CN111276744A - Local high-concentration lithium metal battery electrolyte containing anion receptor additive - Google Patents
Local high-concentration lithium metal battery electrolyte containing anion receptor additive Download PDFInfo
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Abstract
The invention belongs to the field of lithium batteries, and particularly relates to a local high-concentration lithium metal battery electrolyte containing an anion receptor additive. In the local high-concentration lithium metal battery electrolyte provided by the invention, the anion receptor changes the decomposition mode of anions on the surface of lithium metal through the interaction with the anions, so that a solid-liquid interface film which is beneficial to uniform and rapid transmission of lithium ions is formed, the cycle stability and safety of the lithium metal battery are obviously improved, and the local high-concentration lithium metal battery electrolyte has a wide application prospect.
Description
Technical Field
The invention belongs to the technical field of lithium batteries, and particularly relates to a local high-concentration lithium metal battery electrolyte containing an anion receptor additive.
Background
The metal lithium has extremely low electrode potential (-3.04V vs standard hydrogen electrode) and ultrahigh theoretical specific capacity (3860mAh g-1), and is an ideal negative electrode material of the next generation of high-energy-density lithium metal battery. Due to potential safety hazards caused by the growth of lithium dendrites, low coulombic efficiency and the like, the large-scale commercial application of the lithium metal cathode is not realized yet. The growth of lithium dendrites is mainly due to the inhomogeneous solid-liquid interface phase formed by the reaction of metallic lithium with the electrolyte. Therefore, the construction of a uniform and stable solid-liquid interface film is the key to improve the cycle life and the safety performance of the lithium metal battery.
In order to solve the problem of the growth of lithium dendrites, researchers propose various strategies such as the adoption of a three-dimensional framework, electrolyte modification, solid electrolyte introduction, artificial interface layer introduction and the like. In recent years, a great deal of research shows that the high-concentration electrolyte can remarkably improve the cycling stability of the lithium metal negative electrode. In a highly concentrated electrolyte, anions participate in the solvation of lithium ions and the free solvent molecules are drastically reduced. The special solvation structure brings a series of outstanding performances, and the reason is mainly that anions participate in the formation of the solid-liquid interface film, so that the physical and chemical properties of the solid-liquid interface film are greatly changed. The solid-liquid interfacial film formed by anion decomposition can promote the uniform deposition of lithium, thereby remarkably improving the cycle stability and safety performance of the lithium metal battery. However, the high-concentration electrolyte has low ion conductivity due to high viscosity, which hinders the improvement of the rate capability of the battery, and is difficult to realize large-scale application. In addition, it is difficult to satisfy the demand for practical use of a lithium metal battery only by a solid-liquid interface film formed by decomposition of anions in a high concentration electrolyte. From the viewpoint of safety, the safety performance of the electrolyte itself should be taken into account in the process of developing the electrolyte.
Disclosure of Invention
Technical problem to be solved by the invention
The invention aims to provide a local high-concentration lithium metal battery electrolyte containing an anion receptor additive, which reduces the viscosity of the electrolyte by introducing nonflammable hydrofluoroether as a diluent on the basis of the high-concentration electrolyte and improves the safety of the electrolyte. In addition, in order to further improve the performance of the electrolyte in the lithium metal battery, the uniformity and stability of the solid-liquid interface film are improved by introducing an anion receptor as an additive, and the cycle stability and safety performance of the lithium metal battery are obviously improved.
Means for solving the technical problem
In view of the above problems, the present invention provides a localized high concentration lithium metal battery electrolyte containing an anion receptor additive.
The electrolyte of the lithium metal battery contains a lithium salt, a solvent, a diluent and an anion receptor additive, wherein the anion receptor additive is one or more selected from organic compounds taking boron as a center.
