CN114512722A - Metal lithium-based secondary battery electrolyte and application thereof - Google Patents
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Abstract
The invention provides a metal lithium-based secondary battery electrolyte and application thereof, belonging to the technical field of electrolytes and comprising a dioxygen ring compound, a fluorine-containing solvent, a fluorine-free ether solvent, a fluorine-containing lithium salt and lithium nitrate. According to the invention, the fluorine-containing solvent is added into the electrolyte, so that the uniformity of the interface current distribution is ensured, the deposition morphology of the metal lithium is regulated and controlled, and the formation of dendritic crystals is inhibited; adding a dioxygen ring compound to perform ring-opening polymerization reaction on the surface of the metallic lithium to form an organic layer with certain elasticity, so that the deposition dissolution coulomb efficiency of the metallic lithium is improved; lithium nitrate is added, so that the interfacial film can be stabilized and the cycle stability can be improved by cooperating with lithium fluoride; the composition of the electrolyte is controlled, and the deposition and dissolution coulombic efficiency of the metallic lithium can be improved when the concentration of the fluorine-containing lithium salt is lower. The results of the examples show that the first coulombic efficiency of the electrolyte provided by the invention reaches 92.3%, and after 700 cycles, the coulombic efficiency can still be stabilized at 98.6%, so that the electrolyte has excellent cycle stability.
Description
Technical Field
The invention relates to the technical field of electrolyte, in particular to a metal lithium-based secondary battery electrolyte and application thereof.
Background
With the continuous development of portable electronic products and the rapid expansion of the electric automobile market, the requirement on the energy density of a battery system is higher and higher, and the development of a negative electrode material with high capacity and long service life is one of important ways for improving the energy density, and metal lithium is a commonly used negative electrode material. However, coulombic efficiency and safety problems associated with the lack of effective interface protection for lithium metal remain major obstacles limiting their development. In view of the above problems, researchers have common knowledge of various approaches, wherein the adjustment and design of the metal lithium interfacial film is the key to change the deposition-dissolution behavior of the metal lithium, because the interfacial film can effectively block the continuous non-faradaic reaction between the metal lithium and the electrolyte, improve the coulombic efficiency and cycle life of the lithium electrode, and determine the uniformity of the current density distribution on the surface of the electrode. The electrolyte serves as an important source of interfacial film components and has a significant impact on battery performance.
It has been shown that lithium fluoride in the interfacial film enhances cell performance, and that lithium fluoride is obtained primarily by decomposition of a fluorine-containing lithium salt in the electrolyte, such as LiPF6LiTFST or LiFST, compared to conventional LiPF6LiFSI and LiTFSI are used as lithium salts, and the distribution uniformity of the obtained interface LiF and the compatibility with metallic lithium are better. However, in the prior art, a high concentration of fluorine-containing lithium salt (more than 7 mol/L) is usually required to be added to inhibit dendrites, but an excessively high concentration of fluorine-containing lithium salt not only increases the cost of the electrolyte, but also increases the viscosity of the electrolyte and reduces the electrochemical properties such as ionic conductivity.
Therefore, it is difficult to improve the electrolyte performance by suppressing dendrites even when the lithium salt concentration is low.
Disclosure of Invention
The invention aims to provide a lithium metal-based secondary battery electrolyte and application thereof. The electrolyte of the lithium metal-based secondary battery provided by the invention has excellent coulombic efficiency and stability.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a lithium metal-based secondary battery electrolyte, which comprises a dioxygen ring compound, a fluorine-containing solvent, a fluorine-free ether solvent, a fluorine-containing lithium salt and lithium nitrate.
Preferably, the dioxolane compound comprises 1, 3-dioxolane DOL or 1, 4-dioxane DOX.
Preferably, the fluorine-containing solvent comprises 1H,1H, 5H-octafluoropentyl-1, 1,2, 2-tetrafluoroethyl ether OFE, 2,2, 2-trifluoroethyl-1, 1,2, 2-tetrafluoroethyl ether HFE or 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether TTE.
