CN111293371B - Method for inhibiting lithium side reaction and dendritic crystal growth of electrolyte reservoir - Google Patents

Method for inhibiting lithium side reaction and dendritic crystal growth of electrolyte reservoir Download PDF

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CN111293371B
CN111293371B CN202010034571.2A CN202010034571A CN111293371B CN 111293371 B CN111293371 B CN 111293371B CN 202010034571 A CN202010034571 A CN 202010034571A CN 111293371 B CN111293371 B CN 111293371B
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electrolyte
lithium
electrolyte reservoir
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CN111293371A (en
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康毅进
徐英
李涛
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University of Electronic Science and Technology of China
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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
    • H01M10/42—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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
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    • Y02E60/10—Energy storage using batteries

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Abstract

The invention discloses a method for inhibiting lithium side reaction and dendritic crystal growth by an electrolyte reservoir. The method comprises the following specific processes: and inserting the electrolyte reservoir between the positive electrode and the negative electrode of the battery for storing the electrolyte to reduce side reaction between the electrolyte and the electrode material and inhibit dendritic crystal growth. The electrolyte reservoir in the invention is a hollow three-dimensional material rich in a functional group which is compatible with lithium ions and can form hydrogen bonds with an electrolyte solvent. Elements compatible with lithium ions in the liquid storage device can adjust the distribution of the lithium ions, inhibit the growth of dendritic crystals and enable the electrolyte to smoothly enter the liquid storage device; and the hollow structure of the liquid storage device is combined, so that the electrolyte is concave in the liquid storage device, the contact between the electrolyte and an electrode material is reduced, and the occurrence of side reaction is inhibited. And the functional group in the liquid storage device is combined with the electrolyte solvent through hydrogen bond action, so that the solvation action of lithium ions in the electrolyte is weakened, the transference number of the lithium ions is increased, and the growth of dendritic crystals is further inhibited.

Description

Method for inhibiting lithium side reaction and dendritic crystal growth of electrolyte reservoir
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a method for inhibiting lithium side reaction and dendritic crystal growth by an electrolyte reservoir.
Background
The traditional lithium ion battery takes graphite carbon as a negative electrode and lithium iron phosphate, lithium cobaltate or ternary materials as a positive electrode, however, the theoretical specific capacity of the electrode materials is limited, and the requirements of people on energy storage and conversion devices with high energy density and high power density cannot be met gradually. Therefore, the search for new electrode materials to replace conventional lithium battery electrode materials has received a great deal of attention. Lithium metal has an extremely high capacity density and a minimum oxidation-reduction potential, and is an excellent material for a battery negative electrode. However, the application of metallic lithium has many problems, the most important of which are a side reaction between the metallic lithium and the electrolyte and dendritic growth of lithium during deposition. Wherein dendrite growth is affected by various factors such as non-uniform lithium ion distribution, too high effective current density at the electrode surface, and concentration polarization near the electrode.
In order to alleviate the problem of side reaction of lithium, some researchers add additives into the electrolyte to stabilize the interface between lithium and the electrolyte, however, the additives as sacrificial agents cannot protect the lithium metal surface for a long time; or polymer/solid electrolyte is used instead of electrolyte, but causes too high interfacial contact resistance to affect the application of the battery. In order to suppress the dendrite growth problem, researchers increase the specific surface area of the electrode to reduce the effective current density on the electrode surface, or adjust the lithium ion distribution by a "lithium-philic" element (an element having affinity with lithium ions), and increase the transport number of lithium ions by adjusting a functional group to reduce the concentration polarization on the electrode surface. However, the growth of dendrites is a result of the combined influence of a plurality of factors, and a single means cannot completely inhibit the growth of dendrites, and even in the process of inhibiting the growth of dendrites, lithium side reactions are also aggravated, for example, the growth of dendrites can be inhibited by increasing the specific surface area of an electrode, but the contact area between metal lithium and electrolyte is also increased, and the side reactions of metal lithium are aggravated. In summary, it is the key of the present research on lithium metal batteries to find a method that can not only suppress dendrites from various aspects, but also reduce the side reactions between lithium and electrolyte, thereby comprehensively improving various aspects of battery performance.
Disclosure of Invention
In view of the above-mentioned deficiencies in the prior art, the present invention provides a method for simultaneously suppressing lithium side reactions and dendrite growth by adding an electrolyte reservoir. According to the invention, the electrolyte is stored in the liquid storage device through the electrolyte storage device so as to reduce the contact with lithium and further inhibit the occurrence of side reactions, and meanwhile, the growth of dendritic crystals is inhibited in two aspects of regulating the distribution of lithium ions through the lithium-philic element and improving the transference number of the lithium ions through reducing the solvation volume of the lithium ions, so that the cycle performance, the coulombic efficiency and the safety of the battery are improved.
In order to achieve the purpose, the technical scheme adopted by the invention for solving the technical problem is as follows:
a method for inhibiting lithium side reaction and dendritic crystal growth of an electrolyte reservoir comprises the following specific processes:
(1) preparing a hollow three-dimensional material which is rich in a lithium-philic element and a functional group capable of forming a hydrogen bond with an electrolyte solvent;
(2) and (2) directly placing the electrolyte reservoir obtained in the step (1) between the anode and the cathode of the battery.
Further, the lithium-philic element in the step (1) is one or more of nitrogen, boron, oxygen, fluorine, sulfur and phosphorus.