An embodiment is wherein the boron-centered organic compound comprises at least one of tris (2,2, 2-trifluoroethyl) borate, tris (pentafluorophenyl) borate, tetrafluorocatechol-pentafluorophenylborane, tris (hexafluoroisopropyl) borate, a 2,4, 6-tris (pentafluorophenyl) borato six-membered ring, tris (pentafluorophenyl) borane, tris (phenyl) borate, bis (1,1,1,3,3, 3-hexafluoroisopropyl) pentafluorophenylborate.
In one embodiment, the lithium salt is at least one selected from the group consisting of lithium bis (fluorosulfonyl) imide, lithium bis (trifluoromethylsulfonyl) imide, lithium nitrate, lithium difluorooxalato borate, lithium hexafluorophosphate, and lithium tetrafluoroborate.
In one embodiment, the diluent is a hydrofluoroether compound of formula (I),
wherein Rf1 and Rf2 are independently selected from C1-C6 fluoroalkyl groups.
In one embodiment, the hydrofluoroether is at least one of 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether, 1,1,2, 2-tetrafluoroethyl-2, 2, 2-trifluoroethyl ether, bis (2,2, 2-trifluoroethyl) ether, 2,2, 2-trifluoroethyl 1,1,2,3,3, 3-hexafluoropropyl ether, difluoromethyl 2,2,3, 3-tetrafluoropropyl ether, and fluoromethyl-1, 1,1,3,3, 3-hexafluoroisopropyl ether.
In one embodiment, 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, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether.
In one embodiment, the molar concentration of the lithium salt in the electrolyte is 0.5-6.0 mol/L; the mass fraction of the anion receptor additive is 0.1-5.0%, and the mass fraction of the diluent is 20-80%.
According to a second aspect of the invention, there is provided the use of an electrolyte according to the above in a lithium metal battery having lithium metal as the negative electrode.
The invention has the advantages of
Compared with the prior art, the invention has the following advantages and prominent effects: (1) in the electrolyte of the local high-concentration lithium metal battery, the anion receptor changes the decomposition mode of anions on the surface of the metal lithium through the interaction with the anions to form a solid-liquid interfacial film which is beneficial to the uniform and rapid transmission of the lithium ions; (2) in the electrolyte of the local high-concentration lithium metal battery, the proportion of the nonflammable diluent is large, and meanwhile, the safety of the electrolyte and the battery can be greatly improved due to the reduction of the free solvent; (3) the electrolyte has good wettability and low additive consumption, and has good industrial application prospect.
Further features of the present invention will become apparent from the following description of exemplary embodiments.
Drawings
Fig. 1 shows the cycle performance of the electrolyte for a lithium metal battery according to application example 2.
Detailed Description
One embodiment of the present disclosure will be specifically described below, but the present disclosure is not limited thereto.
Examples
The present invention is described in more detail by way of examples, but the present invention is not limited to the following examples. The abbreviations for the lithium salt, solvent, and diluent described in the following examples are as follows:
lithium salt: lithium bis (fluorosulfonyl) imide is LiFSI, lithium bis (trifluoromethylsulfonyl) imide is LiTFSI, lithium nitrate is LiNO3, lithium difluorooxalato borate is liddob, lithium hexafluorophosphate is LiPF6, lithium tetrafluoroborate is LiBF4, and lithium bis (oxalato) is LiBOB.
In the examples, a 2032 type button cell was used for evaluation under the following test conditions: lithium nickel cobalt manganese oxide and lithium nickel cobalt aluminate are used as anode materials, the surface capacity is 2.5mAh/cm2, a lithium sheet with the thickness of 33 mu m is used as a cathode, and the dosage of electrolyte in each battery is 50 microliters. The battery cycle life was calculated as 80% capacity retention.
The only difference between each set of examples and the corresponding comparative examples is that the examples contain an anion acceptor additive and the comparative examples do not.
