CN115966767A - Ultralow temperature-resistant lithium battery electrolyte and preparation method thereof - Google Patents
Ultralow temperature-resistant lithium battery electrolyte and preparation method thereof Download PDFInfo
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- CN115966767A CN115966767A CN202310063084.2A CN202310063084A CN115966767A CN 115966767 A CN115966767 A CN 115966767A CN 202310063084 A CN202310063084 A CN 202310063084A CN 115966767 A CN115966767 A CN 115966767A
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Abstract
The invention relates to the technical field of lithium batteries, in particular to an ultralow temperature resistant lithium battery electrolyte and a preparation method thereof, wherein the ultralow temperature resistant lithium battery electrolyte comprises three types of organic solvents, an electrolyte and additives, the organic solvents comprise ethylene carbonate, propylene carbonate, diethyl carbonate, dimethyl carbonate and ethyl methyl carbonate, the electrolyte comprises a lithium source and a modification material, the additives comprise an SEI (solid electrolyte interphase) film forming additive, a conductive additive, a low-temperature additive and other additives, the lithium source comprises lithium hexafluorophosphate, lithium iron phosphate and anhydrous lithium hydrogen fluoride organic liquid, and the modification material comprises lithium carbonate and thiophene; the low-temperature additive designed by the invention can heat liquid low-temperature radiation paint in the low-temperature additive under a low-temperature condition, so that the heat productivity of the lithium battery is improved, the lithium battery can conduct electricity normally due to the temperature rise, and meanwhile, the conducting capacity of the lithium battery under a low-temperature environment can be improved by matching with the anhydrous conducting silicon micropowder organic solution dissolved in liquid, and the discharge performance of the lithium battery is improved.
Description
Technical Field
The invention relates to the technical field of lithium batteries, in particular to an ultralow temperature resistant lithium battery electrolyte and a preparation method thereof.
Background
At present, lithium batteries are widely used due to their advantages of portability, high energy density, small self-discharge, long service life, high discharge power, environmental protection, and the like, and include four major materials, namely positive electrodes, negative electrodes, separators, and electrolytes, and the service life of lithium batteries generally depends on the quality of the electrolytes.
Chinese patent No. CN109449485B provides an ultralow temperature resistant lithium battery electrolyte, which comprises: an organic solvent; a lithium salt electrolyte; the additive is one or more groups selected from potassium bromide, sodium bis (trifluoromethylsulfonyl) imide, potassium bis (trifluoromethylsulfonyl) imide and zinc bis [ bis (trifluoromethylsulfonyl) imide ], and the mass content of the additive is 0.05-0.15%. The potassium bromide with specific content is adopted as an additive to be applied to an organic solvent containing a lithium salt electrolyte, so that the electrolyte has higher conductivity below 0 ℃, the normal operation of the lithium battery cycle is ensured, and the cycle performance and the safety performance of the lithium battery under the extreme low-temperature condition are greatly improved.
At present, the self electronic conductance of the existing lithium battery is low, and particularly, the lithium battery almost becomes a non-conductive insulator in a low-temperature environment, so that the lithium battery cannot meet the use requirement in cold weather, and therefore, the development of an ultralow-temperature-resistant lithium battery electrolyte and a preparation method thereof are urgently needed.
Disclosure of Invention
The invention aims to provide an ultralow temperature resistant lithium battery electrolyte and a preparation method thereof, so as to solve the problems in the background technology.
The technical scheme of the invention is as follows: the utility model provides an ultra-low temperature resistant lithium cell electrolyte, includes three types of organic solvent, electrolyte, additive, and organic solvent includes ethylene carbonate, propylene carbonate, diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate, the electrolyte includes lithium source, modified material, the additive includes SEI film forming additive, conductive additive, low temperature additive and surplus additive.
Further, the lithium source comprises lithium hexafluorophosphate, lithium iron phosphate and anhydrous lithium hydrogen fluoride organic liquid, and the modification material comprises lithium carbonate and thiophene.
Further, the SEI film forming additive is one of fluoroethylene carbonate and propylene sulfite, and the conductive additive is one of SP conductive agent, graphite conductive agent, CNT conductive agent and Ketjen black.
Further, the low-temperature additive is a conductive silicon micro powder organic solution dissolved in liquid anhydrous and a liquid low-temperature radiation coating.
Further, the remaining additives include a stabilizing additive, an anti-overcharge additive, a flame retardant additive, a high voltage additive.
