CN115678000A - Polytrimethylene carbonate electrolyte, lithium ion battery and preparation method - Google Patents
Polytrimethylene carbonate electrolyte, lithium ion battery and preparation method Download PDFInfo
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- CN115678000A CN115678000A CN202211349445.1A CN202211349445A CN115678000A CN 115678000 A CN115678000 A CN 115678000A CN 202211349445 A CN202211349445 A CN 202211349445A CN 115678000 A CN115678000 A CN 115678000A
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 82
- -1 Polytrimethylene carbonate Polymers 0.000 title claims abstract description 56
- 229920000166 polytrimethylene carbonate Polymers 0.000 title claims abstract description 44
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- YFHICDDUDORKJB-UHFFFAOYSA-N trimethylene carbonate Chemical compound O=C1OCCCO1 YFHICDDUDORKJB-UHFFFAOYSA-N 0.000 claims abstract description 45
- 230000005496 eutectics Effects 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 18
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 17
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 238000012656 cationic ring opening polymerization Methods 0.000 claims abstract description 5
- 239000003999 initiator Substances 0.000 claims abstract description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 29
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 28
- 238000011065 in-situ storage Methods 0.000 claims description 13
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 10
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 8
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 8
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 7
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 6
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 6
- 239000004014 plasticizer Substances 0.000 claims description 6
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 5
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 5
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 5
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical compound C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 claims description 4
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 4
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 claims description 4
- 229940116357 potassium thiocyanate Drugs 0.000 claims description 4
- YUOWTJMRMWQJDA-UHFFFAOYSA-J tin(iv) fluoride Chemical compound [F-].[F-].[F-].[F-].[Sn+4] YUOWTJMRMWQJDA-UHFFFAOYSA-J 0.000 claims description 4
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 3
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 2
- FKOASGGZYSYPBI-UHFFFAOYSA-K bis(trifluoromethylsulfonyloxy)alumanyl trifluoromethanesulfonate Chemical compound [Al+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F FKOASGGZYSYPBI-UHFFFAOYSA-K 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 10
- 230000007547 defect Effects 0.000 abstract description 6
- 230000000977 initiatory effect Effects 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 230000009977 dual effect Effects 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 238000002955 isolation Methods 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 238000010586 diagram Methods 0.000 description 5
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 4
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 4
- 230000008021 deposition Effects 0.000 description 3
- HNCXPJFPCAYUGJ-UHFFFAOYSA-N dilithium bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].[Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F HNCXPJFPCAYUGJ-UHFFFAOYSA-N 0.000 description 3
- 239000011245 gel electrolyte Substances 0.000 description 3
- 239000005518 polymer electrolyte Substances 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- UFVGIXRFPGCCAM-UHFFFAOYSA-N aluminum;bis(trifluoromethylsulfonyl)azanide Chemical compound [Al+3].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F UFVGIXRFPGCCAM-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- CMWINYFJZCARON-UHFFFAOYSA-N 6-chloro-2-(4-iodophenyl)imidazo[1,2-b]pyridazine Chemical compound C=1N2N=C(Cl)C=CC2=NC=1C1=CC=C(I)C=C1 CMWINYFJZCARON-UHFFFAOYSA-N 0.000 description 1
- NCZYUKGXRHBAHE-UHFFFAOYSA-K [Li+].P(=O)([O-])([O-])[O-].[Fe+2].[Li+] Chemical compound [Li+].P(=O)([O-])([O-])[O-].[Fe+2].[Li+] NCZYUKGXRHBAHE-UHFFFAOYSA-K 0.000 description 1
- SYRDSFGUUQPYOB-UHFFFAOYSA-N [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O SYRDSFGUUQPYOB-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001768 cations Chemical group 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000003181 co-melting Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- VILAVOFMIJHSJA-UHFFFAOYSA-N dicarbon monoxide Chemical group [C]=C=O VILAVOFMIJHSJA-UHFFFAOYSA-N 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011066 ex-situ storage Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Images
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a polytrimethylene carbonate electrolyte, a lithium ion battery and a preparation method thereof. The preparation method of the polytrimethylene carbonate electrolyte comprises the following steps: the method comprises the steps of uniformly mixing trimethylene carbonate and a lithium salt to obtain a deep eutectic electrolyte, wherein the trimethylene carbonate and the unavoidable water in the lithium salt are used as an initiator, and the trimethylene carbonate is subjected to a cationic ring-opening polymerization reaction under a heating condition to obtain the polytrimethylene carbonate electrolyte. The invention overcomes the defects of harsh preparation conditions, difficult removal of non-electrolyte components and the like of the traditional polytrimethylene carbonate electrolyte by designing the deep eutectic electrolyte with dual functions of catalysis and initiation as a polymerization reaction precursor solution for preparing the polytrimethylene carbonate electrolyte.
