CN110854436B - Secondary lithium metal battery electrolyte and preparation method thereof - Google Patents
Secondary lithium metal battery electrolyte and preparation method thereof Download PDFInfo
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- CN110854436B CN110854436B CN201911193284.XA CN201911193284A CN110854436B CN 110854436 B CN110854436 B CN 110854436B CN 201911193284 A CN201911193284 A CN 201911193284A CN 110854436 B CN110854436 B CN 110854436B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to the technical field of secondary lithium metal batteries, and particularly relates to a secondary lithium metal battery electrolyte and a preparation method thereof. The invention provides a secondary lithium metal battery electrolyte, which comprises a lithium salt, an organic solvent and an additive; the lithium salt is dissolved in the organic solvent, and the additive is one or more selected from 5-chlorothiophene-2-carboxylic acid, 2-thiophenecarboxylic acid and 2, 5-thiophenedicarboxylic acid. The electrolyte is applied to the secondary lithium metal battery, the additive in the electrolyte can react with lithium metal at the initial cycle stage of the secondary lithium metal battery to generate LiCl, and a layer of solid electrolyte interface film with high mechanical strength, uniformity and stability is formed on the surface of a lithium metal cathode ex-situ, the growth of lithium dendrite can be inhibited in the charge-discharge process, the electrochemical performance of the lithium metal secondary battery is obviously improved, and the electrolyte has good application prospect.
Description
Technical Field
The invention belongs to the technical field of secondary lithium metal batteries, and particularly relates to a secondary lithium metal battery electrolyte and a preparation method thereof.
Background
The practical energy density of the conventional lithium ion battery cannot meet the practical production requirement, and the metal lithium is considered as the most potential negative electrode material of the next generation lithium battery due to the high theoretical capacity and the low electrochemical potential. However, in the repeated lithium stripping/deposition process of the metallic lithium negative electrode, dendrite growth caused by non-uniform lithium deposition on the surface of the electrode causes disadvantages such as short circuit of the battery, safety hazard and shortened cycle life, so that the application of the metallic lithium negative electrode is seriously hindered.
Therefore, in order to effectively advance the practical application of lithium metal batteries, a method for effectively inhibiting the growth of metallic lithium dendrites must be found.
To solve the problem of dendritic crystal growth of lithium metal, researchers at home and abroad have already madeA lot of modification work is carried out. The subject group of the professor Zhou Yongning university of Compound Dan designs a foamed nickel (CONF) skeleton decorated by CoO nano fibers and uses the skeleton as a three-dimensional conductive frame matrix loaded with metallic lithium. A composite lithium negative electrode (CONF-Li) capable of suppressing the growth of lithium dendrites was prepared by a lithium hot-melt method. CoO nanofibers uniformly distributed on a foamed Nickel skeleton can effectively improve the Lithium affinity of foamed Nickel and reduce the local current density on the surface of an electrode, thereby obtaining a mild and uniform Lithium deposition/stripping behavior, and effectively inhibiting the formation of Lithium dendrites (CoO Nanofiber depleted Nickel Foams as Lithium dentrite compressing Host metals, Energy Storage materials.2018,14, 335-) 344). The Wanhaiyan topic group of the university of Zhongnan adopts a novel plasma strengthening strategy under nitrogen atmosphere, constructs a nitrogen-doped three-dimensional porous copper oxide nanosheet growing on a copper-based current collector, and deeply discusses a regulation mechanism of nitrogen plasma strengthening. The plasma enhanced nitrogen doping strategy can provide enough active sites for lithium nucleation and improve the deposition stability of the metallic lithium on the copper-based current collector. Meanwhile, the strategy improves the conductivity of the material, reduces the over potential of Lithium nucleation, and further induces the uniform deposition of metallic Lithium (Plasma-stranded Lithium hydroxide permeability of coater Oxide nano-coated Cu Foil for Stable Lithium Metal Anode, adv. sci.2019,6,1901433). In addition, the university of southeast university Chenjian and the professor of Sun Zhengzheng utilize ion nitriding technology to design Ni3The N modified nickel foam (PNNF) is used as a 3D current collector of the lithium negative electrode. Generating a layer of Ni on the surface of the foamed nickel by plasma in nitrogen atmosphere3N, Ni after electrodeposition of lithium metal3Conversion of N to Li3N, due to the high ionic conductivity and excellent Lithium affinity of the two, Lithium Metal can be uniformly deposited and extracted on the surface of the current collector, and the generation of dendrite is effectively inhibited (Lithium Metallic nitride Modified Nickel Foam by Plasma for Stable Lithium Metal Anode, Energy Storage Materials,2019, DOI: 10.1016/j.ensm.2019.04.005). Although the research results provide a new idea for solving the problem of dendritic crystal growth of the lithium metal, the research results provide a new idea for solving the problem of dendritic crystal growth of the lithium metalThe operation process is complicated and not beneficial to industrialization.
