CN114284559A - Electrolyte containing additive and lithium metal secondary battery - Google Patents

Electrolyte containing additive and lithium metal secondary battery Download PDF

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CN114284559A
CN114284559A CN202111655879.XA CN202111655879A CN114284559A CN 114284559 A CN114284559 A CN 114284559A CN 202111655879 A CN202111655879 A CN 202111655879A CN 114284559 A CN114284559 A CN 114284559A
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lithium
additive
electrolyte
lithium metal
secondary battery
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CN114284559B (en
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高学平
王宇旸
刘胜
李国然
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Nankai University
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Abstract

The invention relates to an electrolyte containing an additive and a lithium metal secondary battery, wherein the additive of the electrolyte is selected from one or more of perfluoropolyether-based surfactants shown in a formula I; wherein M = Li, Na, K or NH4，X=COO、SO3The polymerization degree n is 0-100. The perfluoropolyether-based surface active agent is added, so that the distribution of an electric double layer structure at the interface of lithium metal and electrolyte is changed, the dynamic step of lithium ion deposition is influenced, the interface stability and the deposition quality of the lithium metal are improved, and the lithium metal secondary battery has longer cycle life.
Figure DEST_PATH_IMAGE002

Description

Electrolyte containing additive and lithium metal secondary battery
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to an electrolyte containing an additive and a lithium metal secondary battery.
Background
The lithium metal has ultrahigh theoretical specific capacity (1860 mAh/g) and extremely low electrochemical potential (-3.04V vs. SHE), and the lithium metal secondary battery taking the lithium metal as the negative electrode is considered as a new generation high-energy-density electric energy storage device for upgrading and updating the lithium ion battery.
At present, the main obstacle restricting the large-scale commercial application of lithium metal secondary batteries is the instability of the lithium metal/electrolyte interface, which is manifested by easy rupture of a solid electrolyte membrane formed by spontaneous lithium metal and electrolyte, formation of lithium dendrite, continuous consumption of electrolyte, increase of interface impedance and the like. Non-uniform deposition of metallic lithium is one of the main causes of instability of the lithium electrode interface and poor cycle life of the battery. Therefore, improving the uniform deposition of lithium is an effective technical path for improving the cycle life of the lithium metal secondary battery.
In order to obtain a stable and efficient lithium metal battery system, researchers have proposed strategies such as constructing an artificial passivation film on the surface of a lithium electrode, modifying the interface of the lithium electrode by using an electrolyte additive, and loading metal lithium by using a three-dimensional conductive framework. The technical route of using the electrolyte additive can avoid a complex lithium electrode pretreatment process, and has the advantages of simple method and low cost. It is reported (Ding, f.; Xu, w.; Graff, g. l.; Zhang, j.; Sushko, m. l.; Chen, x.; Shao, y.; Engelhard, m. h.; Nie, z.; Xiao, j.; Liu, x.; Sushko, p. v.; Liu, j.; Zhang, j. g., bendate-free lithium deposition section selected-insulating shield leather.J Am Chem Soc 2013,135(11) 4450-6.), a small amount of metal cesium ions are introduced into the electrolyte, the cesium ions are adsorbed to the surface of the lithium metal with negative electricity under the action of coulomb force, and the uneven deposition problem in the reduction process of the lithium ions is relieved through the electrostatic repulsive force between cations.
However, in order to achieve the above electrostatic shielding effect, it is thermodynamically satisfied that the reduction potential of the added metal cation is lower than that of the lithium ion, and only Cs is present+、Rb+Etc. of a few metal ions. Therefore, finding a more effective electrolyte additive is very important in improving the interface of the metal lithium electrode and improving the stability of the battery.
Disclosure of Invention
The invention aims to provide an electrolyte containing an additive and a lithium metal secondary battery, wherein the additive is adsorbed to the surface of lithium metal through a non-electrostatic acting force, so that the stability and the coulombic efficiency of lithium ions in a deposition and dissolution process are improved, and the cycle stability of the lithium metal secondary battery is improved.
