CN112993399A - Method for inhibiting corrosion of aluminum foil of current collector of lithium battery - Google Patents

Method for inhibiting corrosion of aluminum foil of current collector of lithium battery Download PDF

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CN112993399A
CN112993399A CN201911285879.8A CN201911285879A CN112993399A CN 112993399 A CN112993399 A CN 112993399A CN 201911285879 A CN201911285879 A CN 201911285879A CN 112993399 A CN112993399 A CN 112993399A
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aluminum foil
electrolyte
litfsi
lithium
corrosion
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张灵志
闫晓丹
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Guangzhou Institute of Energy Conversion of CAS
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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
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    • 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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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract

The invention discloses a method for inhibiting corrosion of a current collector aluminum foil of a lithium battery, which comprises the following steps: adding
Figure DDA0002317964190000011
One or more of organosilicon compounds or choline ionic liquid
Figure DDA0002317964190000012
The electrolyte has outstanding technical effects on inhibiting lithium salt LiTFSI, LiFSI and other corrosion aluminum foils in an electrolyte containing lithium salt for corroding the aluminum foils, and the batteries manufactured by using the electrolyte have excellent cycle stability, thermal stability and safety.

Description

Method for inhibiting corrosion of aluminum foil of current collector of lithium battery
The technical field is as follows:
the invention relates to the technical field of electrochemical energy storage, in particular to a method for inhibiting corrosion of a current collector aluminum foil of a lithium battery.
Background art:
lithium ion batteries have been widely used in portable electronic devices because of their advantages of high energy density, high operating voltage, no memory function, long service life, and the like. With the rapid development of the application field in recent years, people propose the energy density, rate capability, use temperature, cycle life and safety of lithium ion batteriesHigher requirements are imposed. The electrolyte is an important component of the lithium ion battery, and the lithium salt, as a provider of lithium ions in the electrolyte, is an important factor determining the performance of the electrolyte. The lithium salt of current commercial electrolytes is mainly LiPF6(lithium hexafluorophosphate), but LiPF6The lithium ion battery has poor thermal stability and chemical stability, is very sensitive to water, and is very easy to decompose to generate acid substances such as HF (hydrogen fluoride) and the like, so that transition metals on the surface of a positive electrode material are dissolved and migrate to the surface of a negative electrode, a solid interfacial film (SEI) is damaged, the capacity of the lithium ion battery is reduced, and the service life of the lithium ion battery is prolonged. Therefore, it is necessary to use the LiPF with6Excellent lithium salts, such as lithium salts of the sulphonimide type (LiTFSI, LiFSI, etc.), which have comparable electrochemical properties and at the same time avoid their disadvantages. The lithium salts of the sulfonyl imide series are more stable to water, have better thermal stability and chemical stability, and the application of the lithium salts of the sulfonyl imide series in practice is not limited by two factors at all, the first is a cost factor, but the production cost of the lithium salts of the sulfonyl imide series is continuously reduced along with the continuous breakthrough of the production technology, and the lithium salts of the sulfonyl imide series have wide prospect in the field of lithium ion battery materials of passenger cars. Another limiting factor is the problem of corrosion of aluminum foil by the anions of lithium salts such as LiTFSI, for example, LiTFSI can severely corrode the aluminum foil current collector at voltages higher than 3.7V, and LiFSI can corrode the aluminum foil at voltages higher than 4.2V, which greatly limits the application range of the lithium salt in energy storage batteries, especially in 5V high-voltage electrode material battery systems. Therefore, the problem of corrosion of aluminum foil by lithium salts of sulfimide becomes a critical problem to be solved urgently. By researching and developing a lithium ion battery with high safety, high specific capacity and long cycle life by researching and developing a lithium ion battery system of the sulfonyl imide lithium salt which is matched with an electrode material and does not corrode an aluminum foil, theoretical value and practical significance are provided for promoting commercial application of the sulfonyl imide lithium salt, and important guiding significance is provided for development of high specific energy and high safety electric automobile industry.
The current methods for inhibiting the corrosion of aluminum foil by the lithium salt electrolyte of the sulfonyl imide mainly comprise the following steps: one is the addition of corrosion inhibiting additives, e.g. aluminum trifluoride (AlF)3) Thereafter, during the cycling of the electrode, aluminum trifluoride (A)lF3) Will be deposited uniformly on the aluminum foil by reversible reaction with the current collector aluminum foil to form a passivation layer, preventing the reaction of aluminum with LiTFSI, thus acting to prevent corrosion of the aluminum foil (see CN 103377835A). Lithium bis (oxalato) borate (LiBOB) and the like, which can inhibit the corrosion of aluminum foil, can also be added (see CN 106450365A). Secondly, the use of high concentration electrolyte, research shows that when the concentration of LiTFSI is increased to 1.8M, the corrosion of aluminum foil can be effectively inhibited (Journal of Power Sources,2013,231, 234-. These exciting findings do have scientific heuristics, but in view of the reduction of lithium ion conductivity and the significant increase in cost, these findings seem not to be technically feasible. Third, changing the electrolyte solvent composition, such as using fluorinated solvents in place of some of the carbonate solvents, other methods, such as fine control and modification of anion size, have met with limited success.