Description
Technical Field
The invention belongs to the technical field of polymer electrolytes, and particularly relates to a polytrimethylene carbonate electrolyte, a lithium ion battery and a preparation method of the polytrimethylene carbonate electrolyte and the lithium ion battery.
Background
The solid polymer-based lithium ion battery can simultaneously meet the requirements of energy storage equipment on high energy density and safety, and therefore becomes a research hotspot in the field of energy sources. However, the most widely studied polyether electrolyte systems are limited by the windows of ionic conductivity and electrochemical stability, and cannot meet the practical application requirements of lithium batteries. Compared with polyether electrolyte matrixes, the polycarbonate electrolyte matrix has more excellent comprehensive performance and is one of the most potential matrix materials in the field of polymer electrolytes. The polytrimethylene carbonate has the advantages of good biocompatibility, low crystallinity, high thermodynamic and electrochemical stability and the like, and is an excellent lithium ion carrier. However, the preparation of polytrimethylene carbonate generally employs a ring-opening reaction catalyzed by a transition metal complex or an organic compound containing an ionic hydrogen bond (see non-patent document 1,prog.polym.sci.,2022,125,101484), and has disadvantages such as severe reaction conditions and difficulty in removing non-electrolyte components such as a solvent and a catalyst.
In addition, the polytrimethylene carbonate obtained by the above method is further mixed with a lithium salt by a solution casting film-forming method to prepare an electrolyte. However, the solvent remaining in the preparation process is liable to react with the electrode material, and the prepared polytrimethylene carbonate electrolyte has poor contact and compatibility with the electrode interface, and it is difficult to realize stable cycling of a lithium battery for a long time (see non-patent document 2,solid State ionics,2014,262,738-742).
Disclosure of Invention
Aiming at the defects or improvement requirements of the prior art, the invention provides a polytrimethylene carbonate electrolyte, a lithium ion battery and a preparation method, aiming at overcoming the defects of harsh preparation conditions, impurity introduction and the like of the existing polytrimethylene carbonate electrolyte and solving the defects of poor compatibility between a polymer electrolyte and electrodes, large interface resistance, poor circulation stability and the like in the non-in-situ lithium battery assembly technology.
In order to achieve the above objects, according to one aspect of the present invention, there is provided a method for preparing a polytrimethylene carbonate electrolyte, which comprises obtaining a novel deep eutectic electrolyte having both catalytic and initiating functions based on the coordination of trimethylene carbonate and lithium salt, uniformly mixing trimethylene carbonate and lithium salt to obtain the deep eutectic electrolyte, wherein unavoidable water present in the trimethylene carbonate and the lithium salt is used as an initiator, and heating the trimethylene carbonate to perform a cationic ring-opening polymerization reaction to obtain the polytrimethylene carbonate electrolyte.
Preferably, the lithium salt includes at least one of lithium bistrifluoromethanesulfonylimide, lithium difluorooxalato borate, lithium perchlorate, lithium hexafluorophosphate, lithium tetrafluoroborate, and lithium trifluoromethanesulfonate.
Preferably, the molar ratio of trimethylene carbonate to lithium salt in the deep eutectic electrolyte is 1.
Preferably, the reaction temperature of the cation ring-opening polymerization reaction is 30-80 ℃, and the reaction time is 0.5-24 hours.
Preferably, the mass concentration of the unavoidable water present in the trimethylene carbonate and lithium salt is 0.01% to 0.3%.
