CN112864459A - Electrolyte, preparation method thereof and secondary lithium metal battery - Google Patents

Electrolyte, preparation method thereof and secondary lithium metal battery Download PDF

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CN112864459A
CN112864459A CN201911193272.7A CN201911193272A CN112864459A CN 112864459 A CN112864459 A CN 112864459A CN 201911193272 A CN201911193272 A CN 201911193272A CN 112864459 A CN112864459 A CN 112864459A
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lithium
electrolyte
lithium metal
battery
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CN112864459B (en
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党岱
付祥祥
吴传德
曾燃杰
安璐
陈超
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Guangdong University of Technology
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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
    • 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
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract

The invention belongs to the technical field of secondary lithium metal batteries, and particularly relates to an electrolyte, a preparation method of the electrolyte and a secondary lithium metal battery. The invention provides an electrolyte suitable for a secondary lithium metal battery, 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 the group consisting of lithium perchlorate, hypochlorous acid, chlorous acid, and chloric acid. The additive in the electrolyte can react with the electrolyte at the initial cycle stage of the secondary lithium metal battery to form a stable, uniform and conductive solid electrolyte interface layer containing inorganic salt LiCl on the surface of the lithium metal cathode ex-situ, so that the growth of lithium dendrites can be inhibited in the charging and discharging processes, and the safety of the lithium metal secondary battery is effectively improved.

Description

Electrolyte, preparation method thereof and secondary lithium metal battery
Technical Field
The invention belongs to the technical field of secondary lithium metal batteries, and particularly relates to an electrolyte, a preparation method of the electrolyte and a secondary lithium metal battery.
Background
Because the practical application requirements of energy storage equipment are increasing day by day, the traditional lithium ion battery can not meet the practical requirements, and lithium metal has ultrahigh theoretical specific capacity (3860mAh/g), lower oxidation-reduction potential (-3.04V, relative to a standard hydrogen electrode) and lowest mass density (0.534 g/cm)3) Considered as an ideal anode material. However, the highly active lithium metal can react with most of the salts in the aqueous electrolyte and the non-aqueous electrolyte, consuming too much electrolyte and lithium metal, and thus making the coulombic efficiency during the charge-discharge cycle insufficient. Meanwhile, in the process of charge and discharge circulation, lithium metal is repeatedly electroplated/stripped to easily form metal lithium dendrites, and the metal lithium dendrites can pierce through the diaphragm to connect the positive electrode and the negative electrode, so that the battery generates internal short circuit, thermal runaway is caused, and a series of safety problems are caused.
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.
In order to solve the problem of dendritic crystal growth of lithium metal, researchers at home and abroad have already made much work. For example, when Shen et al directly grows porous carbon nanotubes on copper foil, unlike any lithium nucleation on conventional copper foil, where high concentration of lithium ions is concentrated at the tips of lithium particles, accelerating the growth of lithium dendrites, and finally forming fatal lithium dendrites, deposited lithium metal tends to nucleate uniformly on the surface of CNTs due to the high specific surface area and one-dimensional characteristics of carbon nanotubes, effectively suppressing dendrite formation (Direct growth of 3D host on Cu foil for stable lithium metal anode, Energy Storage materials.2018,13, 323-. By constructing a submicron skeleton three-dimensional current collector with a high-electrical activity surface, the Guo Yu-Guo team realizes that lithium fully fills the pores of the current collector on a submicron copper skeleton, so that the lithium is uniformly deposited, and lithium dendrites are effectively inhibited (integrating lithium into 3D current collectors with a submicron crystal particles long-life metals, nat. Commun.2015,6,8058). In addition, the Tao Xin-Yong group used bamboo-derived three-dimensional hierarchical porous carbon decorated with zinc oxide quantum dots as a lithium-philic scaffold for dendrite-free lithium metal anodes. The carbon support is stable to severe volume change in the circulation process, can effectively reduce local current density, and lithium-philic ZnO quantum dots of the carbon can be used for inducing lithium deposition, so that acceptable volume expansion is realized, overpotential is greatly reduced, and dendritic crystal growth is effectively inhibited (3D lithium metal embedded with lithium metal lithium for stable lithium metal batteries, Nano energy.2017,37, 177-186). The research results can provide innovative insight for the dendrite growth problem of the lithium negative electrode, but the operation process is complicated, and the industrialization is not facilitated.