Preferably, the volume ratio of the dioxygen ring compound to the fluorine-containing solvent is 1: (0.25 to 1.5).
Preferably, the fluorine-free ether solvent includes glyme DME or triglyme TEGDME.
Preferably, the volume ratio of the dioxygen ring compound to the fluorine-free ether solvent is (1-2): 1.
preferably, the lithium salt containing fluorine comprises lithium bis (fluorosulfonyl) imide, LiFSI, or lithium difluorooxalato borate, LiODFB.
Preferably, the concentration of the fluorine-containing lithium salt in the electrolyte of the lithium metal-based secondary battery is 0.8-1.5 mol/L.
Preferably, the concentration of lithium nitrate in the electrolyte of the lithium metal-based secondary battery is 0.1-0.3 mol/L.
The invention also provides the application of the electrolyte of the lithium metal-based secondary battery in the technical scheme in the secondary battery.
The invention provides a lithium metal-based secondary battery electrolyte, which comprises a dioxygen ring compound, a fluorine-containing solvent, a fluorine-free ether solvent, a fluorine-containing lithium salt and lithium nitrate. According to the invention, the fluorine-containing solvent is added into the electrolyte, and the fluorine-containing solvent and the fluorine-containing lithium salt act together, so that the formed lithium fluoride is more uniform and compact, the uniformity of the distribution of interface current is ensured, the deposition morphology of the metal lithium is regulated and controlled, and the formation of dendritic crystals is inhibited; the dioxygen ring compound is added to carry out ring-opening polymerization reaction on the surface of the metallic lithium to form an organic layer with certain elasticity, so that the integrity of an interfacial film structure is ensured, the non-faradaic reaction between the metallic lithium and the electrolyte is effectively prevented, and the deposition dissolution coulomb efficiency of the metallic lithium is improved; lithium nitrate is added, on one hand, inorganic components decomposed by nitrate ions form an inorganic bottom layer of the membrane, and can cooperate with lithium fluoride to stabilize an interface membrane, on the other hand, shuttle effect of polysulfide in a lithium-sulfur battery system is inhibited, and cycle stability is improved; the composition of the electrolyte is controlled, and the deposition and dissolution coulombic efficiency of the metallic lithium can be improved when the concentration of the fluorine-containing lithium salt is lower. The results of the examples show that the first coulombic efficiency of the lithium metal-stainless steel Li-SS symmetrical battery assembled by the electrolyte provided by the invention reaches 92.3%, the coulombic efficiency after 700 cycles is still as high as 98.6%, and the lithium metal-stainless steel Li-SS symmetrical battery has excellent cycling stability.
Drawings
FIG. 1 is a graph of deposition-dissolution coulombic efficiency for a lithium metal-stainless steel Li-SS symmetrical battery assembled using an electrolyte of example 1 of the present invention, an electrolyte of comparative example 1, and a commercially available electrolyte;
FIG. 2 is a graph of coulombic efficiency stability for long-term cycling of a lithium metal-stainless steel Li-SS symmetrical battery assembled with the electrolyte of example 1 of the present invention;
FIG. 3 is a polarization curve of a lithium metal-stainless steel Li-SS symmetrical battery assembled using the electrolyte of example 1 of the present invention.
Detailed Description
The invention provides a lithium metal-based secondary battery electrolyte, which comprises a dioxygen ring compound, a fluorine-containing solvent, a fluorine-free ether solvent, a fluorine-containing lithium salt and lithium nitrate.
In the present invention, the sources of the components are not particularly limited, unless otherwise specified, and commercially available products known to those skilled in the art may be used.
In the present invention, the dioxolane compound preferably comprises 1, 3-dioxolane DOL or 1, 4-dioxane DOX. In the invention, the dioxygen cyclic compound generates ring-opening polymerization reaction on the surface of the metallic lithium to form an organic layer with certain elasticity, thereby ensuring the integrity of an interfacial film structure, effectively preventing the illegal second reaction between the metallic lithium and electrolyte and improving the deposition dissolution coulomb efficiency of the metallic lithium.
