CN112993405A - Electrolyte additive for high-voltage lithium ion battery and application thereof - Google Patents
Electrolyte additive for high-voltage lithium ion battery and application thereof Download PDFInfo
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- CN112993405A CN112993405A CN202110435980.8A CN202110435980A CN112993405A CN 112993405 A CN112993405 A CN 112993405A CN 202110435980 A CN202110435980 A CN 202110435980A CN 112993405 A CN112993405 A CN 112993405A
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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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- 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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
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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
Abstract
The invention relates to an electrolyte additive for a high-voltage lithium ion battery and application thereof, and solves the problem of poor cycle performance of a high-voltage anode material of the lithium ion battery through a carotenoid additive. The mass fraction of the carotenoid additive is 0.05-5%, the battery assembled by the electrolyte containing the additive still can show high coulombic efficiency and good circulation stability under high voltage, and the used additive is green, low in cost, non-toxic and pollution-free.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a high-voltage electrolyte additive for improving the cycle performance of a high-voltage lithium ion battery and application thereof.
Background
Chemical power sources hold a very important position in new energy economy. Among them, lithium ion batteries have been widely used in various fields as pioneers of chemical power sources. However, with the development of electric vehicles and various electronic products, the current energy and power density cannot meet all the requirements of people. The anode material is always the core of the lithium ion battery, the optimized promotion of the anode material can greatly improve the use prospect of the lithium ion battery, and especially the promotion of the voltage can greatly improve the use prospect of the lithium ion batteryEnergy density of the battery. Wherein the lithium-rich manganese-based positive electrode material (xLi)2MnO3·(1-x)LiMO2M ═ Transition Metal (TM), 0<x<1) High-voltage positive electrode materials such as lithium cobaltate and the like have high specific energy, low cost and good thermal stability, and become a hotspot of research on the positive electrode materials. Unfavorable decomposition of the carbonate electrolyte easily occurs at high operating voltage, resulting in uneven accumulation of by-products on the electrode surface and consumption of active lithium ions and electrons, and on the other hand, highly oxidized transition metal ions easily absorb electrons from electrolyte components at high voltage, the valence state is reduced, and irreversible phase transition occurs.
Recently, attention has been focused on a method of forming a protective layer on a positive electrode oxide using an electrolyte additive to form a uniform and stable positive electrode-electrolyte interface layer on the surface of the positive electrode without inhibiting the interfacial charge transfer reaction. In addition, the superlattice component Li in the first-turn charging process of the lithium-rich manganese base2MnO3Inevitably releases active oxygen, including oxygen (O)2) And superoxide radical (O)2·—) The superoxide radical will produce gaseous products, such as CO and CO, by reaction with Ethylene Carbonate (EC) solvent in the electrolyte2Degradation process of the anode-electrolyte interface at high voltage (surface O)2Run off, Li2CO3Decomposition, electrolyte gassing, etc.) can lead to increased interfacial resistance and rapid degradation of battery cycling performance.
Disclosure of Invention
The invention aims to overcome the problem of poor cycle stability of high-voltage lithium ion batteries, in particular to the problem of poor cycle performance of the existing lithium-rich manganese-based and lithium cobaltate positive electrode materials and the like, and provides a method for modifying the electrolyte of the high-voltage lithium ion battery.
In order to achieve the purpose, the invention is realized by the following technical scheme:
an electrolyte additive for a high-voltage lithium ion battery is characterized in that the additive is carotenoid, wherein the carotenoid is any one or combination of two of beta-carotene and lutein.
Further, the high-voltage lithium ion battery comprises a high-voltage lithium ion battery with a lithium-rich manganese base and lithium cobaltate as anode materials.
The invention further provides a method for modifying the electrolyte of the high-voltage lithium ion battery, which comprises the following steps:
the modification method of the battery electrolyte comprises the steps of adding an additive into the lithium ion battery electrolyte to prepare a solution, and filtering the solution to obtain the modified electrolyte; wherein the additive is the carotenoid additive.
Furthermore, the concentration of carotenoid in the electrolyte after modification is 0.05-5.0 wt%.
Further, the solution was filtered using a 0.22 μm filter.