Disclosure of Invention
In view of the above, the invention provides an electrolyte, a preparation method thereof and a secondary lithium metal battery, which are used for solving the problems that the lithium metal battery can cause the growth of metal lithium dendrites and the existing method has a complicated process.
The specific technical scheme of the invention is as follows:
an electrolyte suitable 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 lithium perchlorate (LiClO)4) Hypochlorous acid (HClO), chlorous acid (HClO)2) And chloric acid (HClO)3) One or more of (a).
The electrolyte can form a stable solid electrolyte interface layer 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, and effectively improves the safety of the lithium metal secondary battery.
Preferably, the mass percentage of the additive in the electrolyte is 0.1-10%, and more preferably 1-10%.
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 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 0.1M to 5M, more preferably 1M to 5M.
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 suitable 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 one or more selected from the group consisting of lithium perchlorate, hypochlorous acid, chlorous acid, and chloric acid. The additive in the electrolyte can react with the electrolyte at the initial cycle stage of the secondary lithium metal battery to form a stable, uniform and conductive solid electrolyte interface layer containing inorganic salt LiCl on the surface of the lithium metal cathode ex-situ, so that the growth of lithium dendrites can be inhibited in the charging and discharging processes, and the safety of the lithium metal secondary battery is effectively improved. 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 stable solid electrolyte layer containing inorganic salt on the surface of the metal lithium cathode, can inhibit dendritic crystal growth in the reciprocating deposition process, and greatly improves 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 after charge-discharge cycling of a Li | Li battery of example 4;
FIG. 2 is an SEM image of the lithium metal surface of a comparative example 4Li | | | Li battery after charge-discharge cycling;
fig. 3 is a charge and discharge voltage/time graph of Li | | | Li batteries of example 4 and comparative example 4;
fig. 4 is a charge-discharge first-turn capacity-voltage diagram of Li | | | Cu batteries of example 4 and comparative example 4;
fig. 5 is a charge and discharge graph of Li | | | Cu batteries of example 4 and comparative example 4.
Detailed Description
The invention provides an electrolyte, a preparation method thereof and a secondary lithium metal battery, which are used for solving the problems that the 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
Will purchase LiBF4Preserving under the protection of high-purity argon atmosphere for later use;
storing the commercial HClO under the protection of 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 3: 1 proportion of the mixtureMixing to obtain mixed organic solvent, dissolving lithium salt LiBF into the mixed organic solvent4Prepared into LiBF with lithium salt concentration of 5M4V (MEC + MPC) lithium salt solution;
dissolving appropriate amount of commercially available HClO in the prepared LiBF4/(MEC + MPC) lithium salt solution and thoroughly stirred to homogeneity to give 5M LiBF containing 10 wt% HClO additive4/(MEC + MPC) electrolyte.
(2) Assembly of battery
1) The metal lithium sheet is used as the anode and cathode material, the PP film is used as the diaphragm, and the LiBF prepared in the step (1) of the embodiment4And (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 LiBF prepared in step (1) of this example was applied to a copper foil as the positive electrode material, a lithium metal plate as the negative electrode material, and a PP film as the separator4And (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 LiBF4And storing the LiTFSI in a high-purity argon atmosphere for later use;
will purchase HClO2Preserving under the protection of high-purity argon atmosphere for later use;
under the protection of a high-purity argon (purity 99.999%), PC and DEC are mixed according to a volume ratio of 1: 2 to obtain a mixed organic solvent, and dissolving lithium salt LiBF into the mixed organic solvent4And LiTFSI, fully stirred to prepare (LiBF) with the lithium salt concentration of 3M4+ LiTFSI)/(PC + DEC) lithium salt solution.
