkoxyl group; N=1,2,3.
As another kind of preferred version, the structure of Tetrafluoroboric acid alcoxyl salt of the present invention is: R
3o
+bF
4 -; Wherein: R is alkyl, containing alkoxy base.
Further, Tetrafluoroboric acid alcoxyl salt of the present invention is Tetrafluoroboric acid front three oxonium salt or Tetrafluoroboric acid three ethoxy salt.
The mol ratio of tertiary amine of the present invention and Tetrafluoroboric acid alcoxyl salt is: 1: 1～4.
As a kind of preferred version, the mol ratio of tertiary amine of the present invention and Tetrafluoroboric acid alcoxyl salt is: 1: 1～2.
Further, temperature of reaction of the present invention is 0～150 ℃.
In addition, reaction solvent of the present invention is one or more the mixture in methylene dichloride, trichloromethane, ethyl acetate, butylacetate, NSC 11801, propylene carbonate.
It is reaction raw materials that tertiary amine and Tetrafluoroboric acid alcoxyl salt are take in the present invention, carries out single step reaction, can high yield, highly selective makes tetrafluoroborate.The method of the invention operation steps is simple, and selectivity is good, and transformation efficiency is high, and product purity is high, and not halogen-containing ion, can meet the requirement of high-performance super capacitor.Using the tetrafluoroborate making as ionogen for ultracapacitor, the product capacity that obtains is high, internal resistance is little, capacity attenuation is little under high temperature.
The present invention relates to chemical principle as follows:
Reaction process is: in suitable organic solvent, by tertiary amine and Tetrafluoroboric acid alcoxyl salt at a certain temperature, single step reaction, obtains corresponding tetrafluoroborate;
The structure of tetrafluoroborate is as follows:
R1, R2, R3 is alkyl, containing thiazolinyl, alkynyl, alkoxyl group etc.; N=1,2,3.
In reaction process, tertiary amine used is for having the structures such as chain (A) or ring-type (B), (C), (D).
Corresponding construction is as follows:
Wherein: R
1, R
2, R
3for alkyl, containing thiazolinyl, alkynyl, alkoxyl group etc.; N=1,2,3.
Tetrafluoroboric acid alcoxyl salt structure related in reaction process is as follows: R
3o
+bF
4 -; Wherein: R is alkyl, containing alkoxy base, be preferably Tetrafluoroboric acid front three oxonium salt, Tetrafluoroboric acid three ethoxy salt.
In reaction process, temperature of reaction is: 0～150 ℃, be preferably 0～100 ℃.
The tetrafluoroborate making is dissolved in the organic solvents such as alcohol, ketone, nitrile, adds activated carbon, molecular sieve etc., carries out purifying and obtains target product.
Synthetic tetrafluoroborate method of the present invention and existing method comparison, the selectivity of target product is good, and yield is high, and quality is good, has eliminated the impact of halide-ions on quality product, can meet the requirement of ultracapacitor organic electrolyte.
Tetrafluoroborate prepared in accordance with the present invention, purity is high, not halogen-containing ion.Ionogen for ultracapacitor, can improve proof voltage and safe reliability.
Embodiment
The invention will be further described for following examples, but content of the present invention is not subject to the restriction of this embodiment.
Related Tetrafluoroboric acid three ethoxy salt and Tetrafluoroboric acid front three oxonium salt reference method (Curphy T J.Org.Synth., 1971,51:142 in embodiment of the present invention; Mccrwein H.Org.Synth., 1973, Coll.Vol.5:1080; Mccrwein H.Org.Synth., 1973, Coll.Vol.5:1096) synthetic making.
Embodiment 1
The preparation of Tetrafluoroboric acid triethyl methyl ammonium salt
Under nitrogen atmosphere, by Tetrafluoroboric acid three ethoxy salt (47.5 grams, 0.25 mole), join and contain N, in 500 milliliters of reaction flasks of N-diethyl-N-methylamine (26.1 grams, 0.3 mole) and 150 milliliters of methylene dichloride, stirring at room 15 hours.Filter the concentrated Tetrafluoroboric acid triethyl methyl ammonium salt crude product that obtains of filtrate.With dissolve with ethanol, add activated carbon, reflux 30 minutes, filters, and filtrate is cooling, obtains 46.6 grams of the white crystals of Tetrafluoroboric acid triethyl methyl ammonium salt, and yield is 92%.