Disclosure of Invention
In view of the above, the invention provides a secondary lithium metal battery electrolyte and a preparation method thereof, which are used for solving the problems that a lithium metal battery can generate metal lithium dendrite growth and the operation process of the existing method is complicated.
The specific technical scheme of the invention is as follows:
a secondary lithium metal battery electrolyte comprising a lithium salt, an organic solvent, and an additive;
the lithium salt is dissolved in the organic solvent, and the additive is selected from 5-chlorothiophene-2-carboxylic acid (C)5H3ClO2S), 2-Thiophenecarboxylic acid (C)5H4O2S) and 2, 5-thiophenedicarboxylic acid (C)6H4O4S) is selected.
The electrolyte can form a layer of stable solid electrolyte interface film containing inorganic salt on the surface of the lithium metal negative electrode, can inhibit the growth of lithium dendrite in the charging and discharging process, obviously improves the electrochemical performance of the lithium metal secondary battery, and effectively improves the safety of the lithium metal secondary battery.
Preferably, the mass percentage of the additive in the electrolyte is 1-5%.
Preferably, the organic solvent is selected from one or more of Ethylene Carbonate (EC), Propylene Carbonate (PC), Vinylene Carbonate (VC), dimethyl carbonate (DMC), ethyl methyl carbonate (MEC), propyl methyl carbonate (MPC), diethyl carbonate (DEC), 1, 3-Dioxolane (DOL), ethylene glycol dimethyl ether (DME), and diethylene glycol Dimethyl Ether (DEDM).
Preferably, the lithium salt is selected from lithium perchlorate (LiClO)4) Lithium tetrafluoroborate (LiBF)4) Lithium hexafluoroarsenate (LiAsO)6) Lithium hexafluorophosphate (LiPF)6) Lithium bistrifluoromethanesulfonylimide (LiTFSI), lithium trifluoromethanesulfonate (LiCF)3SO3) And lithium hexafluoroaluminate (Li)3AlF6) One or more of (a).
Preferably, the concentration of the lithium salt in the electrolyte is 1M to 10M.
The invention also provides a preparation method of the electrolyte solution, which comprises the following steps:
under the protection of inert gas and/or nitrogen atmosphere, preferably under the protection of argon, dissolving lithium salt in an organic solvent to obtain a lithium salt solution, adding an additive into the lithium salt solution, preferably fully and uniformly stirring to obtain the electrolyte.
The invention does not need to adopt expensive additives and complex preparation devices when preparing the electrolyte, and has low cost.
The invention also provides a secondary lithium metal battery which comprises the electrolyte solution in the technical scheme.
The secondary lithium metal battery further includes a positive electrode, a spring, a gasket, a separator, and a negative electrode.
Preferably, the negative electrode material of the secondary lithium metal battery is lithium metal.
Preferably, the positive electrode material of the secondary lithium metal battery is selected from LiFePO4、LiV3(PO4)3、LixCoO2、LiyMnO2、mLiMnO2·(1-m)LiAO2、LiNibCoaMn1-aO2、LiNi0.5Mn1.5O4、Li2TiO3、FeF3·jH2One or more of O, S, Se, Li, Cu, metal oxide and metal sulfide, wherein x is more than or equal to 0.4 and less than or equal to 1, y is more than or equal to 0.4 and less than or equal to 1, and 0<m<1, A is selected from one of Ni, Co, Mn, Al and Fe, b is more than or equal to 0.5 and less than or equal to 1, a is more than or equal to 0 and less than or equal to 0.2, and j is more than or equal to 0 and less than or equal to 0.5.