In order to solve the above technical problems, according to an aspect of the present invention, there is provided an additive-containing electrolyte comprising a lithium salt, a solvent and an electrolyte additive, wherein the electrolyte additive is selected from one or more of perfluoropolyether-based surfactants represented by formula I;
Figure 855507DEST_PATH_IMAGE001
，
wherein M = Li, Na, K or NH4，X=COO、SO3The polymerization degree n is 0-100.
The anion of the perfluoropolyether surfactant is a carboxylic acid group or a sulfonic acid group. The cation of the perfluoropolyether surfactant is lithium ion, sodium ion, potassium ion or ammonium ion. The addition of the perfluoropolyether surfactant improves the interface stability and the deposition quality of lithium metal by influencing the kinetic step of lithium ion deposition, so that the lithium metal secondary battery has longer cycle life.
Further, the lithium salt is selected from at least one of lithium bis (fluorosulfonyl) imide, lithium bis (trifluoromethyl) sulfonyl imide, lithium hexafluorophosphate, lithium difluorooxalato borate, lithium tetrafluoroborate and lithium perchlorate.
Further, the solvent is at least one selected from the group consisting of ethylene carbonate, fluoroethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and 1, 3-dioxolane.
Further, the molar concentration of the lithium salt in the electrolyte is 0.7-4 mol/L.
Further, the molar concentration of the perfluoropolyether-based surfactant in the electrolyte is 10−5 -0.2 mol/L。
According to another aspect of the present invention, there is provided a use of the additive-containing electrolyte in a lithium metal secondary battery having metallic lithium or a metallic lithium composite as a negative electrode.
According to another aspect of the present invention, there is provided a lithium metal secondary battery comprising a lithium metal negative electrode or a lithium metal composite negative electrode, a separator, a positive electrode, and the additive-containing electrolyte described above.
Compared with the electrolyte additive of the lithium metal secondary battery in the prior art, the technical scheme of the invention at least has the following beneficial technical effects:
due to the addition of the perfluoropolyether-based surfactant, the redox process of the lithium-intermediate negative electrode of the lithium metal secondary battery becomes more reversible. The specific action is that anions of the perfluoropolyether surfactant can be adsorbed on the surface of the lithium negative electrode, so that the double-electric-layer structure of the lithium metal surface is changed, and the dynamic process of the lithium ion reduction process is accelerated. The mechanism is that because the adsorbed particles are negatively charged, a potential difference between the particles and a dispersion layer can be formed, the diffusion rate of lithium ions is accelerated, the concentration gradient in the deposition process of the lithium ions is reduced and slowed, the uniformity of a lithium deposition layer is improved, the reversibility of a lithium cathode is improved, and the cycle stability of the lithium metal secondary battery is improved.
The concrete outstanding effects and advantages are as follows: (1) the stability of the surface of the lithium electrode is improved, and the occurrence of side reactions is reduced; (2) the electrolyte additive is small in amount, the lithium metal cycling stability and the coulombic efficiency are obviously improved, and the method has a very good industrial application prospect.
Drawings
Fig. 1 is a graph of cycle performance of a lithium metal full cell of example 1.
Fig. 2 is a coulombic efficiency performance graph for a lithium metal half cell of example 1.
Fig. 3 is a coulombic efficiency graph of the lithium metal half cell of example 2.
FIG. 4 is a scanning electron micrograph of the surface of the control (without additives) lithium metal of example 3 after cycling.
FIG. 5 is a scanning electron micrograph of the surface of example 3 (with additives) after cycling of lithium metal.
Detailed Description
The lithium salts, solvents, electrolyte additives and abbreviations thereof described in the following examples are as follows:
lithium salt: LiFSI, LiTFSI, LiPF6Lithium difluorooxalato borate LiDFOB and lithium tetrafluoroborate LiBF4。
Solvent: ethylene carbonate EC, fluoroethylene carbonate FEC, dimethyl carbonate DMC, diethyl carbonate DEC, ethyl methyl carbonate EMC, ethylene glycol dimethyl ether DME, diethylene glycol dimethyl ether DDME, triethylene glycol dimethyl ether TEGDME, tetraethylene glycol dimethyl ether TEGDEM, 1, 3-dioxolane DOL.
