CN115732783A - Composite metal lithium cathode with artificial solid electrolyte interface layer and preparation method and application thereof - Google Patents
Composite metal lithium cathode with artificial solid electrolyte interface layer and preparation method and application thereof Download PDFInfo
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- CN115732783A CN115732783A CN202211557484.0A CN202211557484A CN115732783A CN 115732783 A CN115732783 A CN 115732783A CN 202211557484 A CN202211557484 A CN 202211557484A CN 115732783 A CN115732783 A CN 115732783A
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Abstract
The invention discloses a composite metal lithium cathode with an artificial solid electrolyte interface layer, and a preparation method and application thereof, and relates to the technical field of metal lithium batteries. The method comprises the following steps: and carrying out plasma reaction on the halogenated organic liquid and the metallic lithium negative electrode by adopting a plasma enhanced chemical vapor deposition method in an inert gas atmosphere to prepare the composite metallic lithium negative electrode with the artificial solid electrolyte interface layer. The artificial solid electrolyte interface layer prepared by the invention has the characteristics of high mechanical strength and high ionic conductivity, and the prepared composite metal lithium cathode can improve the deposition behavior of metal lithium in the charging and discharging processes and improve the stability and cycle performance of the metal lithium battery. The invention solves the problem of dendritic crystal growth of the negative electrode of the metal lithium battery in the prior art.
Description
Technical Field
The invention relates to the technical field of metal lithium batteries, in particular to a composite metal lithium cathode with an artificial solid electrolyte interface layer, and a preparation method and application thereof.
Background
Since the first introduction of commercial lithium ion batteries, theyThe large number of applications in portable electronic devices and clean energy vehicles has profoundly affected our lives, however, such batteries are unlikely to meet the ever-increasing energy density requirements due to the inherent limitations of the theoretical specific capacity of graphite-based cathodes. Therefore, there is an urgent need to develop a next-generation high energy density energy storage device, since metallic lithium has an ultra-high theoretical capacity (3860 mAh/g or 2061 mAh/cm) 3 ) And a very low electrochemical potential (-3.04 vs. standard hydrogen electrode), lithium metal is recognized as the most promising negative electrode material in high performance lithium batteries. In addition, as the research on lithium-sulfur batteries and lithium-air batteries has been advanced, the advantages of the lithium metal-based batteries in terms of increasing energy density have been further highlighted, which is why the lithium metal-based batteries are considered as the most competitive power sources for electric vehicles. However, before lithium metal anodes become a viable technology, significant challenges need to be overcome. First, metallic lithium has high reactivity and inevitably reacts with organic liquids and electrolytes to directly form a weak solid electrolyte interface layer (SEI) having low lithium ion conductivity. In addition, metallic lithium is a typical conversion type non-host negative electrode, which determines that infinite volume change occurs in the lithium intercalation/deintercalation process, and the huge volume change can cause the rupture of unstable SEI and even lead to the pulverization of the metallic lithium negative electrode, thereby causing the complete loss of the protection effect of the SEI on the metallic lithium negative electrode, and further aggravating the consumption of active lithium and electrolyte.
In the current strategy, interfacial modification engineering is considered as an important way to stabilize metallic lithium anodes and to facilitate their practical application and development, and the interfacial modification strategy is of high interest because almost all of the troublesome problems faced by metallic lithium anodes can be attributed to the instability of the metallic lithium/electrolyte interface. Therefore, how to reasonably design and construct an effective interface layer is the key for realizing the long-term stable operation of the metal lithium battery.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a composite lithium metal cathode with an artificial solid electrolyte interface layer, and a preparation method and application thereof, so as to solve the problem of dendritic growth of the cathode of a lithium metal battery in the prior art.
The technical scheme for solving the technical problems is as follows: the preparation method of the composite metal lithium negative electrode with the artificial solid electrolyte interface layer comprises the following steps: and carrying out plasma reaction on the halogenated organic liquid and the metal lithium negative electrode by adopting a plasma enhanced chemical vapor deposition method in an inert gas atmosphere to prepare the composite metal lithium negative electrode with the artificial solid electrolyte interface layer.
