CN111653822A - Gel type ionic liquid electrolyte for lithium ion battery and preparation method and application thereof - Google Patents

Gel type ionic liquid electrolyte for lithium ion battery and preparation method and application thereof Download PDF

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CN111653822A
CN111653822A CN202010526344.1A CN202010526344A CN111653822A CN 111653822 A CN111653822 A CN 111653822A CN 202010526344 A CN202010526344 A CN 202010526344A CN 111653822 A CN111653822 A CN 111653822A
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lithium
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lithium salt
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于乐
李念武
关俊
陈晨
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Beijing University of Chemical Technology
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Abstract

The invention provides a gel type ionic liquid electrolyte for a lithium ion battery and a preparation method and application thereof, wherein a Lewis acid type lithium salt initiator is added to initiate in-situ ring-opening polymerization of a cyclic ether organic solvent at low temperature to form a three-dimensional cross-linked network polymer, and the three-dimensional cross-linked network polymer is used as a skeleton structure to limit ionic liquid, lithium salt and the like in a three-dimensional polymer structure, so that the in-situ preparation of the gel type ionic liquid electrolyte is realized, the full contact between the electrolyte and an electrode material and a diaphragm is ensured, the interface impedance can be effectively reduced, and the Lewis acid type lithium salt initiator and a multi-lithium salt solution form a multi-lithium salt system, which is beneficial to improving the cycle performance and stability of the gel type ionic liquid electrolyte; in addition, the invention also introduces the ionic liquid, obviously inhibits the growth of the lithium dendrite, simultaneously improves the thermal stability and the electrochemical window of the electrolyte, and effectively improves the safety performance of the electrolyte.

Description

Gel type ionic liquid electrolyte for lithium ion battery and preparation method and application thereof
Technical Field
The invention relates to a gel type ionic liquid electrolyte for a lithium ion battery and a preparation method and application thereof, belonging to the technical field of lithium ion batteries.
Background
The continuous increase in energy demand has promoted the development of sustainable storage technologies, and electronic devices have become necessities for people's life and work. The lithium metal as a negative electrode material has high theoretical specific capacity (3860mAh g)-1) Low standard reduction potential (-3.04V vs. SHE) and low mass density (0.54g cm)-3) Therefore, research on secondary batteries using lithium metal as a negative electrode is important to meet the requirements of new intelligent electronic devices on energy density and safety of secondary batteries.
The traditional liquid electrolyte battery is easy to form metal lithium dendrite during the charging process, so that the coulomb efficiency and the capacity of the battery are greatly reduced. More seriously, the lithium dendrites may pierce the separator to cause short-circuiting between the positive and negative electrodes, causing a large amount of heat to be generated inside the battery, causing decomposition of the volatile and flammable liquid electrolyte and even explosion of the battery. The solid electrolyte can inhibit the growth of lithium dendrite and is not easy to generate thermal decomposition, so that the safety of the lithium metal battery is greatly improved, but the further development of the solid electrolyte is limited due to the higher interface resistance and the lower ionic conductivity of the solid electrolyte. The gel type polymer electrolyte is in a state between the state of an all-solid electrolyte and the state of a liquid electrolyte, has higher ionic conductivity than the all-solid electrolyte, and also has higher electrochemical stability and thermal stability than the liquid electrolyte, thereby being an electrolyte with wide application prospects.
Although the gel-type polymer electrolyte prepared by the traditional ex-situ polymerization has the advantages, the contact wettability of the gel-type polymer electrolyte with a solid electrode material is poorer than that of a liquid electrolyte, and a certain interface contact problem exists. These contact problems may aggravate the breakage and regeneration of a Solid Electrolyte Interface (SEI) film caused by volume expansion during the charge and discharge of a battery, thereby consuming an electrolyte. In addition, the thermal stability and electrochemical stability of the gel-type electrolyte itself are also required to be further improved.
The ionic liquid is a salt which is in a molten state at room temperature, and has the characteristics of high boiling point, difficult volatilization, nonflammability, wider electrochemical window and the like. When the ionic liquid is used in an electrolyte, the ionic liquid can effectively improve the thermal stability of the electrolyte and increase the thermal decomposition temperature of the electrolyte. In addition, the ionic liquid can also obviously inhibit the growth of dendrites, further improve the safety of the electrolyte, and therefore the ionic liquid can be used for modifying the gel-type electrolyte and improving the lithium dendrite inhibition capability and electrochemical property of the gel-type electrolyte.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a gel-type ionic liquid electrolyte for a lithium ion battery, a preparation method and application thereof, wherein the gel-type ionic liquid electrolyte for the lithium ion battery can remarkably improve the interface contact problem of the traditional ex-situ polymerization gel-type ionic liquid electrolyte; the inhibition effect of the gel type ionic liquid electrolyte on lithium dendrites is strengthened, and the stability of an interface is improved; further improving the thermal stability and electrochemical stability of the gel type ionic liquid electrolyte.