Taking a proper amount of commercially available HClO2(LiBF) soluble in the above-mentioned compound4+ LiTFSI)/(PC + DEC) lithium salt solution and stirring well to obtain solution containing 5 wt% HClO2Of 3M of the additive (LiBF)4+ LiTFSI)/(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 LiBF is obtained in the step (1) of the present example4+ LiTFSI)/(PC + DEC) electrolyte isAnd assembling the electrolyte under the protection of a high-purity argon atmosphere to obtain the Li battery.
2) Copper foil is used as a positive electrode material, a metal lithium sheet is used as a negative electrode material, a PP/PE film is used as a diaphragm, and the LiBF is performed in the step (1) of the embodiment4And assembling the electrolyte of + LiTFSI)/(PC + DEC) as an electrolyte under the protection of high-purity argon to obtain the Li | | | Cu battery.
Example 3
(1) Preparation of the electrolyte
Will purchase LiPF6Preserving under the protection of high-purity argon atmosphere for later use;
will purchase HClO3Preserving under the protection of high-purity argon atmosphere for later use;
under the protection of a high-purity argon (purity 99.999%), PC and DEC are mixed according to a volume ratio of 1: 1 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 4M6V (PC + DEC) lithium salt solution.
Taking a proper amount of commercially available HClO3Dissolved in LiPF prepared as described above6/(PC + DEC) lithium salt solution, and thoroughly stirring to obtain a solution containing 3 wt% HClO3Additive 4M LiPF6/(PC + DEC) electrolyte.
(2) Assembly of battery
1) The LiPF prepared in the step (1) of this example is prepared by using a metal lithium plate as a positive electrode material and a negative electrode material, using a PP/PE/PP film as a diaphragm6And (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 LiPF prepared in the step (1) of this embodiment is prepared by using a copper foil as a positive electrode material, a metal lithium sheet as a negative electrode material, and a PP/PE/PP film as a diaphragm6And (v) taking the (PC + DEC) electrolyte as an electrolyte, and assembling under the protection of a high-purity argon atmosphere to obtain the Li | Cu battery.
Example 4
(1) Preparation of the electrolyte
Storing the commercial LiTFSI under the protection of high-purity argon atmosphere for later use;
commercial LiClO4Storing under the protection of 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 commercially available LiClO4Dissolving the solution in the lithium salt LiTFSI/(DOL + DME) solution prepared above, and fully and uniformly stirring to obtain the solution containing 1 wt% LiClO4Additive 1M LiTFSI/(DOL + DME) electrolyte.
(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 LiBF containing no additive in step (1) of this example4V (MEC + MPC) solution.
Comparative example 2
Comparative examples Li | | Li batteries and Li | | | Cu batteries were prepared as in example 2, but the electrolyte used in example 2 was the electrolyte described in step (1) of this example without additives (LiBF)4+ LiTFSI)/(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 used in example 3 was LiPF without additives as described in step (1) of this example6V (PC + DEC) solution.
Comparative example 4
The comparative examples Li | | Li battery and Li | | | Cu battery were prepared as in example 4, but the electrolyte solution used in example 4 was the additive-free LiTFSI/(DOL + DME) solution described in step (1) of this example.
Example 5
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 2mAh/cm2Deposition capacity of 1mA/cm2The charge-discharge cycle test was performed on the Li | Li batteries of example 1 and comparative example 1; at 1mAh/cm2Deposition capacity of 0.5mA/cm2Current density of (1), charge voltage of 1V charge-discharge cycle tests were performed on the Li | | | Cu batteries of example 1 and comparative example 1.
2) At 3mAh/cm2Deposition capacity of 1mA/cm2The charge-discharge cycle test was performed on the Li | Li batteries of example 2 and comparative example 2; at 1mAh/cm2Deposition capacity of 1mA/cm2Current density of (1V), charge voltage charge-discharge cycle test was performed on the Li | | | Cu batteries of example 2 and comparative example 2.
3) At 1mAh/cm2Deposition capacity of 3mA/cm2The charge-discharge cycle test was performed on the Li | Li batteries of example 3 and comparative example 3; at 2mAh/cm2Deposition capacity of 1mA/cm2Current density of (1V), charge voltage charge-discharge cycle test was performed on the Li | | | Cu batteries of example 3 and comparative example 3.