Example 1
A high-concentration electrolyte for local use is prepared from LiTFSI as lithium salt, ethylene carbonate and dimethyl carbonate as solvent, 1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether as diluent, and tri (hexafluoroisopropyl) borate as additive. The preparation method comprises the following steps: mixing ethylene carbonate and dimethyl carbonate according to a volume ratio of 1:3, and then adding lithium salt to enable the concentration of the lithium salt to reach 4.0 mol/L. And then adding a diluent to ensure that the overall concentration of the LiTFSI in the electrolyte is 0.5mol/L, and finally adding an additive with the mass fraction of 0.1%. The electrolyte system is used for full-cell tests with a metal lithium sheet as a negative electrode and LiNi0.5Co0.2Mn0.3O2 as a positive electrode, and tests show that the cycle life of the cell can reach 115 circles, while the cycle life of the cell in a comparative example is only 78 circles.
Example 2
A local high-concentration electrolyte is prepared from LiFSI as lithium salt, fluoroethylene carbonate and dimethyl carbonate as solvent, 1,2, 2-tetrafluoroethyl-2, 2, 2-trifluoroethyl ether as diluent, and tri (2,2, 2-trifluoroethyl) borate as additive. The preparation method comprises the following steps: fluoroethylene carbonate and dimethyl carbonate are mixed according to the volume ratio of 1:4, and then lithium salt is added to make the concentration of the lithium salt reach 6.0 mol/L. And then adding a diluent to ensure that the overall concentration of LiFSI in the electrolyte is 2.0mol/L, and finally adding an additive with the mass fraction of 0.5%. The electrolyte system is used for full-cell tests with a metal lithium sheet as a negative electrode and LiNi0.8Co0.1Al0.1O2 as a positive electrode, and tests show that the cycle life of the cell can reach 150 circles, while the cycle life of the cell in a comparative example is only 100 circles.
Example 3
A local high-concentration electrolyte is prepared from LiFSI as lithium salt, glycol dimethyl ether as solvent, bis (2,2, 2-trifluoroethyl) ether as diluent, and tris (pentafluorophenyl) borane as additive. The preparation method comprises the following steps: lithium salt is added into the ethylene glycol dimethyl ether to make the concentration of the lithium salt reach 8.0 mol/L. And then adding a diluent to ensure that the overall concentration of LiFSI in the electrolyte is 6.0mol/L, and finally adding an additive with the mass fraction of 2.0%. The electrolyte system is used for full-cell test with a metal lithium sheet as a negative electrode and LiNi0.8Co0.1Mn0.1O2 as a positive electrode, and the test shows that the cycle life of the cell can reach 302 circles, while the cycle life of the cell in a comparative example is only 185 circles.
Example 4
A local high-concentration electrolyte is prepared from LiTFSI as lithium salt, tetraglyme as solvent, bis (2,2, 2-trifluoroethyl) ether as diluent, and 2,4, 6-tri (pentafluorophenyl) borato-oxygen hexatomic ring as additive. The preparation method comprises the following steps: lithium salt is added into the tetraethylene glycol dimethyl ether to make the concentration of the lithium salt reach 6.0 mol/L. And then adding a diluent to ensure that the overall concentration of LiFSI in the electrolyte is 3.0mol/L, and finally adding an additive with the mass fraction of 2.0%. The electrolyte system is used for full-cell test with a metal lithium sheet as a negative electrode and LiNi0.8Co0.1Mn0.1O2 as a positive electrode, and the test shows that the cycle life of the cell can reach 268 circles, while the cycle life of the cell in a comparative example is only 152 circles.
Example 5
A high-concentration electrolyte for local use is prepared from LiPF6 as lithium salt, fluoroethylene carbonate and diethylene glycol dimethyl ether as solvent, 2,2, 2-trifluoroethyl 1,1,2,3,3, 3-hexafluoropropyl ether as diluent, and tri (phenyl) borate as additive. The preparation method comprises the following steps: fluoroethylene carbonate and diethylene glycol dimethyl ether were mixed in a ratio of 1:4, and then a lithium salt was added to make a concentration of 4.0 mol/L. And then adding a diluent to ensure that the overall concentration of LiFSI in the electrolyte is 0.5mol/L, and finally adding an additive with the mass fraction of 5.0%. The electrolyte system is used for a full-cell test with a metal lithium sheet as a negative electrode and LiNi0.6Co0.2Mn0.2O2 as a positive electrode, and the cycle life of the cell can reach 130 circles through the test, while the cycle life of the cell in a comparative example is only 67 circles.