In the present invention, the fluorine-containing solvent preferably includes 1H, 5H-octafluoropentyl-1, 1,2, 2-tetrafluoroethyl ether OFE, 2,2, 2-trifluoroethyl-1, 1,2, 2-tetrafluoroethyl ether HFE or 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether TTE. In the invention, the fluorine-containing solvent and the fluorine-containing lithium salt cooperate to participate in the formation of the interfacial film, so that the formed lithium fluoride is more uniform and compact, the uniformity of the interfacial current distribution is ensured, the deposition morphology of the metal lithium is regulated and controlled, and the formation of dendritic crystals is inhibited.
In the present invention, the volume ratio of the dioxygen ring compound to the fluorine-containing solvent is preferably 1: (0.25 to 1.5), more preferably 1: (0.5 to 1.0). The present invention limits the volume ratio of the dioxygen cyclic compound to the fluorine-containing solvent to the above range, and can further suppress the formation of dendrites and improve the electrochemical performance of the electrolyte.
In the present invention, the fluorine-free ether solvent preferably includes glyme DME or triglyme TEGDME.
In the invention, the volume ratio of the dioxygen cyclic compound to the fluorine-free ether solvent is preferably (1-2): 1, more preferably (1.2 to 1.8): 1, most preferably (1.4-1.6): 1. the volume ratio of the dioxygen ring compound to the fluorine-free ether solvent is limited in the range, so that all components can be fully dissolved, the electrolyte has low viscosity, and the ionic conductivity of the electrolyte is improved.
In the present invention, the fluorine-containing lithium salt preferably includes lithium bis (fluorosulfonyl) imide LiFSI or lithium difluorooxalato borate LiODFB. The invention limits the type of the fluorine-containing lithium salt in the range, and the fluorine-containing lithium salt anion and LiF generated by the decomposition of the fluorine-containing solvent jointly construct a more compact and uniform interface inorganic layer, and the fluorine-containing lithium salt has higher ionic conductivity, simpler decomposition product and better compatibility with metallic lithium, thereby further improving the performance of the electrolyte.
In the invention, the concentration of the fluorine-containing lithium salt in the electrolyte of the lithium metal-based secondary battery is preferably 0.8-1.5 mol/L, more preferably 1.0-1.4 mol/L, and most preferably 1.2-1.3 mol/L. According to the invention, the concentration of the fluorine-containing lithium salt in the electrolyte of the metal lithium-based secondary battery is limited within the range, so that the formed lithium fluoride layer is more compact and uniform, the ionic conductivity is higher, and the performance of the electrolyte is further improved.
In the invention, the lithium nitrate is used as an additive, and the inorganic component decomposed by nitrate ions forms an inorganic bottom layer of the membrane, so that the lithium fluoride can be cooperated to stabilize an interface membrane, and the shuttle effect of polysulfide in a battery system is inhibited, and the cycle stability is increased.
In the present invention, the concentration of lithium nitrate in the electrolyte of the lithium metal-based secondary battery is preferably 0.1 to 0.3mol/L, more preferably 0.15 to 0.25mol/L, and most preferably 0.2 mol/L. The invention limits the concentration of lithium nitrate in the electrolyte of the metal lithium-based secondary battery within the range, and can further improve the performance of the electrolyte.
The invention controls the composition of the electrolyte, adds the fluorine-containing solvent, the dioxygen ring compound and the lithium nitrate, and can improve the deposition and dissolution coulombic efficiency of the metallic lithium when the concentration of the fluorine-containing lithium salt is lower.
The preparation method of the electrolyte of the lithium metal-based secondary battery is not particularly limited, and the technical scheme for preparing the mixed solution, which is well known by the technical personnel in the field, can be adopted. In the present invention, the method for preparing the electrolyte for a lithium metal-based secondary battery is preferably: under the conditions of high-purity argon atmosphere, water and oxygen content of less than 50ppm, mixing a dioxygen compound, a fluorine-containing solvent and a fluorine-free ether solvent, adding a fluorine-containing lithium salt, stirring for 3-5 hours, adding lithium nitrate, and stirring for 10-14 hours.