Further, the lithium-philic element in the step (1) is nitrogen and oxygen.
Further, the functional group capable of forming a hydrogen bond with the electrolyte solvent in the step (1) is one or more of carboxyl, amino and hydroxyl.
Further, the functional group capable of forming a hydrogen bond with the electrolyte solvent in the step (1) is a carboxyl group.
Further, the hollow three-dimensional material in the step (1) is one or more of a carbon material, a polymer material and an electrostatic spinning material.
Further, the hollow three-dimensional material in the step (1) is carbon foam.
Further, the specific process for preparing the electrolyte reservoir in the step (1) is as follows:
(a) placing commercial melamine foam into deionized water, carrying out ultrasonic cleaning for 3 times, and then drying the melamine foam in an 80-degree oven;
(b) putting the cleaned and dried melamine foam into a tube furnace, and adding N 2 Under the protection of gas, the temperature is programmed to 300-1100 ℃ at the temperature rising rate of 2-20 ℃ per minute, and is kept for 2-10 hours, and then the temperature is cooled to the room temperature.
Further, the battery positive electrode in the step (2) is one or more of sulfur, air, lithium cobaltate, lithium iron phosphate, lithium nickel cobalt manganese oxide or lithium nickel cobalt aluminate.
Further, the positive electrode of the battery in the step (2) is sulfur and lithium cobaltate.
Further, the battery cathode in the step (2) is a metal lithium sheet.
Further, the battery electrolyte salt in the step (2) is lithium hexafluorophosphate (LiPF) 6 ) Or lithium bis (trifluoromethanesulfonyl) imide (LiTFSI).
Further, the battery electrolyte solvent in the step (2) is one or more of EC, PC, DEC, DMC, EMC, DOL and DME.
Further, the electrolyte in the step (2) is 1M LiPF 6 + EC + DEC (where EC and DEC are in a 1:1 volume ratio) or 1M LiTFSI + DOL + DME (where DOL and DME are in a 1:1 volume ratio).
The method for inhibiting the lithium side reaction and the dendritic crystal growth by the electrolyte reservoir has the following advantages:
(1) the lithium-philic element has an affinity effect with lithium ions and can adjust the distribution of the lithium ions, thereby inhibiting dendritic crystal growth caused by uneven distribution of the lithium ions;
(2) the functional group capable of forming hydrogen bonds with the electrolyte solvent can reduce solvent molecules which move freely in the electrolyte, thereby weakening the solvation effect between the electrolyte solvent and lithium ions, reducing the volume of a lithium ion solvation structure, promoting the movement of the lithium ions, improving the mobility of the lithium ions, reducing the concentration polarization near an electrode, and inhibiting the growth of dendritic crystals;
(3) the existence of the 'lithium-philic' element also promotes the affinity between the electrolyte and the foam carbon, so that the electrolyte can enter the electrolyte reservoir, and the electrolyte is in a concave liquid surface in the reservoir by combining the capillary action of the hollow structure of the reservoir, thereby reducing the contact between the electrolyte and the metal lithium and further reducing the side reaction between the metal lithium and the electrolyte;
(4) the use of the electrolyte reservoir can simultaneously inhibit dendritic growth from multiple aspects and reduce side reactions of metallic lithium, so that the coulombic efficiency, the cycle life and the safety of the battery can be effectively improved;
(5) the electrolyte reservoir used by the invention has the advantages of simple preparation method, low cost and large-scale use.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) view of an electrolyte reservoir in accordance with the present invention;
FIG. 2 is an X-ray photoelectron spectroscopy (XPS) plot of an electrolyte reservoir of the present invention;
FIG. 3 is a XPS plot of the nitrogen content of the electrolyte reservoir of the present invention;
FIG. 4 is an XPS plot of oxygen for an electrolyte reservoir according to the invention;
FIG. 5 is a Fourier transform infrared (FT-IR) plot of the electrolyte reservoir of the present invention;
FIG. 6 shows 1mA cm/cm in 1M LiTFSI/DOL/DME (DOL to DME volume ratio 1:1) electrolyte -2 Current density of 1mAh cm -2 Lithium-copper battery with or without electrolyte reservoir at specific capacityCoulombic efficiency versus plating/stripping lithium cycles for the cells;
FIG. 7 shows 1mA cm in 1M LiTFSI/DOL/DME (volume ratio of DOL to DME is 1:1) electrolyte -2 Current density of 1mAh cm -2 A voltage-time curve comparison plot of plating/stripping lithium cycles for lithium-copper batteries with and without electrolyte reservoirs at specific capacities;
FIG. 8 shows a volume ratio of 1M LiTFSI/DOL/DME (DOL to DME is 1:1) in 5mA cm in electrolyte -2 Current density of 5mAh cm -2 Coulombic efficiency comparison plots of plating/stripping lithium cycles for lithium-copper batteries with no electrolyte reservoir at specific capacity;
FIG. 9 shows the concentration of 1M LiTFSI/DOL/DME (volume ratio of DOL to DME is 1:1) in 10mAcm electrolyte -2 Current density, 10mAh cm -2 Coulombic efficiency plots of plating/stripping lithium cycles of lithium-copper batteries with electrolyte reservoirs at specific capacities;