Example 6
A local high-concentration electrolyte is prepared from LiPF6 as lithium salt, fluoroethylene carbonate and diethylene glycol dimethyl ether as solvent, 2,2, 2-trifluoroethyl 1,1,2,3,3, 3-hexafluoropropyl ether as diluent, and tetrafluorocatechol-pentafluorophenyl borane as additive. The preparation method comprises the following steps: fluoroethylene carbonate and triethylene glycol dimethyl ether were mixed in a ratio of 1:4, and then a lithium salt was added to make the concentration 4.0 mol/L. And then adding a diluent to ensure that the overall concentration of LiFSI in the electrolyte is 0.5mol/L, and finally adding an additive with the mass fraction of 5.0%. The electrolyte system is used for a full-cell test with a metal lithium sheet as a negative electrode and LiNi0.6Co0.2Mn0.2O2 as a positive electrode, and the cycle life of the cell can reach 135 circles through the test, while the cycle life of the cell in a comparative example is only 74 circles.
Example 7
A local high-concentration electrolyte is prepared from LiFSI as lithium salt, diglyme as solvent, difluoromethyl 2,2,3, 3-tetrafluoropropyl ether as diluent, and bis (1,1,1,3,3, 3-hexafluoroisopropyl) pentafluorophenyl borate as additive. The preparation method comprises the following steps: lithium salt is added to the diglyme to make the concentration of the lithium salt reach 6.0 mol/L. And then adding a diluent to ensure that the overall concentration of LiFSI in the electrolyte is 2.5mol/L, and finally adding an additive with the mass fraction of 1.5%. When the electrolyte system is used for a full-cell test with a metal lithium sheet as a negative electrode and LiNi0.6Co0.2Mn0.2O2 as a positive electrode, the cycle life of the cell can reach 189 circles through the test, and the cycle life of the cell in a comparative example is only 122 circles.
Example 8
A local high-concentration electrolyte is prepared from LiTFSI as lithium salt, triglyme as solvent, difluoromethyl 2,2,3, 3-tetrafluoropropyl ether as diluent, and tri (phenyl) borate as additive. The preparation method comprises the following steps: lithium salt is added into triglyme to make the concentration reach 6.0 mol/L. And then adding a diluent to ensure that the overall concentration of LiFSI in the electrolyte is 2.5mol/L, and finally adding an additive with the mass fraction of 1.5%. The electrolyte system is used for full-cell test with a metal lithium sheet as a negative electrode and LiNi0.6Co0.2Mn0.2O2 as a positive electrode, and the cycle life of the cell can reach 185 circles through the test, while the cycle life of the cell in a comparative example is only 125 circles.
Example 9
A local high-concentration electrolyte is prepared from LiFSI and LiPF6 as lithium salt, fluoroethylene carbonate and diethyl carbonate as solvent, fluoromethyl-1, 1,1,3,3, 3-hexafluoroisopropyl ether as diluent, and tri (2,2, 2-trifluoroethyl) borate as additive. The preparation method comprises the following steps: fluoroethylene carbonate and diethyl carbonate were mixed in a ratio of 1:4, and then lithium salt (LiFSI: LiPF6 molar ratio of 3:1) was added to make a concentration of 6.0 mol/L. Then, a diluent is added to ensure that the overall concentration of the lithium salt in the electrolyte is 2.0mol/L, and finally, an additive with the mass fraction of 1.5 percent is added. The electrolyte system is used for a full-cell test with a metal lithium sheet as a negative electrode and a LiNi0.5Co0.2Mn0.3O2 as a positive electrode, and the test shows that the cycle life of the cell can reach 276 circles, while the cycle life of the cell in a comparative example is only 184 circles.