4) At 1mAh/cm2Deposition capacity of 1mA/cm2Current density of example 4 and comparative example 4Li | | | Li batteries were subjected to charge-discharge cycle testing; at 0.5mAh/cm2Deposition capacity of 0.5mA/cm2Current density of (1V), charge voltage charge-discharge cycle test was performed on the Li | | | Cu batteries of example 4 and comparative example 4.
Referring to table 1 and fig. 1 to 4, table 1 shows the coulombic efficiency after 50 cycles of the Li | | | Cu batteries of examples 1 to 4 and comparative examples 1 to 4. FIG. 1 is an SEM image of the lithium metal surface after charge-discharge cycling of a Li | Li battery of example 4; FIG. 2 is an SEM image of the lithium metal surface of a comparative example 4Li | | | Li battery after charge-discharge cycling; fig. 3 is a charge and discharge voltage/time graph of Li | | | Li batteries of example 4 and comparative example 4; fig. 4 is a charge-discharge first-turn capacity-voltage diagram of Li | | | Cu batteries of example 4 and comparative example 4; fig. 5 is a charge and discharge graph of Li | | | Cu batteries of example 4 and comparative example 4.
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 2mAh/cm2Under the condition, hysteresis voltage exceeding 450mV appears already at the initial stage of charge-discharge cycle, the hysteresis voltage is obviously increased after 100 hours of cycle, the battery which circulates for 100 circles is disassembled, and after the battery is repeatedly washed by electrolyte, a large amount of lithium dendrites appear on the surface of the metal lithium without the additive. Comparative example 1Li | | Cu cell at a current density of 0.5mA/cm2The deposition capacity is 1mAh/cm2Under the condition, the coulombic efficiency of the lithium cathode is reduced irregularly and unstably after 50 cycles, and the coulombic efficiency of the Li & ltI & gt Cu battery modified by adding the HClO additive is 75% (shown in table 1) after 50 cycles, so that the electrochemical performance of the lithium cathode is obviously improved.
Example 2Li cell at a current density of 1mA/cm2The deposition capacity was 3mAh/cm2Under the condition that the hysteresis voltage is about 230mV after the charging and discharging cycle is 200 hours, 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 5 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 80 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 3mA/cm2The deposition capacity is 1mAh/cm2Under the condition, the charge-discharge curve is stable, the charge-discharge cycle can reach 250h, the battery circulating for 100 circles is disassembled, and after the battery is repeatedly washed by electrolyte, HClO is added3The metallic lithium surface of the additive has few lithium dendrites, indicating that the additive is effective in suppressing the growth of dendrites. Example 3Li | Cu cell at a current density of 1mA/cm2The deposition capacity is 2mAh/cm2Under the condition, the coulombic efficiency of the lithium secondary battery is 72 percent after 50 cycles (Table 1), and the electrolyte added with the additive is beneficial to improving the electrochemical performance of the lithium secondary battery。
Example 4Li cell at a current density of 1mA/cm2The deposition capacity is 1mAh/cm2Under the condition, the charge-discharge curve is stable, the charge-discharge cycle can reach 500h, the hysteresis voltage is about 19mV (figure 3), and a voltage-capacity diagram of a first circle (figure 4) shows that the hysteresis voltage is obviously lower than that of a Li battery of a comparative example 4. After the battery was disassembled and repeatedly washed with the electrolyte for 100 cycles, the results of fig. 1 and 2 showed that the surface of the lithium metal of example 4 was very flat and no lithium dendrites appeared, indicating LiClO4The addition of the electrolyte effectively suppresses the growth of dendrites. Example 4Li | | Cu cell at a current density of 0.5mA/cm2The deposition capacity was 0.5mAh/cm2Under these conditions, the coulombic efficiency remained 94% after 100 cycles (FIG. 5), indicating that LiClO was added4Lithium batteries with additive electrolytes exhibit very 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 cycling for examples 1-4 and comparative examples 1-4 Li | | Cu batteries
Figure BDA0002294106550000091
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. An electrolyte suitable for use in 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 one or more selected from the group consisting of lithium perchlorate, hypochlorous acid, chlorous acid, and chloric acid.