FIG. 10 shows 1mA cm in 1M LiTFSI/DOL/DME (volume ratio of DOL to DME is 1:1) electrolyte -2 Current density of 1mAh cm -2 An SEM image of the surface of a copper electrode of a lithium-copper battery with an electrolyte storage under the specific capacity after 100 circles of lithium are circularly electroplated/stripped;
FIG. 11 is a graph of 0.5mA cm/DME in 1M LiTFSI/DOL/DME (DOL to DME volume ratio of 1:1) electrolyte -2 Current density of 0.5mAh cm -2 A comparative plot of plating/stripping lithium for lithium-lithium batteries with electrolyte reservoir-free cells at specific capacity;
FIG. 12 shows a volume ratio of 1M LiTFSI/DOL/DME (DOL to DME is 1:1) in 5mA cm in electrolyte -2 Current density of 5mAh cm -2 A comparative plot of plating/stripping lithium for lithium-lithium batteries with electrolyte reservoir-free cells at specific capacity;
FIG. 13 shows 1mA cm/cm in 1M LiTFSI/DOL/DME (DOL to DME volume ratio 1:1) electrolyte -2 Current density of 1mAh cm -2 An SEM image of a lithium-lithium battery with an electrolyte reservoir existing under a specific capacity after 100 circles of lithium is circularly electroplated/stripped;
FIG. 14 shows 1mA cm in 1M LiTFSI/DOL/DME (volume ratio of DOL to DME is 1:1) electrolyte -2 Current density of 1mAh cm -2 Specific capacity with electrolyte storageSEM image of cross-section of a lithium-lithium cell in the presence of the cell after 50 cycles of cyclic plating/stripping of lithium;
FIG. 15 shows 1mA cm/cm in 1M LiTFSI/DOL/DME (DOL to DME volume ratio 1:1) electrolyte -2 Current density, 1mAh cm -2 Electrochemical Impedance Spectroscopy (EIS) diagram of lithium-lithium battery with electrolyte reservoir under specific capacity under different times of cycle plating/stripping lithium;
FIG. 16 is a graph of the change in current at 10mV polarization voltage and the change in impedance before and after polarization for a lithium-lithium symmetric cell with an electrolyte reservoir in a 1M LiTFSI/DOL/DME (DOL to DME volume ratio of 1:1) electrolyte;
FIG. 17 shows 1M LiPF 6 In the electrolyte of EC/DEC (EC to DEC volume ratio is 1:1) at 1mA cm -2 Current density of 1mAh cm -2 Coulombic efficiency comparison plots of plating/stripping lithium cycles for lithium-copper batteries with no electrolyte reservoir at specific capacity;
FIG. 18 is 1M LiPF 6 EC/DEC (EC to DEC volume ratio 1:1) electrolyte at 1mA cm -2 Current density of 1mAh cm -2 A comparative plot of plating/stripping lithium cycles for lithium-lithium batteries with no electrolyte reservoir at specific capacity;
FIG. 19 is a graph comparing rate performance, cycle performance, and specific discharge capacity for a full cell with a positive electrode of sulfur, a negative electrode of a lithium metal plate, and an electrolyte of 1M LiTFSI/DOL/DME (volume ratio of DOL to DME is 1:1) without an electrolyte reservoir;
FIG. 20 shows lithium cobaltate as the positive electrode, lithium metal plate as the negative electrode, and 1M LiPF as the electrolyte 6 A graph comparing rate performance, cycle performance and specific discharge capacity of a full cell of/EC/DEC (EC to DEC volume ratio of 1:1) with or without an electrolyte reservoir;
Detailed Description
The following description of the embodiments of the present invention is provided to facilitate the understanding of the present invention by those skilled in the art, but it should be understood that the present invention is not limited to the scope of the embodiments, and it will be apparent to those skilled in the art that various changes may be made without departing from the spirit and scope of the invention as defined and defined in the appended claims, and all matters produced by the invention using the inventive concept are protected.
Example 1
A method for inhibiting lithium side reaction and dendritic crystal growth of an electrolyte reservoir comprises the following specific processes:
(1) the preparation method of the hollow three-dimensional material rich in the lithium-philic element and the functional group capable of forming the hydrogen bond with the electrolyte solvent comprises the following specific steps:
(a) placing commercial melamine foam into deionized water, carrying out ultrasonic cleaning for 3 times, and then drying the melamine foam in an 80-degree oven;
(b) putting the cleaned and dried melamine foam into a tube furnace, and adding N 2 The temperature is programmed to 400 ℃ at the temperature rise rate of 4 ℃ per minute under the protection of gas, and the temperature is kept for 3 hours and then the temperature is cooled to the room temperature.
(2) And (2) directly placing the electrolyte reservoir obtained in the step (1) between the anode and the cathode of the battery, wherein the electrolyte component is 1M LiTFSI/DOL/DME (the volume ratio of DOL to DME is 1: 1).
Example 2
A method for inhibiting lithium side reaction and dendritic crystal growth of an electrolyte reservoir comprises the following specific processes:
(1) the preparation method of the hollow three-dimensional material rich in the lithium-philic element and the functional group capable of forming the hydrogen bond with the electrolyte solvent comprises the following specific steps:
(a) placing commercial melamine foam into deionized water for ultrasonic cleaning for 3 times, and then drying the commercial melamine foam in an 80-DEG oven;
(b) putting the cleaned and dried melamine foam into a tube furnace, and adding N 2 The temperature is programmed to 400 ℃ at the temperature rise rate of 4 ℃ per minute under the protection of gas, and the temperature is kept for 3 hours and then the temperature is cooled to the room temperature.