Furthermore, the electrolyte of the lithium ion battery is ternary electrolyte (1.0M LiPF6 in EC: DMC: EMC: 1:1:1 Vol%) or sulfone electrolyte (1.0M LiPF6 in PC: EMC: SUL: 1:1:1 Vol%).
The prepared modified electrolyte is applied to a high-voltage battery taking lithium-rich manganese and lithium cobaltate as anode materials.
A high-voltage lithium ion battery comprises an anode, a cathode and the prepared modified electrolyte.
The carotenoid has the function of eliminating singlet oxygen and superoxide radical, and is selected as an additive component to be applied to the battery electrolyte, so that the carotenoid can eliminate active oxygen generated in the high-voltage positive electrode charging process on one hand, and can form a stable positive electrode-electrolyte interface layer on the other hand to inhibit the poor decomposition of the electrolyte. Besides, the carotenoid has low cost and wide source, and is a green pollution-free high-efficiency electrolyte additive.
Compared with the prior art, the invention has the following beneficial effects:
1) the invention adopts carotenoid additive, can react with anode material, especially lithium-rich manganese base, to oxygen free radical generated by high voltage, and can reduce CO and CO in the first charging process2And the like.
2) The carotenoid additive can form a stable and uniform anode-electrolyte interface layer on the surface of the anode in the circulation process, and shows good circulation stability. And the introduction of the additive can slow down the formation of a spinel phase in the layered phase of the lithium-rich manganese-based positive electrode material, and the voltage attenuation phenomenon is relieved.
3) The additive used in the invention has the advantages of green and cheap components and easy preparation.
Drawings
Fig. 1 is a first cycle charge and discharge curve of a lithium-rich manganese-based positive electrode in a high-voltage electrolyte containing an additive according to the present invention and a reference electrolyte without the additive; (wherein the current density is 20mA/g)
Fig. 2 is a graph of cycle life for a lithium-rich manganese-based positive electrode in a high-pressure electrolyte containing an additive of the present invention and a baseline electrolyte without the additive. (wherein the current density is the first 20mA/g low current activation, then the current density is 200mA/g)
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but 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.
The chemical formula of the lithium-rich manganese-based cathode material adopted in the embodiment is xLi2MnO3·(1-x)LiMO2M is nickel element, cobalt element and manganese element, the stoichiometric ratio is 1:1:1, and x is 0.5. Adding a lithium-rich manganese-based positive electrode material, a carbon black conductive agent and an LA binder according to the mass ratio of 8:1: 1. And uniformly coating the slurry on an aluminum foil to obtain a lithium-rich manganese-based positive pole piece, assembling the lithium-rich manganese-based positive pole piece into a battery in a glove box in an argon atmosphere by taking metal lithium as a negative pole, standing for 6 hours, and then testing on a shelf, wherein the test voltage range is 2-4.8V.
Example 1:
1) an amount of beta-carotene was weighed into a clear glass bottle in an argon-filled glove box and stirred overnight to dissolve the additive thoroughly after addition of an amount of a baseline ternary electrolyte (1.0M LiPF6 in EC: DMC: EMC: 1:1:1 Vol%).
2) Filtering the solution obtained in 1) by using a 0.22-micron filter membrane to obtain a clear 0.5 wt% electrolyte.
3) A battery is assembled with the electrolyte.
Meanwhile, as a comparison, a battery was assembled using a reference electrolyte containing no additive as a comparative example.
The test result is shown in fig. 1, the specific charge capacity of the first loop of the battery of the high-voltage electrolyte containing the beta-carotene additive is 315mAh/g, the specific discharge capacity is 257mAh/g, and the coulomb efficiency of the first loop is 81.6%. The specific charge capacity of the first circle of the battery without the additive is 356mAh/g, the specific discharge capacity is 254mAh/g, and the coulomb efficiency of the first circle is 71.1%. Thus, the electrolyte with the additive exhibits a higher first turn coulombic efficiency.