The invention also provides the application of the electrolyte of the lithium metal-based secondary battery in the technical scheme in the secondary battery.
The operation of the application of the metal lithium-based secondary battery electrolyte in the secondary battery is not particularly limited, and the technical scheme of the application of the metal lithium-based secondary battery electrolyte in the secondary battery, which is well known to those skilled in the art, can be adopted.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The electrolyte of the lithium-based metal secondary battery of the embodiment is prepared from 1, 3-dioxolane DOL, 1H, 5H-octafluoropentyl-1, 1,2, 2-tetrafluoroethyl ether OFE, ethylene glycol dimethyl ether DME, lithium bis (fluorosulfonyl) imide LiFSI and lithium nitrate LiNO3Composition is carried out; wherein the volume ratio of the 1, 3-dioxolane to the 1H,1H, 5H-octafluoropentyl-1, 1,2, 2-tetrafluoroethyl ether is 1:1, the volume ratio of the 1,1, 3-dioxolane to the ethylene glycol dimethyl ether is 1:1, the concentration of lithium bis (fluorosulfonyl) imide is 1mol/L, and the concentration of lithium nitrate is 0.2 mol/L; it is marked as DOL + OFE + DME + LiFSI +0.2M LiNO3；
The preparation method comprises the following steps: under the conditions of high-purity argon atmosphere, water and oxygen content of less than 50ppm, 1, 3-dioxolane, 1H, 5H-octafluoropentyl-1, 1,2, 2-tetrafluoroethyl ether and ethylene glycol dimethyl ether are sequentially mixed, bis (fluorosulfonyl) imide lithium is added, magnetic stirring is carried out for 4 hours, and then lithium nitrate is added, and magnetic stirring is carried out for 12 hours.
Comparative example 1
The electrolyte consists of 1, 3-dioxolane DOL, ethylene glycol dimethyl ether DME, lithium bis (fluorosulfonyl) imide LiFSI and lithium nitrate LiNO3Composition is carried out; wherein the volume ratio of the 1, 3-dioxolane to the ethylene glycol dimethyl ether is 1:1, the concentration of lithium bis (fluorosulfonyl) imide is 1mol/L, and the concentration of lithium nitrate is 0.2 mol/L; it is marked as DOL + DME + LiFSI +0.2M LiNO3；
The preparation method comprises the following steps: under the conditions of high-purity argon atmosphere, water and oxygen content of less than 50ppm, 1, 3-dioxolane and ethylene glycol dimethyl ether are mixed, bis (fluorosulfonyl) imide lithium is added, magnetic stirring is carried out for 4 hours, and then lithium nitrate is added, and magnetic stirring is carried out for 12 hours.
Test example 1, comparative example 1 electrolyte and existing commercial lithium ion battery electrolyte (Shanghai Song static New energy science Co., Ltd., composition: EC + DMC (volume ratio 1:1) +1M LiPF6) Deposition of metallic lithiumDissolution efficiency: the lithium-stainless steel (Li-SS) button cell is used for testing, a positive electrode is a stainless steel sheet, a negative electrode is a metal lithium sheet, a diaphragm is a PE diaphragm, electrolyte to be tested and reference electrolyte are respectively dripped into the lithium-SS button cell to be tested and the reference electrolyte to be assembled, the Li-SS button cell is tested on a LAND-CT3002AU test system, and the test current density is 0.25mA/cm2The amount of lithium metal deposited on the stainless steel per cycle was 0.92C/cm2The elution of metallic lithium was carried out by controlling the limiting voltage to 1.2V, and the standing time between each charge and discharge was 30 seconds. The results of the coulombic efficiency comparison of metallic lithium are shown in fig. 1. As can be seen from fig. 1, the first coulombic efficiency of the electrolyte of example 1 is as high as 92.3%, which is higher than 45.52% of that of comparative example 1 and 72.3% of that of the conventional electrolyte, and the cycling stability is better, and the average coulombic efficiency of 200 cycles is 98.7%; the coulombic efficiency of the conventional electrode liquid is gradually reduced along with the increase of the cycle times, the coulombic efficiency is suddenly reduced by only 30 percent after 130 cycles, and the battery fails; the electrolyte of comparative example 1 had poor cycle stability and remarkable fluctuation, although the coulombic efficiency did not tend to decrease abruptly.