The invention content is as follows:
the invention aims to provide a method for inhibiting corrosion of aluminum foil of a lithium battery current collector.
The invention is realized by the following technical scheme:
a method for inhibiting corrosion of aluminum foil of a current collector of a lithium battery, the method comprising the steps of: adding
Figure BDA0002317964170000021
Figure BDA0002317964170000022
One or more organosilicon compounds of
Figure BDA0002317964170000031
Into an electrolyte containing a lithium salt that corrodes aluminum foil, including lithium bis (trifluoromethanesulfonyl) imide (abbreviated as LiTFSI), lithium bis (fluorosulfonyl) imide (abbreviated as LiFSI), and the like; r1,R2,R3Selected from the same or different CH3Or alkoxy, wherein alkoxy is of the structure-O (CH)2CH2O)m1(CH2)n1CH3M1 and n1 are integers of 0 to 3; r4Is- (CH)2)m2-a group, m2 is an integer from 1 to 3; r5Selected from the group consisting of: [ - (CH)2)m3O(CH2)n3-, m3, n3 are integers from 1 to 3; r6,R7,R8、R9、R10、R11Selected from the same or different alkyl radicals- (CH)2)xCH3X is an integer of 0 to 3, or a fluoro substituent, and R6,R7,R8Having at least one fluorine substituent group, R9、R10、R11Wherein at least one fluorine substituent group is present; r12Is alkoxy-O (CH)2)yCH3Y is an integer of 0 to 3; m is an integer of 1 to 3, n is an integer of 1 to 3; a is- (CH)2)x1(OCH2CH2)y1-structural polyether segments, x1, y1 being integers from 1 to 3; d is- (CH)2)m4CN or-SiR25R26R27M4 is an integer of 1 to 2, R13、R14Selected from the same or different alkyl radicals- (CH)2)xCH3X is an integer of 0 to 3, R15，R16，R21，R22、R23、R25、R26And R27Selected from the same or different C1-C3 alkyl groups, R17Selected from the group consisting of-O-SiR18R19R20,R18,R19And R20Are alkyl of the same or different C1-C3; r24Selected from the group-O (CH)2)n4N4 is an integer from 1 to 3.
Preferably, the following organosilicon compounds are added
Figure BDA0002317964170000032
(BNS for short),
Figure BDA0002317964170000033
(DESCN for short),
Figure BDA0002317964170000034
(abbreviated as MFGC),
Figure BDA0002317964170000035
(abbreviation TFGC)
Figure BDA0002317964170000036
(MFSM 2 for short),
Figure BDA0002317964170000037
(MFSM 1 for short),
Figure BDA0002317964170000041
(DN 2) or choline ionic liquid compound
Figure BDA0002317964170000042
(SN 1-IL for short),
Figure BDA0002317964170000043
(CN-IL for short) to the electrolyte containing lithium salt corroding the aluminum foil, the using amount of the electrolyte accounts for 1-100% of the total volume of the electrolyte solvent, and the rest solvents are any one or more of common carbonate organic solvents (such as Ethylene Carbonate (EC), Propylene Carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC)), gamma-butyrolactone (GBL for short) and ether organic solvents (such as 1, 3-dioxolane, dimethoxymethane, 1, 2-dimethoxyethane, diethylene glycol dimethyl ether and the like).
The electrolyte may contain other additives selected from one or more of fluoroethylene carbonate (abbreviated as FEC), propane sultone (abbreviated as PS), vinylene carbonate (abbreviated as VC), succinonitrile, lithium bis (oxalato) borate (abbreviated as LiBOB), and lithium difluoro (oxalato) borate (abbreviated as LiODFB).
The invention has the beneficial effects that: the organic silicon compound or the choline ionic liquid is applied to the lithium battery, has an outstanding technical effect on inhibiting lithium salt LiTFSI, LiFSI and other corrosion aluminum foils, and the battery prepared by using the organic silicon compound or the choline ionic liquid has excellent cycle stability, thermal stability and safety.