Electrolyte additive: lithium perfluoro (2-methyl-3-oxaacetic acid), ammonium perfluoro (2-methyl-3-oxaacetic acid), lithium perfluoropropylpolydimethylcarboxylate, potassium perfluorononylpolydimethylsulfonate, sodium perfluoro-2, 5-dimethyl-3, 6-dioxanonanoate.
In the electrolyte of the embodiment, the molar concentration of the lithium salt in the electrolyte is 0.7-4.0 mol/L, and the preferable concentration range is 0.9-2.0 mol/L; the molar concentration of the perfluoropolyether-based surfactant is 10−50.2 mol/L, preferably in the concentration range 10−4mol/L-20mmol/L。
In the embodiment, a 2032 type button cell is adopted for evaluation, and the half-cell test conditions are as follows: the copper foil with the diameter of 12 mm is used as the anode, and the test current density is 0.5 mA/cm2The density of the test capacity is 1 mAh/cm2. The full cell test conditions were as follows: a lithium titanate battery having a diameter of 10 mm was used as the positive electrode, and a lithium foil having a diameter of 16 mm and a thickness of 50 μm was used as the negative electrode.
The examples described below all include comparative examples corresponding to the examples. The only difference between the examples and the corresponding control examples is that the electrolyte in the examples contains a perfluoropolyether-based surfactant, while the control example does not contain an additive.
Example 1
The lithium secondary battery electrolyte containing the additive comprises lithium salt LiFSI, solvent dimethyl ether DME and 1, 3-dioxolane DOL and additive perfluoro (2-methyl-3-oxaacetic acid) lithium. The preparation method comprises the following steps: mixing a solvent ethylene glycol dimethyl ether DME and 1, 3-dioxolane DOL according to a volume ratio of 1:1, and then adding lithium salt lithium bis (fluorosulfonyl) imide LiFSI with the concentration of 0.7 mol/L. Finally, the additive is added to make the concentration of the additive be 100 mmol/L. The control contained no additives as described above.
Load per unit area of 2.0 mg/cm2The lithium titanate electrode plate is used as a positive electrode, the addition amount of electrolyte is 40 mu L, and the charge and discharge test is carried out at the multiplying power of 1C. The test result shows that the capacity retention rate of the battery applying the electrolyte containing the additive is still more than 90% after 300 cycles, while the capacity retention rate of the battery of the comparative example is only 30% at 45 cycles. In the half-cell coulombic efficiency test, the coulombic efficiency of the cell using the electrolyte containing the additive still remained over 95% after 150 cycles, while the coulombic efficiency of the comparative example started to decrease and be unstable after 70 cycles.
Example 2
The lithium metal secondary battery electrolyte containing the additive comprises lithium salt LiTFSI, solvent TEGDME and 1, 3-dioxolane DOL, and additive perfluoro (2-methyl-3-oxaacetic acid) ammonium. The preparation method comprises the following steps: mixing a solvent of Triglyme (TEGDME) with 1, 3-dioxolane DOL according to a volume ratio of 1:1, and then adding lithium salt lithium bistrifluoromethylsulfonyl imide (LiTFSI) with a concentration of 1.9 mol/L. Finally, perfluoro (2-methyl-3-oxaacetic acid) ammonium additive is added to make the concentration to be 20 mmol/L. The control contained no additives as described above.
The positive electrode is 3.0 mg/cm of lithium titanate load capacity per unit area2The addition amount of the electrolyte of the electrode sheet (2) was 40. mu.L, and a charge and discharge test was carried out at a magnification of 1C. The test result shows that the capacity retention rate of the battery applying the electrolyte containing the additive is still more than 95% after 360 circles of circulation, while the capacity retention rate of the battery of the comparative example is less than 50% at 160 circles. In the half-cell coulombic efficiency test, the coulombic efficiency of the cell using the electrolyte containing the additive still remained over 95% after 100 cycles, while the coulombic efficiency of the comparative example started to decrease to 70% and be unstable after 40 cycles.
