CN110994029B - Sulfone-based high-voltage electrolyte containing triphenylphosphine additives for lithium ion battery - Google Patents

Sulfone-based high-voltage electrolyte containing triphenylphosphine additives for lithium ion battery Download PDF

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CN110994029B
CN110994029B CN201911380737.XA CN201911380737A CN110994029B CN 110994029 B CN110994029 B CN 110994029B CN 201911380737 A CN201911380737 A CN 201911380737A CN 110994029 B CN110994029 B CN 110994029B
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sulfone
electrolyte
triphenylphosphine
lithium ion
ion battery
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白莹
邬文雅
吴川
吴锋
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Beijing Institute of Technology BIT
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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
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    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract

The invention provides a sulfone-based high-voltage electrolyte containing triphenylphosphine additives for a lithium ion battery, belonging to the technical field of lithium ion batteries. The electrolyte includes: triphenylphosphine additives, sulfone-based solvents and lithium salts. In the charging and discharging processes of the lithium battery prepared by the electrolyte, a low-impedance and stable protective film can be formed on the surfaces of the lithium-rich manganese-based positive electrode and the graphite negative electrode, the stability of the interfaces of the positive electrode, the negative electrode and the electrolyte is improved, the cycle stability of the lithium ion battery under the high-voltage condition is improved, and meanwhile, the compound containing the phosphorus-oxygen double bond can also improve the high-temperature safety performance of the battery.

Description

Sulfone-based high-voltage electrolyte containing triphenylphosphine additives for lithium ion battery
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a sulfone-based high-voltage electrolyte containing triphenylphosphine additives for a lithium ion battery.
Background
As a most remarkable technical innovation of modern electrochemistry in the past decades, lithium ion batteries have the advantages of high energy density, long cycle life and the like, are widely applied to portable electronic equipment such as consumer electronics and electric tools, and are also popularized in the fields of large-scale energy storage such as smart grids and electric vehicles. With the increasing year by year of the market share of the power lithium ion battery, higher requirements are put on the energy density, the cycle life and the safety of the power lithium ion battery. Increasing the operating voltage of a lithium ion battery is considered to be the most effective method for increasing the energy density thereof, and thus, the operating voltage of a lithium ion battery can be increased from the aspect of improving the positive and negative electrode materials and the electrolyte. In current lithium ion battery research, many high voltage positive electrode materials with charging voltages up to 5V have been developed, but such high voltages exceed the electrochemical stability of conventional carbonate-based solvents. The maximum limiting voltage of the conventional carbonate electrolyte is 4.35V, and the electrolyte becomes extremely unstable when the voltage is higher than 4.5V, and reacts with a high-oxidation-state cathode material in a charging state, so that a large amount of combustible gas is generated, the performance of the high-voltage cathode material is influenced, and the degradation of the cycle performance and the safety of the battery are accelerated by side reaction between the electrolyte and the cathode. Meanwhile, as an important component of lithium ion batteries, electrolytes have been proven to have a great influence on their energy density, power density and operating temperature range as well as their cycle stability, safety and cost. Therefore, it is very necessary to develop a new electrolyte solvent system that can be matched with high performance electrode materials.
Developing stable and safe electrolytes to operate at voltages as high as 5V is a formidable challenge to market high voltage lithium ion power cells. To address this challenge, several viable solutions have been proposed and studied, including the development of new lithium salts, high-pressure solvents, and high-pressure electrolyte additives. Aiming at the challenge, the invention provides a sulfone-based high-voltage electrolyte containing triphenylphosphine additives for a lithium ion battery.
Disclosure of Invention
The invention aims to provide a sulfone-based high-voltage electrolyte containing triphenylphosphine additives for a lithium ion battery. The electrolyte is used for the lithium ion battery, and the problems of battery cycle performance, safety performance reduction and the like caused by the aggravation of side reactions of the electrolyte and positive and negative electrode materials under the high-voltage condition are effectively solved.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a sulfone-based high-voltage electrolyte containing triphenylphosphine additives for lithium ion batteries is prepared by mixing an organic solvent, lithium salt and triphenylphosphine additives.
The organic solvent is a preferable sulfone-based solvent with an electrochemical window larger than 5V, and mainly comprises one or two of sulfolane (TMS), methyl ethyl sulfone (EMS), methoxyethyl methyl sulfone (MEMS), ethylmethoxyethyl sulfone (EMES), ethylvinyl sulfone (EVS), ethylmethoxyethoxyethyl sulfone (EMEES), n-Butyl Sulfone (BS) and fluoromethyl methyl sulfone (FS).