The traditional method for preparing the gel type ionic liquid electrolyte in an ex-situ manner is to dissolve the electrolyte polymerized in an ex-situ manner into an organic solvent, so that the operation process is complicated, the gel type ionic liquid electrolyte and an electrode material cannot be completely wetted, a certain contact problem is caused, and the interface impedance is large. The invention adopts an in-situ polymerization method, completes polymerization at low temperature, realizes the preparation of the gel type ionic liquid electrolyte, can realize the full contact of the gel type ionic liquid electrolyte with electrode materials and diaphragms by the in-situ polymerization method, improves the interface property, is beneficial to forming a more stable SEI film, and further reduces the interface impedance. Meanwhile, a gel-state polymer formed by ring-opening polymerization of a cyclic ether organic solvent initiated by a Lewis acid type lithium salt initiator has certain elasticity, and can effectively inhibit volume change of an electrode in the charging and discharging processes; hair brushAlso introduces a lithium salt system containing both LiTFSI and LiFSI, and the FSI in the lithium salt system-The S-F bond in (1) will have a higher priority than TFSI-Wherein the C-F bond is broken to form F-Will combine with Li+LiF capable of promoting compact and uniform deposition of lithium and effectively stabilizing an SEI film is generated, so that the interfacial property of an electrolyte and an electrode is improved, and the growth of dendritic crystals is inhibited. The combination of the lithium salts and the gel-state polymer can jointly improve the effect of the gel-type ionic liquid electrolyte on inhibiting dendritic crystal growth, improve the stability of an interface and improve the mechanical property of an SEI film.
In addition to the two remarkable advantages, the ionic liquid capable of improving the thermal stability and the electrochemical window of the gel type ionic liquid electrolyte is added, so that the problems of low boiling point and narrow electrochemical window of the used cyclic ether organic solvent can be solved. The ionic liquid is a salt which is in a molten state at room temperature, and has the advantages of high boiling point, difficult volatilization, nonflammability, wider electrochemical window and the like. In addition, the ionic liquid containing pyrrolidinium (salt), piperidinium (salt) and imidazolidinium (salt) cations has an "electrostatic shielding" effect, so that uniform deposition and exfoliation of lithium ions can be promoted, thereby inhibiting growth of lithium dendrites. And the invention adds the TFSI-containing-And FSI-The ionic liquid is the same as the multi-lithium salt anion, so that the anion synergistic effect is further enhanced, and the dendritic growth is effectively inhibited. Therefore, the ionic liquid is introduced into the lithium salt electrolyte, so that the thermal stability of the electrolyte can be improved, the electrochemical window of the electrolyte is improved, and the growth of lithium dendrite can be effectively inhibited.
The purpose of the invention is realized by the following technical scheme:
a gel-type ionic liquid electrolyte, wherein the gel-type ionic liquid electrolyte comprises the following components: ionic liquid, cyclic ether organic solvent, Lewis acid type lithium salt initiator, multi-lithium salt solute and optional inorganic nanoparticle filler.
According to the invention, the electrolyte comprises the following components in percentage by mass:
0.5-25 wt% of ionic liquid, 20-60 wt% of cyclic ether organic solvent, 2-20 wt% of Lewis acid type lithium salt initiator, 2-25 wt% of multi-lithium salt solution and 0-10 wt% of inorganic nano-particle filler.
Preferably, the electrolyte comprises the following components in percentage by mass:
5-25 wt% of ionic liquid, 35-60 wt% of cyclic ether organic solvent, 4-20 wt% of Lewis acid type lithium salt initiator, 6-25 wt% of multi-lithium salt solution and 0-5 wt% of inorganic nano-particle filler.
Still preferably, the electrolyte comprises the following components in percentage by mass:
10-25 wt% of ionic liquid, 50-60 wt% of cyclic ether organic solvent, 8-20 wt% of Lewis acid type lithium salt initiator, 10-20 wt% of lithium salt solute and 0-3 wt% of inorganic nano particle filler.
Wherein the mass percentage of the ionic liquid is 5 wt%, 10 wt%, 15 wt%, 20 wt% and 25 wt%; the content of the cyclic ether organic solvent is 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt% and 60 wt%; the mass percentage of the Lewis acid type lithium salt initiator is 4 wt%, 5 wt%, 10 wt%, 15 wt% and 20 wt%; the mass percentage of the lithium salt solute is 6 wt%, 5 wt%, 10 wt%, 15 wt% and 20 wt%; the inorganic nano-particle filler accounts for 1 wt%, 2 wt%, 3 wt%, 4 wt% and 5 wt% of the mass.