Example 3
An electrolyte for lithium metal secondary battery containing additive, the lithium salt isLithium hexafluorophosphate LiPF6The solvent is ethylene carbonate EC and dimethyl carbonate DMC, and the additive is perfluoropropyldimethyl lithium polycarboxylate. The preparation method comprises the following steps: mixing a solvent ethylene carbonate EC and dimethyl carbonate DMC according to a volume ratio of 1:1, and then adding lithium salt lithium hexafluorophosphate LiPF6The concentration was 1.1 mol/L. Finally, adding a perfluoropropyldimethyl lithium carboxylate additive to make the concentration of the additive be 0.2 mol/L. The control contained no additives as described above.
The lithium titanate load capacity of the anode per unit area is 4.6 mg/cm2The addition amount of the electrolyte of the electrode sheet (2) was 40. mu.L, and a charge and discharge test was carried out at a magnification of 1C. The test result shows that the capacity retention rate of the battery using the electrolyte containing the additive is still more than 96% after 500 cycles, while the capacity retention rate of the battery of the comparative example is less than 60% after 200 cycles. In the coulombic efficiency test of the half-cell, the coulombic efficiency of the cell using the electrolyte containing the additive is still kept above 96% after 120 circles, while the coulombic efficiency of the comparative example starts to drop to 70% after 60 circles.
Example 4
Lithium metal secondary battery electrolyte containing additive, lithium salt is lithium hexafluorophosphate LiPF6The solvent is fluoroethylene carbonate FEC and diethyl carbonate DEC, and the additive is perfluorononyl potassium polydimethylsulfonate. The preparation method comprises the following steps: mixing solvent fluoroethylene carbonate FEC and diethyl carbonate DEC according to the volume ratio of 1:1, and then adding lithium salt lithium hexafluorophosphate LiPF6The concentration was 1.5 mol/L. Finally, adding a potassium perfluorononyl polydimethylcarboxylate additive to make the concentration of the potassium perfluorononyl polydimethylcarboxylate additive be 10 mmol/L. The control contained no additives as described above.
The lithium titanate load capacity of the anode per unit area is 3.4 mg cm-2The electrode sheet (2) was used as a positive electrode, and a charge/discharge test was performed at a 1C rate with an electrolyte addition of 40. mu.L. The test result shows that the capacity retention rate of the battery using the electrolyte containing the additive is still more than 98% after 300 cycles, while the capacity retention rate of the battery of the comparative example is less than 60% after 100 cycles. In the coulomb efficiency test of the half-cell, the coulomb efficiency of the cell applying the electrolyte containing the additive still keeps more than 94% after 130 circles, while the coulomb efficiency of the comparative example starts to decrease after 60 circles。
Example 5
Lithium metal secondary battery electrolyte containing additive, lithium salt is lithium hexafluorophosphate LiPF6The solvent is ethylene carbonate EC, dimethyl carbonate DMC and ethyl methyl carbonate EMC. The additive is perfluoro-2, 5-dimethyl-3, 6-dioxa sodium nonanoate. The preparation method comprises the following steps: mixing solvents of ethylene carbonate EC, dimethyl carbonate DMC and methyl ethyl carbonate EMC according to the volume ratio of 1:1:1, and then adding lithium salt lithium hexafluorophosphate LiPF6The concentration was 1.1 mol/L. Finally, the additive of perfluoro-2, 5-dimethyl-3, 6-dioxa sodium nonanoate is added to make the concentration of the additive be 10−5mol/L. The control contained no additives as described above.
The lithium titanate load capacity of the anode per unit area is 4.1 mg/cm2The addition amount of the electrolyte of the electrode sheet (2) was 40. mu.L, and a charge and discharge test was carried out at a magnification of 1C. The test result shows that the capacity retention rate of the battery using the electrolyte containing the additive is still over 93 percent after 550 cycles, while the capacity retention rate of the battery of the comparative example is less than 60 percent at 120 cycles. In a half-cell coulombic efficiency test, the coulombic efficiency of the cell using the electrolyte containing the additive is still maintained to be more than 94% after 180 turns, while the coulombic efficiency of the comparative example is less than 80% after 60 turns.