Preferably, the preparation method further comprises adding an inorganic salt to the deep eutectic electrolyte, wherein the inorganic salt comprises at least one of lithium fluoride, lithium chloride, lithium bromide, lithium iodide, lithium nitrate, lithium acetate, potassium thiocyanate, tin fluoride and aluminum trifluoromethanesulfonate, and the molar ratio of the lithium salt to the inorganic salt is preferably 1: (0.01-0.1). The addition of the inorganic salt can increase the polymerization rate and improve the cycle stability of the battery.
Preferably, the preparation method further comprises adding a plasticizer to the deep eutectic electrolyte, the plasticizer comprising at least one of sulfolane and divinyl sulfone.
It should be noted that the moisture content in the environment during the preparation of the polytrimethylene carbonate electrolyte affects the polymerization degree of the polymer, so that, as a preferred mode, the polytrimethylene carbonate electrolyte is prepared under the anhydrous and anaerobic conditions, and the polymerization degree of the polymerization reaction is more controllable under the anhydrous condition.
According to another aspect of the present invention, a polytrimethylene carbonate electrolyte is provided.
According to another aspect of the invention, a preparation method of a lithium ion battery is provided, comprising the steps of uniformly mixing trimethylene carbonate and lithium salt to obtain a deep co-molten electrolyte, and heating the lithium ion battery after the lithium ion battery is assembled by using the deep co-molten electrolyte to form a polytrimethylene carbonate electrolyte in situ in the lithium ion battery; preferably, the heating temperature is 30-80 ℃, and the heating time is 0.5-24 hours.
According to yet another aspect of the present invention, a lithium ion battery is provided.
In general, at least the following advantages can be obtained by the above technical solution contemplated by the present invention compared to the prior art.
(1) In the present invention, trimethylene carbonate has a low melting point of 46 ℃ and is capable of forming a liquid deep eutectic electrolyte by coordination of an electron-rich carbonyl group to lithium ions. Meanwhile, the coordination of the trimethylene carbonate and lithium ions reduces the electron cloud density of carbonyl carbon atoms, thereby catalyzing the trimethylene carbonate to carry out cationic ring-opening polymerization to form the polytrimethylene carbonate electrolyte in situ. Therefore, the invention overcomes the defects of harsh preparation conditions, difficult removal of non-electrolyte components and the like of the traditional polytrimethylene carbonate electrolyte by designing the deep eutectic electrolyte with dual functions of catalysis and initiation as a polymerization reaction precursor solution for preparing the polytrimethylene carbonate electrolyte.
(2) The method prepares the poly-trimethylene carbonate electrolyte by an in-situ polymerization method of the deep eutectic electrolyte, and overcomes the defects of poor contact property and compatibility of an electrolyte-electrode interface and the like existing in the preparation of the poly-trimethylene carbonate electrolyte by an ex-situ method, thereby reducing the interface impedance and promoting the lithium ion conduction.
(3) The invention optimizes the components of the deep eutectic electrolyte, and adds inorganic salt to improve the polymerization reaction rate and the stability of an electrolyte-electrode interface, thereby realizing the long-time stable cycle performance of the polytrimethylene carbonate lithium battery.
(4) According to the invention, sulfolane and divinyl sulfone plasticizers can be added to prepare the polytrimethylene carbonate gel electrolyte, so that the ionic conductivity is improved, and the rate capability of the applied lithium battery is improved.
Drawings
FIG. 1 is a charge-discharge cycle diagram of a lithium-iron phosphate battery based on polytrimethylene carbonate electrolyte of example 2;
FIG. 2 is a graph of the ionic conductivity of a lithium battery based on polytrimethylene carbonate electrolyte in example 3;
FIG. 3 is a lithium deposition diagram for a lithium battery based on polytrimethylene carbonate electrolyte of example 4;
fig. 4 is a graph of the electrochemical stability window of a lithium battery based on polytrimethylene carbonate electrolyte in example 5.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention. In addition, the technical features involved in the respective embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1
The present embodiment provides a polytrimethylene carbonate electrolyte, which is prepared by a method comprising:
under the conditions of no water and oxygen isolation, mixing trimethylene carbonate, bis (trifluoromethanesulfonimide) lithium and trifluoromethanesulfonimide aluminum, and stirring at room temperature to form a deep eutectic electrolyte; the molar ratio of trimethylene carbonate, lithium bis (trifluoromethanesulfonylimide) and trifluoromethanesulfonylaluminum was 5; heating at 80 ℃ for 12 hours gave a polytrimethylene carbonate electrolyte.