Example 10
A local high-concentration electrolyte is prepared from LiFSI and LiBOB as lithium salt, fluoroethylene carbonate and methyl ethyl carbonate as solvent, bis (2,2, 2-trifluoroethyl) ether as diluent, and tris (pentafluorophenyl) borate as additive. The preparation method comprises the following steps: fluoroethylene carbonate and ethyl methyl carbonate were mixed in a ratio of 1:4, and then lithium salt (LiFSI: LiBOB molar ratio 4:1) was added to make the concentration 6.0 mol/L. Then, a diluent is added to ensure that the overall concentration of the lithium salt in the electrolyte is 2.0mol/L, and finally, an additive with the mass fraction of 1.5 percent is added. The electrolyte system is used for full-cell test with a metal lithium sheet as a negative electrode and LiNi0.5Co0.2Mn0.3O2 as a positive electrode, and the test shows that the cycle life of the cell can reach 203 circles, while the cycle life of the cell in a comparative example is only 114 circles.
Example 11
A high-concentration electrolyte for local use is prepared from LiFSI, LiBOB and LiNO3 as lithium salt, fluoroethylene carbonate, methyl ethyl carbonate and tetraglyme as solvent, bis (2,2, 2-trifluoroethyl) ether as diluent and tris (hexafluoroisopropyl) borate as additive. The preparation method comprises the following steps: fluoroethylene carbonate, ethyl methyl carbonate and tetraglyme were mixed in a ratio of 1:1:8, and then a lithium salt (LiFSI: LiBOB: LiNO3 molar ratio of 8:1:1) was added to make the concentration 4.0 mol/L. Then adding a diluent to ensure that the overall concentration of the lithium salt in the electrolyte is 1.0mol/L, and finally adding an additive with the mass fraction of 3.0%. The electrolyte system is used for a full-cell test with a metal lithium sheet as a negative electrode and LiNi0.5Co0.2Mn0.3O2 as a positive electrode, and the test shows that the cycle life of the cell can reach 267 circles, while the cycle life of the cell in a comparative example is only 176 circles.
Example 12
A local high-concentration electrolyte is prepared from LiFSI, LiDFOB and LiNO3 as lithium salt, fluoroethylene carbonate, ethylmethyl carbonate and tetraglyme as solvent, 1,2, 2-tetrafluoroethyl-2, 2, 2-trifluoroethyl ether as diluent, and tris (pentafluorophenyl) borane as additive. The preparation method comprises the following steps: fluoroethylene carbonate, ethylmethyl carbonate and tetraglyme were mixed in a ratio of 1:1:8, and then a lithium salt (LiFSI: LiDFOB: LiNO3 molar ratio of 7:2:1) was added to make a concentration of 5.0 mol/L. Then adding a diluent to ensure that the overall concentration of the lithium salt in the electrolyte is 1.0mol/L, and finally adding an additive with the mass fraction of 2.0%. The electrolyte system is used for full-cell test with a metal lithium sheet as a negative electrode and LiNi0.5Co0.2Mn0.3O2 as a positive electrode, and the test shows that the cycle life of the cell can reach 312 circles, while the cycle life of the cell in a comparative example is only 217 circles.
Example 13
A high-concentration electrolyte for local use is prepared from LiTFSI and LiNO3 as lithium salt, fluoroethylene carbonate and diglycol dimethyl ether as solvent, 1,2, 2-tetrafluoroethyl-2, 2, 2-trifluoroethyl ether as diluent, and tri (hexafluoroisopropyl) borate as additive. The preparation method comprises the following steps: fluoroethylene carbonate and diethylene glycol dimethyl ether were mixed in a ratio of 1:4, and then lithium salt (LiTFSI: LiNO3 molar ratio of 4:1) was added to make the concentration 6.0 mol/L. Then adding a diluent to ensure that the overall concentration of the lithium salt in the electrolyte is 4.0mol/L, and finally adding an additive with the mass fraction of 3.0%. The electrolyte system is used for full-cell test with a metal lithium sheet as a negative electrode and LiNi0.8Co0.1Mn0.1O2 as a positive electrode, and the test shows that the cycle life of the cell can reach 276 circles, while the cycle life of the cell in a comparative example is only 157 circles.