Example 6
Lithium metal secondary battery electrolyte containing additive, lithium salt is lithium hexafluorophosphate LiPF6The solvent is ethylene carbonate EC, dimethyl carbonate DMC and ethyl methyl carbonate EMC. The additive is perfluoropropyldimethyl lithium carboxylate and perfluorononyl dimethyl potassium sulfonate. The preparation method comprises the following steps: mixing solvents of ethylene carbonate EC, dimethyl carbonate DMC and methyl ethyl carbonate EMC according to the volume ratio of 1:1:1, and then adding lithium salt lithium hexafluorophosphate LiPF6The concentration was 1.9 mol/L. Finally, adding additives of perfluoropropyldimethyl lithium carboxylate and perfluorononyl dimethyl potassium sulfonate to make the concentrations of the additives respectively 20 mmol/L. The control contained no additives as described above.
The lithium titanate load capacity of the positive electrode per unit area is 4.7 mg/cm2The addition amount of the electrolyte of the electrode sheet (2) was 40. mu.L, and a charge and discharge test was carried out at a magnification of 1C. The test result shows that the additive-containing electricity is appliedThe capacity retention rate of the electrolyte battery is still more than 94% after 660 cycles, while the capacity retention rate of the comparative battery is less than 65% after 105 cycles. In the coulombic efficiency test of the half-cell, the coulombic efficiency of the cell applying the electrolyte containing the additive is still kept more than 92% after 150 turns, while the coulombic efficiency of the comparative example is less than 70% after 68 turns.
Example 7
The lithium secondary battery electrolyte containing the additive comprises lithium difluoro oxalate lithium borate LiDFOB as a lithium salt and ethylene carbonate EC and ethyl methyl carbonate EMC as solvents. The additive is perfluoro (2-methyl-3-oxaacetic acid) lithium. The configuration method comprises the following steps: the solvents ethylene carbonate EC and ethyl methyl carbonate EMC were mixed in a volume ratio of 1:1, and then the lithium salt lithium difluorooxalate borate LiDFOB was added at a concentration of 1.0 mol/L. Finally, the additive of lithium perfluoro (2-methyl-3-oxa-acetate) was added to a concentration of 30 mmol/L. The control contained no additives as described above.
The lithium titanate load capacity of the anode per unit area is 2.3 mg/cm2The addition amount of the electrolyte of the electrode sheet (2) was 40. mu.L, and a charge and discharge test was carried out at a magnification of 1C. The test result shows that the capacity retention rate of the battery using the electrolyte containing the additive is still more than 91% after 550 cycles, while the capacity retention rate of the battery of the comparative example is less than 70% after 65 cycles. In a half-cell coulombic efficiency test, the coulombic efficiency of the cell using the electrolyte containing the additive is still kept above 95% after 115 turns, while the coulombic efficiency of the comparative example is less than 70% after 70 turns.
Example 8
Lithium metal secondary battery electrolyte containing additive, lithium salt is lithium tetrafluoroborate LiBF4The solvent is ethylene carbonate EC and ethyl methyl carbonate EMC. The additive is perfluoropropyldimethyl lithium carboxylate. The preparation method comprises the following steps: mixing ethylene carbonate EC and ethyl methyl carbonate EMC according to the volume ratio of 1:1, and then adding lithium salt LiBF4The concentration was 3.0 mol/L. Finally, the additive of the lithium perfluoropropyldimethylcarboxylate is added to make the concentration of the lithium perfluoropropyldimethylcarboxylate to be 30 mmol/L. The control contained no additives as described above.
The lithium titanate load capacity of the anode per unit area is 2.7 mg/cm2The pole piece and the electrolyteThe amount of the additive was 40. mu.L, and charge and discharge tests were performed at a magnification of 1C. The test result shows that the capacity retention rate of the battery applying the electrolyte containing the additive is still more than 92% after 380 cycles, while the capacity retention rate of the battery of the comparative example is less than 70% at 106 cycles. In the coulombic efficiency test of the half-cell, the coulombic efficiency of the cell using the electrolyte containing the additive is still kept above 95% after 145 circles, while the coulombic efficiency of the comparative example is less than 70% after 60 circles.