Through chromatography of ions, detect: Na:2.1ppm, K:3.5ppm, Fe:1.6ppm, Mg:1.0ppm, Ca:2.5ppm, halide-ions has no.
Embodiment 2
The preparation of Tetrafluoroboric acid triethyl methyl ammonium salt
Under nitrogen atmosphere, by Tetrafluoroboric acid front three oxonium salt (29.6 grams, 0.2 mole), join and contain N, in 250 milliliters of reaction flasks of N-diethyl-N-methylamine (20.9 grams, 0.24 mole) and 150 milliliters of methylene dichloride, 40 ℃ are reacted 8 hours.Filter the concentrated Tetrafluoroboric acid triethyl methyl ammonium salt crude product that obtains of filtrate.With dissolve with methanol, add activated carbon, reflux 30 minutes, filters, and filtrate is cooling, obtains 38.2 grams of the white crystals of Tetrafluoroboric acid triethyl methyl ammonium salt, and yield is 94%.
Through chromatography of ions, detect: Na:2.2ppm, K:2.6ppm, Fe:1.6ppm, Mg:1.6ppm, Ca:2.4ppm, halide-ions has no.
Embodiment 3
The preparation of tetraethylammonium tetrafluoroborate salt
Under nitrogen atmosphere, by Tetrafluoroboric acid three ethoxy salt (47.5 grams, 0.25 mole), join in 500 milliliters of reaction flasks that contain triethylamine (28.3 grams, 0.28 mole) and 200 milliliters of trichloromethanes, 60 ℃ 10 hours.Filter, the concentrated tetraethylammonium tetrafluoroborate salt crude product that obtains of filtrate, with dissolve with methanol, adds activated carbon, and reflux 30 minutes, filters, and filtrate is cooling obtains 47.7 grams of the white crystals of tetraethylammonium tetrafluoroborate salt, and yield is 88%.
Through chromatography of ions, detect: Na:1.8ppm, K:2.8ppm, Fe:1.5ppm, Mg:2.4ppm, Ca:3.2ppm, halide-ions has no.
Embodiment 4
The preparation of Tetrafluoroboric acid (2-methoxy ethyl) triethyl ammonium salt
Under nitrogen atmosphere, by Tetrafluoroboric acid three ethoxy salt (47.5 grams, 0.5 mole), join and contain N-(2-methoxy ethyl)-N, in 500 milliliters of reaction flasks of N-diethylamide (78.6 grams, 0.6 mole) and 200 milliliters of methylene dichloride, stirring at room 12 hours.Through deionized water (2x50 milliliter) washing, after separation, add activated carbon, reflux 30 minutes, filters, and filtrate is concentrated; With normal hexane (2x100 milliliter) washing, concentrate and obtain 113.6 grams of faint yellow oily matter, yield is 92%.
Product structure is Tetrafluoroboric acid (2-methoxy ethyl) triethyl ammonium salt through nuclear magnetic resonance spectroscopy.
Through chromatography of ions, detect: Na:2.9ppm, K:3.2ppm, Fe:1.3ppm, Mg:2.2ppm, Ca:2.3ppm, halide-ions has no.
Embodiment 5
Tetrafluoroboric acid N-(2-methoxy ethyl)-N, the preparation of N-diethylmethyl ammonium salt
Under nitrogen atmosphere, by Tetrafluoroboric acid front three oxonium salt (44.4 grams, 0.3 mole), join and contain N-(2-methoxy ethyl)-N, in 500 milliliters of reaction flasks of N-diethylamide (43.2 grams, 0.33 mole) and 300 milliliters of propylene carbonates, 100 ℃ 6 hours.Through deionized water (2x50 milliliter) washing, after separation, add activated carbon, reflux 30 minutes, filters, and filtrate is concentrated; With normal hexane (2x100 milliliter) washing, concentrate and obtain 62.9 grams of faint yellow oily matter, yield is 90%.
Product structure is Tetrafluoroboric acid N-(2-methoxy ethyl)-N through nuclear magnetic resonance spectroscopy, N-diethylmethyl ammonium salt.
Through chromatography of ions, detect: Na:2.4ppm, K:2.5ppm, Fe:1.3ppm, Mg:2.1ppm, Ca:2.6ppm, halide-ions has no.