According to the invention, the cyclic ether organic solvent can be used as a polymer monomer, and the ring-opening polymerization reaction of the cyclic ether polymer monomer is initiated by a Lewis acid type lithium salt initiator to form a three-dimensional cross-linked polymer network. The cyclic ether organic solvent is at least one selected from 1, 3-Dioxolane (DOL), ethylene glycol diglycidyl ether, 1, 4-butanediol glycidyl ether, 1,2,3, 4-diepoxybutane, and the like.
According to the invention, the inorganic nanoparticle filler is selected from one or more of silicon dioxide, titanium dioxide, aluminum oxide, lithium nitride, lithium phosphate and titanium aluminum lithium phosphate, and the particle diameter of the inorganic nanoparticle filler is between 5 and 500nm, preferably between 5 and 350 nm.
According to the invention, anions of the Lewis acid type lithium salt initiator can be combined with trace water in a reaction system, and Lewis acid is generated through hydrolysis reaction, so that the polymerization of the cyclic ether organic solvent is initiated.
According to the invention, the Lewis acid type lithium salt initiator is selected from lithium hexafluorophosphate (LiPF)6) Lithium tetrafluoroborate (LiBF)4) Lithium perchlorate (LiClO)4) One or more of lithium difluoroborate (LiDFOB), and the like. The Lewis acid type lithium salt initiator is used as the initiator, and the solution heat of the Lewis acid type lithium salt initiator is enough to initiate the polymerization reaction of the cyclic ether organic solvent, so that the polymerization can be completed without heating, and the performance test can be carried out without standing for a long time. Compared with the polymerization which needs heating, has certain advantages.
According to the invention, the multi-lithium salt solute is selected from bis-fluorosulfonyl imide Lithium (LiFSI) and bis-trifluoromethanesulfonyl imide Lithium (LiTFSI) in a mass ratio of 1: 10-10: 1, and optionally other non-Lewis acid type lithium salts (such as lithium bis-oxalato-borate (LiBOB), lithium nitrate (LiNO)3) Lithium chloride (LiCl), etc.). The multi-lithium salt solute in the invention is a mixed system of LiFSI and LiTFSI, because of FSI-The S-F chemical bond in the anion is prone to be broken to generate F-With Li in a solvent+Combine to form LiF, which is a substance that can improve interface stability, help to inhibit the growth of lithium dendrites, and induce lithium to deposit densely and uniformly.
According to the invention, the ionic liquid is selected from substances of which the cations and the anions do not react with the anode and cathode materials and the electrolyte of the lithium battery, and which have high thermal stability and electrochemical window (more than or equal to 4V).
Illustratively, the anion comprises bis (trifluoromethanesulfonyl) imide anion (TFSI)-) And bis-fluorosulfonylimide anion (FSI)-)。
Illustratively, the general structural formula of the cation is shown as the following formula (1), formula (2) and formula (3):
Figure BDA0002531520240000051
wherein R is selected from methyl, ethyl, propyl, isopropyl, n-butyl or dodecane.
Illustratively, the cation is selected from the group consisting of azoles: such as N-butyl-N-methylpyrrole cation; piperidines: such as N-methyl-N-propylpiperidine cation; imidazoles: such as 1-ethyl-3-methylimidazolium cation.
According to the present invention, the thermal decomposition temperature of the gel-type ionic liquid electrolyte is increased to 300 ℃ or higher.
The invention also provides a preparation method of the gel-type ionic liquid electrolyte, which comprises the following steps: uniformly mixing an ionic liquid, a cyclic ether organic solvent, a Lewis acid type lithium salt initiator, a lithium salt solute and an optional inorganic nanoparticle filler, standing, and forming the gel type ionic liquid electrolyte in situ.
According to the invention, the temperature of the rest is room temperature, for example 20-35 ℃. The standing time is 5 minutes to 30 days, preferably 1 to 15 days.
According to the invention, in the standing process, the Lewis acid type lithium salt initiator can initiate ring-opening polymerization of a cyclic ether organic solvent to form a three-dimensional cross-linked polymer network, and meanwhile, the ionic liquid, a multi-lithium salt solute and optionally an inorganic nanoparticle filler are filled in the three-dimensional cross-linked polymer network, so that in-situ formation of the gel type ionic liquid electrolyte is realized.
According to the invention, the method comprises the following steps: uniformly mixing an ionic liquid, a cyclic ether organic solvent, a Lewis acid type lithium salt initiator, a multi-lithium salt solute and optionally an inorganic nanoparticle filler, injecting the mixture between a positive plate and a negative plate of a lithium battery, standing, and forming a gel type ionic liquid electrolyte in situ.
According to the invention, the method comprises the following steps:
uniformly dispersing a lithium salt solute and an optional inorganic nano particle filler in a cyclic ether organic solvent under the argon atmosphere, then adding an ionic liquid, adding a Lewis acid type lithium salt initiator as a ring-opening initiator, uniformly stirring by magnetic force, uniformly dispersing, and standing to obtain the gel type ionic liquid electrolyte.
The invention also provides a lithium battery which comprises the gel type ionic liquid electrolyte.