Referring to the attached figure 2, after the activation is carried out by using a small current with the current density of 20mA/g, and then the circulation is carried out for 100 circles by using the current density of 200mA/g, the battery discharge capacity of the high-voltage electrolyte containing the beta-carotene additive is 156mAh/g, and the capacity retention rate reaches 93.4%. The battery discharge capacity without the additive is 113mAh/g, the capacity retention rate is 62.5%, and a system containing the additive has more excellent capacity retention rate, wherein the oxidative decomposition of the electrolyte under high voltage and the migration of transition metal are obviously inhibited, and the cycle stability is improved.
Example 2:
1) an amount of beta-carotene was weighed into a clear glass bottle in an argon-filled glove box and stirred overnight to dissolve the additive thoroughly after addition of an amount of a baseline ternary electrolyte (1.0M LiPF6 in EC: DMC: EMC: 1:1:1 Vol%).
2) Filtering the solution in 1) with a 0.22 μm filter membrane to obtain a clear 0.1 wt% electrolyte.
3) A battery is assembled by using the electrolyte.
And (3) testing results: when the current density is 20mA/g, the charging specific capacity of the first loop is 319mAh/g, the discharging specific capacity is 243mAh/g, and the coulomb efficiency of the first loop is 76.2%. Then, after the current density is 200mA/g and the circulation is 100 circles, the battery discharge capacity is 164mAh/g, and the capacity retention rate reaches 92.7 percent.
Example 3:
1) an amount of beta-carotene was weighed into a clear glass bottle in an argon-filled glove box and stirred overnight to dissolve the additive thoroughly after addition of an amount of a baseline ternary electrolyte (1.0M LiPF6 in EC: DMC: EMC: 1:1:1 Vol%).
2) Filtering the solution in 1) with a 0.22 μm filter membrane to obtain a clear 5.0 wt% electrolyte.
3) A battery is assembled by using the electrolyte.
And (3) testing results: when the current density is 20mA/g, the charging specific capacity of the first loop is 305mAh/g, the discharging specific capacity is 214mAh/g, and the coulomb efficiency of the first loop is 70.1%. Then, after the current density is 200mA/g and the circulation is 100 circles, the battery discharge capacity is 144mAh/g, and the capacity retention rate reaches 97.3%.
Example 4:
1) an amount of lutein was weighed into a clear glass bottle in an argon atmosphere glove box and stirred overnight to dissolve the additive after addition of an amount of baseline ternary electrolyte (1.0M LiPF6 in EC: DMC: EMC ═ 1:1:1 Vol%).
2) Filtering the solution obtained in 1) by using a 0.22-micron filter membrane to obtain a clear 0.5 wt% electrolyte.
3) A battery is assembled by using the electrolyte.
And (3) testing results: when the current density is 20mA/g, the charging specific capacity of the first loop is 254mAh/g, the discharging specific capacity is 315mAh/g, and the coulomb efficiency of the first loop is 80.9%. Then, after the current density is 200mA/g and the circulation is 100 circles, the battery discharge capacity is 157mAh/g, and the capacity retention rate reaches 94.8%.
Example 5:
1) a certain amount of beta-carotene was weighed in a glove box under argon atmosphere and placed in a transparent glass bottle, and a certain amount of a reference sulfone electrolyte (1.0M LiPF6 in PC: EMC: SUL ═ 1:1:1 Vol%) was added and stirred overnight to dissolve the additive sufficiently.
2) Filtering the solution obtained in 1) by using a 0.22-micron filter membrane to obtain a clear 0.5 wt% electrolyte.
3) The electrolyte was used to assemble a half cell.
And (3) testing results: when the current density is 20mA/g, the charging specific capacity of the first loop is 331mAh/g, the discharging specific capacity is 230mAh/g, and the coulomb efficiency of the first loop is 69.4%. Then, after the current density is 200mA/g and the circulation is 100 circles, the battery discharge capacity is 167mAh/g, and the capacity retention rate reaches 98.7%.
Example 6:
1) an amount of beta-carotene was weighed into a clear glass bottle in an argon-filled glove box and stirred overnight to dissolve the additive after addition of an amount of a baseline ternary electrolyte (1.0M LiPF6 in EC: DMC: EMC: 1:1:1 Vol%).
2) Filtering the solution obtained in 1) by using a 0.22-micron filter membrane to obtain a clear 0.5 wt% electrolyte.