Embodiment 6
The preparation of Tetrafluoroboric acid N-methyl-N-ethyl Pyrrolidine ammonium salt
Under nitrogen atmosphere, by Tetrafluoroboric acid three ethoxy salt (95 grams, 0.5 mole), join in 500 milliliters of reaction flasks that contain N-methyl Pyrrolidine (51 grams, 0.6 mole) and 200 milliliters of methylene dichloride, 40 ℃ are reacted 7 hours.Filter, the concentrated Tetrafluoroboric acid N-methyl-N-ethyl Pyrrolidine ammonium salt crude product that obtains of filtrate, with dissolve with methanol, add activated carbon, reflux 30 minutes, filters, filtrate is cooling obtains 88.4 grams of the white crystals of Tetrafluoroboric acid N-methyl-N-ethyl Pyrrolidine ammonium salt, and yield is 88%.
Through chromatography of ions, detect: Na:2.4ppm, K:1.6ppm, Fe:2.6ppm, Mg:2.0ppm, Ca:2.3ppm, halide-ions has no.
Embodiment 7
The preparation of Tetrafluoroboric acid N-(2-methoxy ethyl)-N-ethyl Pyrrolidine ammonium salt
Under nitrogen atmosphere, by Tetrafluoroboric acid three ethoxy salt (66.5 grams, 0.35 mole), join and contain (54.2 grams of N-(2-methoxy ethyl) Pyrrolidines, 0.42 mole) and 500 milliliters of reaction flasks of 200 milliliters of methylene dichloride in, stirring at room 16 hours.Through deionized water (2x50 milliliter) washing, after separation, add activated carbon, reflux 30 minutes, filters, and filtrate is concentrated; With normal hexane (2x200 milliliter) washing, concentrate and obtain 77.1 grams of faint yellow oily matter, yield is 90%.
Product structure is Tetrafluoroboric acid N-(2-methoxy ethyl)-N-ethyl Pyrrolidine ammonium salt through nuclear magnetic resonance spectroscopy.
Through chromatography of ions, detect: Na:3.0ppm, K:2.3ppm, Fe:1.5ppm, Mg:2.2ppm, Ca:2.5ppm, halide-ions has no.
Embodiment 8
The preparation of 1-methyl-3-ethyl imidazol(e) a tetrafluoro borate
Under nitrogen atmosphere, by Tetrafluoroboric acid three ethoxy salt (47.5 grams, 0.25 mole), join in 500 milliliters of reaction flasks that contain N-Methylimidazole (24.6 grams, 0.3 mole) and 200 milliliters of methylene dichloride stirring at room 14 hours.Through deionized water (2x50 milliliter) washing, after separation, add activated carbon, reflux 30 minutes, filters, and filtrate is concentrated; With normal hexane (2x100 milliliter) washing, concentrate and obtain 42 grams of faint yellow oily matter, yield is 85%.
Product structure is 1-methyl-3-ethyl imidazol(e) a tetrafluoro borate through nuclear magnetic resonance spectroscopy.
Through chromatography of ions, detect: Na:2.4ppm, K:1.6ppm, Fe:2.3ppm, Mg:2.5ppm, Ca:2.4ppm, halide-ions has no.
Embodiment 9
The preparation of 1-(2-methoxy ethyl)-3-methyl imidazolium tetrafluoroborate
Under nitrogen atmosphere, by Tetrafluoroboric acid front three oxonium salt (59.2 grams, 0.4 mole), join in 500 milliliters of reaction flasks that contain N-methoxy ethyl imidazoles (60.5 grams, 0.48 mole) and 200 milliliters of methylene dichloride stirring at room 16 hours.Through deionized water (2x50 milliliter) washing, after separation, add activated carbon, reflux 30 minutes, filters, and filtrate is concentrated; With normal hexane (2x150 milliliter) washing, concentrate and obtain 81 grams of faint yellow oily matter, yield is 88%.
Product structure is 1-(2-methoxy ethyl)-3-methyl imidazolium tetrafluoroborate through nuclear magnetic resonance spectroscopy
Through chromatography of ions, detect: Na:2.4ppm, K:1.6ppm, Fe:2.6ppm, Mg:2.2ppm, Ca:2.4ppm, halide-ions has no.