Description of the drawings:
FIG. 1: example 1 cyclic voltammogram of anodic polarization of aluminum foil in BNS-LiTFSI electrolyte;
FIG. 2: example 1 cyclic voltammetry curves of anodic polarization of aluminum foil in BNS-LiTFSI + VC + PS + LiBOB electrolyte;
FIG. 3: comparative example 1 cyclic voltammogram of anodic polarization of aluminum foil in EC/DMC-LiTFSI electrolyte;
FIG. 4: comparative example 2 cyclic voltammogram of anodic polarization of aluminum foil in EC/DMC-LiTFSI + LiBOB electrolyte;
FIG. 5: comparative example 3 cyclic voltammogram of anodic polarization of aluminum foil in LB301 electrolyte;
FIG. 6: example 2 cyclic voltammogram of anodic polarization of aluminum foil in MFGC-LiTFSI electrolyte;
FIG. 7: example 3 cyclic voltammogram of anodic polarization of aluminum foil in MFSM2-LiTFSI electrolyte;
FIG. 8: example 3 cyclic voltammogram of anodic polarization of aluminum foil in MFSM2-LiTFSI + VC + PS + LiBOB electrolyte;
FIG. 9: comparative example 4 cyclic voltammogram of anodic polarization of aluminum foil in FEC-LiTFSI electrolyte;
FIG. 10: example 4 cyclic voltammogram of anodic polarization of aluminum foil in SN1-IL-LiTFSI electrolyte;
FIG. 11: example 5 cyclic voltammogram of anodic polarization of aluminum foil in EC/DMC-LiTFSI + DN2 electrolyte;
FIG. 12: example 6 cyclic voltammogram of anodic polarization of aluminum foil in PC/EC/MFSM2-LiTFSI + LiBOB electrolyte;
FIG. 13: example 7 SEM images of aluminum foil after cyclic voltammetry tests in different electrolytes;
FIG. 14: example 8 charge and discharge curves of the NCM 523/graphite battery at 25 ℃ in MFSM2-LiTFSI + VC + PS + LiBOB electrolyte;
FIG. 15: comparative example 5 charge and discharge curves of the NCM 523/graphite battery at 55 ℃ in different electrolytes;
FIG. 16: example 9 cyclic voltammogram of anodic polarization of aluminum foil in MFSM1-LiTFSI electrolyte;
FIG. 17: example 10 cyclic voltammogram of anodic polarization of aluminum foil in DESCN-LiTFSI electrolyte;
FIG. 18: example 11 cyclic voltammogram of anodic polarization of aluminum foil in TFGC/EC/DMC-LiTFSI electrolyte;
FIG. 19: example 12 cyclic voltammogram of anodic polarization of aluminum foil in CN-IL/EC/DMC-LiTFSI electrolyte.
The specific implementation mode is as follows:
the following is a further description of the invention and is not intended to be limiting.
Example 1:
preparing lithium ion battery electrolyte in an argon glove box with the water content and the oxygen content of less than 0.1 ppm: dissolving 1M lithium bis (trifluoromethanesulfonylimide) LiTFSI in an organic silicon cyanide compound BNS to prepare a BNS pure solvent electrolyte (abbreviated as BNS-LiTFSI electrolyte), adding 2% of vinylene carbonate VC and 2% of propiolactone PS into the electrolyte, and adding 0.05M LiBOB to prepare a BNS-LiTFSI + VC + PS + LiBOB electrolyte, and then preparing a button cell (CR2025) by using an aluminum foil as a working electrode, a lithium sheet as a counter electrode and a polyethylene film as a diaphragm. The specific test method of the battery comprises the following steps: and (3) performing cyclic voltammetry test on the battery on a Shenzhen Xinwei battery charge-discharge test system at the room temperature of 25 ℃, wherein the voltage range is 2.5-5.5V, the test speed is 1mV/s, and the cycle is 6 times. The test results are shown in fig. 1 and 2. FIG. 1 is an enlarged view of cyclic voltammetry Curves (CV) of anodic polarization of aluminum foil in BNS-LiTFSI electrolyte, in which the embedded graph is shown in 1-6 circles. As can be seen, in the 1 st cycle CV, the return knee voltage of the negative sweep after polarization to 5.5V is 4.25V, reaching a maximum anode current of about 0.17mA at 4.75V. Furthermore, the anode current increased with the progress of the cycle, but did not change much after the 4 th turn, with a maximum current of about 0.4mA, probably due to the concomitant passivation. FIG. 2 is an enlarged view of a Cyclic Voltammogram (CV) of anodic polarization of aluminum foil in BNS-LiTFSI + VC + PS + LiBOB electrolyte, in which the circle is 1-6. It can be seen from the figure that with the addition of a small amount of VC, PS and LiBOB, the anodic polarization current decreased significantly, with the anodic current increasing somewhat as the cycling proceeded, but after 5 th cycle, there was no significant change, with a maximum anodic current of about 0.08mA, one fifth that of the BNS-LiTFSI electrolyte.
Comparative example 1:
preparing lithium ion battery electrolyte in an argon glove box with the water content and the oxygen content of less than 0.1 ppm: dissolving 1M LiTFSI in a solvent with a volume ratio of 1:1 ethylene carbonate EC and dimethyl carbonate DMC solvent (EC/DMC (v: v ═ 1:1)) an EC/DMC-LiTFSI electrolyte was prepared as a comparative electrolyte 1, and then a button cell (CR2025) was prepared using an aluminum foil as a working electrode, a lithium sheet as a counter electrode, and a polyethylene film as a separator. The specific test method of the battery was the same as in example 1. The test results are shown in FIG. 3.
FIG. 3 shows the Cyclic Voltammograms (CV) of anodic polarization of aluminum foil in EC/DMC-LiTFSI electrolyte for 1-6 cycles. As can be seen, in cycle 1 CV, the voltage at the knee point of the negative sweep back after polarization to 5.5V was 3.8V, which is the voltage at which LiTFSI salt in conventional carbonate solvent starts to corrode aluminum foil, and the maximum anode current reached about 6mA at 5.5V, indicating that the aluminum foil was severely corroded. Furthermore, the anode current decreased with the progress of the cycle, but did not change much after the 4 th turn, probably due to passivation.