Example 14
A local high-concentration electrolyte is prepared from LiTFSI as lithium salt, fluoroethylene carbonate and diethylene glycol dimethyl ether as solvent, 1,2, 2-tetrafluoroethyl-2, 2, 2-trifluoroethyl ether as diluent, and tri (2,2, 2-trifluoroethyl) borate as additive. The preparation method comprises the following steps: fluoroethylene carbonate and diethylene glycol dimethyl ether were mixed in a ratio of 1:4, and then a lithium salt was added to make a concentration of 5.0 mol/L. Then adding a diluent to ensure that the overall concentration of the lithium salt in the electrolyte is 4.0mol/L, and finally adding an additive with the mass fraction of 3.0%. The electrolyte system is used for full-cell test with a metal lithium sheet as a negative electrode and LiNi0.8Co0.1Mn0.1O2 as a positive electrode, and the test shows that the cycle life of the cell can reach 216 circles, while the cycle life of the cell in a comparative example is only 124 circles.
Industrial applicability
The electrolyte can obviously improve the cycle stability and safety of the lithium metal battery, and has wide application prospect.
The present invention is not limited to the above embodiments, and any changes or substitutions that can be easily made by those skilled in the art within the technical scope of the present invention are also within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (8)
1. The electrolyte of the lithium metal battery is characterized by comprising a lithium salt, a solvent, a diluent and an anion receptor additive, wherein the anion receptor additive is one or more selected from organic compounds taking boron as a center.
2. The electrolyte solution of claim 1, wherein the boron-centered organic compound comprises at least one of tris (2,2, 2-trifluoroethyl) borate, tris (pentafluorophenyl) borate, tetrafluorocatechol-pentafluorophenylborane, tris (hexafluoroisopropyl) borate, a 2,4, 6-tris (pentafluorophenyl) boroxy six-membered ring, tris (pentafluorophenyl) borane, tris (phenyl) borate, bis (1,1,1,3,3, 3-hexafluoroisopropyl) pentafluorophenylborate.
3. The electrolyte of any of claims 1-2, wherein the lithium salt is selected from at least one of lithium bis (fluorosulfonyl) imide, lithium bis (trifluoromethyl) sulfonyl imide, lithium nitrate, lithium difluoro (oxalato) borate, lithium hexafluorophosphate, and lithium tetrafluoroborate.
5. The electrolyte solution according to any one of claims 1 to 4, wherein the hydrofluoroether is at least one of 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether, 1,1,2, 2-tetrafluoroethyl-2, 2, 2-trifluoroethyl ether, bis (2,2, 2-trifluoroethyl) ether, 2,2, 2-trifluoroethyl 1,1,2,3,3, 3-hexafluoropropyl ether, difluoromethyl 2,2,3, 3-tetrafluoropropyl ether, fluoromethyl-1, 1,1,3,3, 3-hexafluoroisopropyl ether.
6. The electrolyte as claimed in any one of claims 1 to 5, wherein the solvent is at least one selected from the group consisting of 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, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether.
7. The electrolyte of any one of claims 1-6, wherein the molar concentration of the lithium salt in the electrolyte is 0.5-6.0 mol/L; the mass fraction of the anion receptor additive is 0.1-5.0%, and the mass fraction of the diluent is 20-80%.
8. Use of the electrolyte according to any one of claims 1 to 7 in a lithium metal battery with metallic lithium as the negative electrode.
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