A preparation method of an ultralow temperature resistant lithium battery electrolyte is characterized by comprising the following steps: the method comprises the following steps:
s1, taking and weighing: weighing three materials of organic solvent, electrolyte and additive by using a weighing device according to the production scheme, and classifying and placing the materials when weighing;
s2, primary mixing: mixing the weighed organic solvents, electrolytes and additives by using a stirrer in an argon environment to obtain the mixed organic solvents, electrolytes and additives;
s3, secondary mixing: pouring the mixed organic solvent, electrolyte and additive into a stirrer in turn in an argon environment, and then starting the stirrer to mix the organic solvent, the electrolyte and the additive together to obtain electrolyte;
s4, filtering and removing impurities: pouring the obtained electrolyte into a filtering device, and then carrying out filter pressing treatment to obtain impurity-free electrolyte;
s5, finished product detection: the prepared electrolyte and the electrolyte on the market are poured into a container, and then testing is carried out at room temperature and low temperature to judge the quality of the product.
Further, when the ethylene carbonate, the propylene carbonate, the diethyl carbonate, the dimethyl carbonate and the ethyl methyl carbonate are mixed in the step S2, the ratio of ethylene carbonate to propylene carbonate to diethyl carbonate to dimethyl carbonate to ethyl methyl carbonate is 1:1.2:1:1.13:0.9.
further, the ratio of the lithium source to the modified material when the electrolyte is mixed in S2 is 1:0.8.
further, when the S2 additive is mixed, the proportion of the SEI film-forming additive, the conductive additive, the low-temperature additive and the rest additives is 1-3:2-3:1-2:1-1.5.
Further, the mixing ratio of the organic solvent, the electrolyte and the additive in the S3 is 1:1.2:0.8.
the invention provides an ultralow temperature resistant lithium battery electrolyte and a preparation method thereof through improvement, and compared with the prior art, the ultralow temperature resistant lithium battery electrolyte has the following improvements and advantages:
(1) The low-temperature additive designed by the invention can heat liquid low-temperature radiation paint in the low-temperature additive under a low-temperature condition, so that the heat productivity of the lithium battery is improved, the lithium battery can conduct electricity normally due to the temperature rise, and meanwhile, the conducting capacity of the lithium battery under a low-temperature environment can be improved by matching with a liquid anhydrous conducting silica powder organic solution.
(2) The lithium carbonate and lithium carbonate designed by the invention can reduce the decomposition of the electrolyte on the surface of the anode, reduce the content of HF in the electrolyte and the corrosion of the HF on the surface of the anode, and obviously improve the cycle stability of the lithium battery
(3) According to the thiophene designed by the invention, thiophene is polymerized in situ on the surface of the anode material under voltage to generate a layer of polythiophene film, and the polythiophene coating improves the conductivity of the material and reduces the polarization impedance. And the polythiophene membrane is coated to avoid the contact between the electrolyte and the surface of the material, and reduce the catalytic decomposition of the ions on the surface of the material on the electrolyte, so that the occurrence of side reactions is reduced, and the cycle stability and the high-rate discharge performance are improved.
Drawings
The invention is further explained below with reference to the figures and examples:
FIG. 1 is a flow chart of the method of the present invention.
Detailed Description
The present invention will be described in detail with reference to fig. 1, and the technical solutions in the embodiments of the present invention will be clearly and completely described, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The invention provides an ultralow temperature-resistant lithium battery electrolyte through improvement, which comprises three types of organic solvents, an electrolyte and additives, wherein the organic solvents comprise ethylene carbonate, propylene carbonate, diethyl carbonate, dimethyl carbonate and methyl ethyl carbonate, the electrolyte comprises a lithium source and a modification material, and the additives comprise an SEI film-forming additive, a conductive additive, a low-temperature additive and the rest of additives.
Further, the lithium source comprises lithium hexafluorophosphate, lithium iron phosphate and anhydrous lithium hydrogen fluoride organic liquid, and the modified material comprises lithium carbonate and thiophene.
Furthermore, the SEI film forming additive is one of fluoroethylene carbonate and propylene sulfite, and the conductive additive is one of SP conductive agent, graphite conductive agent, CNT conductive agent and Ketjen black.
Further, the low-temperature additive is a conductive silicon micro powder organic solution dissolved in liquid anhydrous and a liquid low-temperature radiation coating.
Further, the remaining additives include stabilizing additives, anti-overcharge additives, flame retardant additives, high voltage additives.