The beneficial effects of the invention are as follows: in the invention, under the atmosphere of inert atmosphere, halogenated organic liquid is plasmatized by adopting a plasma enhanced chemical vapor deposition method, and reacts in situ on the lithium metal negative electrode to carry out surface modification, thus obtaining the composite lithium metal negative electrode with an artificial solid electrolyte interface layer rich in halide. The prepared artificial solid electrolyte interface layer is an organic-inorganic composite interface layer, and the halide-rich inorganic layer can adjust the diffusion and migration of lithium ions, improve the mechanical stability of the interface and inhibit the growth of lithium dendrites; the organic layer can ensure the integrity of the interface layer during circulation, enhance the circulation stability of the lithium metal battery and improve the deposition behavior of metal lithium in the subsequent charging and discharging processes. The composite lithium metal cathode prepared by the invention improves the stability and cycle performance of the lithium metal battery, and has wide application prospects in the fields of mobile communication, electric automobiles, solar power generation, aerospace and the like.
On the basis of the technical scheme, the invention can be further improved as follows:
further, the halogenated organic liquid is at least one of dimethyl bromomalonate, diethyl dibromomalonate, diethyl fluoromalonate, dimethyl chloromalonate and diethyl chloromalonate.
Further, the flow rate of the inert gas is 5-50SCCM.
Further, the inert gas flow rate was 10SCCM.
Further, the inert gas is at least one of argon, helium and nitrogen.
Further, the material of the metallic lithium negative electrode is lithium and/or a lithium alloy.
Further, the material of the lithium metal negative electrode is lithium.
Further, the thickness of the metallic lithium negative electrode is 50 to 600 μm.
Further, the power of the plasma reaction is 20-300W.
Further, the power of the plasma reaction was 100W.
Further, plasma reaction is carried out for 1-300s.
Further, the plasma reacted for 60s.
The invention also provides the composite metal lithium cathode prepared by the preparation method of the composite metal lithium cathode with the artificial solid electrolyte interface layer.
Furthermore, the thickness of the artificial solid electrolyte interface layer of the composite metal lithium cathode with the artificial solid electrolyte interface layer is 1-30 μm.
The invention also provides application of the composite metal lithium negative electrode in a metal lithium secondary battery.
The present invention also provides the above-mentioned lithium metal secondary battery, wherein the negative electrode is the composite lithium metal negative electrode having the artificial solid electrolyte interface layer according to claim 8, and the positive electrode is sulfur, lithium cobaltate, lithium iron phosphate, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate or lithium manganese oxide.
The invention has the following beneficial effects:
1. the artificial solid electrolyte interface layer prepared by the invention has the characteristics of high mechanical strength and high ionic conductivity, and the prepared composite metal lithium cathode can improve the deposition behavior of metal lithium in the charging and discharging processes and improve the stability and cycle performance of the metal lithium battery.
2. The invention has the characteristics of simple and convenient operation, rapid reaction, energy saving and mass preparation.
Drawings
FIG. 1 is a plot of performance testing of Li | Li button cell symmetric batteries assembled with negative electrodes made in examples 1-3 and comparative examples;
FIG. 2 is a graph of the average coulombic efficiency performance of negative assembled Li | Cu button half cells from examples 1-3 and comparative example;
FIG. 3 is a plot of Li | NCM811 buckled full cell cycle performance testing of the negative electrode assemblies made in examples 1-3 and comparative example;
fig. 4 is a scanning electron micrograph of the back surface of a negative assembled Li button cell cycle 50 cycles of examples 1-3 and comparative example.
Detailed Description
The principles and features of this invention are described below in conjunction with the following drawings, which are set forth by way of illustration only and are not intended to limit the scope of the invention. The examples, in which specific conditions are not specified, were carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1:
a composite metal lithium cathode with an artificial solid electrolyte interface layer is prepared by the following steps:
(1) Under the inert gas argon atmosphere, bromomalonic acid dimethyl ester (shown as C) 5 Br) is placed at the air inlet end of a Plasma Enhanced Chemical Vapor Deposition (PECVD) device, and a metal lithium pole piece with the diameter of 10mm and the thickness of 300 mu m is placed in the reaction zone of the Plasma Enhanced Chemical Vapor Deposition (PECVD) device;
(2) Setting argon flow as 10SCCM, PECVD equipment power as 100W, adopting plasma enhanced chemical vapor deposition method to make plasma reaction for 60s at room temperature to obtain composite C 5 Br/lithium metal negative electrode, i.e. composite metal lithium negative electrode with artificial solid electrolyte interface layer.