More preferably, the sulfone-based solvent is sulfolane.
The lithium salt is preferably lithium hexafluorophosphate (LiPF)6) Lithium perchlorate (LiClO)4) Lithium tetrafluoroborate (LiBF)4)、Lithium bis (oxalato) borate (LiBOB), lithium bis (fluorooxalato) borate (lidob), lithium bis (trifluoromethylsulfonyl) imide (LiTFSI), lithium hexafluoroarsenate (LiAsF)6) One or a mixture of several of them.
More preferably, the lithium salt is lithium bis (fluorooxalato) borate (LiDFOB), wherein the concentration of the lithium salt relative to the sulfone-based solvent is 0.5-2M.
The triphenylphosphine additive is one or more of triphenylphosphine oxide, triphenylphosphine, tris (4-trihydroxyphenyl) phosphine oxide, bis (4-methoxycarbonylphenyl) phenylphosphine oxide and bis (4-carboxyphenyl) phenylphosphine oxide.
More preferably, the triphenylphosphine-based additive is triphenylphosphine oxide (TPPO), which has the following structural formula:
Figure BDA0002342156030000031
more preferably, the mass of the triphenylphosphine additive accounts for 0.5-5% of the total mass of the sulfone-based high-voltage electrolyte.
The specific preparation method of the sulfone-based high-voltage electrolyte containing the triphenylphosphine additives for the lithium ion battery comprises the steps of firstly melting a certain amount of sulfone-based solvent into a liquid state under a heating condition in a glove box filled with argon protection, then adding a lithium salt with the concentration of 0.5-2M relative to the sulfone-based solvent, finally adding the triphenylphosphine additives accounting for 0.5-5% of the total mass of the electrolyte, and finally uniformly stirring to obtain the sulfone-based high-voltage electrolyte containing the triphenylphosphine additives for the lithium ion battery.
Another object of the present invention is to provide a lithium ion battery comprising a positive electrode sheet containing a positive electrode active material, a separator, and the electrolyte provided herein.
The preparation method of the positive plate comprises the following steps: uniformly mixing a positive electrode active material, a conductive agent (MWCNTs slurry: conductive carbon black: conductive graphite: 22:2:1 (mass ratio)) and a binder PVDF according to the mass ratio of 95:3:2 to prepare positive electrode slurry with certain viscosity, and coating the positive electrode slurry on an aluminum current collector, wherein the coating weight is 2mg/cm2After vacuum drying at 80 ℃ for 24h, the pellets were cut into 11 mm-diameter pellets. The positive electrode active material is: LiNi1-xMxO2(one or a combination of more of Co, Mn and Al), Li1+xM1-xO2(M ═ Mn, Ni, Co, etc. in combination with one or more), LiNi0.5Mn1.5O4And the like.
The diaphragm is made of glass fiber.
Compared with the prior art, the invention has the advantages that:
the lithium salt (LiDFOB) preferably used in the electrolyte has good thermal stability, a wider electrochemical window and excellent matching property to an aluminum current collector, and a stable SEI film can be formed on the surface of the graphite negative electrode, so that the interface property of the sulfone-based electrolyte and the graphite negative electrode is improved, and the rate capability and the high-low temperature cycle performance of the lithium ion battery are improved.
The triphenylphosphine oxide additive (TPPO) preferably used in the electrolyte can form a layer of low-impedance and uniform CEI film on the surface of a high-voltage positive electrode material such as a lithium-rich manganese base and the like and the surface of a graphite negative electrode in the charging and discharging processes, so that the high-voltage positive electrode/electrolyte and graphite negative electrode/electrolyte interface properties of a lithium ion battery are improved, the cycle performance of lithium ions under high voltage is improved, and the problems of aggravation of side reactions of the electrolyte with the positive electrode material and the negative electrode material, reduction of the cycle performance and the safety performance of the battery and the like under the high voltage condition are effectively solved.
The sulfoether-based solvent sulfolane (TMS) preferably used in the electrolyte has a specific cyclic chain structure, has good compatibility with TPPO, and can form a good SEI film on the surface of a graphite cathode, so that the interface property of the sulfoether-based electrolyte and the graphite cathode is improved.
Drawings
Fig. 1 is a graph showing the charge and discharge curves of the button cell 1 st and 50 th times, which contains the sulfone-based electrolyte containing the novel additive prepared in example 1.
Fig. 2 is a graph showing charge and discharge curves of button cells 1 st and 50 th times, which contain the electrolyte of the conventional commercial lithium ion battery prepared in comparative example 1.
