CN109830748B - Lithium ion battery electrolyte - Google Patents
Lithium ion battery electrolyte Download PDFInfo
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Abstract
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a lithium ion battery electrolyte, which comprises an organic solvent, lithium salt, an additive A and an additive B; the additive A comprises vinylene carbonate, fluoroethylene carbonate and 1, 3-propane sultone, and the additive B comprises one or a combination of diisopropyl azodicarboxylate, N' -dinitrosopentamethylenetetramine, diethyl azodicarboxylate and N, N-dinitroso-N, N-dimethyl terephthalamide. Compared with the prior art, the additive B is added, and the additive B can be decomposed to generate nitrogen and components for forming an SEI film after the battery is pre-charged, so that the electrolyte soaked in the pores of the pole piece is foamed, the porosity of the surface of the pole piece is improved, the conduction speed of lithium ions is improved, and the cycle performance of the battery is improved.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a lithium ion battery electrolyte.
Background
The lithium ion battery has many advantages as a high-capacity long-life environment-friendly battery, and is widely applied to the fields of energy storage, electric automobiles, portable electronic products and the like.
The lithium ion battery generally comprises a positive plate, a negative plate, an isolating membrane arranged between the positive plate and the negative plate at intervals and electrolyte. The positive/negative plate is the basis of the lithium ion battery, and directly determines the electrochemical performance and safety of the battery. The positive/negative plate is composed of a metal current collector and a composite material coating coated on the metal current collector, the composite material coating is mainly composed of a composition phase (carbon gel phase) formed by mixing active substance particles, a conductive agent and a binding agent, pores and the like, and the pores are filled with electrolyte. The electrolyte is an important component of the lithium ion battery, and the quality of the electrolyte directly influences the optimization and improvement of the battery performance.
In the prior art, in order to improve the cycle performance of the battery, part of the prior art is improved by aiming at an electrode material or an electrode preparation method, and the other part of the prior art is optimized by aiming at the components of an electrolyte. Chinese patent CN106099045A discloses a cold pressing method of electrode plate, the porosity of the obtained electrode plate surface is increased to 10% -30%, although the charging capability and the cycling capability of the battery are improved, the method is inconvenient to operate and needs to consume a large amount of manpower and capital. As known to those skilled in the art, it is beneficial to improve the cycle performance of the battery to properly increase the porosity of the pole piece, but most of the additives added in the existing electrolyte contain unsaturated gel monomer components, and during the production, transportation, storage and use of the electrolyte, the electrolyte may become gel-like, thereby affecting the use of the electrolyte and reducing the shelf life, and even causing blockage of pores on the pole piece, affecting the conduction of lithium ions, and further causing the performance of the battery to be poor.
In view of the above, it is necessary to provide a new lithium ion battery electrolyte to solve the problems in the prior art.
Disclosure of Invention
The invention aims to: aiming at the defects of the prior art, the lithium ion battery electrolyte is provided, and the cycle performance of the lithium ion battery is improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
a lithium ion battery electrolyte comprises an organic solvent, lithium salt, an additive A and an additive B; the additive A comprises vinylene carbonate, fluoroethylene carbonate and 1, 3-propane sultone, and the additive B comprises one or a combination of diisopropyl azodicarboxylate, N' -dinitrosopentamethylenetetramine, diethyl azodicarboxylate and N, N-dinitroso-N, N-dimethyl terephthalamide.
The additive A belongs to a film forming additive, and has the main function of forming a stable SEI film on the surface of the pole piece, and effectively inhibiting solvent molecules from being continuously decomposed on the surface of the pole piece, so that the performance of the pole piece is improved. The additive B can be decomposed to generate nontoxic and harmless nitrogen and ester substances capable of forming an SEI film after the battery is precharged, so that not only can the electrolyte not form gel, but also the decomposed nitrogen can foam the electrolyte in the pores of the pole piece, the porosity of the surface of the pole piece is improved, more space is provided for the conduction of the lithium ion battery, and the charging capacity and the cycle performance of the battery are improved.
As an improvement of the lithium ion battery electrolyte, the content of the additive A accounts for 0.03-10% of the total weight of the electrolyte.
As an improvement of the lithium ion battery electrolyte, the content of the vinylene carbonate accounts for 0.01-4% of the total weight of the electrolyte.
As an improvement of the lithium ion battery electrolyte, the content of the fluoroethylene carbonate accounts for 0.01-3% of the total mass of the electrolyte.
As an improvement of the lithium ion battery electrolyte, the content of the 1, 3-propane sultone accounts for 0.01-3% of the total weight of the electrolyte.