(2) Directly placing the electrolyte reservoir obtained in the step (1) between the anode and the cathode of the battery, wherein the electrolyte component is 1M LiPF 6 EC/DEC (EC to DEC volume ratio of 1: 1).
Example 3
A method for inhibiting lithium side reaction and dendritic crystal growth of an electrolyte reservoir comprises the following specific processes:
(1) the preparation method of the hollow three-dimensional material rich in the lithium-philic element and the functional group capable of forming hydrogen bonds with the electrolyte solvent comprises the following specific steps:
(a) placing commercial melamine foam into deionized water, carrying out ultrasonic cleaning for 3 times, and then drying the melamine foam in an 80-degree oven;
(b) putting the cleaned and dried melamine foam into a tube furnace, and adding N 2 Under the protection of gas, the temperature is programmed to 300 ℃ at the temperature rise rate of 1 ℃ per minute, and is kept for 1 hour, and then the temperature is cooled to the room temperature.
(2) And (2) directly placing the electrolyte reservoir obtained in the step (1) between the anode and the cathode of the battery, wherein the electrolyte component is 1M LiTFSI/DOL/DME (the volume ratio of DOL to DME is 1: 1).
Example 4
A method for inhibiting lithium side reaction and dendritic crystal growth of an electrolyte reservoir comprises the following specific processes:
(1) the preparation method of the hollow three-dimensional material rich in the lithium-philic element and the functional group capable of forming the hydrogen bond with the electrolyte solvent comprises the following specific steps:
(a) placing commercial melamine foam into deionized water, carrying out ultrasonic cleaning for 3 times, and then drying the melamine foam in an 80-degree oven;
(b) putting the cleaned and dried melamine foam into a tube furnace, and adding N 2 The temperature is programmed to 600 ℃ at the temperature rise rate of 6 ℃ per minute under the protection of gas, and the temperature is kept for 4 hours and then the temperature is cooled to the room temperature.
(2) And (2) directly placing the electrolyte reservoir obtained in the step (1) between the anode and the cathode of the battery, wherein the electrolyte component is 1M LiTFSI/DOL/DME (the volume ratio of DOL to DME is 1: 1).
Example 5
A method for inhibiting lithium side reaction and dendritic crystal growth of an electrolyte reservoir comprises the following specific processes:
(1) the preparation method of the hollow three-dimensional material rich in the lithium-philic element and the functional group capable of forming the hydrogen bond with the electrolyte solvent comprises the following specific steps:
(a) placing commercial melamine foam into deionized water, carrying out ultrasonic cleaning for 3 times, and then drying the melamine foam in an 80-degree oven;
(b) putting the cleaned and dried melamine foam into a tube furnace, and adding N 2 Under the protection of gas, the temperature is programmed to 800 ℃ at the temperature rise rate of 8 ℃ per minute, and is kept for 5 hours, and then the temperature is cooled to the room temperature.
(2) And (2) directly placing the electrolyte reservoir obtained in the step (1) between the anode and the cathode of the battery, wherein the electrolyte component is 1M LiTFSI/DOL/DME (the volume ratio of DOL to DME is 1: 1).
Example 6
A method for inhibiting lithium side reaction and dendritic crystal growth of an electrolyte reservoir comprises the following specific processes:
(1) the preparation method of the hollow three-dimensional material rich in the lithium-philic element and the functional group capable of forming the hydrogen bond with the electrolyte solvent comprises the following specific steps:
(a) placing commercial melamine foam into deionized water, carrying out ultrasonic cleaning for 3 times, and then drying the melamine foam in an 80-degree oven;
(b) putting the cleaned and dried melamine foam into a tube furnace, and adding N 2 Under the protection of gas, the temperature is programmed to 1000 ℃ at the temperature rise rate of 4 ℃ per minute, and is kept for 5 hours, and then the temperature is cooled to the room temperature.
(2) And (2) directly placing the electrolyte reservoir obtained in the step (1) between the anode and the cathode of the battery, wherein the electrolyte component is 1M LiTFSI/DOL/DME (the volume ratio of DOL to DME is 1: 1).
Example 7
A method for inhibiting lithium side reaction and dendritic crystal growth of an electrolyte reservoir comprises the following specific processes:
(1) the preparation method of the hollow three-dimensional material rich in the lithium-philic element and the functional group capable of forming the hydrogen bond with the electrolyte solvent comprises the following specific steps:
(a) placing commercial melamine foam into deionized water, carrying out ultrasonic cleaning for 3 times, and then drying the melamine foam in an 80-degree oven;
(b) after being cleaned and driedIs placed in a tube furnace in N 2 Under the protection of gas, the temperature is programmed to 1000 ℃ at the temperature rise rate of 6 ℃ per minute, and the temperature is kept for 2 hours, and then the temperature is cooled to the room temperature.
(2) Directly placing the electrolyte reservoir obtained in the step (1) between the anode and the cathode of the battery, wherein the electrolyte component is 1M LiPF 6 EC/DEC (EC to DEC volume ratio of 1: 1).
Example 8
A method for inhibiting lithium side reaction and dendritic crystal growth of an electrolyte reservoir comprises the following specific processes:
(1) the preparation method of the hollow three-dimensional material rich in the lithium-philic element and the functional group capable of forming the hydrogen bond with the electrolyte solvent comprises the following specific steps:
(a) placing commercial melamine foam into deionized water for ultrasonic cleaning for 3 times, and then drying the commercial melamine foam in an 80-DEG oven;
(b) putting the cleaned and dried melamine foam into a tube furnace, and adding N 2 The temperature is programmed to 600 ℃ at the temperature rise rate of 4 ℃ per minute under the protection of gas, and the temperature is kept for 3 hours and then the temperature is cooled to the room temperature.