Comparing the experimental results of example 1 and comparative example 1 (fig. 1,2 and 3), it can be seen that, when conventional ethylene carbonate EC and dimethyl carbonate DMC are used as solvents, the LiTFSI salt causes severe corrosion to the aluminum foil of the current collector, and the initial voltage of the aluminum foil corrosion is about 3.8V; however, when the organic silicon cyanide compound BNS is used as a solvent, the initial voltage of the aluminum foil corrosion is increased to 4.25V, the anodic polarization current is significantly reduced, and the maximum current is only 1/15 of the carbonate solvent, which indicates that the organic silicon cyanide compound BNS significantly inhibits the LiTFSI salt from corroding the aluminum foil. When a small amount of common additives such as VC, PS, LiBOB and the like are further added into the BNS electrolyte, the anode current is further reduced, the maximum current is only 1.3 percent of the carbonate solvent, and the aluminum foil is considered to be basically not corroded.
Comparative example 2
Preparing lithium ion battery electrolyte in an argon glove box with the water content and the oxygen content of less than 0.1 ppm: an EC/DMC-LiTFSI electrolyte was prepared by dissolving 1M LiTFSI in EC/DMC (v: v ═ 1:1), 0.1M LiBOB was added to the above electrolyte to prepare a comparative electrolyte 2, and then a button cell (CR2025) was prepared using an aluminum foil as a working electrode, a lithium sheet as a counter electrode, and a polyethylene film as a separator. The specific test method of the battery was the same as in example 1. The test results are shown in FIG. 4.
FIG. 4 is a graph showing the cyclic voltammetry Curves (CV) of anodic polarization of aluminum foil in EC/DMC-LiTFSI + LiBOB electrolyte for 1-6 circles, with the inset being an enlarged view thereof. As can be seen, in the 1 st cycle CV, a maximum anodic current of about 0.074mA was reached at 5.2V. Furthermore, the anode current decreases with the progress of the cycle, which may be due to passivation. The maximum anode current for the first 6 turns was about 0.1 mA.
The experimental results (fig. 1,2 and 4) of comparative example 1 and comparative example 2 show that the anodic polarization current for corrosion of aluminum foil is not much different compared to the method of adding the corrosion-inhibiting lithium salt LiBOB to the carbonate solvent electrolyte, indicating that the same or even better effect of inhibiting corrosion of aluminum foil can be achieved with the electrolyte of the pure solvent of the organic silicon cyanide compound BNS.
Comparative example 3
Preparing lithium ion battery electrolyte in an argon glove box with the water content and the oxygen content of less than 0.1 ppm: mixing 1M LiPF6Electrolyte LB301 (EC: DMC: EMC (v: v: v ═ 1: 1:1) as comparative electrolyte 3, then button cell (CR2025) was prepared with aluminum foil as working electrode, lithium sheet as counter electrode, and polyethylene film as separator, the specific test method of the cell was the same as in example 2, the test results are shown in fig. 5.
FIG. 5 shows the Cyclic Voltammograms (CV) of anodic polarization of aluminum foil in LB301 electrolyte in 1-6 cycles, and the inset shows an enlarged view thereof. As can be seen from the figure, LiPF6As lithium salt, in a test range of 2.5-5.5V, the anode polarization current is very small, the maximum current is about 0.03mA, and the lithium salt LiPF6Is believed not to corrode the aluminum foil.
The experimental results (fig. 1,2 and 5) of comparative example 1 and comparative example 3 show that the BNS-based electrolyte using LiTFSI as the lithium salt has anodic polarization substantially close to that of LiPF for aluminum foil6The level of electrolyte, which is lithium salt, is believed not to corrode the aluminum foil, indicating that the organic silicon cyanide compound BNS electrolyte achieves an excellent effect of inhibiting corrosion of the aluminum current collector.
Example 2:
preparing lithium ion battery electrolyte in an argon glove box with the water content and the oxygen content of less than 0.1 ppm: 1M LiTFSI was dissolved in an organic silicon fluorocarbon carbonate compound MFGC to prepare an MFGC pure solvent electrolyte, and then a button cell (CR2025) was prepared using an aluminum foil as a working electrode, a lithium sheet as a counter electrode, and a polyethylene film as a separator. The specific test method of the battery comprises the following steps: and (3) performing cyclic voltammetry test on the battery on a Shenzhen Xinwei battery charge-discharge test system at the room temperature of 25 ℃, wherein the voltage range is 2.5-5.5V, the test speed is 1mV/s, and the cycle is 6 times. The test results are shown in FIG. 6.
FIG. 6 shows the Cyclic Voltammograms (CV) of anodic polarization of aluminum foil in MFGC-LiTFSI electrolyte in 1-6 circles, which are shown in the inset. As can be seen, the maximum anodic current is about 0.08 mA.
Example 3
Preparing lithium ion battery electrolyte in an argon glove box with the water content and the oxygen content of less than 0.1 ppm: dissolving 1M LiTFSI in an organic silicon fluoropolyether compound MFSM2 to prepare MFSM2 pure solvent electrolyte, adding 2% of VC and 2% of PS in volume fraction into the electrolyte, and preparing MFSM2-LiTFSI + VC + PS + LiBOB electrolyte from 0.05M LiBOB, and then preparing a button cell (CR2025) by taking an aluminum foil as a working electrode, a lithium sheet as a counter electrode and a polyethylene film as a diaphragm. The specific test method of the battery was the same as in example 2. The test results are shown in fig. 7 and 8.
