CN106279099A - A kind of sulfuric acid vinyl ester except water acid reduction method - Google Patents
A kind of sulfuric acid vinyl ester except water acid reduction method Download PDFInfo
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- CN106279099A CN106279099A CN201610651817.4A CN201610651817A CN106279099A CN 106279099 A CN106279099 A CN 106279099A CN 201610651817 A CN201610651817 A CN 201610651817A CN 106279099 A CN106279099 A CN 106279099A
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- Prior art keywords
- except water
- vinyl ester
- sulfuric acid
- acid vinyl
- deacidification
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D327/00—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms
- C07D327/10—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms two oxygen atoms and one sulfur atom, e.g. cyclic sulfates
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M10/0567—Liquid materials characterised by the additives
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
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- General Chemical & Material Sciences (AREA)
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Abstract
The invention discloses a kind of sulfuric acid vinyl ester except water acid reduction method, except water deacidification step is as follows: in hybrid reactor, sulfuric acid vinyl ester is dissolved in lithium-ion battery electrolytes organic solvent, it is uniformly mixed, then homogeneous mixture solotion is squeezed into except in water deacidification tank, adding except water acid lowering agent in decontaminating column, will be connected with decontaminating column sealing except water deacidification tank with stainless steel pipes, ON cycle system makes mixed solution constantly circulate to carry out except water deacidification.What the present invention provided reduce in the sulfuric acid vinyl ester sulfuric acid vinyl ester of moisture and acidity except water acid reduction method, there is simple, quick, effective, the advantage of low cost, new impurity component will not be introduced again, meet the high-end field electrolyte quality requirements to sulfuric acid vinyl ester raw material, be highly suitable for the sulfuric acid vinyl ester extensive industrialization in lithium-ion battery electrolytes field.
Description
Technical field
The present invention relates to lithium-ion battery electrolytes technical field, be specifically related to a kind of sulfuric acid vinyl ester except water deacidification side
Method.
Background technology
Sulfuric acid vinyl ester (DTD, CAS:1072-53-3), white crystal or crystalline powder, can be as the hydroxyl of organic synthesis
Ethylating agent is used for synthetic drug intermediate, is alternatively arranged as synthesizing gelatin hardening certain heterocyclic compound, resisting hypertension
Medicine and the raw material of novel Dual Surfactants.
Research shows, highly purified sulfuric acid vinyl ester is as in additive application to lithium-ion battery electrolytes, at battery
Formation process contributes to electrode surface and forms the SEI protecting film of function admirable, can effectively suppress the appearance during circulating battery
Amount decay, reduces the cell expansion after high temperature is placed, is especially applicable in lithium ion battery with high energy density, and effect is more aobvious
Write, there is the boundless market space.
But, sulfuric acid vinyl ester is limited by synthetic method route, there is the acid impurities of high level, is configured to electrolysis
After liquid, electrolyte acidity is too high, and colourity rises also very fast, and this will seriously reduce electrolyte quality, shortens electrolyte and effectively guarantees the quality
Phase.
Summary of the invention
In view of problem present in background technology, it is an object of the invention to provide a kind of simple, effectively reduce sulphuric acid second
In alkene ester the sulfuric acid vinyl ester of moisture and acidity except water acid reduction method, improve sulfuric acid vinyl ester material quality.
To achieve these goals, the technical solution used in the present invention is:
A kind of sulfuric acid vinyl ester except water acid reduction method, except water deacidification step is as follows: in hybrid reactor, by sulfuric acid vinyl ester
It is dissolved in lithium-ion battery electrolytes organic solvent, is uniformly mixed, then homogeneous mixture solotion is squeezed into except water deacidification
In tank, adding except water acid lowering agent, will be connected with decontaminating column sealing except water deacidification tank with stainless steel pipes in decontaminating column, unlatching follows
Loop systems makes mixed solution constantly circulate to carry out except water deacidification.