Example 9
Lithium metal secondary battery electrolyte containing additive, lithium salt is lithium tetrafluoroborate LiBF4The solvent is ethylene carbonate EC and ethyl methyl carbonate EMC. The additive is perfluorononyl polydimethyl sulfonate potassium. The preparation method comprises the following steps: mixing ethylene carbonate EC and ethyl methyl carbonate EMC according to the volume ratio of 1:1, and then adding lithium salt LiBF4The concentration was 3.0 mol/L. Finally, adding an additive of potassium perfluorononyl polydimethylcarboxylate to ensure that the concentration of the potassium perfluorononyl polydimethylcarboxylate is 10 mmol/L. The control contained no additives as described above.
The lithium titanate load capacity of the anode per unit area is 2.1 mg/cm2The addition amount of the electrolyte of the electrode sheet (2) was 40. mu.L, and a charge and discharge test was carried out at a magnification of 1C. The test result shows that the capacity retention rate of the battery applying the electrolyte containing the additive is still more than 90% after 190 cycles, while the capacity retention rate of the battery of the comparative example is less than 80% after 36 cycles. In the coulombic efficiency test of the half-cell, the coulombic efficiency of the cell applying the additive electrolyte is still kept above 95% after 102 turns, while the coulombic efficiency of the comparative example is less than 70% after 36 turns.
Example 10
Lithium metal secondary battery electrolyte containing additive, lithium salt is lithium tetrafluoroborate LiBF4And lithium hexafluorophosphate LiPF6The solvent is ethylene carbonate EC and ethyl methyl carbonate EMC. The additive is perfluoro-2, 5-dimethyl-3, 6-dioxa sodium nonanoate. The preparation method comprises the following steps: mixing ethylene carbonate EC and ethyl methyl carbonate EMC according to the volume ratio of 1:1, and then adding lithium salt LiBF4And lithium hexafluorophosphate LiPF6The concentration was 4.0 mol/L. Finally adding additive perfluoro-2, 5-dimethyl-3, 6-dioxa sodium nonanoateThe concentration was adjusted to 10 mmol/L. The control contained no additives as described above.
The lithium titanate load capacity of the anode per unit area is 2.2 mg/cm2The addition amount of the electrolyte of the electrode sheet (2) was 40. mu.L, and a charge and discharge test was carried out at a magnification of 1C. The test result shows that the capacity retention rate of the battery using the electrolyte containing the additive is still more than 92% after 230 cycles, while the capacity retention rate of the battery of the comparative example is less than 80% at 43 cycles. In the coulombic efficiency test of the half-cell, the coulombic efficiency of the cell using the electrolyte containing the additive is still kept above 95% after 170 turns, while the coulombic efficiency of the comparative example is less than 70% after 56 turns.
In examples 1 to 10 above, the positive electrode active material of the lithium metal battery was Li4Ti5O12The negative electrode is lithium metal, the diaphragm is a polypropylene PP diaphragm, and the electrolyte is the electrolyte of the lithium metal secondary battery containing the additive in each embodiment.
Preparing a positive pole piece: mixing the positive electrode active material Li4Ti5O12Mixing the conductive agent Super-P conductive carbon black and the adhesive PVDF according to the mass ratio of 8:1:1, adding NMP solvent, uniformly stirring, coating on a current collector aluminum foil, transferring to an oven for drying, and slicing to obtain the positive pole piece.
Preparing a lithium metal negative pole piece: and rolling the lithium foil on the surface of the negative copper foil, and slicing to obtain the negative pole piece.
Preparing an electrolyte:
the lithium salt, solvent and electrolyte additive as described in each example were mixed and stirred for 12 hours to obtain an electrolyte.
A diaphragm: the selected material is a polypropylene PP diaphragm, and the diaphragm is cut into a circular diaphragm with the diameter of 16 mm.