Example 2
The embodiment provides a lithium ion battery, and a preparation method thereof is as follows:
under the conditions of no water and oxygen isolation, mixing trimethylene carbonate, bis (trifluoromethanesulfonimide) lithium and trifluoromethanesulfonimide aluminum, and stirring at room temperature to form a deep eutectic electrolyte; the molar ratio of trimethylene carbonate, lithium bis (trifluoromethanesulfonylimide) and trifluoromethanesulfonylaluminum was 5; adding 20 mass percent of sulfolane, uniformly stirring, dropwise adding the sulfolane on a cellulose support membrane, and assembling a lithium-iron phosphate lithium battery; the assembled battery was heated at 80 ℃ for 12 hours and a battery charge-discharge cycle test was performed.
Fig. 1 is a charge-discharge cycle diagram of an in-situ assembled lithium polytrimethylene carbonate-iron phosphate lithium battery as described in example 2. As can be seen from figure 1, the polytrimethylene carbonate electrolyte prepared by the method has good interface stability with lithium metal and lithium iron phosphate electrodes, and the battery can stably charge and discharge for more than 1000 times.
Example 3
The embodiment provides a lithium ion battery, and a preparation method thereof is as follows:
under the conditions of no water and oxygen isolation, mixing trimethylene carbonate, lithium bis (trifluoromethanesulfonimide) and lithium nitrate, and stirring at room temperature to form a deep eutectic electrolyte; trimethylene carbonate, lithium bis (trifluoromethanesulfonylimide) and lithium nitrate were assembled in a molar ratio of 5. Figure 2 is a graph of the ionic conductivity of the in situ assembled polytrimethylene carbonate electrolyte coin cells described in example 3.
Example 4
The embodiment provides a lithium ion battery, and a preparation method thereof is as follows:
under the conditions of no water and oxygen isolation, mixing trimethylene carbonate and lithium bis (trifluoromethanesulfonimide) and stirring at room temperature to form a deep eutectic electrolyte; trimethylene carbonate, lithium bis (trifluoromethanesulfonylimide) in a molar ratio of 5, was assembled with a lithium sheet into a coin lithium symmetric cell and heated at 80 ℃ for 24 hours and tested for lithium deposition. Fig. 3 is a lithium deposition diagram of the in situ assembled polytrimethylene carbonate electrolyte coin cells described in example 4.
Example 5
The embodiment provides a lithium ion battery, and a preparation method thereof is as follows:
under the conditions of no water and oxygen isolation, mixing trimethylene carbonate, bis (trifluoromethanesulfonimide) lithium and lithium bromide, and stirring at room temperature to form a deep eutectic electrolyte; trimethylene carbonate, lithium bis (trifluoromethanesulfonylimide) and lithium nitrate in a molar ratio of 8.1, assembled into a lithium symmetrical coin cell and heated at 80 ℃ for 1 hour and subjected to electrochemical stability window testing. Figure 4 is a diagram of the electrochemical stability window of an in situ assembled polytrimethylene carbonate electrolyte lithium symmetrical cell as described in example 5.
Example 6
The embodiment provides a lithium ion battery, and a preparation method thereof is as follows:
under the conditions of no water and oxygen isolation, mixing trimethylene carbonate, lithium trifluoromethanesulfonate and lithium acetate, and stirring at room temperature to form a deep eutectic electrolyte; the molar ratio of trimethylene carbonate, lithium trifluoromethanesulfonate and lithium fluoride is 5.
Example 7
The embodiment provides a lithium ion battery, and a preparation method thereof is as follows:
under the conditions of no water and oxygen isolation, mixing trimethylene carbonate, lithium trifluoromethanesulfonate and lithium acetate, and stirring at room temperature to form a deep eutectic electrolyte; the molar ratio of the trimethylene carbonate to the lithium bis (trifluoromethanesulfonyl) imide to the lithium acetate is 5.