To further examine the coulombic efficiency stability of the long-term cycling of the electrolyte of example 1, a long-cycle test was performed on a Li-SS button cell using it as an electrode solution, and the results are shown in fig. 2. As can be seen from fig. 2, after 700 cycles, the coulombic efficiency is still stable and the average coulombic efficiency is as high as 98.6%, which indicates that the electrolyte can form a special and effective interface protective film on the surface of the metal lithium electrode, effectively block the occurrence of irreversible electrode reactions, thereby obtaining stable and high deposition and dissolution efficiency of the metal lithium and ensuring the application of the electrolyte in the metal lithium-based secondary battery.
The results of testing the polarization curves of the electrolyte of example 1 are shown in FIG. 3, and it can be seen from FIG. 3 that the polarization voltage of the metal lithium corresponding to the electrolyte is small and is only-12 mV, and the stability is high, and the polarization overpotential can still be stabilized at-12 mV after the circulation of more than 1500 hours, indicating that the stability of the interface film formed by the electrolyte is high.
In conclusion, the electrolyte provided by the invention has excellent coulombic efficiency and cycle stability.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A lithium-based secondary battery electrolyte comprises a dioxygen ring compound, a fluorine-containing solvent, a fluorine-free ether solvent, a fluorine-containing lithium salt and lithium nitrate.
2. The lithium metal-based secondary battery electrolyte according to claim 1, wherein the dioxygen ring compound comprises 1, 3-dioxolane DOL or 1, 4-dioxane DOX.
3. The lithium metal-based secondary battery electrolyte according to claim 1, wherein the fluorine-containing solvent comprises 1H, 5H-octafluoropentyl-1, 1,2, 2-tetrafluoroethyl ether OFE, 2,2, 2-trifluoroethyl-1, 1,2, 2-tetrafluoroethyl ether HFE, or 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether TTE.
4. The electrolyte for lithium metal-based secondary batteries according to any one of claims 1 to 3, wherein the volume ratio of the dioxygen ring compound to the fluorine-containing solvent is 1: (0.25 to 1.5).
5. The lithium metal-based secondary battery electrolyte according to claim 1, wherein the fluorine-free ether-based solvent includes glyme DME or triglyme TEGDME.
6. The electrolyte for lithium metal-based secondary batteries according to claim 1,2 or 5, wherein the volume ratio of the dioxygen ring compound to the fluorine-free ether solvent is (1-2): 1.
7. the lithium metal-based secondary battery electrolyte of claim 1 wherein the lithium fluoride-containing salt comprises lithium bis (fluorosulfonyl) imide, LiFSI, or lithium difluorooxalato borate, LiODFB.
8. The electrolyte for a lithium metal-based secondary battery according to claim 1 or 7, wherein the concentration of the fluorine-containing lithium salt in the electrolyte for a lithium metal-based secondary battery is 0.8 to 1.5 mol/L.
9. The electrolyte for a lithium metal-based secondary battery according to claim 1, wherein the concentration of lithium nitrate in the electrolyte for a lithium metal-based secondary battery is 0.1 to 0.3 mol/L.
10. Use of the electrolyte for a lithium metal-based secondary battery according to any one of claims 1 to 9 in a secondary battery.
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| CN115395098A (en) * | 2022-09-19 | 2022-11-25 | 电子科技大学 | Electrolyte for high-voltage lithium metal battery and preparation method thereof |
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