According to the present invention, the lithium battery further includes a positive electrode material, a negative electrode material, and a separator.
The positive electrode material comprises lithium iron phosphate, lithium manganese iron phosphate, lithium nickel cobalt manganese oxide material and the like.
The negative electrode material is metal lithium, graphite, carbon fiber, a carbon nano tube, a silicon-carbon negative electrode, a tin-carbon negative electrode, graphene and the like.
Wherein the separator includes at least one of a polypropylene (PP) film, a Polyethylene (PE) film, a PP/PE/PP film, a cellulose separator, a glass fiber film, and the like.
The invention also provides a preparation method of the lithium battery, which comprises the following steps:
(1) uniformly dispersing a lithium salt solute and an optional inorganic nano particle filler in a cyclic ether organic solvent under the argon atmosphere, then adding an ionic liquid, adding a Lewis acid type lithium salt initiator as a ring-opening initiator, and uniformly dispersing by magnetic stirring to obtain a precursor solution;
(2) injecting the precursor solution between the positive and negative pole pieces, and packaging the battery by using a packaging machine;
(3) standing for a period of time at normal temperature to complete ring-opening polymerization, and obtaining the lithium battery containing the gel type ionic liquid electrolyte.
Has the advantages that:
the invention provides a gel type ionic liquid electrolyte for a lithium ion battery and a preparation method and application thereof, wherein a Lewis acid type lithium salt initiator is added to initiate in-situ ring-opening polymerization of a cyclic ether organic solvent at low temperature to form a three-dimensional cross-linked network polymer, and the three-dimensional cross-linked network polymer is used as a skeleton structure to limit ionic liquid, lithium salt and the like in a three-dimensional polymer structure, so that the in-situ preparation of the gel type ionic liquid electrolyte is realized, the full contact between the electrolyte and an electrode material and a diaphragm is ensured, the interface impedance can be effectively reduced, and the Lewis acid type lithium salt initiator and a multi-lithium salt solution form a multi-lithium salt system, which is beneficial to improving the cycle performance and stability of the gel type ionic liquid electrolyte; in addition, the invention also introduces the ionic liquid, obviously inhibits the growth of the lithium dendrite, simultaneously improves the thermal stability and the electrochemical window of the electrolyte, and effectively improves the safety performance of the electrolyte. The method has the advantages of simple and easy process, mild reaction conditions and easy production control, and is expected to be applied to high-energy density memory devices in a large scale.
Drawings
FIG. 1 shows the assembly of the ionic liquid-free trilithium salt gel-type electrolyte of comparative example 1 into a lithium symmetrical cell at a current of 0.5mA cm-2Field emission Scanning Electron Microscope (SEM) images of the lithium negative electrode after 340h of next operation.
FIG. 2 shows the ionic liquid-containing N-butyl-N-methylpyrrolidine bis (trifluoromethanesulfonyl) imide salt (Pyr) in example 114TFSI) into a lithium symmetrical battery at a current of 0.5mA cm-2SEM image of lithium negative electrode after 340h of next work.
FIG. 3 shows Pyr-containing compounds of example 114Trilithiumsalt gel-type ionic liquid electrolyte of TFSI and lithium symmetric cell without ionic liquid trilithium salt gel-type electrolyte of comparative example 1, current density at lithium deposition/dissolution was 0.5mA cm-2The capacity is 1mAh cm-2Next, a comparative graph of the change in polarization voltage with time.
FIG. 4 shows Pyr-containing samples obtained in example 114Tri-lithium salt gel-type ionic liquid electrolyte of TFSI and lithium symmetric cell without ionic liquid tri-lithium salt gel-type electrolyte in comparative example 1, current density at lithium deposition/dissolution was 1mA cm-2The capacity is 1mAh cm-2Next, a comparative graph of the change in polarization voltage with time.
FIG. 5 shows Pyr-containing particles obtained in example 114TFSI trilithium salt gel type ionic liquid electrolyte and Pyr-containing electrolyte of comparative example 314Lithium symmetric battery with TFSI dilithium salt ionic liquid electrolyte, in lithium deposition/dissolutionThe flow density is 1mAcm-2The capacity is 1mAh cm-2Next, a comparative graph of the change in polarization voltage with time.
FIG. 6 shows Pyr-containing samples obtained in example 114Coulombic efficiency and cyclic ratio capacity comparative plots of the trilithium salt gel-type ionic liquid electrolyte of TFSI and the trilithium salt gel-type electrolyte without ionic liquid of comparative example 1 applied to lithium iron phosphate batteries.
FIG. 7 shows Pyr-containing samples obtained in example 114Thermogravimetric comparison plots of the trilithium salt gel-type ionic liquid electrolyte of TFSI and the ionic liquid-free trilithium salt gel-type electrolyte of comparative example 1.