The preparation method of the lithium metal secondary battery comprises the following steps:
the electrode material obtained by the preparation method is sequentially stacked according to the sequence of the negative electrode shell, the elastic sheet, the gasket, the negative electrode piece, the electrolyte, the diaphragm, the electrolyte, the positive electrode piece and the positive electrode shell, and the button type lithium metal secondary battery is prepared under the pressure of 0.5 MPa of an oil press.
The technical solution claimed by the present invention is further explained by some embodiments. However, the examples and comparative examples are intended to illustrate the embodiments of the present invention without departing from the scope of the subject matter of the present invention, and the scope of the present invention is not limited by the examples. Unless otherwise specifically indicated, the materials and reagents used in the present invention are available from commercial products in the art.

Claims (7)

1. An additive-containing electrolyte comprising a lithium salt, a solvent and an electrolyte additive, wherein: the electrolyte additive is selected from one or more of perfluoropolyether surfactants shown in the formula I;
Figure DEST_PATH_IMAGE001
，
wherein M = Li, Na, K or NH4，X=COO、SO3The polymerization degree n is 0-100.
2. The additive-containing electrolyte of claim 1, wherein: the lithium salt is selected from at least one of lithium bis (fluorosulfonyl) imide, lithium bis (trifluoromethyl) sulfonyl imide, lithium hexafluorophosphate, lithium difluoro (oxalato) borate, lithium tetrafluoroborate and lithium perchlorate.
3. Additive-containing electrolyte according to claim 1 or 2, characterized in that: the solvent is at least one selected from ethylene carbonate, fluoroethylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether and 1, 3-dioxolane.
4. Additive-containing electrolyte according to claim 3, characterized in that: the molar concentration of the lithium salt in the electrolyte is 0.7-4 mol/L.
5. The additive-containing electrolyte according to claim 4, wherein the electrolyte is a solution containing a metal oxide: the molar concentration of the perfluoropolyether-based surfactant in the electrolyte is 10−5 -0.2 mol/L。
6. Use of the additive-containing electrolyte according to any one of claims 1 to 5 in a lithium metal secondary battery having metallic lithium or a metallic lithium composite as a negative electrode.
7. A lithium metal secondary battery characterized in that: comprising a lithium metal negative electrode or a lithium metal composite negative electrode, a separator, a positive electrode and the additive-containing electrolyte according to any one of claims 1 to 5.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116230946A (en) * 2023-05-08 2023-06-06 中南大学 Composite lithium electrode material and preparation method and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002033118A (en) * 2000-07-14 2002-01-31 Mitsubishi Heavy Ind Ltd Lithium secondary battery
JP2002033117A (en) * 2000-07-14 2002-01-31 Matsushita Electric Ind Co Ltd Nonaqueous electrolyte secondary battery
CN112002943A (en) * 2020-09-10 2020-11-27 中国科学院过程工程研究所 Electrolyte and preparation method and application thereof
CN112210033A (en) * 2020-09-30 2021-01-12 氟金(上海)新材料有限公司 Lithium sulfonate-containing ionic copolymer and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002033118A (en) * 2000-07-14 2002-01-31 Mitsubishi Heavy Ind Ltd Lithium secondary battery
JP2002033117A (en) * 2000-07-14 2002-01-31 Matsushita Electric Ind Co Ltd Nonaqueous electrolyte secondary battery
CN112002943A (en) * 2020-09-10 2020-11-27 中国科学院过程工程研究所 Electrolyte and preparation method and application thereof
CN112210033A (en) * 2020-09-30 2021-01-12 氟金(上海)新材料有限公司 Lithium sulfonate-containing ionic copolymer and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
HAILEMARIAM KASSA BEZABH ETAL.: "Bridging role of ethyl methyl carbonate in fluorinated electrolyte on ionic transport and phase stability for lithium-ion batteries", 《JOURNAL OF POWER SOURCES》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116230946A (en) * 2023-05-08 2023-06-06 中南大学 Composite lithium electrode material and preparation method and application thereof

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