Described except water acid lowering agent be 3A, 4A, 5A, 10X, 13X equal sphere molecular sieve, activated carbon, aluminosilicate oxide, work
Property aluminium oxide, calcium oxide, silica gel etc. therein one or more.
Described except water acid lowering agent addition be the 5% ~ 30% of mixed solution quality.
Described sulfuric acid vinyl ester mass percent in mixed solution is 10% ~ 30%.
Described except water acid lowering agent addition be the 10% ~ 20% of mixed solution quality.
Except water deacidification process decontaminating column temperature is 10 ~ 25 DEG C, except water deacidification tank temperature is 10 ~ 25 DEG C, except the water deacidification time
It it is 4 ~ 48 hours.
Described lithium-ion battery electrolytes organic solvent is dimethyl carbonate, diethyl carbonate, Ethyl methyl carbonate, propanoic acid third
In ester, ethyl propionate any one.
The invention has the beneficial effects as follows:
The inventive method has simple, quick, effective, the advantage of low cost, will not introduce again new impurity component, meet high-end
The field electrolyte quality requirements to sulfuric acid vinyl ester raw material, is highly suitable for sulfuric acid vinyl ester and leads at lithium-ion battery electrolytes
The extensive industrialization in territory.
Accompanying drawing explanation
Fig. 1 is that embodiment 1 mixed solution is except water deacidification process moisture, acidity transition diagram.
Detailed description of the invention
Being described further the present invention below in conjunction with embodiment, the enforcement of the present invention includes but not limited to following embodiment party
Formula.Any change without departing from present invention or replacement can be understood by the person skilled in the art, all should be in the present invention
Protection domain within.
Embodiment 1
In the 50L hybrid reactor of full nitrogen atmosphere, 5KG sulfuric acid vinyl ester is dissolved in 20KG diethyl carbonate solvent
In, it is uniformly mixed, then homogeneous mixture solotion is squeezed into except in water deacidification tank, and add in sealing the decontaminating column being connected
The 5A molecular sieve of 5KG, ON cycle system carry out mixed solution except water deacidification；Except water deacidification process pot temperature and decontaminating column
Temperature is 25 DEG C, except 8 hours water deacidification time, every 1 hour sampling and testing mixed liquor moisture, acidity.Moisture measurement method is selected
Selecting karr-Fei Xiu moisture measurement method, instrument is that moisture tester is led in Switzerland ten thousand；Acidity Test Method uses acid-base titrations, mark
Quasi-alkali liquor is 0.1M NaOH solution.
Embodiment 2
In the 50L hybrid reactor of full nitrogen atmosphere, 4KG sulfuric acid vinyl ester is dissolved in 20KG methyl ethyl carbonate ester solvent
In, it is uniformly mixed, then homogeneous mixture solotion is squeezed into except in water deacidification tank, and add in sealing the decontaminating column being connected
The 3A molecular sieve of 3.6KG, ON cycle system carry out mixed solution except water deacidification；Except water deacidification process pot temperature and purification
Column temperature is 25 DEG C, except 8 hours water deacidification time, every 1 hour sampling and testing mixed liquor moisture, acidity.Moisture measurement method
Selecting karr-Fei Xiu moisture measurement method, instrument is that moisture tester is led in Switzerland ten thousand；Acidity Test Method uses acid-base titrations,
Standard alkali liquor is 0.1M NaOH solution.
Embodiment 3
In the 50L hybrid reactor of full nitrogen atmosphere, 3KG sulfuric acid vinyl ester is dissolved in 21KG propyl propionate solvent,
It is uniformly mixed, then homogeneous mixture solotion is squeezed into except in water deacidification tank, and add in sealing the decontaminating column being connected
The 5A molecular sieve of 4.8KG, ON cycle system carry out mixed solution except water deacidification；Except water deacidification process pot temperature and purification
Column temperature is 25 DEG C, except 8 hours water deacidification time, every 1 hour sampling and testing mixed liquor moisture, acidity.Moisture measurement method
Selecting karr-Fei Xiu moisture measurement method, instrument is that moisture tester is led in Switzerland ten thousand；Acidity Test Method uses acid-base titrations,
Standard alkali liquor is 0.1M NaOH solution.