As an improvement of the lithium ion battery electrolyte, the content of the additive B accounts for 0.5-4% of the total mass of the electrolyte.
As an improvement of the lithium ion battery electrolyte, the organic solvent is any one or a combination of more of ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propylene carbonate, methyl propyl carbonate, butylene carbonate, ethyl acetate, fluorobenzene, fluoroethylene carbonate and gamma-butyrolactone.
As an improvement of the lithium ion battery electrolyte, the lithium salt is one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium difluorophosphate, lithium difluorobis (oxalate) phosphate, lithium bis (oxalate) borate, lithium difluorooxalate sulfate, lithium bis (trifluoromethylsulfonyl) imide and lithium trifluoromethylsulfonate.
As an improvement of the lithium ion battery electrolyte, the concentration of the lithium salt in the electrolyte is 0.8-1.5 mo 1/L.
The invention has the beneficial effects that: the invention provides a lithium ion battery electrolyte, which comprises an organic solvent, lithium salt, an additive A and an additive B; the additive A comprises vinylene carbonate, fluoroethylene carbonate and 1, 3-propane sultone, and the additive B comprises one or a combination of diisopropyl azodicarboxylate, N' -dinitrosopentamethylenetetramine, diethyl azodicarboxylate and N, N-dinitroso-N, N-dimethyl terephthalamide. Compared with the prior art, the additive B is added, and the additive B can be decomposed to generate nitrogen and components for forming an SEI film after the battery is pre-charged, so that the electrolyte soaked in the pores of the pole piece is foamed, the porosity of the surface of the pole piece is improved, the conduction speed of lithium ions is improved, and the cycle performance of the battery is improved.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but the embodiments of the present invention are not limited thereto.
Comparative example 1
Preparing lithium ion battery electrolyte:
lithium salt LiPF6Dissolving in mixed solvent of ethylene carbonate/dimethyl carbonate/ethyl methyl carbonate (mass ratio 3/6/4) to obtain solvent, adding vinylene carbonate 2%, fluoroethylene carbonate 2%, and 1, 3-propane sultone 2%, wherein LiPF6The concentration was 1.0mol/L, giving a comparative electrolyte.
Example 1
An electrolyte was prepared in the same manner as in comparative example 1, except that diisopropyl azodicarboxylate in an amount of 0.5% by mass based on the total mass of the electrolyte was added.
Example 2
An electrolyte was prepared in the same manner as in comparative example 1, except that diisopropyl azodicarboxylate was added in an amount of 2% by mass based on the total mass of the electrolyte.
Example 3
An electrolyte was prepared in the same manner as in comparative example 1, except that N, N' -dinitrosopentamethylenetetramine was added in an amount of 0.5% by mass based on the total mass of the electrolyte.
Example 4
An electrolyte was prepared in the same manner as in comparative example 1, except that N, N' -dinitrosopentamethylenetetramine was added in an amount of 2% by mass based on the total mass of the electrolyte.
Example 5
An electrolyte was prepared in the same manner as in comparative example 1, except that diethyl azodicarboxylate in an amount of 0.5% by mass based on the total mass of the electrolyte was added.
Example 6
An electrolyte was prepared in the same manner as in comparative example 1, except that diethyl azodicarboxylate in an amount of 2% by mass based on the total mass of the electrolyte was added.
Example 7
An electrolyte was prepared in the same manner as in comparative example 1, except that N, N-dinitroso-N, N.dimethyl terephthalamide was added in an amount of 0.5% by mass based on the total mass of the electrolyte.
Example 8
An electrolyte was prepared in the same manner as in comparative example 1, except that N, N-dinitroso-N, N.dimethyl terephthalamide was added in an amount of 2% by mass based on the total mass of the electrolyte.
Example 9
An electrolyte was prepared in the same manner as in comparative example 1, except that N, N' -dinitrosopentamethylenetetramine was added in an amount of 0.5% by mass based on the total mass of the electrolyte and diethyl azodicarboxylate was added in an amount of 0.5% by mass based on the total mass of the electrolyte.
Example 10
An electrolyte was prepared in the same manner as in comparative example 1, except that N, N' -dinitrosopentamethylenetetramine was added in an amount of 0.5% by mass based on the total mass of the electrolyte and N, N-dinitroso-N, N.dimethyl terephthalamide was added in an amount of 0.5% by mass based on the total mass of the electrolyte.
Example 11
An electrolyte was prepared in the same manner as in comparative example 1, except that N, N' -dinitrosopentamethylenetetramine was added in an amount of 2% by mass based on the total mass of the electrolyte and diethyl azodicarboxylate was added in an amount of 2% by mass based on the total mass of the electrolyte.