FIG. 7 shows Cyclic Voltammograms (CV) of anodic polarization of aluminum foil in MFSM2-LiTFSI electrolyte for 1-6 cycles. As can be seen, the anode current increased with the progress of the cycle, but did not change much after cycle 3, with a maximum current of about 0.4 mA. FIG. 8 is a cyclic voltammetry Curve (CV) of anodic polarization of aluminum foil in MFSM2-LiTFSI + VC + PS + LiBOB electrolyte, with an inset diagram being an enlarged view thereof, for 1-6 circles. As can be seen, with the addition of a small amount of VC, PS and LiBOB, the anodic polarization current decreased significantly, the anodic current decreased with the progress of the cycle, and did not change much after 2 nd turn, with a maximum anodic current of about 0.035mA, which was ten times smaller than the MFSM2-LiTFSI electrolyte.
Comparative example 4
Preparing lithium ion battery electrolyte in an argon glove box with the water content and the oxygen content of less than 0.1 ppm: 1M LiTFSI was dissolved in fluoroethylene ester FEC to prepare FEC-LiTFSI electrolyte as comparative electrolyte 4, and then a button cell (CR2025) was prepared using aluminum foil as a working electrode, a lithium sheet as a counter electrode, and a polyethylene film as a separator. The specific test method of the battery was the same as in example 2. The test results are shown in FIG. 9.
FIG. 9 shows Cyclic Voltammograms (CV) of anodic polarization of aluminum foil in FEC-LiTFSI electrolyte for 1-6 cycles. It can be seen from the figure that the 2 nd turn anodisation current reaches a maximum of 1mA and that from the 3 rd turn the current decreases somewhat as the cycle progresses, probably due to passivation.
The experimental results (fig. 6, 7, 8 and 9) of comparative examples 2 and 3 and comparative example 4 show that the maximum current for aluminum foil corrosion anodizing is reduced by more than 10 times by the MFGC of the silicone fluorocarbon ester compound and 2 times by the MFSM2 of the silicone fluoropolyether compound, compared to the FEC of the fluoro carbonate solvent. Both MFGC and MFSM2 compounds were shown to be more effective than FEC in inhibiting corrosion of aluminum foil by LiTFSI salts. When a small amount of VC, PS and LiBOB additives are added into the MFSM2-LiTFSI electrolyte, the polarization current can be further reduced, a better anti-corrosion effect is achieved, and the corrosion resistance effect is basically close to that of LiPF6The level of electrolyte being lithium salt.
Example 4
Preparing lithium ion battery electrolyte in an argon glove box with the water content and the oxygen content of less than 0.1 ppm: dissolving 0.5M LiTFSI in choline organic silicon-based ionic liquid SN1-IL to prepare SN1-IL pure solvent electrolyte (abbreviated as SN1-IL-LiTFSI electrolyte), and then preparing the button cell (CR2025) by using aluminum foil as a working electrode, a lithium sheet as a counter electrode and a polyethylene film as a diaphragm. The specific test method of the battery comprises the following steps: and (3) performing cyclic voltammetry test on the battery on a Shenzhen Xinwei battery charge-discharge test system at the room temperature of 25 ℃, wherein the voltage range is 2.5-5.5V, the test speed is 1mV/s, and the cycle is 6 times. The test results are shown in FIG. 10.
FIG. 10 shows the Cyclic Voltammograms (CV) of anodic polarization of aluminum foil in SN1-IL-LiTFSI electrolyte for 1-6 circles, which are shown in the inset. As can be seen from the figure, the anodic polarization current of the aluminum foil in the SN1-IL-LiTFSI electrolyte is very small, the maximum anodic current is about 0.03mA, and the maximum anodic current reaches LiPF6SN1-IL inhibits L at the level of electrolyte being lithium saltiTFSI corrodes aluminum foil.
Example 5
Preparing lithium ion battery electrolyte in an argon glove box with the water content and the oxygen content of less than 0.1 ppm: the method comprises the steps of dissolving 1M LiTFSI in EC/DMC (v: v ═ 1:1) to prepare an EC/DMC-LiTFSI electrolyte, adding 1% volume fraction of organic silicon amine compound DN2 into the electrolyte to prepare an EC/DMC-LiTFSI + DN2 electrolyte, and then preparing a button cell (CR2025) by using an aluminum foil as a working electrode, a lithium sheet as a counter electrode and a polyethylene film as a diaphragm. The specific test method of the battery was the same as in example 1. The test results are shown in FIG. 11.
FIG. 11 shows the Cyclic Voltammograms (CV) of anodic polarization of aluminum foil in EC/DMC-LiTFSI + DN2 electrolyte for 1-6 cycles. As can be seen, the current at the anode reached a maximum of about 6mA at the 1 st turn, but decreased significantly from the 2 nd turn, which may be a passivation effect, and after the 4 th turn the current dropped below 0.3 mA.