From Fig. 1, moisture, acidity transition diagram are it can be seen that sulfuric acid vinyl ester mixed solution is the most aobvious except water deacidification effect
Writing, can effectively reduce moisture in mixed solution, acidity content within 5 hours, wherein moisture is reduced to 5ppm from 69.3ppm
Hereinafter, acidity is reduced to below 6ppm from 48.7ppm.
By in above-described embodiment 1 except the sulfuric acid vinyl ester mixed solution after water deacidification, according to 1M LiPF6, EC:DEC=1:3
System, the electrolyte prescription adding 5% sulfuric acid vinyl ester produces 50KG electrolyte, produces and tests electrolyte moisture, acidity after terminating
Result；
Meanwhile, by the sulfuric acid vinyl ester crystal without any process according to 1M LiPF6, EC:DEC=1:3 system, add 5% sulfur
The electrolyte prescription of vinyl acetate produces 50KG electrolyte, produces and tests electrolyte moisture, acidity result after terminating.Two batches of electrolysis
Liquid moisture, acidity test result are as shown in table 1:
| Electrolyte batch | Sulfuric acid vinyl ester disposition | Moisture/ppm | Acidity/ppm |
| 1 | Except water deacidification treatment | 9.8 | 18.4 |
| 2 | Untreated | 20.5 | 50.3 |
Table 1
Table 1 Comparative result understands, and uses the electrolyte that the method for the invention produces except the sulfuric acid vinyl ester after water deacidification treatment
The most all it is greatly reduced at moisture and acidity, it is ensured that the index of quality that electrolyte is good, there is the wide market space.
It is above illustrating of the section Example for the present invention, is not intended to limit the scope of the claims of the present invention,
All changes without departing from present invention or replacement, all should be within protection scope of the present invention.
Claims (7)
1. a sulfuric acid vinyl ester except water acid reduction method, it is characterised in that: except water deacidification step is as follows: at hybrid reactor
In, sulfuric acid vinyl ester is dissolved in lithium-ion battery electrolytes organic solvent, is uniformly mixed, then will uniformly mix molten
Liquid is squeezed into except, in water deacidification tank, adding except water acid lowering agent in decontaminating column, will be except water deacidification tank and decontaminating column with stainless steel pipes
Sealing and be connected, ON cycle system makes mixed solution constantly circulate to carry out except water deacidification.
A kind of sulfuric acid vinyl ester the most according to claim 1 except water acid reduction method, it is characterised in that described except water deacidification
Agent is 3A, 4A, 5A, 10X, 13X equal sphere molecular sieve, activated carbon, aluminosilicate oxide, activated alumina, calcium oxide, silica gel
Etc. therein one or more.
A kind of sulfuric acid vinyl ester the most according to claim 1 except water acid reduction method, it is characterised in that described except water deacidification
Agent addition is the 5% ~ 30% of mixed solution quality.
A kind of sulfuric acid vinyl ester the most according to claim 1 except water acid reduction method, it is characterised in that described sulphuric acid ethylene
Ester mass percent in mixed solution is 10% ~ 30%.
A kind of sulfuric acid vinyl ester the most according to claim 1 except water acid reduction method, it is characterised in that described except water deacidification
Agent addition is the 10% ~ 20% of mixed solution quality.
A kind of sulfuric acid vinyl ester the most according to claim 1 except water acid reduction method, it is characterised in that except water deacidification process
Decontaminating column temperature is 10 ~ 25 DEG C, except water deacidification tank temperature is 10 ~ 25 DEG C, except the water deacidification time is 4 ~ 48 hours.