Example 12
An electrolyte was prepared in the same manner as in comparative example 1, except that N, N' -dinitrosopentamethylenetetramine was added in an amount of 2% by mass based on the total mass of the electrolyte and N, N-dinitroso-N, N.dimethyl terephthalamide was added in an amount of 2% by mass based on the total mass of the electrolyte.
Example 13
An electrolyte was prepared in the same manner as in comparative example 1, except that diethyl azodicarboxylate in an amount of 0.5% by mass based on the total mass of the electrolyte and N, N-dinitroso-N, N.dimethyl terephthalamide in an amount of 0.5% by mass based on the total mass of the electrolyte were added.
Example 14
An electrolyte was prepared in the same manner as in comparative example 1, except that diethyl azodicarboxylate in an amount of 2% by mass based on the total mass of the electrolyte and N, N-dinitroso-N, N.dimethyl terephthalamide in an amount of 2% by mass based on the total mass of the electrolyte were added.
Example 15
An electrolyte was prepared in the same manner as in comparative example 1, except that N, N' -dinitrosopentamethylenetetramine was added in an amount of 0.5% by mass based on the total mass of the electrolyte and diethyl azodicarboxylate was added in an amount of 2% by mass based on the total mass of the electrolyte.
Example 16
An electrolyte was prepared in the same manner as in comparative example 1, except that N, N' -dinitrosopentamethylenetetramine was added in an amount of 0.5% by mass based on the total mass of the electrolyte and N, N-dinitroso-N, N.dimethyl terephthalamide was added in an amount of 2% by mass based on the total mass of the electrolyte.
Example 17
An electrolyte was prepared in the same manner as in comparative example 1, except that diisopropyl azodicarboxylate in an amount of 0.5% by mass based on the total mass of the electrolyte and diethyl azodicarboxylate in an amount of 0.5% by mass based on the total mass of the electrolyte were added.
Example 18
An electrolyte was prepared in the same manner as in comparative example 1, except that diisopropyl azodicarboxylate in an amount of 2% by mass based on the total mass of the electrolyte and diethyl azodicarboxylate in an amount of 2% by mass based on the total mass of the electrolyte were added.
Performance testing
Testing one:
1) selecting batteries with the nominal capacity of 1500mAh and without electrolyte injection, selecting the batteries which are produced in the same batch and have no electrolyte injection, vacuumizing at the temperature of 80 +/-5 ℃, replacing atmosphere with nitrogen every 2 hours, vacuum-baking for 24 hours, and then cooling for 2 hours to perform electrolyte injection operation.
2) The cell injected with the electrolyte was allowed to stand at room temperature for 24 hours.
3) And performing pre-charging operation, and performing 1C 300-time cycle performance test at 0-4.2V in a normal temperature environment.
And (2) testing:
in contrast to the test one: in the step 2), the battery injected with the electrolyte is kept stand for 4 hours at 60 ℃, and then is cooled to normal temperature and kept stand for 20 hours.
The room-temperature cycle capacity retention rates of the lithium ion batteries respectively filled with the electrolytes prepared in comparative example 1 and examples 1 to 18 were measured and are shown in table 1.
TABLE 1 Normal temperature cycle capacity retention ratio of the battery
The test data in table 1 show that the capacity retention rate of the electrolyte prepared by the invention after being injected into a lithium ion battery at 0-4.2V and 1C multiplying power is obviously higher than that of the battery prepared by the electrolyte of the comparative example, that is, the electrolyte of the invention can effectively improve the cycle performance of the battery. In addition, as can be seen from comparison of the test results of the first test and the second test, the lithium ion battery injected with the electrolyte properly controls the standing time and temperature, maintains a certain vacuum degree, and is beneficial to the permeation of the electrolyte in the battery, thereby being beneficial to improving the electrical property.
Variations and modifications to the above-described embodiments may also occur to those skilled in the art, which fall within the scope of the invention as disclosed and taught herein. Therefore, the present invention is not limited to the above-mentioned embodiments, and any obvious improvement, replacement or modification made by those skilled in the art based on the present invention is within the protection scope of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
Claims (8)
1. A lithium ion battery electrolyte is characterized in that: comprises an organic solvent, lithium salt, an additive A and an additive B; the additive A comprises vinylene carbonate, fluoroethylene carbonate and 1, 3-propane sultone, and the additive B comprises one or a combination of diisopropyl azodicarboxylate, N' -dinitrosopentamethylenetetramine and N, N-dinitroso-N, N-dimethyl terephthalamide; the content of the additive B accounts for 0.5-4% of the total mass of the electrolyte.