Embodiment 10
The preparation of Tetrafluoroboric acid N-methyl-N-ethylpiperidine ammonium salt
Under nitrogen atmosphere, by Tetrafluoroboric acid front three oxonium salt (59.2 grams, 0.4 mole), join in 500 milliliters of reaction flasks that contain N-ethylpiperidine (56.5 grams, 0.5 mole) and 200 milliliters of methylene dichloride stirring at room 15 hours.Filter, the concentrated Tetrafluoroboric acid N-methyl-N-ethylpiperidine ammonium salt crude product that obtains of filtrate, with dissolve with methanol, add activated carbon, reflux 30 minutes, filters, filtrate is cooling obtains 73 grams of the white crystals of Tetrafluoroboric acid N-methyl-N-ethylpiperidine ammonium salt, and yield is 85%.
Through chromatography of ions, detect: Na:2.0ppm, K:3.2ppm, Fe:1.8ppm, Mg:2.0ppm, Ca:2.5ppm, halide-ions has no.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (10)
1. a preparation method for high-purity alkylammonium tetrafluoroborate for super capacitor, is characterized in that, under nitrogen atmosphere, by the Tetrafluoroboric acid of 0.25 mole three ethoxy salt, joins and contains 0.3 mole
n,N-diethyl-
nin 500 milliliters of reaction flasks of-methylamine and 150 milliliters of methylene dichloride, stirring at room 15 hours; Filter the concentrated Tetrafluoroboric acid triethyl methyl ammonium salt crude product that obtains of filtrate; With dissolve with ethanol, add activated carbon, reflux 30 minutes, filters, and filtrate is cooling, obtains 46.6 grams of the white crystals of Tetrafluoroboric acid triethyl methyl ammonium salt, and yield is 92%.
2. a preparation method for high-purity alkylammonium tetrafluoroborate for super capacitor, is characterized in that: under nitrogen atmosphere, by the Tetrafluoroboric acid front three oxonium salt of 0.2 mole, join and contain 0.24 mole
n,N-diethyl-
nin 250 milliliters of reaction flasks of-methylamine and 150 milliliters of methylene dichloride, 40 ℃ are reacted 8 hours; Filter the concentrated Tetrafluoroboric acid triethyl methyl ammonium salt crude product that obtains of filtrate; With dissolve with methanol, add activated carbon, reflux 30 minutes, filters, and filtrate is cooling, obtains 38.2 grams of the white crystals of Tetrafluoroboric acid triethyl methyl ammonium salt, and yield is 94%.
3. the preparation method of a high-purity alkylammonium tetrafluoroborate for super capacitor, it is characterized in that: under nitrogen atmosphere, by the Tetrafluoroboric acid of 0.25 mole three ethoxy salt, join in 500 milliliters of reaction flasks of the triethylamine that contains 0.28 mole and 200 milliliters of trichloromethanes, 60 ℃ 10 hours; Filter, the concentrated tetraethylammonium tetrafluoroborate salt crude product that obtains of filtrate, with dissolve with methanol, adds activated carbon, and reflux 30 minutes, filters, and filtrate is cooling obtains 47.7 grams of the white crystals of tetraethylammonium tetrafluoroborate salt, and yield is 88%.
4. a preparation method for high-purity alkylammonium tetrafluoroborate for super capacitor, is characterized in that: under nitrogen atmosphere, by the Tetrafluoroboric acid of 0.5 mole three ethoxy salt, join and contain 0.6 mole
n-(2-methoxy ethyl)-
n,Nin 500 milliliters of reaction flasks of-diethylamide and 200 milliliters of methylene dichloride, stirring at room 12 hours; Through 2 * 50 ml deionized water washings, after separation, add activated carbon, reflux 30 minutes, filters, and filtrate is concentrated; With 2 * 100 ml n-hexane washings, concentrate and obtain 113.6 grams of faint yellow oily matter, yield is 92%.
5. a preparation method for high-purity alkylammonium tetrafluoroborate for super capacitor, is characterized in that: under nitrogen atmosphere, by the Tetrafluoroboric acid front three oxonium salt of 0.3 mole, join and contain 0.33 mole
n-(2-methoxy ethyl)-
n,Nin 500 milliliters of reaction flasks of-diethylamide and 300 milliliters of propylene carbonates, 100 ℃ 6 hours; Through 2 * 50 ml deionized water washings, after separation, add activated carbon, reflux 30 minutes, filters, and filtrate is concentrated; With 2 * 100 ml n-hexane washings, concentrate and obtain 62.9 grams of faint yellow oily matter, yield is 90%.