A kind of sulfuric acid vinyl ester the most according to claim 1 except water acid reduction method, it is characterised in that described lithium-ion electric
Pond electrolyte organic solvent is any one in dimethyl carbonate, diethyl carbonate, Ethyl methyl carbonate, propyl propionate, ethyl propionate
Kind.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610651817.4A CN106279099A (en) | 2016-08-10 | 2016-08-10 | A kind of sulfuric acid vinyl ester except water acid reduction method |
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| CN201610651817.4A CN106279099A (en) | 2016-08-10 | 2016-08-10 | A kind of sulfuric acid vinyl ester except water acid reduction method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109776361A (en) * | 2017-11-14 | 2019-05-21 | 石家庄圣泰化工有限公司 | The synthetic method of sulfuric acid vinyl ester |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102070444A (en) * | 2010-12-21 | 2011-05-25 | 东莞市杉杉电池材料有限公司 | Ethyl acetate dehydration and impurity removing method |
| CN102079741A (en) * | 2010-12-21 | 2011-06-01 | 东莞市杉杉电池材料有限公司 | Novel dewatering and purifying method of ethylene carbonate (EC) |
| CN102107093A (en) * | 2010-12-29 | 2011-06-29 | 东莞市杉杉电池材料有限公司 | Method for carrying out water removal and acid reduction on electrolyte of lithium ion battery and lithium type molecular sieve thereof |
| CN102161613A (en) * | 2010-12-21 | 2011-08-24 | 东莞市杉杉电池材料有限公司 | Dewatering method of fluorobenzene |
| CN203425559U (en) * | 2013-08-19 | 2014-02-12 | 东莞市杉杉电池材料有限公司 | Molecular sieve column for dewatering solvent for battery electrolyte |
| CN104538673A (en) * | 2014-12-31 | 2015-04-22 | 东莞市杉杉电池材料有限公司 | Lithium-ion battery electrolyte with dehydration function and acidity reduction function |
-
2016
- 2016-08-10 CN CN201610651817.4A patent/CN106279099A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102070444A (en) * | 2010-12-21 | 2011-05-25 | 东莞市杉杉电池材料有限公司 | Ethyl acetate dehydration and impurity removing method |
| CN102079741A (en) * | 2010-12-21 | 2011-06-01 | 东莞市杉杉电池材料有限公司 | Novel dewatering and purifying method of ethylene carbonate (EC) |
| CN102161613A (en) * | 2010-12-21 | 2011-08-24 | 东莞市杉杉电池材料有限公司 | Dewatering method of fluorobenzene |
| CN102107093A (en) * | 2010-12-29 | 2011-06-29 | 东莞市杉杉电池材料有限公司 | Method for carrying out water removal and acid reduction on electrolyte of lithium ion battery and lithium type molecular sieve thereof |
| CN203425559U (en) * | 2013-08-19 | 2014-02-12 | 东莞市杉杉电池材料有限公司 | Molecular sieve column for dewatering solvent for battery electrolyte |
| CN104538673A (en) * | 2014-12-31 | 2015-04-22 | 东莞市杉杉电池材料有限公司 | Lithium-ion battery electrolyte with dehydration function and acidity reduction function |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109776361A (en) * | 2017-11-14 | 2019-05-21 | 石家庄圣泰化工有限公司 | The synthetic method of sulfuric acid vinyl ester |
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Address after: 523000 Guangdong province Dongguan city Dongguan Ecological Industrial Park Xingye Road Applicant after: Dongguan City Kai Xin battery material Co., Ltd Address before: 523000 Guangdong province Dongguan City Chashan Town Ecological Industrial Park Industrial Road Applicant before: Dongguan City Kai Xin battery material Co., Ltd |
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Effective date of registration: 20190329 Address after: 510000 No. 8 Kangda Road, Dongcheng District, Yunpu Industrial Zone, Huangpu District, Guangzhou City, Guangdong Province Applicant after: Guangzhou Tianci High-Tech Material Co., Ltd. Address before: 523000 Dongguan Eco-Industrial Park, Dongguan City, Guangdong Province Applicant before: Dongguan City Kai Xin battery material Co., Ltd |
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Application publication date: 20170104 |
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