Example 8
The embodiment provides a lithium ion battery, and a preparation method thereof is as follows:
under the conditions of no water and oxygen isolation, mixing trimethylene carbonate, lithium perchlorate and potassium thiocyanate, and stirring at room temperature to form a deep eutectic electrolyte; the molar ratio of trimethylene carbonate, lithium bistrifluoromethanesulfonimide and potassium thiocyanate is 5
A trimethylene carbonate gel electrolyte.
Example 9
The embodiment provides a lithium ion battery, and a preparation method thereof is as follows:
under the conditions of no water and oxygen isolation, mixing trimethylene carbonate, lithium difluoro-oxalate borate and lithium iodide, and stirring at room temperature to form a deep eutectic electrolyte; the molar ratio of trimethylene carbonate, lithium difluoro-oxalato-borate and lithium iodide is 10.1, divinyl sulfone plasticizer is added, and lithium symmetrical button cells and lithium-iron phosphate cells are assembled respectively and heated at 80 ℃ for 5 hours to prepare the polytrimethylene carbonate gel electrolyte in situ.
Example 10
The embodiment provides a lithium ion battery, and a preparation method thereof is as follows:
under the conditions of no water and oxygen isolation, mixing trimethylene carbonate, lithium hexafluorophosphate and lithium chloride, and stirring at room temperature to form a deep eutectic electrolyte; the molar ratio of trimethylene carbonate, lithium hexafluorophosphate and lithium chloride is 5.05, and the lithium symmetrical button cell and the lithium-iron phosphate cell are assembled respectively and heated at 80 ℃ for 12 hours to prepare the polytrimethylene carbonate electrolyte in situ.
Example 11
The embodiment provides a lithium ion battery, and a preparation method thereof is as follows:
under the conditions of no water and oxygen isolation, mixing trimethylene carbonate, lithium tetrafluoroborate and tin fluoride, and stirring at room temperature to form a deep eutectic electrolyte; the molar ratio of the trimethylene carbonate, the lithium tetrafluoroborate and the tin fluoride is 5.
According to the invention, the polytrimethylene carbonate electrolyte is prepared by designing the trimethylene carbonate-based deep eutectic electrolyte with dual functions of catalysis and initiation, and the in-situ polymerization based on the deep eutectic electrolyte and is applied to the lithium ion battery, and the polytrimethylene carbonate electrolyte with excellent comprehensive electrochemical performance is obtained by improving the overall synthesis route design of the corresponding preparation method, the parameter conditions (such as the types and the proportions of reactants in each reaction step, the reaction temperature and the reaction time) of each process step, and the like; on the other hand, the in-situ polymerization method can remarkably reduce the interface impedance between the electrolyte and the electrode, and can remarkably improve the interface stability of the electrolyte and the electrode by optimizing the components of the deep co-melting precursor solution, thereby endowing the lithium battery with ultra-long charge-discharge cycle performance.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A method for preparing a polytrimethylene carbonate electrolyte, comprising:
the method comprises the steps of uniformly mixing trimethylene carbonate and a lithium salt to obtain a deep eutectic electrolyte, wherein unavoidable water in the trimethylene carbonate and the lithium salt is used as an initiator, and under the heating condition, the trimethylene carbonate undergoes a cationic ring-opening polymerization reaction to obtain the polytrimethylene carbonate electrolyte.
2. The method of claim 1, wherein the lithium salt comprises at least one of lithium bistrifluoromethanesulfonylimide, lithium difluorooxalato borate, lithium perchlorate, lithium hexafluorophosphate, lithium tetrafluoroborate, and lithium trifluoromethanesulfonate.
3. The method of claim 1 or 2, wherein the molar ratio of trimethylene carbonate to lithium salt in the deep eutectic electrolyte is 1.
4. The production method according to claim 1 or 2, wherein the reaction temperature of the cationic ring-opening polymerization is 30 to 80 ℃ and the reaction time is 0.5 to 24 hours.
5. The method according to claim 1, wherein the concentration of unavoidable water present in the trimethylene carbonate and the lithium salt is 0.01 to 0.3% by mass.
6. The method of claim 1, further comprising adding an inorganic salt to the deep eutectic electrolyte, the inorganic salt comprising at least one of lithium fluoride, lithium chloride, lithium bromide, lithium iodide, lithium nitrate, lithium acetate, potassium thiocyanate, tin fluoride, and aluminum triflate, preferably in a molar ratio of 1: (0.01-0.1).