Fig. 3 is a cycle-specific capacity graph of a coin cell containing the general commercial lithium ion battery electrolyte prepared in example 3, cycled 50 times.
Detailed description of the invention
The technical solution of the present application will be further described below with reference to specific embodiments. In the following examples, the lithium ion battery was subjected to a charge and discharge test on a LAND CT2001A tester (blue electronics, Inc., Wuhan City).
Example 1
The sulfone-based high-voltage electrolyte containing the triphenylphosphine additives for the lithium ion battery of the embodiment is composed of the triphenylphosphine additives, a sulfone-based solvent and lithium salt. The sulfone-based solvent is TMS; the conductive lithium salt is LiDFOB with the concentration of 1M; the triphenylphosphine additive is TPPO which accounts for 0.5 percent of the total mass of the sulfone-based high-voltage electrolyte.
The preparation method of the sulfone-based high-voltage electrolyte containing the triphenylphosphine additive comprises the following steps: electrolyte is prepared in a glove box filled with argon, the moisture in the glove box is controlled to be less than or equal to 0.1ppm, the oxygen is controlled to be less than or equal to 0.1ppm, and the temperature is room temperature. A certain amount of TMS was melted to a liquid state at 60 ℃ as a solvent, then 1M liddob was slowly added, and finally 0.5 wt% of TPPO was added, and magnetic stirring was performed at room temperature for 24 hours to obtain the electrolyte of example 1.
The lithium ion battery of the embodiment is a CR-2025 button battery, the sulfone-based high-voltage electrolyte containing triphenylphosphine additives of the embodiment is used as electrolyte, the usage amount of each battery electrolyte is 150 mu L, glass fiber is used as a diaphragm, and Li is used as a separator1.165Ni0.278Mn0.54Co0.018O2Is a positive plate.
The preparation method of the lithium ion battery of the embodiment comprises the following steps: sequentially placing Li with the diameter of 11mm at the bottom of the positive shell of the CR-2025 button cell1.165Ni0.278Mn0.54Co0.018O2And a glass fiber separator having a diameter of 19mm, 150. mu.l of the electrolyte in this example was injected, and a metal lithium sheet having a diameter of 16mm and metallic luster was attached to the upper side of the separator,and covering a button battery cathode shell, and sealing by using a button battery packaging machine (purchased from Shenzhenjian crystal). Standing at room temperature for 48h for later use.
Example 2
The preparation method of the sulfone-based high voltage electrolyte containing the triphenylphosphine-based additive in this example is the same as that in example 1, except that 1 wt% of TPPO was added.
The lithium ion battery of this embodiment uses the sulfone-based high voltage electrolyte containing triphenylphosphine additives of this embodiment as an electrolyte, and the rest is completely the same as in embodiment 1.
Example 3
The preparation method of the sulfone-based high voltage electrolyte containing the triphenylphosphine-based additive in this example is the same as that in example 1, except that 2 wt% of TPPO was added.
The lithium ion battery of this embodiment uses the sulfone-based high voltage electrolyte containing triphenylphosphine additives of this embodiment as an electrolyte, and the rest is completely the same as in embodiment 1.
Example 4
The preparation method of the sulfone-based high voltage electrolyte containing the triphenylphosphine-based additive in this example is the same as that in example 1, except that 3 wt% of TPPO was added.
The lithium ion battery of this embodiment uses the sulfone-based high voltage electrolyte containing triphenylphosphine additives of this embodiment as an electrolyte, and the rest is completely the same as in embodiment 1.
Example 5
The preparation method of the sulfone-based high voltage electrolyte containing the triphenylphosphine-based additive in this example is the same as that in example 1, except that 5 wt% of TPPO was added.
The lithium ion battery of this embodiment uses the sulfone-based high voltage electrolyte containing triphenylphosphine additives of this embodiment as an electrolyte, and the rest is completely the same as in embodiment 1.
Comparative example 1
The preparation method of the electrolyte of the comparative example was: electrolyte is prepared in a glove box filled with argon, the moisture in the glove box is controlled to be less than or equal to 0.1ppm, the oxygen is controlled to be less than or equal to 0.1ppm, and the temperature is room temperature. Mixing Ethylene Carbonate (EC) with carbonic acidDiethyl Ester (DEC) is uniformly mixed according to the mass ratio of 1:1, and then 1M LiPF is slowly added into the mixed solvent6And magnetically stirring for 24 hours at room temperature to obtain the common commercial lithium ion battery electrolyte in the comparative example.
The lithium ion battery of the comparative example uses the common commercial lithium ion battery electrolyte in the comparative example as the electrolyte, and the rest is completely the same as example 1.