2. The lithium ion battery electrolyte of claim 1, wherein: the content of the additive A accounts for 0.03-10% of the total weight of the electrolyte.
3. The lithium ion battery electrolyte of claim 2, wherein: the content of the vinylene carbonate accounts for 0.01-4% of the total weight of the electrolyte.
4. The lithium ion battery electrolyte of claim 2, wherein: the content of the fluoroethylene carbonate accounts for 0.01-3% of the total mass of the electrolyte.
5. The lithium ion battery electrolyte of claim 2, wherein: the content of the 1, 3-propane sultone accounts for 0.01-3% of the total weight of the electrolyte.
6. The lithium ion battery electrolyte of claim 1, wherein: the organic solvent is any one or a combination of more of ethylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, propylene carbonate, methyl propyl carbonate, butylene carbonate, ethyl acetate, fluorobenzene, fluoroethylene carbonate and gamma-butyrolactone.
7. The lithium ion battery electrolyte of claim 1, wherein: the lithium salt is one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium difluorophosphate, lithium difluorobis (oxalate) phosphate, lithium bis (oxalate) borate, lithium difluorooxalate sulfate, lithium bis (trifluoromethylsulfonyl) imide and lithium trifluoromethylsulfonate.
8. The lithium ion battery electrolyte of claim 1, wherein: the concentration of the lithium salt in the electrolyte is 0.8-1.5 mo 1/L.
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| CN110600804B (en) * | 2019-10-18 | 2021-03-02 | 深圳市比克动力电池有限公司 | Lithium ion battery electrolyte suitable for NCM811 and SiO-C material system and preparation method thereof |
| CN114552001A (en) * | 2020-11-24 | 2022-05-27 | 中国科学院大连化学物理研究所 | Electrolyte for improving high-temperature shelving performance of ternary lithium ion battery and application |
| CN115668568A (en) * | 2020-12-29 | 2023-01-31 | 远景动力技术(江苏)有限公司 | Sulfate compound, nonaqueous electrolyte solution containing same, and electricity storage device |
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| KR100308690B1 (en) * | 1998-12-22 | 2001-11-30 | 이 병 길 | Microporous polymer electrolyte containing absorbent and its manufacturing method |
| KR100467435B1 (en) * | 2002-09-06 | 2005-01-24 | 삼성에스디아이 주식회사 | An electrolyte for a lithium battery and a lithium battery comprising the same |
| JP2006073308A (en) * | 2004-09-01 | 2006-03-16 | Matsushita Electric Ind Co Ltd | Non-aqueous electrolytic liquid secondary battery |
| KR20070080776A (en) * | 2006-02-08 | 2007-08-13 | 주식회사 엘지화학 | Nonaqueous electrolyte having excellent safety and electrochemical device comprising the same |
| JP5652029B2 (en) * | 2010-07-20 | 2015-01-14 | 日本電気株式会社 | Electrode and manufacturing method thereof, power storage device provided with electrode, and manufacturing method |
| WO2013176275A1 (en) * | 2012-05-25 | 2013-11-28 | 日本電気株式会社 | Electricity storage device |
| CN103515607B (en) * | 2012-06-27 | 2016-03-02 | 比亚迪股份有限公司 | A kind of lithium ion battery cathode slurry, negative pole and battery |
| TWI538281B (en) * | 2013-03-08 | 2016-06-11 | 台灣塑膠工業股份有限公司 | Additive of electrolyte of lithium battery and electrolyte of lithium battery using the same |
| JP2015153720A (en) * | 2014-02-19 | 2015-08-24 | 凸版印刷株式会社 | Laminate for positive electrode, positive electrode, and nonaqueous electrolyte secondary battery |
| CN104979588A (en) * | 2015-07-09 | 2015-10-14 | 深圳新宙邦科技股份有限公司 | Lithium ion battery non-aqueous electrolyte and lithium ion battery |
| CN105633350A (en) * | 2016-04-01 | 2016-06-01 | 深圳市沃特玛电池有限公司 | Porous pole piece and preparation method thereof and lithium ion battery |
| JP6489095B2 (en) * | 2016-10-17 | 2019-03-27 | トヨタ自動車株式会社 | Method for producing lithium ion secondary battery |
| CN107910586B (en) * | 2017-11-07 | 2020-06-23 | 广州天赐高新材料股份有限公司 | Electrolyte and lithium secondary battery comprising same |
| CN108199046B (en) * | 2017-12-26 | 2020-10-30 | 欣旺达电子股份有限公司 | Binder and lithium ion battery |
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