7. The method of claim 1, further comprising adding a plasticizer to the deep eutectic electrolyte, the plasticizer comprising at least one of sulfolane and divinylsulfone; preferably, the polytrimethylene carbonate electrolyte is prepared under anhydrous and oxygen-free conditions.
8. A polytrimethylene carbonate electrolyte prepared by the preparation method of any one of claims 1 to 7.
9. A preparation method of a lithium ion battery is characterized in that trimethylene carbonate and lithium salt are uniformly mixed to obtain a deep co-molten electrolyte, the lithium ion battery is heated after the lithium ion battery is assembled by using the deep co-molten electrolyte, and a poly trimethylene carbonate electrolyte is formed in the lithium ion battery in situ; preferably, the heating temperature is 30-80 ℃, and the heating time is 0.5-24 hours.
10. A lithium ion battery prepared by the preparation method of claim 9.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202211349445.1A CN115678000B (en) | 2022-10-31 | 2022-10-31 | Polytrimethylene carbonate electrolyte, lithium ion battery and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202211349445.1A CN115678000B (en) | 2022-10-31 | 2022-10-31 | Polytrimethylene carbonate electrolyte, lithium ion battery and preparation method |
Publications (2)
| Publication Number | Publication Date |
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| CN115678000A true CN115678000A (en) | 2023-02-03 |
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1449422A (en) * | 2000-02-29 | 2003-10-15 | 国际壳牌研究有限公司 | Improved method for production of poly(trimethylene carbonate) |
| US20050113594A1 (en) * | 2002-02-07 | 2005-05-26 | Jurgen Van Holen | Process using a cyclic carbonate reactant |
| CN108923064A (en) * | 2018-07-10 | 2018-11-30 | 山西长韩新能源科技有限公司 | A kind of solid macromolecule electrolyte and preparation method thereof and lithium ion secondary battery |
| CN110350243A (en) * | 2019-07-30 | 2019-10-18 | 华中科技大学 | A kind of in-situ preparation method and its application of polymer dielectric |
| CN110854429A (en) * | 2019-11-18 | 2020-02-28 | 成都新柯力化工科技有限公司 | Particle composite membrane coated polymer electrolyte and preparation method thereof |
| CN111916819A (en) * | 2020-07-08 | 2020-11-10 | 成都新柯力化工科技有限公司 | Preparation method of layered polymer solid electrolyte of lithium battery |
| EP4011947A1 (en) * | 2020-12-10 | 2022-06-15 | Commissariat à l'Energie Atomique et aux Energies Alternatives | Preparation of a solid electrolyte made of polycarbonates |
| US20220293934A1 (en) * | 2021-03-09 | 2022-09-15 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Composite electrode having a solid electrolyte based on polycarbonates |
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Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1449422A (en) * | 2000-02-29 | 2003-10-15 | 国际壳牌研究有限公司 | Improved method for production of poly(trimethylene carbonate) |
| US20050113594A1 (en) * | 2002-02-07 | 2005-05-26 | Jurgen Van Holen | Process using a cyclic carbonate reactant |
| CN108923064A (en) * | 2018-07-10 | 2018-11-30 | 山西长韩新能源科技有限公司 | A kind of solid macromolecule electrolyte and preparation method thereof and lithium ion secondary battery |
| CN110350243A (en) * | 2019-07-30 | 2019-10-18 | 华中科技大学 | A kind of in-situ preparation method and its application of polymer dielectric |
| CN110854429A (en) * | 2019-11-18 | 2020-02-28 | 成都新柯力化工科技有限公司 | Particle composite membrane coated polymer electrolyte and preparation method thereof |
| CN111916819A (en) * | 2020-07-08 | 2020-11-10 | 成都新柯力化工科技有限公司 | Preparation method of layered polymer solid electrolyte of lithium battery |
| EP4011947A1 (en) * | 2020-12-10 | 2022-06-15 | Commissariat à l'Energie Atomique et aux Energies Alternatives | Preparation of a solid electrolyte made of polycarbonates |
| US20220293934A1 (en) * | 2021-03-09 | 2022-09-15 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Composite electrode having a solid electrolyte based on polycarbonates |
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