2. The electrolyte of claim 1, wherein the additive is present in the electrolyte in an amount of 0.1-10% by weight.
3. The electrolyte of 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 electrolyte of claim 1, wherein the lithium salt is selected from one or more of lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium hexafluorophosphate, lithium bistrifluoromethanesulfonylimide, lithium trifluoromethanesulfonate, and lithium hexafluoroaluminate.
5. The electrolyte of claim 4, wherein the concentration of the lithium salt in the electrolyte is between 0.1M and 5M.
6. The method for preparing the electrolyte of 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. A secondary lithium metal battery comprising the electrolyte of any one of claims 1 to 5.
8. The secondary lithium metal battery of claim 7, wherein the negative electrode material of the secondary lithium metal battery is lithium metal.
9. The secondary lithium metal battery of claim 8, wherein 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.
10. The secondary lithium metal battery according to claim 7, 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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Citations (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SE7503540L (en) * 1969-02-21 1975-03-26 Unigate Ltd
JPS56116275A (en) * 1980-02-18 1981-09-11 Hitachi Maxell Ltd Nonaqueous-electrolyte battery
JPH06310173A (en) * 1993-04-20 1994-11-04 Matsushita Electric Ind Co Ltd Electrochemical device and secondary battery
JP2002280064A (en) * 2001-03-16 2002-09-27 Sony Corp Electrolyte and battery
US20030124433A1 (en) * 2001-10-31 2003-07-03 Samsung Sdi Co., Ltd. Organic electrolytic solution and lithium secondary battery employing the same
US6884546B1 (en) * 1999-09-20 2005-04-26 Sony Corporation Secondary battery
JP2006222064A (en) * 2005-01-14 2006-08-24 Matsushita Electric Ind Co Ltd Nonaqueous electrolyte for lithium secondary battery, and lithium secondary battery using the same
US20060216612A1 (en) * 2005-01-11 2006-09-28 Krishnakumar Jambunathan Electrolytes, cells and methods of forming passivation layers
US20130130128A1 (en) * 2010-08-05 2013-05-23 Wako Pure Chemical Industries, Ltd. Nonaqueous electrolyte solution and nonaqueous electrolyte battery using same
US20130143129A1 (en) * 2010-08-05 2013-06-06 Wako Pure Chemical Industries, Ltd. Nonaqueous electrolyte solution, method for producing same, and nonaqueous electrolyte battery using the electrolyte solution
KR20130076679A (en) * 2011-12-28 2013-07-08 국립대학법인 울산과학기술대학교 산학협력단 Method for preparing positive active material for rechargeable lithium battery, positive active material prepared using same, and rechargeable lithium battery including same
US20130295449A1 (en) * 2011-01-21 2013-11-07 Takayuki Kobatake Ionic compound and process for production thereof, and electrolytic solution and electrical storage device each utilizing the ionic compound
CN104157908A (en) * 2014-08-20 2014-11-19 厦门大学 Lithium salt electrolyte, preparation method and application thereof
KR20160050222A (en) * 2014-10-29 2016-05-11 주식회사 엘지화학 Electrolyte solution for lithium metal battery and lithium metal battery comprising the same
US20160359196A1 (en) * 2015-06-08 2016-12-08 Sk Innovation Co., Ltd. Electrolyte for Lithium Secondary Battery and Lithium Secondary Battery Containing the Same
CN106450460A (en) * 2016-12-09 2017-02-22 中国科学院物理研究所 Lithium ion battery electrolyte additive, electrolyte thereof, preparation method and battery
CN107275671A (en) * 2017-07-07 2017-10-20 东莞市航盛新能源材料有限公司 A kind of electrolyte and preparation method and lithium battery for suppressing Li dendrite