Preferably, the separator of the secondary lithium metal battery is selected from a GF (glass fiber) separator, a PE (polyethylene) separator, a PP (polypropylene) separator, a PP/PE separator, or a PP/PE/PP separator.
In summary, the present invention provides an electrolyte for a secondary lithium metal battery, the electrolyte comprising a lithium salt, an organic solvent and an additive; the lithium salt is dissolved in the organic solvent, and the additive is selected from 5-chlorothiophene-2-carboxylic acid (C)5H3ClO2S)2-Thiophenecarboxylic acid (C)5H4O2S) and 2, 5-thiophenedicarboxylic acid (C)6H4O4S) is selected. The electrolyte is applied to the secondary lithium metal battery, the additive in the electrolyte can react with lithium metal to generate LiCl at the initial cycle stage of the secondary lithium metal battery, a layer of solid electrolyte interface film with high mechanical strength, uniformity and stability is formed on the surface of a lithium metal cathode ex-situ, the growth of lithium dendrite can be inhibited in the charge-discharge process, the electrochemical performance of the lithium metal secondary battery is obviously improved, the safety of the lithium metal secondary battery is effectively improved, and the electrolyte has good application prospect. The lithium metal battery adopts the electrolyte of the invention, does not need to additionally add a mechanical barrier layer or a three-dimensional structure material, has simple application, is close to the prior industrial production technology, is easy for large-scale production, and is suitable for the lithium metal secondary battery.
The electrolyte can inhibit the growth of the dendritic metal lithium crystal, realizes the inhibition on the corrosion of the lithium metal cathode to the maximum extent, and does not form the linear and dendritic metal lithium crystal on the lithium/electrolyte interface. In the circulation process of the secondary lithium metal battery, the electrolyte can form a layer of stable solid electrolyte interfacial film containing inorganic salt on the surface of the metal lithium cathode, and can inhibit dendritic crystal growth in the repeated lithium stripping/deposition process of the metal lithium cathode, thereby greatly improving the electrochemical performance of the secondary lithium metal battery and enhancing the safety of the secondary lithium metal battery.
The electrolyte does not need to add expensive electrolyte salt to increase the concentration of lithium ions, does not need to charge and discharge under specific current density, and does not need to add complex compounds or solvents to stabilize the negative electrode. When the electrolyte is adopted, a mechanical barrier layer or a three-dimensional structure electrode does not need to be additionally added, the application is simple, the electrolyte is close to the existing industrial production technology, the mass production is easy, the electrolyte is suitable for secondary lithium metal batteries, and the problems of poor cycle performance, low coulombic efficiency, poor safety and the like caused by the growth of dendritic crystals in the charge-discharge cycle process of the cathode of the existing secondary lithium metal battery can be solved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
FIG. 1 is an SEM image of the lithium metal surface of a comparative example 1Li | | | Li battery after charge-discharge cycling;
FIG. 2 is an SEM image of the lithium metal surface after charge-discharge cycling of a Li | Li battery of example 3;
fig. 3 is a charge and discharge voltage/time graph of Li | | | Li batteries of example 3 and comparative example 3;
fig. 4 is a charge and discharge graph of Li | | | Cu batteries of example 3 and comparative example 3;
fig. 5 is a graph of medium voltage/cycle cycles to discharge for example 3 and comparative example 3Li cells.
Detailed Description
The invention provides a secondary lithium metal battery electrolyte and a preparation method thereof, which are used for solving the problems that a lithium metal battery can generate metal lithium dendrite growth and the existing method has a more complicated process.