FIG. 8 shows Pyr-containing compounds of example 114The results of the TFSI triple lithium salt gel type ionic liquid electrolyte and the ionic liquid free double lithium salt liquid electrolyte of comparative example 2 were compared with each other by Linear Sweep Voltammetry (LSV).
Detailed Description
The present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
Example 1
Under argon atmosphere, firstly 0.14g of LiTFSI and 0.09g of LiFSI lithium salt solution are dissolved in 0.79g of cyclic ether organic solvent DOL in a glass sample bottle, and then 0.31g of ionic liquid Pyr is added14TFSI, stirring and mixing evenly by magnetic force; finally, 0.15g of Lewis acid type lithium salt initiator LiPF is added6Magnetically stirring to dissolve the active component completely to obtain Pyr-containing14TFSI tri-lithium salt gel type ionic liquid electrolyte precursor solution is stood for 2 days at normal temperature to obtain Pyr-containing electrolyte precursor solution14A trilithium salt gel-type ionic liquid electrolyte of TFSI. Pyr14TFSIThe structure of (a) is as follows:
Figure BDA0002531520240000081
the Pyr-containing compound14In the TFSI tri-lithium salt gel type ionic liquid electrolyte, the content of ionic liquid is 21 wt%, the content of cyclic ether organic solvent is 53.4 wt%, the content of Lewis acid type lithium salt initiator is 10.1 wt%, and the content of multi-lithium salt solution is 15.5 wt%.
Example 2
Under argon atmosphere, 0.17g of LiTFSI and 0.11g of LiFSI were first dissolved in 0.93 g of ethylene glycol diglycidyl ether in a glass sample vial, and 0.03g of SiO having a particle size of 30nm were added2A nanoparticle; then 0.22g of ionic liquid PI is added34FSI, stirring and mixing evenly by magnetic force; finally, 0.18g of a Lewis acid type lithium salt initiator LiBF was added4Magnetically stirring to dissolve the PI-containing compound completely to obtain PI-containing compound34Standing the precursor solution of the FSI trilithium salt gel type ionic liquid electrolyte for 3 days at normal temperature to obtain the electrolyte solution containing PI34A trilithium salt gel-type ionic liquid electrolyte of FSI. PI (proportional integral)34The structure of the FSI is as follows:
Figure BDA0002531520240000091
the said PI-containing34In the FSI trilithium salt gel type ionic liquid electrolyte, the content of ionic liquid is 13.4 wt%, the content of cyclic ether organic solvent is 56.7 wt%, the content of Lewis acid type lithium salt initiator is 11 wt%, the content of polylithium salt solvent is 17.1 wt%, and the content of inorganic nano-particle filler is 1.8 wt%.
Example 3
Under argon atmosphere, 0.11g of LiTFSI and 0.07g of LiFSI were first dissolved in 0.82 g of 1, 4-butanediol glycidyl ether in a glass sample bottle, 0.02g of SiO having a particle size of 50nm were added2A nanoparticle; then 0.16g of ionic liquid PI is added13FSI, stirring and mixing evenly by magnetic force; finally, 0.25g of a lithium salt of the Lewis acid type is addedInitiator LiClO4Magnetically stirring to dissolve the PI-containing compound completely to obtain PI-containing compound13Standing the precursor solution of the FSI trilithium salt gel type ionic liquid electrolyte for 5 days at normal temperature to obtain the electrolyte solution containing PI13A trilithium salt gel-type ionic liquid electrolyte of FSI. PI (proportional integral)13The structure of the FSI is as follows:
Figure BDA0002531520240000092
the said PI-containing13In the FSI trilithium salt gel type ionic liquid electrolyte, the content of the ionic liquid is 11.2 wt%, the content of the cyclic ether organic solvent is 57.3 wt%, the content of the Lewis acid type lithium salt initiator is 17.5 wt%, the content of the multi-lithium salt solvent is 12.6 wt%, and the content of the inorganic nano-particle filler is 1.4 wt%.
Example 4
Under argon atmosphere, 0.17g of LiTFSI, 0.11g of LiFSI and 0.12g of LiBOB were first dissolved in 1.25g of DOL in a glass sample bottle, and 0.01g of Al having a particle size of 40nm was added2O3A nanoparticle; then 0.32g of ionic liquid Pyr was added14TFSI, stirring and mixing evenly by magnetic force; finally, 0.3g of Lewis acid type lithium salt initiator LiDFOB is added and is completely dissolved by magnetic stirring to obtain Pyr-containing14TFSI multi-lithium salt gel type ionic liquid electrolyte precursor solution is stood for 2 days at normal temperature to obtain Pyr-containing electrolyte precursor solution14A multi-lithium salt gel-type ionic liquid electrolyte of TFSI.
The Pyr-containing compound14In the multi-lithium salt gel type ionic liquid electrolyte of TFSI, the content of ionic liquid is 14 wt%, the content of cyclic ether organic solvent is 54.8 wt%, the content of Lewis acid type lithium salt initiator is 13.2 wt%, the content of multi-lithium salt solvent is 17.5 wt%, and the content of inorganic nano-particle filler is 0.5 wt%.