3) The electrolyte and high-pressure lithium cobaltate are assembled into a battery, and the voltage range is 3-4.6V.
And (3) testing results: when the current density is 20mA/g, the charging specific capacity of the first loop is 247mAh/g, the discharging specific capacity is 232mAh/g, and the coulomb efficiency of the first loop is 93.9%. Then, after the current density is 200mA/g and the circulation is 100 circles, the battery discharge capacity is 136mAh/g, and the capacity retention rate reaches 84.1%.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (8)
1. The electrolyte additive for the high-voltage lithium ion battery is characterized in that the additive is carotenoid, wherein the carotenoid is any one or combination of two of beta-carotene and lutein.
2. The electrolyte additive for the high-voltage lithium ion battery according to claim 1, wherein the high-voltage lithium ion battery comprises a high-voltage lithium ion battery with a lithium-rich manganese base and lithium cobaltate as a positive electrode material.
3. A method for modifying high-voltage lithium ion battery electrolyte is characterized by comprising the following steps:
the modification method of the battery electrolyte comprises the steps of adding an additive into the lithium ion battery electrolyte to prepare a solution, and filtering the solution to obtain the modified electrolyte; wherein the additive is the carotenoid additive of claim 1.
4. The method of claim 3, wherein the concentration of the carotenoid in the modified electrolyte is 0.05-5.0 wt%.
5. The method of claim 3, wherein the solution is filtered through a 0.22 μm filter membrane.
6. The method for modifying the electrolyte of the high-voltage lithium ion battery according to claim 3, wherein the electrolyte of the lithium ion battery is ternary electrolyte or sulfone electrolyte.
7. The method for modifying the electrolyte of a high-voltage lithium ion battery according to any one of claims 3 to 6, wherein the modified electrolyte is used in a high-voltage battery with rich lithium manganese and lithium cobaltate as a positive electrode material.
8. A high voltage lithium ion battery, characterized in that it comprises a positive electrode, a negative electrode and the modified electrolyte prepared according to any one of claims 3 to 6.
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Citations (6)
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| US20120171563A1 (en) * | 2010-12-30 | 2012-07-05 | Samsung Electronics Co. Ltd. | Electrolyte for lithium secondary battery and lithium secondary battery including the same |
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| US20160031843A1 (en) * | 2013-03-15 | 2016-02-04 | The Regents Of The University Of California | Synthesis of novel ionic liquids from lignin-derived compounds |
| CN109244602A (en) * | 2018-08-27 | 2019-01-18 | 中国科学院大学 | A kind of method of modifying of lithium-air battery electrolyte |
| CN110635166A (en) * | 2018-06-21 | 2019-12-31 | 比亚迪股份有限公司 | Electrolyte, battery containing electrolyte and electric vehicle |
| CN112467221A (en) * | 2020-12-02 | 2021-03-09 | 珠海市赛纬电子材料股份有限公司 | Additive for inhibiting silicon negative electrode expansion and electrolyte containing additive |
-
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- 2021-04-22 CN CN202110435980.8A patent/CN112993405A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20120171563A1 (en) * | 2010-12-30 | 2012-07-05 | Samsung Electronics Co. Ltd. | Electrolyte for lithium secondary battery and lithium secondary battery including the same |
| US20160031843A1 (en) * | 2013-03-15 | 2016-02-04 | The Regents Of The University Of California | Synthesis of novel ionic liquids from lignin-derived compounds |
| CN104078686A (en) * | 2013-03-26 | 2014-10-01 | Sk新技术株式会社 | Current collector for secondary battery and secondary battery comprising the same |
| CN110635166A (en) * | 2018-06-21 | 2019-12-31 | 比亚迪股份有限公司 | Electrolyte, battery containing electrolyte and electric vehicle |
| CN109244602A (en) * | 2018-08-27 | 2019-01-18 | 中国科学院大学 | A kind of method of modifying of lithium-air battery electrolyte |
| CN112467221A (en) * | 2020-12-02 | 2021-03-09 | 珠海市赛纬电子材料股份有限公司 | Additive for inhibiting silicon negative electrode expansion and electrolyte containing additive |
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