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. 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
(1) Preparation of the electrolyte
Commercial LiClO4Preserving under the protection of high-purity argon atmosphere for later use;
will purchase C5H4O2S, storing the product under the protection of a high-purity argon atmosphere for later use;
under the protection of a high-purity argon (purity 99.999%), adding MEC and MPC in a volume ratio of 2: 1 proportion to obtain a mixed organic solvent, and dissolving lithium salt LiCF into the mixed organic solvent3SO3LiClO was prepared at a lithium salt concentration of 1M4V (MEC + MPC) lithium salt solution;
taking a proper amount of commercial C5H4O2S is dissolved in the prepared LiClO4/(MEC + MPC) lithium salt solution, and thoroughly stirred to homogeneity to give a solution containing 1 wt% C5H4O21M LiClO of S additive4/(MEC + MPC) electrolyte.
(2) Assembly of battery
1) The LiClO prepared in the step (1) of this example was used as a separator with a lithium metal sheet as the positive and negative electrode material and a PP film as the separator4And (MEC + MPC) electrolyte is used as electrolyte and is assembled under the protection of high-purity argon atmosphere to obtain the Li battery.
2) The LiClO prepared in the step (1) of the present example was applied to a positive electrode material made of copper foil, a negative electrode material made of lithium metal sheet, and a separator made of PP film4And (MEC + MPC) electrolyte is used as electrolyte and is assembled in a high-purity argon atmosphere to obtain the Li | | Cu battery.
Example 2
(1) Preparation of the electrolyte
Will purchase LiPF6Preserving under the protection of high-purity argon atmosphere for later use;
will purchase C6H4O4S, storing the product under the protection of a high-purity argon atmosphere for later use;
under the protection of a high-purity argon (purity 99.999%) atmosphere, PC and DEC are mixed according to a volume ratio of 2: 3 proportion to obtain a mixed organic solvent, and dissolving lithium salt LiPF into the mixed organic solvent6Fully stirring to prepare LiPF with lithium salt concentration of 5M6V (PC + DEC) lithium salt solution.
Taking a proper amount of commercial C6H4O4S is dissolved in the prepared LiPF6/(PC + DEC) lithium salt solution, and thoroughly stirring to obtain a solution containing 3 wt% of C6H4O45M LiPF of S additive6/(PC + DEC) electrolyte.
(2) Assembly of battery
1) The lithium metal sheet is used as the anode and cathode material, the PP/PE film is used as the diaphragm, and the LiPF is adopted in the step (1) of the embodiment6And (v) taking the (PC + DEC) electrolyte as an electrolyte, and assembling under the protection of a high-purity argon atmosphere to obtain the Li battery.
2) The copper foil is used as a positive electrode material, the metal lithium sheet is used as a negative electrode material, the PP/PE film is used as a diaphragm, and the LiPF is adopted in the step (1) of the embodiment6And (v) (PC + DEC) electrolyte is used as electrolyte, and Li | Cu battery is obtained by assembling under the protection of high-purity argon.
Example 3
(1) Preparation of the electrolyte
Storing the commercial LiTFSI under the protection of high-purity argon atmosphere for later use;
will purchase C5H3ClO2S, storing the product under the protection of a high-purity argon atmosphere for later use;
under the protection of a high-purity argon (purity 99.999%), DOL and DME are mixed according to the volume ratio of 1: 1 proportion to obtain a mixed organic solvent, dissolving lithium salt LiTFSI in the mixed organic solvent, fully stirring to prepare a LiTFSI/(DOL + DME) lithium salt solution with the lithium salt concentration of 1M.
Taking a proper amount of commercial C5H3ClO2S is dissolved in the prepared LiTFSI/(DOL + DME) lithium salt solution and is fully and uniformly stirred to obtain the lithium salt solution containing 2 wt% of C5H3ClO21M LiTFSI/(DOL + DME) electrolyte of S additive.
(2) Assembly of battery
1) And (2) assembling the lithium metal sheet serving as a positive electrode material and a negative electrode material, the PE film serving as a diaphragm, and the LiTFSI/(DOL + DME) electrolyte prepared in the step (1) of the embodiment serving as an electrolyte under the protection of a high-purity argon atmosphere to obtain the Li battery.
2) And (2) assembling the Li | | | Cu battery under the protection of a high-purity argon atmosphere by using copper foil as a positive electrode material, a metal lithium sheet as a negative electrode material, a PE film as a diaphragm and the LiTFSI/(DOL + DME) electrolyte prepared in the step (1) of the embodiment as an electrolyte.