A preparation method of an electrolyte of an ultra-low temperature resistant lithium battery, as shown in figure 1, comprises the following steps:
s1, taking and weighing: weighing three materials of organic solvent, electrolyte and additive by using a weighing device according to the production scheme, and placing the materials in a classified manner when weighing;
s2, primary mixing: mixing the weighed organic solvents, electrolytes and additives by using a stirrer in an argon environment to obtain the mixed organic solvents, electrolytes and additives;
s3, secondary mixing: pouring the mixed organic solvent, electrolyte and additive into a stirrer in turn in an argon environment, and then starting the stirrer to mix the organic solvent, the electrolyte and the additive together to obtain electrolyte;
s4, filtering and removing impurities: pouring the obtained electrolyte into a filtering device, and then carrying out filter pressing treatment to obtain impurity-free electrolyte;
s5, finished product detection: the prepared electrolyte and the electrolyte on the market are poured into a container, and then the container is tested at room temperature and low temperature to judge the quality of the product.
Further, when the ethylene carbonate, the propylene carbonate, the diethyl carbonate, the dimethyl carbonate and the ethyl methyl carbonate are mixed in the S2 in the primary mixing process, the ratio of the ethylene carbonate to the propylene carbonate to the diethyl carbonate to the dimethyl carbonate to the ethyl methyl carbonate is 1:1.2:1:1.13:0.9.
further, the ratio of the lithium source to the modified material when the electrolyte is mixed in S2 is 1:0.8.
further, when the S2 additive is mixed, the ratio of the SEI film forming additive, the conductive additive, the low temperature additive and the rest additives is 1:2:1:1.5.
further, the mixing ratio of the organic solvent, the electrolyte and the additive in the S3 is 1:1.2:0.8.
example one
A preparation method of an ultralow temperature resistant lithium battery electrolyte comprises the following steps:
s1, taking and weighing: weighing three materials of organic solvent, electrolyte and additive by using a weighing device according to the production scheme, and classifying and placing the materials when weighing;
s2, primary mixing: mixing the weighed organic solvents, electrolytes and additives by adopting a stirrer in an argon environment to obtain the mixed organic solvents, electrolytes and additives, wherein the ethylene carbonate, the propylene carbonate, the diethyl carbonate, the dimethyl carbonate and the ethyl methyl carbonate in the organic solvents are 1:1.2:1:1.13:0.9, the ratio of the lithium source to the modified material when the electrolyte is mixed is 1:0.8, when the additives are mixed, the proportion of the SEI film-forming additive, the conductive additive, the low-temperature additive and the rest additives is 1:2:1:1.5;
s3, secondary mixing: and pouring the mixed organic solvent, electrolyte and additive into a stirrer in turn in an argon environment, wherein the mixing ratio of the organic solvent, the electrolyte and the additive is 1:1.2:0.8, then starting a stirrer to mix the organic solvent, the electrolyte and the additive together to obtain an electrolyte;
s4, filtering and removing impurities: pouring the obtained electrolyte into a filtering device, and then carrying out filter pressing treatment to obtain impurity-free electrolyte;
s5, finished product detection: the prepared electrolyte and the electrolyte on the market are poured into a container, and then the container is tested at room temperature and low temperature to judge the quality of the product.
| Additive material | Capacity retention ratio of 100 cycles | Capacity retention ratio of 100 cycles | |
| Market place | Is free of | 73% (Low temperature) | 96% (Normal temperature) |
| Example one | Low-temperature resistance material and modified silver powder | 97% (Low temperature) | 97% (Normal temperature) |
In the above embodiments, the first embodiment is a preferred embodiment, and the cycle stability of the battery cell is the highest in this embodiment.
The working principle is as follows: weighing three materials of organic solvent, electrolyte and additive by using a weighing device according to the production scheme, and classifying and placing the materials when weighing; mixing the weighed various organic solvents, electrolytes and additives by a stirrer in an argon environment to obtain the mixed organic solvents, electrolytes and additives, wherein the ethylene carbonate, propylene carbonate, diethyl carbonate, dimethyl carbonate and ethyl methyl carbonate in the organic solvents are 1:1.2:1:1.13:0.9, the ratio of the lithium source to the modified material when the electrolyte is mixed is 1:0.8, when the additives are mixed, the proportion of the SEI film-forming additive, the conductive additive, the low-temperature additive and the rest additives is 1:2:1:1.5; and pouring the mixed organic solvent, electrolyte and additive into a stirrer in turn in an argon environment, wherein the mixing ratio of the organic solvent, the electrolyte and the additive is 1:1.2:0.8, then starting the stirrer to mix the organic solvent, the electrolyte and the additive together to obtain an electrolyte; pouring the obtained electrolyte into a filtering device, and then carrying out filter pressing treatment to obtain an impurity-free electrolyte; the prepared electrolyte and the electrolyte on the market are poured into a container, and then the container is tested at room temperature and low temperature to judge the quality of the product.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (9)
1. The utility model provides a resistant ultra-low temperature lithium cell electrolyte which characterized in that: the electrolyte comprises a lithium source and a modification material, and the additives comprise an SEI film-forming additive, a conductive additive, a low-temperature additive and the rest of additives.