US20180191033A1 (en) * 2012-11-02 2018-07-05 Natron Energy, Inc. Electrolyte additives for electrochemical devices
CN108376795A (en) * 2018-04-04 2018-08-07 天津大学 A kind of no dendrite, powerful aluminium ion battery
CN109509912A (en) * 2017-09-15 2019-03-22 浙江省化工研究院有限公司 A method of inhibiting metal lithium dendrite growth
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

Patent Citations (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SE7503540L (en) * 1969-02-21 1975-03-26 Unigate Ltd
JPS56116275A (en) * 1980-02-18 1981-09-11 Hitachi Maxell Ltd Nonaqueous-electrolyte battery
JPH06310173A (en) * 1993-04-20 1994-11-04 Matsushita Electric Ind Co Ltd Electrochemical device and secondary battery
US6884546B1 (en) * 1999-09-20 2005-04-26 Sony Corporation Secondary battery
JP2002280064A (en) * 2001-03-16 2002-09-27 Sony Corp Electrolyte and battery
US20030124433A1 (en) * 2001-10-31 2003-07-03 Samsung Sdi Co., Ltd. Organic electrolytic solution and lithium secondary battery employing the same
US20060216612A1 (en) * 2005-01-11 2006-09-28 Krishnakumar Jambunathan Electrolytes, cells and methods of forming passivation layers
JP2006222064A (en) * 2005-01-14 2006-08-24 Matsushita Electric Ind Co Ltd Nonaqueous electrolyte for lithium secondary battery, and lithium secondary battery using the same
US20130130128A1 (en) * 2010-08-05 2013-05-23 Wako Pure Chemical Industries, Ltd. Nonaqueous electrolyte solution and nonaqueous electrolyte battery using same
US20130143129A1 (en) * 2010-08-05 2013-06-06 Wako Pure Chemical Industries, Ltd. Nonaqueous electrolyte solution, method for producing same, and nonaqueous electrolyte battery using the electrolyte solution
US20130295449A1 (en) * 2011-01-21 2013-11-07 Takayuki Kobatake Ionic compound and process for production thereof, and electrolytic solution and electrical storage device each utilizing the ionic compound
KR20130076679A (en) * 2011-12-28 2013-07-08 국립대학법인 울산과학기술대학교 산학협력단 Method for preparing positive active material for rechargeable lithium battery, positive active material prepared using same, and rechargeable lithium battery including same
US20180191033A1 (en) * 2012-11-02 2018-07-05 Natron Energy, Inc. Electrolyte additives for electrochemical devices
CN104157908A (en) * 2014-08-20 2014-11-19 厦门大学 Lithium salt electrolyte, preparation method and application thereof
KR20160050222A (en) * 2014-10-29 2016-05-11 주식회사 엘지화학 Electrolyte solution for lithium metal battery and lithium metal battery comprising the same
US20160359196A1 (en) * 2015-06-08 2016-12-08 Sk Innovation Co., Ltd. Electrolyte for Lithium Secondary Battery and Lithium Secondary Battery Containing the Same
CN106450460A (en) * 2016-12-09 2017-02-22 中国科学院物理研究所 Lithium ion battery electrolyte additive, electrolyte thereof, preparation method and battery
CN107275671A (en) * 2017-07-07 2017-10-20 东莞市航盛新能源材料有限公司 A kind of electrolyte and preparation method and lithium battery for suppressing Li dendrite
CN109509912A (en) * 2017-09-15 2019-03-22 浙江省化工研究院有限公司 A method of inhibiting metal lithium dendrite growth
CN108376795A (en) * 2018-04-04 2018-08-07 天津大学 A kind of no dendrite, powerful aluminium ion battery
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

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
XIANGXIANG FU等: "Sulfuryl chloride as a functional additive towards dendrite-free and long-life Li metal anodes", 《JOURNAL OF MATERIALS CHEMISTRY A》 *
YAN OUYANG等: "Single Additive with Dual Functional-Ions for Stabilizing Lithium Anodes", 《ACS APPLIED MATERIALS & INTERFACES》 *
北京机床研究所十室: "电解液和电解液系统与工艺的关系", 《电加工与模具》 *
唐致远等: "锂离子电池安全性的研究", 《电池》 *
王成云等: "酸和锂盐掺杂对锂-聚苯胺二次电池的影响", 《电池》 *
程新兵等: "金属锂枝晶生长机制及抑制方法", 《化学进展》 *

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