CN109888387A - Capacitor batteries electrolyte and preparation method thereof - Google Patents
Capacitor batteries electrolyte and preparation method thereof Download PDFInfo
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- CN109888387A CN109888387A CN201910104361.3A CN201910104361A CN109888387A CN 109888387 A CN109888387 A CN 109888387A CN 201910104361 A CN201910104361 A CN 201910104361A CN 109888387 A CN109888387 A CN 109888387A
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- 239000003990 capacitor Substances 0.000 title claims abstract description 36
- 239000003792 electrolyte Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 21
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 18
- XRRDNAZMVAXXQP-UHFFFAOYSA-N difluoro(dimethyl)silane Chemical compound C[Si](C)(F)F XRRDNAZMVAXXQP-UHFFFAOYSA-N 0.000 claims abstract description 10
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims abstract description 7
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims abstract description 7
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 claims abstract description 7
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 7
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229960002645 boric acid Drugs 0.000 claims abstract description 7
- 235000010338 boric acid Nutrition 0.000 claims abstract description 7
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 7
- 239000010452 phosphate Substances 0.000 claims abstract description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 7
- 229940014800 succinic anhydride Drugs 0.000 claims abstract description 7
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims abstract description 5
- DGTVXEHQMSJRPE-UHFFFAOYSA-M difluorophosphinate Chemical compound [O-]P(F)(F)=O DGTVXEHQMSJRPE-UHFFFAOYSA-M 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims description 18
- 229920000223 polyglycerol Polymers 0.000 claims description 11
- DFPAKSUCGFBDDF-UHFFFAOYSA-N Nicotinamide Chemical compound NC(=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-UHFFFAOYSA-N 0.000 claims description 9
- 229960003966 nicotinamide Drugs 0.000 claims description 9
- 235000005152 nicotinamide Nutrition 0.000 claims description 9
- 239000011570 nicotinamide Substances 0.000 claims description 9
- KYWMCFOWDYFYLV-UHFFFAOYSA-N 1h-imidazole-2-carboxylic acid Chemical compound OC(=O)C1=NC=CN1 KYWMCFOWDYFYLV-UHFFFAOYSA-N 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 4
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims 1
- 239000005642 Oleic acid Substances 0.000 claims 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims 1
- -1 oleic acid Ester Chemical class 0.000 claims 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 abstract description 12
- 230000000052 comparative effect Effects 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- YSNLHLJYEBEKMC-UHFFFAOYSA-N P(O)(=O)(F)F.[Li] Chemical compound P(O)(=O)(F)F.[Li] YSNLHLJYEBEKMC-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Electric Double-Layer Capacitors Or The Like (AREA)
- Secondary Cells (AREA)
- Primary Cells (AREA)
Abstract
The invention discloses a kind of capacitor batteries electrolyte, it include: 15 parts of lithium hexafluoro phosphate, 1 part of difluorine oxalic acid boracic acid lithium, 0.2 part of LiBF4,0.2 part of difluorophosphate, 23.3 parts of ethylene carbonate, 57.3 parts of methyl ethyl carbonate, 1 part of succinic anhydride, 2 parts of 1,3-propane sultone, 0.05 part of difluorodimethylsilane.The present invention also provides the preparation methods of capacitor batteries electrolyte.The present invention is able to ascend the cryogenic property of capacitor batteries, and is able to suppress the generation of hydrofluoric acid.
Description
Technical field
The present invention relates to the electrolyte of a variety of electrochemical energy storage devices, more particularly, to a kind of electrolysis of capacitor batteries
Liquid and preparation method thereof.
Background technique
Capacitor batteries are that (pole of capacitor batteries or the two poles of the earth, which are added, has super capacitor electric for the fusion of super capacitor and lithium battery
Pole material), compared to lithium battery, the use temperature of capacitor batteries is lower, and charge/discharge speed is fast.But current capacitor batteries electricity
Solution liquid mainly uses for reference lithium battery electrolytes, causes the cryogenic property of capacitor batteries to be restricted, and six in this kind of electrolyte
Lithium fluophosphate is easier to generate hydrofluoric acid, influences performance and the service life of battery.Therefore, needing to design one kind can to a certain degree gram
Take the capacitor batteries electrolyte of drawbacks described above.
Summary of the invention
It is an object of the present invention to provide capacitor batteries electrolyte and preparation method thereof, are able to ascend capacitor batteries
Cryogenic property, and it is able to suppress the generation of hydrofluoric acid.
In order to realize these purposes and other advantages according to the present invention, a kind of capacitor batteries electrolyte is provided, including
The raw material of following parts by weight:
15 parts of lithium hexafluoro phosphate, 1 part of difluorine oxalic acid boracic acid lithium, 0.2 part of LiBF4,0.2 part of difluorophosphate, carbonic acid
23.3 parts of vinyl acetate, 57.3 parts of methyl ethyl carbonate, 1 part of succinic anhydride, 2 parts of 1,3- propane sultone, difluorodimethylsilane
0.05 part.
Preferably, the capacitor batteries electrolyte, further includes: 0.1 part of polyglycerol ester.