6. a preparation method for high-purity alkylammonium tetrafluoroborate for super capacitor, is characterized in that: under nitrogen atmosphere, by the Tetrafluoroboric acid of 0.5 mole three ethoxy salt, join and contain 0.6 mole
nin 500 milliliters of reaction flasks of-methyl Pyrrolidine and 200 milliliters of methylene dichloride, 40 ℃ are reacted 7 hours; Filter, the concentrated Tetrafluoroboric acid N-methyl-N-ethyl Pyrrolidine ammonium salt crude product that obtains of filtrate, with dissolve with methanol, add activated carbon, reflux 30 minutes, filters, filtrate is cooling obtains 88.4 grams of the white crystals of Tetrafluoroboric acid N-methyl-N-ethyl Pyrrolidine ammonium salt, and yield is 88%.
7. a preparation method for high-purity alkylammonium tetrafluoroborate for super capacitor, is characterized in that: under nitrogen atmosphere, by 0.35 mole of Tetrafluoroboric acid, three ethoxy salt, join and contain 0.42 mole
nin 500 milliliters of reaction flasks of-(2-methoxy ethyl) Pyrrolidine and 200 milliliters of methylene dichloride, stirring at room 16 hours; Through 2 * 50 ml deionized water washings, after separation, add activated carbon, reflux 30 minutes, filters, and filtrate is concentrated; With 2 * 200 ml n-hexane washings, concentrate and obtain 77.1 grams of faint yellow oily matter, yield is 90%.
8. a preparation method for high-purity alkylammonium tetrafluoroborate for super capacitor, is characterized in that: under nitrogen atmosphere, by the Tetrafluoroboric acid of 0.25 mole three ethoxy salt, join and contain 0.3 mole
nin 500 milliliters of reaction flasks of-Methylimidazole and 200 milliliters of methylene dichloride, stirring at room 14 hours; Through 2 * 50 ml deionized water washings, after separation, add activated carbon, reflux 30 minutes, filters, and filtrate is concentrated; With 2 * 100 ml n-hexane washings, concentrate and obtain 42 grams of faint yellow oily matter, yield is 85%.
9. a preparation method for high-purity alkylammonium tetrafluoroborate for super capacitor, is characterized in that: under nitrogen atmosphere, by the Tetrafluoroboric acid front three oxonium salt of 0.4 mole, join and contain 0.48 mole
nin 500 milliliters of reaction flasks of-methoxy ethyl imidazoles and 200 milliliters of methylene dichloride, stirring at room 16 hours; Through 2 * 50 ml deionized water washings, after separation, add activated carbon, reflux 30 minutes, filters, and filtrate is concentrated; With 2 * 150 ml n-hexane washings, concentrate and obtain 81 grams of faint yellow oily matter, yield is 88%.
10. a preparation method for high-purity alkylammonium tetrafluoroborate for super capacitor, is characterized in that: under nitrogen atmosphere, by the Tetrafluoroboric acid front three oxonium salt of 0.4 mole, join and contain 0.5 mole
nin 500 milliliters of reaction flasks of-ethyl piperidine and 200 milliliters of methylene dichloride, stirring at room 15 hours; Filter the concentrated Tetrafluoroboric acid that obtains of filtrate
n-methyl-
n-ethyl piperidine ammonium salt crude product, with dissolve with methanol, adds activated carbon, and reflux 30 minutes is filtered the cooling Tetrafluoroboric acid that obtains of filtrate
n-methyl-
n73 grams of the white crystals of-ethyl piperidine ammonium salt, yield is 85%.
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Inventor after: Li Wensheng Inventor after: Chang Liang Inventor after: Gegen Tana Inventor after: Liu Yongjiu Inventor after: Zhang Zifang Inventor before: Wang Daolin Inventor before: Jin Zhenxing |
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Effective date of registration: 20170417 Address after: 121000 Liaoning, Taihe District, Jinzhou City, south of the West Ling Li Road, No. 9 Patentee after: Jinzhou Kaimei Energy Co., Ltd. Address before: 121003 Jinzhou science and Technology Development Zone, Liaoning high tech Road, No. 19 Patentee before: Bohai University |
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