Example 2:
a composite metal lithium cathode with an artificial solid electrolyte interface layer is prepared by the following steps:
(1) Under inert gas argon atmosphere, bromomalonic acid diethyl ester (shown as C) 7 Br) is arranged at the air inlet end of the Plasma Enhanced Chemical Vapor Deposition (PECVD) equipment, and a metal lithium pole piece with the diameter of 10mm and the thickness of 300 mu m is arranged at the air inlet end of the Plasma Enhanced Chemical Vapor Deposition (PECVD) equipmentA reaction zone of a deposition (PECVD) apparatus;
(2) Setting argon flow as 10SCCM, PECVD equipment power as 100W, adopting plasma enhanced chemical vapor deposition method to make plasma reaction for 60s at room temperature to obtain composite C 7 Br/lithium metal negative electrode, i.e. composite metal lithium negative electrode with artificial solid electrolyte interface layer.
Example 3:
a composite metal lithium negative electrode with an artificial solid electrolyte interface layer is prepared by the following steps:
(1) Under an inert gas argon atmosphere, dibromo diethyl malonate (represented as C) 7 Br 2 ) Placing the lithium ion battery at the air inlet end of Plasma Enhanced Chemical Vapor Deposition (PECVD) equipment, and placing a metal lithium pole piece with the diameter of 10mm and the thickness of 300 mu m in a reaction area of the Plasma Enhanced Chemical Vapor Deposition (PECVD) equipment;
(2) Setting argon flow as 10SCCM, PECVD equipment power as 100W, adopting plasma enhanced chemical vapor deposition method to make plasma reaction for 60s at room temperature to obtain composite C 7 Br 2 A lithium metal negative electrode, i.e. a composite metal lithium negative electrode with an artificial solid electrolyte interface layer.
Test examples
1. Performance test
The lithium composite metal cathodes with artificial solid electrolyte interface layers prepared in examples 1-3 were assembled into a Li | Li button symmetric cell, a Li | Cu button half cell and a Li | NCM811 button full cell, respectively, and the button cell structure included: the specific materials of the positive and negative electrode battery cases, the ternary nickel cobalt lithium manganate positive electrode, the composite metal lithium negative electrode and the diaphragm are shown in table 1 in detail;
while an unmodified metallic lithium negative electrode was used as a comparative example, a Li button symmetric cell, a Li Cu button half cell and a Li NCM811 button full cell were assembled as shown in table 2.
Table 1 composite metal lithium negative electrode assembled battery materials
Table 2 battery materials of unmodified lithium metal negative electrode assembly
The CR2025 button cell (diaphragm Celgard 2400 type) was tested at room temperature for charging and discharging with a Xinwei cell test system and with circulation test conditions of both Li | Li button symmetrical cell and Li | Cu button half-cell of 1mA/cm 2 And 1mAh/cm 2 The Li | NCM811 button full cell test voltage range is relative to Li/Li + 2.7-4.4V, the cycle test current is 0.5C, and the reversible charge-discharge specific capacity, charge-discharge cycle performance and high rate characteristic of the corresponding button type lithium metal flow battery are measured, and the results are shown in figures 1-3.
As can be seen from FIG. 1 (comparative example 1 and examples 1-3 in sequence from top to bottom), the Li | Li button cell symmetrical battery assembled in examples 1-3 was at 1mA/cm 2 And 1mAh/cm 2 Under the test condition, overpotentials are respectively 48mV, 26mV and 24mV, and the overpotentials are respectively stable and circulate for more than 700h, 2000h and 2300h; comparative example assembled Li | Li button symmetrical cell at 1mA/cm 2 And 1mAh/cm 2 Under the test condition, the overpotentials are respectively 98mV, and the stable circulation is over 480h.