Comparative example 1
Dissolving 0.14g of LiTFSI and 0.09g of LiFSI in 0.79g of DOL in a glass sample bottle under the atmosphere of argon, and completely dissolving the mixture after magnetic stirring; finally, 0.15g of the Lewis acid type lithium salt initiator LiPF is added6And the three lithium salt gel type electrolyte precursor solution without the ionic liquid is obtained by completely dissolving the three lithium salt gel type electrolyte precursor solution through magnetic stirring. Standing for 2 days at normal temperature to obtain the lithium salt gel electrolyte without ionic liquid.
In the ionic liquid-free trilithium salt gel electrolyte, the content of a cyclic ether organic solvent is 67.5 wt%, the content of a Lewis acid type lithium salt initiator is 12.8 wt%, and the content of a polylithium salt solvent is 19.7 wt%.
Comparative example 2
Under the atmosphere of argon, 0.14g of LiTFSI and 0.09g of LiFSI are dissolved in 0.79g of DOL in a glass sample bottle, and the solution is stirred and mixed uniformly by magnetic force to obtain the ionic liquid-free dilithium salt liquid electrolyte.
In the ionic liquid-free dilithium salt liquid electrolyte, the content of the cyclic ether organic solvent is 77.5 wt%, and the content of the multi-lithium salt solution is 22.5 wt%.
Comparative example 3
Dissolving 0.14g of LiTFSI and 0.09g of LiFSI in 0.79g of DOL in a glass sample bottle under an argon atmosphere, uniformly mixing by magnetic stirring, and adding 0.31g of ionic liquid Pyr14TFSI to obtain Pyr-containing14The dilithium salt ionic liquid electrolyte of TFSI.
The Pyr-containing compound14In the dilithium salt ionic liquid electrolyte of TFSI, the content of ionic liquid is 23.3 wt%, the content of cyclic ether organic solvent is 59.4 wt%, and the content of multi-lithium salt solution is 17.3 wt%.
Test example 1
The Pyr-containing electrolyte described in example 1 was used as a positive and negative electrode of a battery using a lithium plate14Respectively injecting a precursor solution of the TFSI trilithium salt gel type ionic liquid electrolyte and the precursor solution of the ionic liquid-free trilithium salt gel type electrolyte described in the comparative example 1 between the positive and negative pole pieces of the battery, standing for 2 days at normal temperature, and carrying out a polarization performance test after the in-situ ring-opening polymerization reaction is completed. At a current of 0.5mA cm-2And 1mA cm-2The discharging and charging circulation is carried out, and the charging and discharging capacity of each circle of circulation is 1mAh cm-2。
At the currentIs 0.5mA cm-2After 340h of the lower cycle, SEM images of the lithium metal electrode of comparative example 1 using the ionic liquid-free trilithium salt gel-type electrolyte as the electrolyte are shown in fig. 1. Pyr-containing compounds used in example 114SEM images of lithium metal electrodes using TFSI triple lithium salt gel type ionic liquid electrolyte as electrolyte are shown in fig. 2. As can be seen from fig. 1, there is significant dendrite growth on the lithium metal surface of the trilithium salt gel-type electrolyte without ionic liquid; and in FIG. 2 contains Pyr14The lithium metal surface of the trilithium salt gel-type ionic liquid electrolyte of TFSI is free of dendrites and dead lithium layers. The ionic liquid is proved to be capable of effectively inhibiting the growth of lithium dendrite in the gel type ionic liquid electrolyte, improving the cycle performance and improving the safety of the lithium battery.
The results of the polarization test are shown in FIGS. 3 and 4, at a current of 0.5mA cm-2Then, the ionic liquid-free tri-lithium salt gel type electrolyte is broken down in 52 hours, and contains Pyr14The TFSI trilithium salt gel type ionic liquid electrolyte polarization voltage was stable, even after 450h, at 30 mV. At a current of 1mA cm-2Then, the tri-lithium salt gel type electrolyte without ionic liquid is broken down within 30h, and contains Pyr14The TFSI trilithium salt gel type ionic liquid electrolyte polarization voltage was stable, even after 450h, at 60 mV. In combination with the SEM image of the lithium cathode, the addition of the ionic liquid is further proved to be capable of effectively inhibiting the growth of lithium dendrites and reducing the polarization voltage, which shows that the addition of the ionic liquid can reduce the interface impedance.