(2) Directly placing the electrolyte reservoir obtained in the step (1) between the anode and the cathode of the battery, wherein the electrolyte comprises 1M LiPF 6 EC/DEC (EC to DEC volume ratio of 1: 1).
Example 9
A method for inhibiting lithium side reaction and dendritic crystal growth of an electrolyte reservoir comprises the following specific processes:
(1) the preparation method of the hollow three-dimensional material rich in the lithium-philic element and the functional group capable of forming the hydrogen bond with the electrolyte solvent comprises the following specific steps:
(a) placing commercial melamine foam into deionized water, carrying out ultrasonic cleaning for 3 times, and then drying the melamine foam in an 80-degree oven;
(b) putting the cleaned and dried melamine foam into a tube furnace, and adding N 2 Under the protection of gas, the temperature is programmed to 800 ℃ at the temperature rise rate of 6 ℃ per minute, and is kept for 3 hours, and then the temperature is cooled to the room temperature.
(2) Directly placing the electrolyte reservoir obtained in the step (1) between the anode and the cathode of the battery, wherein the electrolyte component is 1M LiPF 6 EC/DEC (EC to DEC volume ratio of 1: 1).
Example 10
A method for inhibiting lithium side reaction and dendritic crystal growth of an electrolyte reservoir comprises the following specific processes:
(1) the preparation method of the hollow three-dimensional material rich in the lithium-philic element and the functional group capable of forming the hydrogen bond with the electrolyte solvent comprises the following specific steps:
(a) placing commercial melamine foam into deionized water, carrying out ultrasonic cleaning for 3 times, and then drying the melamine foam in an 80-degree oven;
(b) putting the cleaned and dried melamine foam into a tube furnace, and adding N 2 Under the protection of gas, the temperature is programmed to 700 ℃ at the temperature rise rate of 8 ℃ per minute, and is kept for 5 hours, and then the temperature is cooled to the room temperature.
(2) And (2) directly placing the electrolyte reservoir obtained in the step (1) between the anode and the cathode of the battery, wherein the electrolyte component is 1M LiTFSI/DOL/DME (the volume ratio of DOL to DME is 1: 1).
Experimental example 1
The electrolyte reservoirs prepared in example 1 were subjected to characterization tests, the results of which are shown in FIGS. 1-5;
as shown in fig. 1, the electrolyte reservoir is a three-dimensional network structure, and the supporting framework is a hollow structure;
the XPS chart in fig. 2 shows that the main elements of the electrolyte reservoir are carbon, nitrogen, oxygen;
as can be seen from the peak separation process of the nitrogen element in fig. 3, the nitrogen in the electrolyte reservoir is mainly pyridine nitrogen and pyrrole nitrogen;
as can be seen from the peak separation of oxygen in fig. 4, oxygen in the electrolyte reservoir is mainly derived from carboxyl functional groups;
in FIG. 5, it can be seen from the FT-IR chart of the electrolyte reservoir that the temperature is 3500 and 2500cm -1 Has a broad absorption peak, thereby proving the existence of O-H and N-H bonds at 1200-1700cm -1 Has absorption peak group, which belongs to the absorption of nitrogen heteroatomPeak, thus confirming the presence of pyrrole type nitrogen, at 806cm -1 Is a typical triazine characteristic respiration peak, thus demonstrating the presence of pyridine-type nitrogen at 1723cm -1 The characteristic absorption at (a) is the C ═ O absorption in the carboxyl group, thus evidencing the presence of the carboxyl function.
Experimental example 2
The electrolyte reservoir obtained in example 1 was used in a lithium-copper battery system, and the lithium-copper battery was assembled in a glove box filled with argon gas in the absence of water and oxygen at 1, 5, 10mA/cm -2 Current density sum of 1, 5, 10mAh/cm -2 Performing constant current charge and discharge test at capacity, and comparing with a lithium-copper battery without an electrolyte reservoir; the results are shown in FIGS. 6-9;
the lithium-copper battery assembling process comprises the following steps:
the method comprises the following steps of (1) adopting commercial lithium with the diameter of 10mm as an electrode, commercial copper foil with the diameter of 16mm as a counter electrode, 1M LiTFSI/DOL/DME (volume ratio of DOL to DME is 1:1) as electrolyte, then adopting Celgard2325 with the diameter of 19mm as a diaphragm, placing an electrolyte reservoir with the diameter of 15mm between two diaphragms, packaging the two diaphragms in a CR2032 button cell, and not adding the electrolyte reservoir in a comparative test;
as can be seen from FIG. 6, the current density was 1mA/cm -2 Current density and 1mAh/cm -2 Under the capacity, the existence of the electrolyte reservoir can assist the battery to circulate for 800 circles, the coulombic efficiency is 99.3%, while the lithium-copper battery without the reservoir can only circulate for 160 circles, and the coulombic efficiency is 97.6%, so that the existence of the electrolyte reservoir is helpful for reducing the side reaction between the metal lithium and the electrolyte, thereby improving the utilization rate of the metal lithium and prolonging the cycle life of the battery;
as can be seen from fig. 7, the lithium-copper battery with the electrolyte reservoir present has a lower overpotential during the lithium deposition process, thereby illustrating that the reservoir facilitates the deposition of metallic lithium;
as is clear from FIGS. 8 and 9, the current density at a high current density (5, 10 mA/cm) -2 ) And a large capacity (5, 10 mAh/cm) -2 ) Now, the lithium-copper battery with the electrolyte reservoir can still run 150 and 70 turns respectively, while the battery without the reservoir is not able to run, thus illustrating that the electrolyte reservoir is favorable for realizing electricityAnd (4) charging and discharging the battery with high current.