Comparative example 2
A general commercial lithium ion battery electrolyte of 2 wt% TPPO in this comparative example was obtained by preparing a general commercial ion battery electrolyte according to comparative example 1 and adding 2 wt% TPPO thereto.
The lithium ion battery of this comparative example uses the common commercial lithium ion battery electrolyte containing 2 wt% of TPPO in this comparative example as an electrolyte, and the rest is completely the same as example 1.
Comparative example 3
The preparation method of the sulfone-based high-voltage electrolyte containing the triphenylphosphine additive is the same as that in example 3, except that the added sulfone-based solvent is methoxyethyl methyl sulfone (MEMS).
The lithium ion battery of this embodiment uses the sulfone-based high voltage electrolyte containing triphenylphosphine additives of this embodiment as an electrolyte, and the rest is completely the same as in embodiment 1.
Comparative example 4
The preparation method of the sulfone-based high-voltage electrolyte containing the triphenylphosphine additive is the same as that in example 3, except that the added sulfone-based solvent is methyl ethyl sulfone (EMS).
The lithium ion battery of this embodiment uses the sulfone-based high voltage electrolyte containing triphenylphosphine additives of this embodiment as an electrolyte, and the rest is completely the same as in embodiment 1.
Comparative example 5
The preparation method of the sulfone-based high-voltage electrolyte containing the triphenylphosphine-based additive is the same as that in example 3, except that the triphenylphosphine-based additive is Triphenylphosphine (TPP).
The lithium ion battery of this embodiment uses the sulfone-based high voltage electrolyte containing triphenylphosphine additives of this embodiment as an electrolyte, and the rest is completely the same as in embodiment 1.
Comparative example 6
The sulfone-based high voltage electrolyte of this example was prepared in the same manner as in example 3, except that fluoroethylene carbonate (FEC) was added as the additive.
The lithium ion battery of this embodiment uses the sulfone-based high-voltage electrolyte of this embodiment as an electrolyte, and the rest is completely the same as in embodiment 1.
Test example
(1) Taking example 1 as an example, the prepared lithium ion battery is charged and discharged under the condition of room temperature under the voltage of 2.0-4.6V and the multiplying power of 0.1C, and the charging and discharging curves of the first time and the fifty times are recorded in figure 1.
(2) Taking comparative example 1 as an example, the prepared lithium ion battery was charged and discharged at a voltage of 2.0-4.6V and a rate of 0.1C under room temperature conditions, and the charging and discharging curves of the first time and the fifty times are recorded in fig. 2.
(3) The performance test results of the lithium ion batteries of examples 1 to 5 and comparative examples 1 to 6 are shown in table 1:
TABLE 1
Capacity retention after 50 cycles at ambient temperature
Example 1 91.6％
Example 2 92.4％
Example 3 94.2％
Example 4 93.1％
Example 5 92.3％
Comparative example 1 84.7％
Comparative example 2 90.0％
Comparative example 3 28.8％
Comparative example 4 24.0％
Comparative example 5 88.2％
Comparative example 6 87.3％
And (3) effect comparison:
comparing the sulfone-based high-voltage electrolyte containing the triphenylphosphine additives for the lithium ion batteries prepared in the examples 1 to 5 with the lithium ion battery electrolytes prepared in the comparative examples 1 to 6:
(1) through comparison of examples 1-5, it can be found that the added triphenylphosphine oxide (TPPO) can not only improve the thermal stability of the electrolyte, but also improve the ionic conductivity to a certain extent, and the ionic conductivity increases with the TPPO contentThe electrolyte shows a trend of increasing first and then decreasing, when TPPO accounts for 2 percent of the total mass of the electrolyte, the ionic conductivity has a maximum value, and the ionic conductivity at room temperature is close to 2mS/cm2And the working requirement of the lithium ion battery at room temperature is met.
(2) It can be seen from comparative examples 1 to 5 that Li1.165Ni0.278Mn0.54Co0.018O2The button cell assembled by the positive plate which is an active substance, the sulfone-based high-voltage electrolyte containing the triphenylphosphine additive and the metal lithium which are negative electrodes has good cycling stability and higher capacity retention rate when being cycled at room temperature, the discharge specific capacity shows the trend of increasing first and then decreasing along with the increase of the TPPO content, and the discharge specific capacity has a maximum value when the TPPO accounts for 2% of the total mass of the electrolyte.