As can be seen from FIG. 2, the Li | Cu button half-cell assembled in examples 1-3 was operated at 1mA/cm 2 Current density and 1mAh/cm 2 Under the capacity test conditions, the average coulombic efficiencies after fifty cycles were 99.39%, 99.44%, and 99.51%, respectively. Comparative example assembled Li | Cu button half cell at 1mA/cm 2 Current density and 1mAh/cm 2 Fifty cycles of capacity testingThe average coulombic efficiency after the reaction was 98.13%.
As can be seen from fig. 3 (example 3, example 2, example 1 and comparative example in the order from top to bottom), the Li | NCM811 button full cells assembled in examples 1-3 had initial discharge capacities of 221mAh/g, 218mAh/g and 232mAh/g at a current density of 0.5C, and capacity retention rates of 41%, 53% and 60% after 200 cycles, respectively; the Li | NCM811 button type full cell assembled in the comparative example has initial discharge capacity of 208mAh/g under the current density of 0.5C, and the capacity retention rate after 200 cycles is 20%, thus the performance of the button type cell assembled by unmodified lithium metal in the comparative example is obviously reduced.
Li | Li button cell symmetrical batteries assembled separately for examples 1-3 and comparative example at 5mA/cm 2 And 1mAh/cm 2 Under the test conditions, the SEM test was performed on the halogenated-rich artificial solid electrolyte interface layer on the surface of the lithium metal negative electrode after 50 cycles, and the results are shown in fig. 4.
As can be seen from fig. 4, the surface of the composite lithium electrode modified by the artificial solid electrolyte interface layer substantially maintains the original morphology without significant dendrite or dead lithium formation.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A preparation method of a composite metal lithium negative electrode with an artificial solid electrolyte interface layer is characterized by comprising the following steps: and carrying out plasma reaction on the halogenated organic liquid and the metal lithium negative electrode by adopting a plasma enhanced chemical vapor deposition method in an inert gas atmosphere to prepare the composite metal lithium negative electrode with the artificial solid electrolyte interface layer.
2. The method of claim 1, wherein the halogenated organic liquid is at least one of dimethyl bromomalonate, diethyl dibromomalonate, diethyl fluoromalonate, dimethyl chloromalonate, and diethyl chloromalonate.
3. The method of making a composite lithium metal anode with an artificial solid electrolyte interfacial layer according to claim 1, wherein the inert gas flow is 5-50SCCM.
4. The method of making a lithium composite anode with an artificial solid electrolyte interfacial layer according to claim 1 or 3, wherein the inert gas is at least one of argon, helium and nitrogen.
5. The method of claim 1, wherein the lithium metal negative electrode material is lithium and/or a lithium alloy.
6. The method of claim 1, wherein the power of the plasma reaction is in the range of 20W to 300W.
7. The method of making a lithium composite anode with an artificial solid electrolyte interface layer as claimed in claim 1, wherein the plasma reaction is performed for 1-300s.
8. The lithium composite metal anode with an artificial solid electrolyte interface layer prepared by the method for preparing a lithium composite anode with an artificial solid electrolyte interface layer according to any one of claims 1 to 7.
9. Use of the composite lithium metal negative electrode with an artificial solid electrolyte interface layer according to claim 8 in a lithium metal secondary battery.
10. A lithium metal secondary battery, characterized in that the negative electrode is the composite lithium metal negative electrode with the artificial solid electrolyte interface layer according to claim 8, and the positive electrode is sulfur, lithium cobaltate, lithium iron phosphate, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate or lithium manganese oxide.
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| CN116417569A (en) * | 2023-06-12 | 2023-07-11 | 蔚来电池科技(安徽)有限公司 | Secondary battery and device |
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| CN116417569A (en) * | 2023-06-12 | 2023-07-11 | 蔚来电池科技(安徽)有限公司 | Secondary battery and device |
| CN116417569B (en) * | 2023-06-12 | 2023-08-22 | 蔚来电池科技(安徽)有限公司 | Secondary battery and device |
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