The experimental results (fig. 11 and 3) of comparative example 5 and comparative example 1 show that the initial voltage of the LiTFSI corrosion aluminum foil is increased, and the anodic polarization current after 2 nd turn is reduced, indicating that the addition of 1% volume fraction DN2 has a certain inhibition effect on the LiTFSI corrosion aluminum foil.
Example 6
Preparing lithium ion battery electrolyte in an argon glove box with the water content and the oxygen content of less than 0.1 ppm: 1M LiTFSI was dissolved in PC/EC/MFSM2(v: v: v ═ 1:5:4), 0.05M LiBOB was added to make a 40% volume fraction MFSM2 co-solvent PC/EC/MFSM2-LiTFSI + LiBOB electrolyte, and then button cells (CR2025) were made with aluminum foil as the working electrode, lithium sheet as the counter electrode, and polyethylene film as the separator. The specific test method of the battery was the same as in example 1. The test results are shown in FIG. 12.
FIG. 12 is a graph showing the cyclic voltammetry Curves (CV) of anodic polarization of aluminum foil in PC/EC/MFSM2-LiTFSI + LiBOB electrolyte for 1-6 circles, with the inset showing the enlarged view. The maximum anodizing current was about 0.25 mA.
The experimental results (fig. 12 and 3) of comparative example 6 and comparative example 1 show that the 40% volume fraction MFSM2 co-solvent electrolyte has a significant reduction in maximum anodizing current compared to conventional carbonate-based solvent electrolytes, only 4% of carbonate-based solvent electrolytes, indicating that the 40% volume fraction MFSM2 electrolyte is effective in inhibiting LiTFSI corrosion of aluminum foil.
Example 7
The button cells of example 3 and comparative example 1 (after 6 cycles of cyclic voltammetry) were disassembled in an argon glove box with a moisture and oxygen content of less than 0.1ppm, and the morphology was observed with a field emission electron microscope (SEM) after the aluminum foil was rinsed with DMC. The results are shown in FIG. 13.
Fig. 13 is an SEM image of aluminum foil after cyclic voltammetry tests in different electrolytes. As can be seen, the surface of the aluminum foil is smooth and flat before the cyclic voltammetry test. After the aluminum foil is subjected to cyclic voltammetry test in EC/DMC-LiTFSI electrolyte using carbonate as a solvent, a surface oxidation film is damaged, a large number of cracks appear, and an aluminum layer with higher activity is exposed; the oxidation products of aluminum at higher potentials dissolve into the electrolyte, causing severe corrosion, consistent with the observed high anodic current in the CV curve. And after the aluminum foil is subjected to cyclic voltammetry test in an MFSM2-LiTFSI electrolyte taking an organic silicon compound MFSM2 as a solvent, the surface of the aluminum foil is flat and only slight cracks appear, which shows that the MFSM2 has a certain effect on protecting an oxide film on the surface of the aluminum foil, can inhibit the corrosion of the LiTFSI to the aluminum foil, and conforms to the observed smaller anode current in a CV curve. When a small amount of VC, PS and LiBOB additives are added into the MFSM2-LiTFSI electrolyte, the surface of the aluminum foil after cyclic voltammetry is still smooth and flat, and almost no cracks exist, which is consistent with the observed very small anode current in the CV curve, and the corrosion of the aluminum foil is effectively inhibited.
Example 8
Preparing lithium ion battery electrolyte in an argon glove box with the water content and the oxygen content of less than 0.1 ppm: dissolving 1M LiTFSI in an organic silicon fluoropolyether compound MFSM2, adding 2% of VC and 2% of PS by volume fraction and 0.05M LiBOB to prepare an MFSM2-LiTFSI + VC + PS + LiBOB electrolyte, and then preparing a button cell (CR2025) by taking NCM523 as a positive electrode, a lithium sheet or graphite as a negative electrode and a polyethylene film as a diaphragm. The specific test method of the battery comprises the following steps: and (3) performing constant current charge and discharge tests on the battery on the Shenzhen Xinwei battery charge and discharge test system at the room temperature of 25 ℃ and the high temperature of 55 ℃, wherein the charge and discharge cutoff voltage range is 3-4.2V, the charge and discharge multiplying power is 0.5C, and the cycle is 200 times. Circulating for 40 times at 55 deg.C. The test results are shown in fig. 14 and 15.
FIG. 14 is the charge and discharge curves of the NCM 523/graphite cell at 25 ℃ in MFSM2-LiTFSI + VC + PS + LiBOB electrolyte. As can be seen from the figure, the first efficiency of the battery is 81.5%, the capacity retention rate of 200 circles is 83.5%, and the battery has good cycling stability.
Comparative example 5
Preparing lithium ion battery electrolyte in an argon glove box with the water content and the oxygen content of less than 0.1 ppm: to 1M LiPF6And (EC: DMC: EMC (V: V: V ═ 1: 1:1) electrolyte LB301 is added with VC of 2% volume fraction, PS of 2% volume fraction, LB301+ VC + PS + LiBOB electrolyte is prepared by 0.05M LiBOB, then NCM523 is used as positive electrode, graphite is used as negative electrode, polyethylene film is used as diaphragm, button cell (CR2025) is prepared.