Preferably, the capacitor batteries electrolyte, the polyglycerol ester are six polyglycerol monooleates.
Preferably, the capacitor batteries electrolyte, further includes:
0.03 part of niacinamide, 0.08 part of imidazole carboxylate.
The present invention also provides the preparation methods of capacitor batteries electrolyte, comprising:
Step 1: taking the ethylene carbonate of above-mentioned parts by weight, methyl ethyl carbonate, mixes, obtain solvent, solvent is divided into two
Part；
Step 2: taking the lithium hexafluoro phosphate of above-mentioned parts by weight, difluorine oxalic acid boracic acid lithium, LiBF4 and difluorophosphoric acid
Lithium is dissolved in first part of solvent, obtains the first solution；
Step 3: taking the succinic anhydride of above-mentioned parts by weight, 1,3- propane sultone, difluorodimethylsilane, six polyglycereol
Monoleate, niacinamide and imidazole carboxylate are dissolved in second part of solvent, obtain the second solution；
Step 4: the second solution is instilled in the first solution, instillation process includes fast phase and stage at a slow speed, quick rank
The time ratio in section and stage at a slow speed is 1:2, and the volume ratio of the second solution of fast phase and at a slow speed discrete consuming is 1:1, wherein
Apply the stationary magnetic field of 0.3T for the first solution during instillation.
Preferably, the preparation method of the capacitor batteries electrolyte, the volume of first part of solvent and second part of solvent
Compare 5:1.
The present invention is include at least the following beneficial effects:
Electrolyte of the invention passes through addition difluorodimethylsilane, six polyglycerol monooleates, niacinamide and imidazoles acid
Ethyl ester can prevent residual water in electrolyte from contacting with fluorine-containing electrolyte, inhibit the generation of hydrofluoric acid, and can neutralize generation
Hydrofluoric acid avoids hydrofluoric acid that side reaction occurs in battery and produces gas and hinder lithium ion mobile, so influence battery performance and
Service life, and lithium ion movement speed under cryogenic can also be improved, improve the cryogenic property of battery.The present invention is in capacitor
Using dissolving respectively in the preparation method of battery electrolyte, quickly-dropwise addition and stationary magnetic field processing at a slow speed, so that of the invention
Difluorodimethylsilane, six polyglycerol monooleates, niacinamide and imidazole carboxylate can be sufficiently dispersed in electrolyte, more
Add and fully plays a role.
Further advantage, target and feature of the invention will be partially reflected by the following instructions, and part will also be by this
The research and practice of invention and be understood by the person skilled in the art.
Specific embodiment
The present invention will be further described in detail below with reference to the embodiments, to enable those skilled in the art referring to specification
Text can be implemented accordingly.
It should be appreciated that such as " having ", "comprising" and " comprising " term used herein do not allot one or more
The presence or addition of a other elements or combinations thereof.
Embodiment 1
Capacitor batteries electrolyte, the raw material including following parts by weight:
15 parts of lithium hexafluoro phosphate, 1 part of difluorine oxalic acid boracic acid lithium, 0.2 part of LiBF4,0.2 part of difluorophosphate, carbonic acid
23.3 parts of vinyl acetate, 57.3 parts of methyl ethyl carbonate, 1 part of succinic anhydride, 2 parts of 1,3- propane sultone, difluorodimethylsilane
0.05 part, 0.1 part of polyglycerol ester, 0.03 part of niacinamide, 0.08 part of imidazole carboxylate.
The polyglycerol ester is six polyglycerol monooleates.
The preparation method of capacitor batteries electrolyte, comprising:
Step 1: taking the ethylene carbonate of above-mentioned parts by weight, methyl ethyl carbonate, mixes, obtain solvent, solvent is divided into two
Part, the volume ratio 5:1 of first part of solvent and second part of solvent.
Step 2: taking the lithium hexafluoro phosphate of above-mentioned parts by weight, difluorine oxalic acid boracic acid lithium, LiBF4 and difluorophosphoric acid
Lithium is dissolved in first part of solvent, obtains the first solution；
Step 3: taking the succinic anhydride of above-mentioned parts by weight, 1,3- propane sultone, difluorodimethylsilane, six polyglycereol
Monoleate, niacinamide and imidazole carboxylate are dissolved in second part of solvent, obtain the second solution；
Step 4: the second solution is instilled in the first solution, instillation process includes fast phase and stage at a slow speed, quick rank
The time ratio in section and stage at a slow speed is 1:2, and the volume ratio of the second solution of fast phase and at a slow speed discrete consuming is 1:1, wherein
Apply the stationary magnetic field of 0.3T for the first solution during instillation.
Comparative example 1
It is added without difluorodimethylsilane, six polyglycerol monooleates, niacinamide and imidazole carboxylate, remaining parameter and reality
Apply identical in example 1, technical process is also identical.
Comparative example 2
Without dissolving respectively, quickly-at a slow speed be added dropwise and stationary magnetic field processing, directly whole raw materials are mixed, remaining
Parameter with it is identical in embodiment 1, technical process is also identical.