Test example 2
The Pyr-containing electrolyte described in example 1 was used as a positive and negative electrode of a battery using a lithium plate14TFSI TRILITHIUM SALT GEL-TYPE IONIC LIQUID ELECTROLYTE PRECURSOR SOLUTION AND PYR-CONTAINING SOLUTION AS COMPARATIVE EXAMPLE 314Respectively injecting the TFSI dilithium ionic liquid electrolyte between the positive and negative pole pieces of the battery, standing for 2 days at normal temperature, and allowing the electrolyte to contain Pyr14And after the in-situ ring-opening polymerization reaction of the TFSI trilithium salt gel type ionic liquid electrolyte precursor solution is completed, carrying out a polarization performance test. At a current of 1mA cm-2The discharging and charging circulation is carried out, and the charging and discharging capacity of each circle of circulation is 1mAh cm-2。
The polarization test results are shown in FIG. 5, containing Pyr14The polarization voltage of the TFSI double-lithium salt ionic liquid electrolyte is always higher than that of the liquid electrolyte containing Pyr14A trilithium salt gel-type ionic liquid electrolyte of TFSI; even after 450h, contains Pyr14The polarization voltage of the TFSI trilithium salt gel type ionic liquid electrolyte can be stabilized at 60mV, which is specific to Pyr14The polarization voltage of the TFSI dilithium salt ionic liquid electrolyte is lower by 10 mV. The gel type ionic liquid electrolyte formed by adding the Lewis acid type lithium salt initiator is proved to be capable of effectively inhibiting the growth of lithium dendrites and reducing the polarization voltage.
Test example 3
Preparing a lithium iron phosphate positive electrode material: mixing lithium iron phosphate, ketjen black and polyvinylidene fluoride according to a mass ratio of 8:1:1, adding a solvent N-methyl pyrrolidone (NMP) to prepare a uniform slurry, coating the uniform slurry on an aluminum foil current collector, heating and drying the uniform slurry at the temperature of 80 ℃ in vacuum for 10 hours, and finally cutting the uniform slurry to obtain the cathode material.
The prepared lithium iron phosphate electrode plate is used as a positive electrode material, lithium metal is used as a negative electrode, and Pyr-containing lithium iron phosphate electrode plate prepared in the example 1 is used as a negative electrode material14Respectively injecting a trilithium salt gel type ionic liquid electrolyte precursor solution of TFSI and a precursor solution of the ionic liquid-free trilithium salt gel type electrolyte in the comparative example 1 between the positive and negative pole pieces of the battery, standing for 3 days at normal temperature, and performing a cycle stability test after the in-situ ring-opening polymerization reaction is completed: and carrying out constant-current charge and discharge tests on the battery by using a charge and discharge instrument, wherein the test voltage interval is 2.5-4V. The charge and discharge multiplying power and the battery capacity are calculated by the mass of the lithium iron phosphate. The current was set to 0.2C (169 mAh g-1C) for the first two battery cycles-1) Performing constant current charge and discharge to activate the electrode material; then, constant current charge and discharge cycles were performed with the current set to 0.5C. The cycling results are shown in FIG. 6: the specific capacity of the battery without the ionic liquid lithium salt gel type electrolyte in the comparative example 1 starts to decay from the 10 th circle and is damaged; while in example 1 containing Pyr14The battery specific capacity of the TFSI tri-lithium salt gel type ionic liquid electrolyte can be still maintained at 137.7mAh g at the 80 th circle-1Namely, 96.6 percent of specific capacity is kept, and the coulombic efficiency is stabilized at 99.9 percent. Demonstration of the addition of an Ionic liquidEffectively improving the cycling stability of the battery.
Test example 4
Pyr-containing compound obtained in example 114The precursor solution of the trilithium salt gel type ionic liquid electrolyte of TFSI and the precursor solution of the ionic liquid-free trilithium salt gel type electrolyte in comparative example 1 were allowed to stand at room temperature for 4 days, and thermogravimetric analysis (TGA) was performed after the in situ ring-opening polymerization reaction was completed: respectively taking 1g of sample, heating at a rate of 10 ℃ for min under the condition of nitrogen-1Firstly, raising the temperature from room temperature to 50 ℃, and keeping the temperature for 30 min; the temperature was again raised to 500 ℃ at the same rate, and the results are shown in FIG. 7: pyr-containing in example 114The decomposition temperature of the TFSI tri-lithium salt gel type ionic liquid electrolyte is higher than that of the ionic liquid-free tri-lithium salt gel type electrolyte of the comparative example 1, and is increased to 400 ℃, so that the thermal stability of the gel type ionic liquid electrolyte can be effectively improved by adding the ionic liquid.
Test example 5
Taking a lithium sheet as a negative electrode material of the battery, and taking a stainless steel sheet as a positive electrode material of the battery; pyr-containing compound obtained in example 114Respectively injecting precursor solution of TFSI tri-lithium salt gel type ionic liquid electrolyte and ionic liquid-free dilithium salt liquid electrolyte described in comparative example 2 between positive and negative pole pieces of the battery, standing at normal temperature for 2 days, and allowing the electrolyte to contain Pyr14After the TFSI tri-lithium salt gel type ionic liquid electrolyte precursor electrolyte solution in-situ ring-opening polymerization reaction is completed, an electrochemical window test is carried out: performing electrochemical window test on the button cell by using an electrochemical workstation, wherein the scanning range is from open-circuit voltage to 5.5V, and the scanning speed is 1mV s-1. The test results are shown in fig. 8: pyr-containing in example 114The electrochemical window of the tri-lithium salt gel type ionic liquid electrolyte of TFSI increased from 4V to 4.3V compared to the ionic liquid free dilithium salt liquid electrolyte of comparative example 2.