Comparative example 1
The comparative examples Li | | Li battery and Li | | | Cu battery were prepared as in example 1, but were different from example 1 in that: the electrolyte of comparative example 1 was LiClO containing no additive in step (1) of example 14V (MEC + MPC) solution.
Comparative example 2
The comparative examples Li | Li battery and Li | Cu batteryThe electrolyte of example 2 was prepared as in example 2, but the electrolyte of example 2 was LiPF without additives as described in step (1) of example 26V (PC + DEC) solution.
Comparative example 3
The comparative examples Li | | Li battery and Li | | | Cu battery were prepared as in example 3, but the electrolyte solution used in example 3 was the additive-free LiTFSI/(DOL + DME) solution described in step (1) of example 3.
Example 4
In this example, electrochemical performance tests were performed on the Li | | | Li battery and the Li | | | Cu battery prepared in the above examples and comparative examples under the following test conditions:
1) at 1mAh/cm2Deposition capacity of 1mA/cm2The current density of the lithium ion battery is tested on the charge-discharge cycle of the Li batteries of the examples 1-3 and the comparative examples 1-3;
2) at 1mAh/cm2Deposition capacity of 1mA/cm2The current density and the charging voltage of 1V were subjected to charge-discharge cycle tests on Li | | | Cu batteries of examples 1 to 3 and comparative examples 1 to 3.
Referring to table 1 and fig. 1 to 5, table 1 shows the coulombic efficiency after 50 cycles of the Li | | | Cu batteries of examples 1 to 3 and comparative examples 1 to 3. FIG. 1 is an SEM image of the lithium metal surface of a comparative example 1Li | | | Li battery after charge-discharge cycling; FIG. 2 is an SEM image of the lithium metal surface after charge-discharge cycling of a Li | Li battery of example 3; fig. 3 is a charge and discharge voltage/time graph of Li | | | Li batteries of example 3 and comparative example 3; fig. 4 is a charge and discharge graph of Li | | | Cu batteries of example 3 and comparative example 3; fig. 5 is a plot of medium voltage/cycle cycles to discharge for example 3 and comparative example 3Li Cu cells.
In the test results, the Li cell of comparative example 1, in which no additive was used, had a current density of 1mA/cm2The deposition capacity is 1mAh/cm2Under the conditions, a hysteresis voltage of over 1000mV occurs already at the beginning of the charge-discharge cycle, the hysteresis voltage increases significantly after 150h of the cycle, the cell is disassembled after 50 cycles of the cycle, and after repeated washing with electrolyte, a large amount of lithium dendrites appear on the surface of the lithium metal without additives (FIG. 1). Comparative example 1Li | Cu cell at a current density of 1mA/cm2The deposition capacity is 1mAh/cm2Under the condition of circulatingThe coulombic efficiency after 50 cycles showed an irregular and unstable decrease, while C was added5H4O2The coulombic efficiency of the Li | | | Cu battery modified by the S additive is 80% (shown in table 1) after 50 cycles, and the electrochemical performance of the lithium cathode is improved.
Example 2Li cell at a current density of 1mA/cm2The deposition capacity is 1mAh/cm2Under the condition that the hysteresis voltage is about 200mV after 250 hours of charge-discharge cycle, the battery which is cycled for 100 circles is disassembled, and after the battery is repeatedly washed by electrolyte, the surface of the metal lithium added with 3 wt% of the additive still keeps very flat and almost no lithium dendrite is formed. Example 2Li | | Cu cell at a current density of 1mA/cm2The deposition capacity is 1mAh/cm2Under the condition, the coulombic efficiency of the cell is 75 percent after 50 cycles of circulation (see table 1), which shows that the additive has a certain promotion effect on the improvement of the electrochemical performance of the cell.