Experimental example 3
The electrolyte reservoir obtained in example 1 was used in a lithium-copper battery system, and the lithium-copper battery was assembled in a water-free and oxygen-free glove box filled with argon gas at 1mA/cm -2 Constant current charge and discharge tests are carried out under the current density, the appearance change of the electrode after 100 cycles of circulation is observed, and the result is shown in figure 10;
the lithium-copper battery assembling process comprises the following steps:
the method comprises the following steps of (1) adopting commercial lithium with the diameter of 10mm as an electrode, commercial copper foil with the diameter of 16mm as a counter electrode, 1M LiTFSI/DOL/DME (the volume ratio of DOL to DME is 1:1) as electrolyte, then Celgard2325 with the diameter of 19mm as a diaphragm, placing an electrolyte reservoir with the diameter of 15mm between two diaphragms, packaging the two diaphragms in a CR2032 button cell, and not adding the electrolyte reservoir in a comparative test;
as can be seen from fig. 10, after 100 cycles, the deposition of lithium on the copper foil was still flat and dense, thus illustrating that the electrolyte reservoir helps to suppress the growth of dendrites and to suppress the occurrence of side reactions.
Experimental example 4
The electrolyte reservoir obtained in example 1 was used in a lithium-lithium battery system assembled in a water-free and oxygen-free glove box filled with argon, at 1, 5mA/cm -2 Current density and 1, 5mAh/cm -2 Performing constant current charge and discharge test at capacity, and comparing with a lithium-lithium battery without an electrolyte storage; the results are shown in FIGS. 11 and 12;
lithium-lithium battery assembly process:
commercial lithium with the diameter of 16mm is used as an electrode, 1M LiTFSI/DOL/DME (volume ratio of DOL to DME is 1:1) is used as electrolyte, Celgard2325 with the diameter of 19mm is used as a diaphragm, an electrolyte reservoir with the diameter of 15mm is placed between the two diaphragms and packaged in a CR2032 button cell, and the electrolyte reservoir is not used in a comparative test;
as can be seen from FIG. 11, the current density was 0.5mA/cm -2 Current density and 0.5mAh/cm -2 At capacity, the presence of an electrolyte reservoir can assist the battery in cycling for 4000 hours without the lithium of the reservoirLithium batteries can only cycle for 1000 hours and batteries with electrolyte reservoirs have a lower lithium deposition overpotential, an improvement of this electrochemical property similar to that in lithium-copper batteries, thus further illustrating that electrolyte reservoirs are beneficial for improving the cycle life of the battery and reducing the deposition potential of the battery;
similarly, as shown in FIG. 12, at a high current density (5 mA/cm) -2 ) And a large capacity (5 mAh/cm) -2 ) Next, the lithium-lithium battery with the electrolyte reservoir can still operate for more than 400 hours, while the battery without the electrolyte reservoir cannot operate, which indicates that the presence of the electrolyte reservoir is beneficial to realizing large-current charging and discharging of the battery.
Experimental example 5
The electrolyte reservoir obtained in example 1 was used in a lithium-lithium battery system assembled in a water-free and oxygen-free glove box filled with argon, at 1mA/cm -2 Constant current charge and discharge tests were performed at current density, and the morphology change of the electrode after cycling for 100 and 50 cycles was observed, the results of which are shown in fig. 13 and 14;
the lithium-lithium battery assembling process comprises the following steps:
commercial lithium with the diameter of 16mm is used as an electrode, 1M LiTFSI/DOL/DME (volume ratio of DOL to DME is 1:1) is used as electrolyte, Celgard2325 with the diameter of 19mm is used as a diaphragm, an electrolyte reservoir with the diameter of 15mm is placed between the two diaphragms and packaged in a CR2032 button cell, and the electrolyte reservoir is not used in a comparative test;
as can be seen from fig. 13, after 100 cycles, the surface of the lithium was still flat and dense, thus illustrating that the electrolyte reservoir helped to suppress the growth of dendrites;
as can be seen from fig. 14, after 50 cycles, the cross section of the lithium metal has only a thin film of solid electrolyte interface, about 1 micron, and this film is uniform but dense, thus indicating that the reservoir helps to reduce side reactions between the electrolyte and the lithium metal.
Experimental example 6
The electrolyte reservoir obtained in example 1 was used in a lithium-lithium battery system, and lithium was assembled in a water-free and oxygen-free glove box filled with argonLithium battery at 1mA/cm -2 Constant current charge and discharge tests were performed at current density, and electrochemical impedance was measured after 1, 10, 100, 200, 400 cycles, and the results are shown in fig. 15;
the lithium-lithium battery assembling process comprises the following steps:
commercial lithium with the diameter of 16mm is used as an electrode, 1M LiTFSI/DOL/DME (volume ratio of DOL to DME is 1:1) is used as electrolyte, Celgard2325 with the diameter of 19mm is used as a diaphragm, an electrolyte reservoir with the diameter of 15mm is placed between the two diaphragms and packaged in a CR2032 button cell, and the electrolyte reservoir is not used in a comparative test;
electrochemical impedance test conditions were as follows:
the cell was at open circuit voltage, amplitude 0.005V, frequency range: 0.01 Hz-100 kHz;
as can be seen from fig. 15, the interface resistance of the battery with the electrolyte reservoir is maintained at about 20-30 Ω after many cycles, which indicates that the electrolyte reservoir is favorable for suppressing the growth of dendrites and reducing the occurrence of side reactions, thereby creating a clean and stable electrode surface, and this phenomenon also corresponds to the topography change of the electrode surface under different cycles.