(3) Through comparative example 3 and comparative examples 3 and 4, it can be found that the sulfone-based high-voltage electrolyte containing 2% of TPPO in example 3, which uses TMS as a sulfone-based solvent, is a stable clear solution after being stored for 30 days at room temperature, and has good chemical stability. MEMS or EMS is taken as a sulfone-based solvent, and the sulfone-based high-voltage electrolyte containing 2% of TPPO in the comparative example 3 and the comparative example 4 is stored for 7 days at room temperature, so that the original clear liquid has obvious color change and a part of solid particles are separated out. Therefore, the application of TPPO as the additive of the sulfone-based high-voltage electrolyte is limited by the compatibility of TPPO and a sulfone-based solvent to a great extent, and researches show that TPPO has good compatibility with TMS and can form a good SEI film on the surface of a graphite cathode so as to improve the interface property of the sulfone-based electrolyte and the graphite cathode.
(4) Through comparison of example 3 and comparative examples 1 and 2, it can be found that the cycle stability and the capacity retention rate of the lithium ion battery can be improved by adding 2% of TPPO into the common commercial carbonate electrolyte, and the improvement is more prominent in a sulfone-based high-voltage electrolyte containing 2% of TPPO. On one hand, TPPO has good film forming property on the surfaces of the anode and cathode materials, so that the interface stability of the anode and cathode and the electrolyte is improved; on the other hand, compared with a commercial carbonate electrolyte, the compatibility of the TMS-based high-voltage electrolyte with TPPO is better, and the high-voltage characteristic of TMS and TPPO have good synergistic effect, so that the cycle stability and the capacity retention rate of the lithium ion battery can be better improved, and particularly the cycle performance under high voltage can be better improved.
(5) It can be found by comparing example 3 with comparative examples 5 and 6 that the sulfone-based high-voltage electrolyte containing the triphenylphosphine additive of 2% of TPPO has higher coulombic efficiency and capacity retention ratio than the sulfone-based high-voltage electrolyte containing the triphenylphosphine additive of 2% of TPP, and meanwhile, the sulfone-based high-voltage electrolyte containing the triphenylphosphine additive has better cycle stability than the sulfone-based high-voltage electrolyte containing FEC. On one hand, the triphenylphosphine additive is more favorable for improving the performance of the sulfuryl high-voltage electrolyte than the fluoro carbonate additive; on the other hand, the triphenylphosphine additive containing phosphine-oxygen double bond has better effect on improving the performance of the high-voltage lithium ion battery than triphenylphosphine.
(6) As can be seen from fig. 1 and fig. 2, the sulfone-based high-voltage electrolyte containing triphenylphosphine additives significantly improves the first-cycle discharge specific capacity and the capacity retention rate of the lithium-rich manganese-based battery. The TPPO can form a layer of uniform CEI film with low impedance on the surface of the lithium-rich manganese-based positive electrode material in the charging and discharging processes, so that the stability of a positive electrode/electrolyte interface under a high voltage condition is improved, and the room temperature cycle performance of the lithium ion battery under the high voltage is improved.

Claims (4)

1. The sulfone-based high-voltage electrolyte containing the triphenylphosphine additives for the lithium ion battery is characterized by comprising the triphenylphosphine additives, a sulfone-based solvent and a lithium salt, wherein the triphenylphosphine additives are selected from triphenylphosphine oxide, and the mass of the triphenylphosphine additives accounts for 0.5-5% of the total mass of the sulfone-based high-voltage electrolyte; the sulfone-based solvent is selected from sulfolane (TMS); the lithium salt is lithium bis (fluorooxalato) borate (LiDFOB), and the concentration of the lithium salt relative to the sulfone-based solvent is 0.5-2M.
2. A method for preparing the sulfone-based high-voltage electrolyte as claimed in claim 1, comprising the steps of: in a glove box filled with argon for protection, a certain amount of sulfone-based solvent is firstly melted into liquid under heating, then lithium salt with the concentration of 0.5-2M relative to the sulfone-based solvent is added, finally triphenylphosphine additive accounting for 0.5-5% of the total mass of the electrolyte is added, and finally the mixture is uniformly stirred to obtain the sulfone-based high-voltage electrolyte containing the triphenylphosphine additive for the lithium ion battery.
3. A lithium ion battery comprising the electrolyte of claim 1, wherein: the lithium ion battery comprises a positive plate, a negative plate, a diaphragm and electrolyte.
4. The lithium ion battery of claim 3, wherein the active materials of the positive electrode sheet are: LiNi1- xMxO2(M＝Co，Mn，Al)、Li1+xM1-xO2(M＝Mn，Ni，Co)、LiNi0.5Mn1.5O4。
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