FIG. 15 is a charge and discharge curve of the NCM 523/graphite cell at 55 ℃ in different electrolytes. The experimental results of comparative example 8 and comparative example 5 revealed that the initial specific capacity of 0.5C in LB301+ VC + PS + LiBOB electrolyte was about 135mAh/g and the initial specific capacity of 0.5C in MFSM2-LiTFSI + VC + PS + LiBOB electrolyte was about 140mAh/g when circulated at high temperature of 55 deg.C, indicating that the same effect as LiPF6Compared with a carbonate electrolyte which is a lithium salt, the organic silicon fluoride electrolyte which takes LiTFSI as a lithium salt has higher specific cyclic capacity at a high temperature of 55 ℃.
Example 9:
preparing lithium ion battery electrolyte in an argon glove box with the water content and the oxygen content of less than 0.1 ppm: 1M LiTFSI was dissolved in an organic silicon fluoropolyether compound MFSM1 to prepare a MFSM1 pure solvent electrolyte, and then a button cell (CR2025) was prepared using an aluminum foil as a working electrode, a lithium sheet as a counter electrode, and a polyethylene film as a separator. The specific test method of the battery comprises the following steps: and (3) performing cyclic voltammetry test on the battery on a Shenzhen Xinwei battery charge-discharge test system at the room temperature of 25 ℃, wherein the voltage range is 2.5-5.5V, the test speed is 1mV/s, and the cycle is 6 times. The test results are shown in FIG. 16.
FIG. 16 is a Cyclic Voltammogram (CV) of anodic polarization of aluminum foil in MFSM1-LiTFSI electrolyte for 1-6 cycles. As can be seen, the anode current increased with the progress of the cycle, but did not change much after cycle 3, with a maximum current of about 0.6 mA. As compared to the experimental results of comparative example 4 (fig. 9), the silicone fluoropolyether compound MFSM1 doubled the maximum current for corrosion anodic polarization of aluminum foil compared to the fluoro carbonate solvent FEC. The MFSM1 compound was shown to be more effective than FEC in inhibiting corrosion of aluminum foil by LiTFSI salts.
Example 10:
preparing lithium ion battery electrolyte in an argon glove box with the water content and the oxygen content of less than 0.1 ppm: 1M LiTFSI is dissolved in an organic silicon cyanide compound DESCN to prepare a DESCN pure solvent electrolyte, and then a button cell (CR2025) is prepared by taking an aluminum foil as a working electrode, a lithium sheet as a counter electrode and a polyethylene film as a diaphragm. The specific test method of the battery comprises the following steps: and (3) performing cyclic voltammetry test on the battery on a Shenzhen Xinwei battery charge-discharge test system at the room temperature of 25 ℃, wherein the voltage range is 2.5-5.5V, the test speed is 1mV/s, and the cycle is 6 times. The test results are shown in FIG. 17.
FIG. 17 shows the Cyclic Voltammograms (CV) of anodic polarization of aluminum foil in DESCN-LiTFSI electrolyte for 1-6 cycles. As can be seen, the maximum anodic current is about 1.5 mA. Compared with the experimental result of the comparative example 1 (fig. 3), the result shows that, when the conventional ethylene carbonate EC and the dimethyl carbonate DMC are used as the solvent, the LiTFSI salt causes serious corrosion to the aluminum foil of the current collector, and the initial voltage of the corrosion of the aluminum foil is about 3.8V; however, when the organic silicon cyanide compound DESCN is used as a solvent, the initial voltage of aluminum foil corrosion is increased to more than 4V, the anodic polarization current is significantly reduced, and the maximum current is only 1/4 of the carbonate solvent, which shows that the organic silicon cyanide compound DESCN significantly inhibits the LiTFSI salt from corroding the aluminum foil.
Example 11:
preparing lithium ion battery electrolyte in an argon glove box with the water content and the oxygen content of less than 0.1 ppm: an EC/DMC-LiTFSI electrolyte was prepared by dissolving 1M LiTFSI in EC/DMC (v: v ═ 1:1), adding a 30% volume fraction of an organosilicon fluorocarbon ester compound TFGC to the above electrolyte to prepare a TFGC/EC/DMC-LiTFSI electrolyte, and replenishing LiTFSI to 1M in the resulting electrolyte. Then, a button cell (CR2025) was prepared using an aluminum foil as a working electrode, a lithium sheet as a counter electrode, and a polyethylene film as a separator. The specific test method of the battery comprises the following steps: and (3) performing cyclic voltammetry test on the battery on a Shenzhen Xinwei battery charge-discharge test system at the room temperature of 25 ℃, wherein the voltage range is 2.5-5.5V, the test speed is 1mV/s, and the cycle is 1 time. The test results are shown in FIG. 18.