Test
Electrolyte is prepared using the method for above-described embodiment 1, comparative example 1 and comparative example 2, using graphite and active carbon as just
Positive plate is made in pole material, and negative electrode tab is made using LTO and active carbon as negative electrode material, according to conventional method composition capacitor electricity
Pond (cylindrical steel shell battery, diameter 15mm, height 50mm).It tests obtained capacitor batteries internal resistance to be substantially reduced, AC internal Resistance knot
Fruit is shown in Table 1, and -40 DEG C and -20 DEG C of discharge capacitance results are shown in Table 2 and table 3 respectively.
Table 1
Table 2
| RT discharge capacity mAh | - 40 DEG C of discharge capacity mAh | - 40 DEG C of discharge capacitances | |
| Embodiment 1 | 510.9 | 333.10 | 65.20% |
| Comparative example 1 | 500.5 | 115.62 | 23.10% |
| Comparative example 2 | 506.3 | 177.21 | 35.00% |
Table 3
| RT discharge capacity mAh | - 20 DEG C of discharge capacity mAh | - 20 DEG C of discharge capacitances | |
| Embodiment 1 | 510.9 | 424.15 | 83.02% |
| Comparative example 1 | 500.5 | 202.84 | 40.53% |
| Comparative example 2 | 506.3 | 243.13 | 48.03% |
As shown in Table 1, embodiment 1 have lower AC internal Resistance, by table 2 and table 3 it is found that embodiment 1-40 DEG C and-
Capacity retention ratio with higher at 20 DEG C is superior to comparative example 1, comparative example 2, shows that method of the invention can be substantially reduced
The AC internal Resistance of capacitor batteries improves the cryogenic property of capacitor batteries.
Number of devices and treatment scale described herein are for simplifying explanation of the invention.To capacitor electricity of the invention
The application of pond electrolyte, modifications and variations will be readily apparent to persons skilled in the art.
Although the embodiments of the present invention have been disclosed as above, but its is not only in the description and the implementation listed
With it can be fully applied to various fields suitable for the present invention, for those skilled in the art, can be easily
Realize other modification, therefore without departing from the general concept defined in the claims and the equivalent scope, the present invention is simultaneously unlimited
In specific details and embodiment shown and described herein.
Claims (6)
1. capacitor batteries electrolyte, which is characterized in that the raw material including following parts by weight:
15 parts of lithium hexafluoro phosphate, 1 part of difluorine oxalic acid boracic acid lithium, 0.2 part of LiBF4,0.2 part of difluorophosphate, ethylene carbonate
23.3 parts of ester, 57.3 parts of methyl ethyl carbonate, 1 part of succinic anhydride, 2 parts of 1,3- propane sultone, 0.05 part of difluorodimethylsilane.
2. capacitor batteries electrolyte as described in claim 1, which is characterized in that further include: 0.1 part of polyglycerol ester.
3. capacitor batteries electrolyte as claimed in claim 2, which is characterized in that the polyglycerol ester is six polyglycereol list oleic acid
Ester.
4. capacitor batteries electrolyte as claimed in claim 3, which is characterized in that further include:
0.03 part of niacinamide, 0.08 part of imidazole carboxylate.
5. the preparation method of capacitor batteries electrolyte as claimed in claim 4 characterized by comprising
Step 1: taking the ethylene carbonate of above-mentioned parts by weight, methyl ethyl carbonate, mixes, obtain solvent, solvent is divided into two parts；
Step 2: the lithium hexafluoro phosphate of above-mentioned parts by weight, difluorine oxalic acid boracic acid lithium, LiBF4 and difluorophosphate are taken, it is molten
In first part of solvent, the first solution is obtained；
Step 3: taking the succinic anhydride of above-mentioned parts by weight, 1,3- propane sultone, difluorodimethylsilane, six polyglycereol list oil
Acid esters, niacinamide and imidazole carboxylate are dissolved in second part of solvent, obtain the second solution；
Step 4: the second solution is instilled in the first solution, instillation process includes fast phase and stage at a slow speed, fast phase and
The time ratio in stage is 1:2 at a slow speed, and the volume ratio of the second solution of fast phase and at a slow speed discrete consuming is 1:1, wherein is being dripped
Apply the stationary magnetic field of 0.3T during entering for the first solution.
6. the preparation method of capacitor batteries electrolyte as claimed in claim 4, which is characterized in that first part of solvent and second part
The volume ratio 5:1 of solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910104361.3A CN109888387B (en) | 2019-02-01 | 2019-02-01 | Capacitor battery electrolyte and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910104361.3A CN109888387B (en) | 2019-02-01 | 2019-02-01 | Capacitor battery electrolyte and preparation method thereof |
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| Publication Number | Publication Date |
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| CN109888387A true CN109888387A (en) | 2019-06-14 |
| CN109888387B CN109888387B (en) | 2021-10-08 |
Family
ID=66927823
Family Applications (1)
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| CN201910104361.3A Active CN109888387B (en) | 2019-02-01 | 2019-02-01 | Capacitor battery electrolyte and preparation method thereof |
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| Country | Link |
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Cited By (1)
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| Publication number | Publication date |
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| CN109888387B (en) | 2021-10-08 |
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