Experimental example 7
The electrolyte reservoir obtained in example 1 was used in a lithium-lithium battery system, and lithium-lithium batteries were assembled in a glove box filled with argon gas in the absence of water and oxygen to test the migration number of lithium ions in the electrolyte, and the results are shown in fig. 16;
lithium-lithium battery assembly process:
commercial lithium with the diameter of 16mm is used as an electrode, 1M LiTFSI/DOL/DME (volume ratio of DOL to DME is 1:1) is used as electrolyte, Celgard2325 with the diameter of 19mm is used as a diaphragm, an electrolyte reservoir with the diameter of 15mm is placed between the two diaphragms and packaged in a CR2032 button cell, and the electrolyte reservoir is not used in a comparative test;
the test conditions of the lithium ion transference number and the steps are as follows:
firstly, testing the alternating current impedance of a battery when the battery is at an open-circuit voltage, wherein the amplitude is 0.005V, and the frequency range is 0.01 Hz-100 kHz;
then, carrying out polarization test on the battery under the polarization voltage of 10mV, and stopping after the current is stable;
finally, testing the alternating current impedance of the battery when the battery is at the open-circuit voltage again, wherein the amplitude is 0.005V, and the frequency range is 0.01 Hz-100 kHz;
the current and impedance change of the cell before and after polarization at a polarization voltage of 10mV were recorded, and the lithium ion mobility was calculated by the following formula:
Figure BDA0002365531390000161
wherein t is Li+ Represents the transference number of lithium ions, I 0 And I ss Respectively representing the initial current and the steady current during the polarization process, Δ V being the DC polarization voltage, R 0 And R ss Respectively, the interface resistance before and after cell polarization.
As can be seen from fig. 16, the currents of the cells before and after polarization were 65 microamperes and 49.6 microamperes, respectively, corresponding to impedances of 84.5 Ω and 98.9 Ω, respectively, and the transport number of lithium ions was found to be 0.67 by calculation, which was greatly improved compared to the transport number (0.2 to 0.4) in the cell without the electrolyte reservoir, thereby indicating that the reservoir contributes to the improvement of the transport number of lithium ions in the cell.
Experimental example 8
The electrolyte reservoir obtained in example 2 was used in a lithium-copper battery system, and the lithium-copper battery was assembled in a water-free and oxygen-free glove box filled with argon gas at 1mA/cm -2 Current density and 1mAh/cm -2 Performing constant current charge and discharge test at capacity, and comparing with a lithium-copper battery without an electrolyte reservoir; the results are shown in FIG. 17;
lithium-copper battery assembly process:
a commercial lithium electrode of 10mm diameter, a commercial copper foil counter electrode of 16mm diameter, 1M LiPF was used as the electrode 6 The electrolyte is EC/DEC (the volume ratio of EC to DEC is 1:1), Celgard2325 with the diameter of 19mm is used as a diaphragm, an electrolyte reservoir with the diameter of 15mm is arranged between the two diaphragms and packaged in a CR2032 button cell, and a comparative test is carried outThe electrolyte reservoir is not added;
as can be seen from fig. 17, the electrolyte reservoir can assist the battery to circulate 140 cycles, the coulombic efficiency is 97.3%, while the lithium-copper battery without the reservoir can only circulate 90 cycles, and the coulombic efficiency is about 85%, which shows that the electrolyte reservoir can also contribute to reducing the side reaction between the metal lithium and the electrolyte in the ester electrolyte, thereby improving the utilization rate of the metal lithium and increasing the cycle life of the battery.
Experimental example 9
The electrolyte reservoir obtained in example 2 was used in a lithium-lithium battery system assembled in a water-free and oxygen-free glove box filled with argon, at 1mA/cm -2 Current density and 1mAh/cm -2 Performing constant current charge and discharge test under the capacity, and comparing the constant current charge and discharge test with a lithium-lithium battery without an electrolyte storage; the results are shown in FIG. 18;
lithium-lithium battery assembly process:
using 16mm diameter commercial lithium as electrode, 1M LiPF 6 The method comprises the following steps of (1) taking EC/DEC (EC/DEC volume ratio is 1:1) as electrolyte, taking Celgard2325 with the diameter of 19mm as a diaphragm, placing an electrolyte reservoir with the diameter of 15mm between two diaphragms, packaging the two diaphragms in a CR2032 button cell, and not adding the electrolyte reservoir in a comparative test;
as can be seen from fig. 18, the electrolyte reservoir can assist the battery to cycle for more than 400 hours, while the lithium-lithium battery without the reservoir can cycle for only 200 hours, and the battery with the electrolyte reservoir has a lower lithium deposition overpotential, which indicates that the electrolyte reservoir is beneficial to improving the cycle life of the battery and reducing the deposition potential of the battery even in the case of the ester electrolyte.