FIG. 18 is a Cyclic Voltammogram (CV) cycle 1 of anodic polarization of aluminum foil in TFGC/EC/DMC-LiTFSI electrolyte. As can be seen, the maximum anodic current is about 1 mA. Compared with the experimental result of the comparative example 1 (fig. 3), the result shows that, when the conventional ethylene carbonate EC and the dimethyl carbonate DMC are used as the solvent, the LiTFSI salt causes serious corrosion to the aluminum foil of the current collector, and the initial voltage of the corrosion of the aluminum foil is about 3.8V; however, when 30% of organic silicon fluorocarbon compound TFGC is added, the anode polarization current is reduced remarkably, and the maximum current of the first circle is only 1/6 of carbonate solvent, which indicates that the TFGC inhibits LiTFSI salt from corroding aluminum foil remarkably.
Example 12:
preparing lithium ion battery electrolyte in an argon glove box with the water content and the oxygen content of less than 0.1 ppm: an EC/DMC-LiTFSI electrolyte is prepared by dissolving 1M LiTFSI in EC/DMC (v: v ═ 1:1), and a CN-IL/EC/DMC-LiTFSI electrolyte is prepared by adding 70% volume fraction of choline-based ionic liquid CN-IL to the above electrolyte, and LiTFSI is supplemented to reach 1M in the resulting electrolyte. Then, a button cell (CR2025) was prepared using an aluminum foil as a working electrode, a lithium sheet as a counter electrode, and a polyethylene film as a separator. The specific test method of the battery comprises the following steps: and (3) performing cyclic voltammetry test on the battery on a Shenzhen Xinwei battery charge-discharge test system at the room temperature of 25 ℃, wherein the voltage range is 2.5-5.5V, the test speed is 1mV/s, and the cycle is 1 time. The test results are shown in FIG. 19.
FIG. 19 is a Cyclic Voltammogram (CV) cycle 1 of anodic polarization of aluminum foil in CN-IL/EC/DMC-LiTFSI electrolyte. As can be seen, the maximum anodic current is about 0.6 mA. Compared with the experimental result of the comparative example 1 (fig. 3), the result shows that, when the conventional ethylene carbonate EC and the dimethyl carbonate DMC are used as the solvent, the LiTFSI salt causes serious corrosion to the aluminum foil of the current collector, and the initial voltage of the corrosion of the aluminum foil is about 3.8V; but when 70% choline ionic liquid CN-IL is added, the anode polarization current is reduced remarkably, the maximum current of the first circle is only 1/10 of carbonate solvent, and the CN-IL is proved to inhibit the corrosion of the aluminum foil by LiTFSI salt remarkably.

Claims (2)

1. The method for inhibiting the corrosion of the aluminum foil of the current collector of the lithium battery is characterized by comprising the following steps of: adding
Figure FDA0002317964160000011
One or more organosilicon compounds of
Figure FDA0002317964160000012
Into an electrolyte comprising a lithium salt that corrodes the aluminum foil, the lithium salt that corrodes the aluminum foil comprising lithium bis (trifluoromethanesulfonyl) imide, lithium bis (fluorosulfonyl) imide; wherein R is1,R2,R3Selected from the same or different CH3Or alkoxy, wherein alkoxy is of the structure-O (CH)2CH2O)m1(CH2)n1CH3M1 and n1 are integers of 0 to 3; r4Is- (CH)2)m2-a group, m2 is an integer from 1 to 3; r5Selected from the group consisting of: [ - (CH)2)m3O(CH2)n3-, m3, n3 are integers from 1 to 3; r6,R7,R8、R9、R10、R11Selected from the same or different alkyl radicals- (CH)2)xCH3X is an integer of 0 to 3, or a fluoro substituent, and R6,R7,R8Having at least one fluorine substituent group, R9、R10、R11Wherein at least one fluorine substituent group is present; r12Is alkoxy-O (CH)2)yCH3Y is an integer of 0 to 3; m is an integer of 1 to 3, n is an integer of 1 to 3; a is- (CH)2)x1(OCH2CH2)y1-structural polyether segments, x1, y1 being integers from 1 to 3; d is: (CH2)m4CN or-SiR25R26R27M4 is an integer of 1 to 2, R13、R14Selected from the same or different alkyl radicals- (CH)2)xCH3X is an integer of 0 to 3, R15，R16，R21，R22、R23、R25、R26And R27Selected from the same or different C1-C3 alkyl groups, R17Selected from the group consisting of-O-SiR18R19R20,R18,R19And R20Are alkyl of the same or different C1-C3; r24Selected from the group-O (CH)2)n4N4 is an integer from 1 to 3.
2. The method for inhibiting corrosion of aluminum foil on a current collector of a lithium battery as claimed in claim 1, wherein the method comprises the steps of adding the following organosilicon compounds:
Figure FDA0002317964160000013
Figure FDA0002317964160000021
Figure FDA0002317964160000022
one or more of or choline ionic liquid compounds
Figure FDA0002317964160000023
Figure FDA0002317964160000024
The amount of the electrolyte solution containing lithium salt for corroding the aluminum foil accounts for 1-100% of the total volume of the electrolyte solution.
CN201911285879.8A 2019-12-13 2019-12-13 Method for inhibiting corrosion of aluminum foil of current collector of lithium battery Pending CN112993399A (en)

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CN105514487A (en) * 2015-12-30 2016-04-20 中国科学院广州能源研究所 Method for matching organic silicon electrolyte with silicon-based electrode material for use
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