Example 3Li cell at a current density of 1mA/cm2The deposition capacity is 1mAh/cm2Under the condition, the Li battery can stably circulate for 500h under the hysteresis voltage lower than 19mV (figure 3), and a discharge medium voltage-circulation circus number graph (figure 5) shows that in the circulation process, the discharge medium voltage of the Li Cu battery without the additive is obviously increased, and 2 wt% of C is added5H3ClO2The Li | Cu battery of S keeps stable discharging medium voltage. After the cell was disassembled and repeatedly washed with the electrolyte for 200 cycles, the results, referring to fig. 4, showed that the surface of the lithium metal of example 3 was very flat and no lithium dendrites appeared, indicating C5H3ClO2The addition of S to the electrolyte effectively suppresses the growth of dendrites. Example 3Li | Cu cell at a current density of 1mA/cm2The deposition capacity is 1mAh/cm2Under these conditions, the coulombic efficiency remained 96% after 100 cycles (FIG. 4), indicating the addition of C-containing solution5H3ClO2Lithium cells with S additive electrolyte show extremely stable cycling performance.
In summary, the electrolyte containing the additive provided by the invention realizes corrosion to the metallic lithium cathode to a great extent, and no linear and dendritic metallic lithium dendrites are formed at the lithium/electrolyte interface. The addition of the additive has an effect of improving the electrochemical performance of the lithium battery containing the additive electrolyte, the coulomb efficiency of the lithium battery is obviously increased, and the lithium battery shows stable cycle performance.
TABLE 1 coulombic efficiencies after 50 cycles of examples 1-3 and comparative examples 1-3 Li | | | Cu cells
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 (7)
1. A secondary lithium metal battery is characterized by comprising an electrolyte, a negative electrode material and a positive electrode material;
the electrolyte comprises a lithium salt, an organic solvent and an additive;
the lithium salt is dissolved in the organic solvent, and the additive is 5-chlorothiophene-2-formic acid;
the negative electrode material is lithium metal;
the anode material is selected from LiFePO4、LiV3(PO4)3、LixCoO2、LiyMnO2、mLiMnO2·(1-m)LiAO2、LiNibCoaMn1-aO2、LiNi0.5Mn1.5O4、Li2TiO3、FeF3·jH2One or more of O, S, Se, Li, Cu, metal oxide and metal sulfide, wherein x is more than or equal to 0.4 and less than or equal to 1, y is more than or equal to 0.4 and less than or equal to 1, and 0<m<1, A is selected from one of Ni, Co, Mn, Al and Fe, b is more than or equal to 0.5 and less than or equal to 1, a is more than or equal to 0 and less than or equal to 0.2, and j is more than or equal to 0 and less than or equal to 0.5.
2. The secondary lithium metal battery of claim 1, wherein the additive is present in the electrolyte in an amount of 1 to 5% by weight.
3. The secondary lithium metal battery according to claim 1, wherein the organic solvent is selected from one or more of ethylene carbonate, propylene carbonate, vinylene carbonate, dimethyl carbonate, ethyl methyl carbonate, propyl methyl carbonate, diethyl carbonate, 1, 3-dioxolane, ethylene glycol dimethyl ether, and diethylene glycol dimethyl ether.
4. The secondary lithium metal battery of claim 1, wherein the lithium salt is selected from one or more of lithium perchlorate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium hexafluorophosphate, lithium bistrifluoromethanesulfonylimide, lithium trifluoromethanesulfonate, and lithium hexafluoroaluminate.
5. The secondary lithium metal battery according to claim 4, wherein a concentration of the lithium salt in the electrolyte is 1M to 10M.
6. The method for preparing the electrolyte of the secondary lithium metal battery according to any one of claims 1 to 5, comprising the steps of:
under the protection of inert gas and/or nitrogen atmosphere, dissolving lithium salt in an organic solvent to obtain a lithium salt solution, and adding an additive into the lithium salt solution to obtain the electrolyte.
7. The secondary lithium metal battery according to claim 1, wherein the separator of the secondary lithium metal battery is selected from a GF separator, a PE separator, a PP/PE separator, or a PP/PE/PP separator.
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| CN110176622A (en) * | 2019-05-15 | 2019-08-27 | 华南理工大学 | A kind of lithium metal secondary battery electrolyte and the preparation method and application thereof |
| CN110416615A (en) * | 2019-05-15 | 2019-11-05 | 华南理工大学 | A kind of electrolyte and lithium battery inhibiting lithium dendrite growth |
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