Therefore, the multi-lithium salt gel type ionic liquid electrolyte containing the ionic liquid, which is prepared by the invention, can effectively inhibit the growth of lithium dendrites, and ensures the safety and stability of battery circulation; meanwhile, the thermal stability and the electrochemical stability of the gel type ionic liquid electrolyte are improved, and the gel type ionic liquid electrolyte has a good application prospect.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A gel-type ionic liquid electrolyte, wherein the gel-type ionic liquid electrolyte comprises the following components: ionic liquid, cyclic ether organic solvent, Lewis acid type lithium salt initiator, multi-lithium salt solute and optional inorganic nanoparticle filler.
2. The ionic liquid electrolyte as claimed in claim 1, wherein the electrolyte comprises the following components in percentage by mass:
0.5-25 wt% of ionic liquid, 20-60 wt% of cyclic ether organic solvent, 2-20 wt% of Lewis acid type lithium salt initiator, 2-25 wt% of multi-lithium salt solution and 0-10 wt% of inorganic nano-particle filler.
Preferably, the electrolyte comprises the following components in percentage by mass:
5-25 wt% of ionic liquid, 35-60 wt% of cyclic ether organic solvent, 4-20 wt% of Lewis acid type lithium salt initiator, 6-25 wt% of multi-lithium salt solution and 0-5 wt% of inorganic nano-particle filler.
3. The ionic liquid electrolyte according to claim 1 or 2, wherein the cyclic ether-based organic solvent is selected from at least one of 1, 3-Dioxolane (DOL), ethylene glycol diglycidyl ether, 1, 4-butanediol glycidyl ether, 1,2,3, 4-diepoxybutane;
the inorganic nano-particle filler is selected from one or more of silicon dioxide, titanium dioxide, aluminum oxide, lithium nitride, lithium phosphate and lithium aluminum titanium phosphate;
the Lewis acid type lithium salt initiator is selected from lithium hexafluorophosphate (LiPF)6) Lithium tetrafluoroborate (LiBF)4) High chlorine contentLithium (LiClO)4) And lithium difluoroborate (LiDFOB).
4. An ionic liquid electrolyte according to any one of claims 1 to 3, wherein the multi-lithium salt solute is selected from lithium bis-fluorosulfonylimide (LiFSI) and lithium bis-trifluoromethanesulfonylimide (LiTFSI) in a mass ratio of 1:10 to 10:1, and optionally other non-Lewis acid type lithium salts (such as lithium bis-oxalato-borate (LiBOB), lithium nitrate (LiNO)3) Lithium chloride (LiCl)).
5. The ionic liquid electrolyte of any of claims 1-4, wherein the anion of the ionic liquid comprises bis (trifluoromethanesulfonyl) imide anion (TFSI)-) And bis-fluorosulfonylimide anion (FSI)-)；
The structural general formula of the cation of the ionic liquid is shown as the following formulas (1), (2) and (3):
Figure FDA0002531520230000021
wherein R is selected from methyl, ethyl, propyl, isopropyl, n-butyl or dodecane;
preferably, the cation is selected from the group consisting of N-butyl-N-methylpyrrole cation, N-methyl-N-propylpiperidine cation, 1-ethyl-3-methylimidazole cation.
6. The ionic liquid electrolyte of any of claims 1-5, wherein the thermal decomposition temperature of the gel-type ionic liquid electrolyte is increased to 300 ℃ or greater.
7. A method of preparing a gel-type ionic liquid electrolyte as claimed in any one of claims 1 to 6, said method comprising the steps of: uniformly mixing an ionic liquid, a cyclic ether organic solvent, a Lewis acid type lithium salt initiator, a lithium salt solute and an optional inorganic nanoparticle filler, standing, and forming the gel type ionic liquid electrolyte in situ.
8. The production method according to claim 7, wherein the temperature of the standing is room temperature, and the time of the standing is 5 minutes to 30 days.
9. A lithium battery comprising the gel-type ionic liquid electrolyte according to any one of claims 1 to 6.
10. The lithium battery of claim 9, wherein the lithium battery further comprises a positive electrode material, a negative electrode material, and a separator;
the positive electrode material comprises lithium iron phosphate, lithium manganese iron phosphate and lithium nickel cobalt manganese oxide materials; the negative electrode material is metal lithium, graphite, carbon fiber, carbon nano tube, silicon carbon negative electrode, tin carbon negative electrode and graphene.
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