Experimental example 10
The electrolyte reservoir obtained in example 1 was used in a lithium-sulfur battery system, a lithium-sulfur battery was assembled in a glove box filled with argon gas in the absence of water and oxygen, and the battery was cycled for 10 cycles at 0.1C, 0.2C, 0.5C, 1C, 2C, 5C rates and then back to 0.1C rate for constant current cycling charge and discharge, respectively, and compared with a lithium-sulfur battery without an electrolyte reservoir; the results are shown in FIG. 19;
lithium-sulfur battery assembly process:
the method comprises the following steps of (1) taking commercial lithium with the diameter of 16mm as a negative electrode, taking a sulfur electrode plate with the diameter of 10mm as a positive electrode, taking 1M LiTFSI/DOL/DME (volume ratio of DOL to DME is 1:1) as electrolyte, taking Celgard2325 with the diameter of 19mm as a diaphragm, placing an electrolyte reservoir with the diameter of 15mm between two diaphragms, packaging in a CR2032 button cell, and not adding the electrolyte reservoir in a comparative test;
as shown in FIG. 19, it is understood by comparison that the first cycle of the lithium-sulfur battery having the electrolyte reservoir can exhibit 1520mAh g at a rate of 0.1C -1 And still can embody 400mAh g under the multiplying power of 5C -1 The capacity of (2) can be stabilized at 1200mAh g when the current returns to 0.1C again after the high-current multiplying power circulation -1 The capacity of the battery is about, and the first circle of the battery without an electrolyte storage can only show 950mAh g at the rate of 0.1C -1 The capacity of (2) is hardly operated at a high rate, for example, 5C, and finally decreases to 400mAh g when the rate is restored to 0.1C -1 And the electrolyte reservoir is favorable for improving the performance of the lithium-sulfur battery.
Experimental example 11
The electrolyte reservoir obtained in example 2 was used in a lithium-cobalt acid lithium battery system, a lithium-cobalt acid lithium battery was assembled in a glove box filled with argon gas in the absence of water and oxygen, and was cycled for 10 cycles at a rate of 0.5C, 1C, 2C, 5C, respectively, and then returned to a rate of 1C for constant current cyclic charge and discharge, and compared with a lithium-cobalt acid lithium battery without an electrolyte reservoir; the results are shown in FIG. 20;
the lithium-cobalt acid lithium battery assembling process comprises the following steps:
commercial lithium with a diameter of 16mm was used as the negative electrode, a lithium cobaltate electrode sheet with a diameter of 10mm was used as the positive electrode, and 1M LiPF was used 6 The method comprises the following steps of (1) taking/EC/DEC (the volume ratio of EC to DEC is 1:1) as electrolyte, taking Celgard2325 with the diameter of 19mm as a diaphragm, placing an electrolyte reservoir with the diameter of 15mm between two diaphragms, packaging in a CR2032 button cell, and not adding the electrolyte reservoir in a comparative test;
from the comparison shown in FIG. 20, it can be seen that the first turn of the lithium-cobalt acid lithium battery with the electrolyte reservoir can be at 0.5CShowing 140mAh g at magnification -1 And still can embody 82mAh g under the multiplying power of 5C -1 The capacity of (2) can be stabilized at 110mAhg when the current returns to 1C again after the high-current multiplying power circulation -1 About (C), whereas the first turn of the cell without electrolyte reservoir can only show 135mAh g at 0.5C rate -1 The capacity of (A) is almost not operated at a high rate, for example, 5C, and finally decreases to 62mAh g when the rate is restored to 1C -1 Furthermore, the battery with the electrolyte reservoir exhibits higher coulombic efficiency during operation, thereby indicating that the electrolyte reservoir is beneficial to improving the performance of the lithium-cobalt acid lithium battery.

Claims (7)

1. A method for inhibiting lithium side reaction and dendritic crystal growth of an electrolyte reservoir is characterized in that a hollow three-dimensional material which is rich in affinity elements with lithium ions and can form carboxyl, amino or hydroxyl functional groups of hydrogen bonds with electrolyte solvents such as Ethylene Carbonate (EC), Propylene Carbonate (PC), diethyl carbonate (DEC), dimethyl carbonate (DMC), Ethyl Methyl Carbonate (EMC), 1, 3-Dioxolane (DOL) and ethylene glycol dimethyl ether (DME) is inserted between a positive electrode and a negative electrode of a battery as the electrolyte reservoir.
2. The method of claim 1, wherein the element having affinity for lithium is one or more of nitrogen, boron, oxygen, fluorine, sulfur, and phosphorus.
3. The method of suppressing lithium side reactions and dendrite growth for an electrolyte reservoir of claim 1 or 2 wherein the elements that have affinity for lithium are nitrogen and oxygen.
4. The method of claim 1, wherein the electrolyte solvent is an ester electrolyte: mixing EC and DEC in a volume ratio of 1:1, and an ether electrolyte: mixture of DOL and DME in a volume ratio of 1: 1.
5. The method of suppressing lithium side reactions and dendrite growth for an electrolyte reservoir of claim 1 wherein the functional group capable of forming hydrogen bonds with the electrolyte solvent is a carboxyl group.
6. The method of suppressing lithium side reactions and dendrite growth for an electrolyte reservoir of claim 1 wherein the hollow three-dimensional material is one or more of a carbon material, a polymer material, an electrospun material.
7. The method of suppressing lithium side reactions and dendrite growth for an electrolyte reservoir of claim 1 or 6 wherein the hollow three-dimensional material is a carbon foam material.
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