2. The electrolyte for ultra-low temperature resistant lithium batteries according to claim 1, wherein: the lithium source comprises lithium hexafluorophosphate, lithium iron phosphate and anhydrous lithium hydrogen fluoride organic liquid, and the modified material comprises lithium carbonate and thiophene.
3. The electrolyte for ultra-low temperature resistant lithium batteries according to claim 1, wherein: the SEI film forming additive is one of fluoroethylene carbonate and propylene sulfite, and the conductive additive is one of SP conductive agent, graphite conductive agent, CNT conductive agent and ketjen black.
4. The electrolyte for ultra-low temperature resistant lithium batteries according to claim 1, wherein: the low-temperature additive is a liquid anhydrous conductive silicon micro powder organic solution or a liquid low-temperature radiation coating.
5. The electrolyte for ultra-low temperature resistant lithium batteries according to claim 1, wherein: the other additives include stabilizing additives, anti-overcharge additives, flame retardant additives, high voltage additives.
6. A preparation method of an ultralow temperature resistant lithium battery electrolyte is characterized by comprising the following steps: the method comprises the following steps:
s1, taking and weighing: weighing three materials of organic solvent, electrolyte and additive by using a weighing device according to the production scheme, and classifying and placing the materials when weighing;
s2, primary mixing: mixing the weighed organic solvents, electrolytes and additives by using a stirrer in an argon environment to obtain mixed organic solvents, electrolytes and additives;
s3, secondary mixing: pouring the mixed organic solvent, electrolyte and additive into a stirrer in turn in an argon environment, and then starting the stirrer to mix the organic solvent, the electrolyte and the additive together to obtain electrolyte;
s4, filtering and removing impurities: pouring the obtained electrolyte into a filtering device, and then carrying out filter pressing treatment to obtain impurity-free electrolyte;
s5, finished product detection: the prepared electrolyte and the electrolyte on the market are poured into a container, and then the container is tested at room temperature and low temperature to judge the quality of the product.
7. The method for preparing the electrolyte of the ultra-low temperature resistant lithium battery as claimed in claim 6, wherein the method comprises the following steps: ethylene carbonate, propylene carbonate, diethyl carbonate, dimethyl carbonate and methyl ethyl carbonate in the organic solvent during preliminary mixing in the S2 are 1:1.2:1:1.13:0.9. the method for preparing the electrolyte for the ultra-low temperature resistant lithium battery of claim 6, wherein the method comprises the following steps: the ratio of the lithium source to the modified material when the electrolyte in S2 is mixed is 1:0.8.
8. the method for preparing the electrolyte of the ultra-low temperature resistant lithium battery as claimed in claim 6, wherein the method comprises the following steps: when the S2 additive is mixed, the proportion of the SEI film-forming additive, the conductive additive, the low-temperature additive and the rest additives is 1-3:2-3:1-2:1-1.5.
9. The method for preparing the electrolyte of the ultra-low temperature resistant lithium battery as claimed in claim 6, wherein the method comprises the following steps: the mixing ratio of the organic solvent, the electrolyte and the additive in the S3 is 1:1.2:0.8.
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| CN202310063084.2A CN115966767A (en) | 2023-01-16 | 2023-01-16 | Ultralow temperature-resistant lithium battery electrolyte and preparation method thereof |
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| CN202310063084.2A CN115966767A (en) | 2023-01-16 | 2023-01-16 | Ultralow temperature-resistant lithium battery electrolyte and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117039166A (en) * | 2023-09-08 | 2023-11-10 | 海南思瑞新能源科技有限公司 | Potassium ion battery electrolyte suitable for low-temperature operation |
| CN117175017A (en) * | 2023-08-10 | 2023-12-05 | 山东泰一新能源股份有限公司 | Low-temperature electrolyte for lithium battery |
-
2023
- 2023-01-16 CN CN202310063084.2A patent/CN115966767A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117175017A (en) * | 2023-08-10 | 2023-12-05 | 山东泰一新能源股份有限公司 | Low-temperature electrolyte for lithium battery |
| CN117175017B (en) * | 2023-08-10 | 2024-09-13 | 山东钠电新材料科技有限公司 | Low-temperature electrolyte for lithium battery |
| CN117039166A (en) * | 2023-09-08 | 2023-11-10 | 海南思瑞新能源科技有限公司 | Potassium ion battery electrolyte suitable for low-temperature operation |
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