CN117013155A - Electrolyte additive for lithium carbon dioxide battery, electrolyte and battery - Google Patents
Electrolyte additive for lithium carbon dioxide battery, electrolyte and battery Download PDFInfo
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- CN117013155A CN117013155A CN202311036808.0A CN202311036808A CN117013155A CN 117013155 A CN117013155 A CN 117013155A CN 202311036808 A CN202311036808 A CN 202311036808A CN 117013155 A CN117013155 A CN 117013155A
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- nitrone
- carbon dioxide
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 60
- WFLRGOXPLOZUMC-UHFFFAOYSA-N [Li].O=C=O Chemical compound [Li].O=C=O WFLRGOXPLOZUMC-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 239000002000 Electrolyte additive Substances 0.000 title claims abstract description 19
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 49
- SQDFHQJTAWCFIB-UHFFFAOYSA-N n-methylidenehydroxylamine Chemical compound ON=C SQDFHQJTAWCFIB-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 27
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 27
- 239000000654 additive Substances 0.000 claims abstract description 22
- 230000000996 additive effect Effects 0.000 claims abstract description 22
- -1 cyclic nitrone derivative Chemical class 0.000 claims abstract description 13
- 150000002460 imidazoles Chemical class 0.000 claims abstract description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 18
- 229910003002 lithium salt Inorganic materials 0.000 claims description 18
- 159000000002 lithium salts Chemical class 0.000 claims description 18
- IYSYLWYGCWTJSG-XFXZXTDPSA-N n-tert-butyl-1-phenylmethanimine oxide Chemical compound CC(C)(C)[N+](\[O-])=C\C1=CC=CC=C1 IYSYLWYGCWTJSG-XFXZXTDPSA-N 0.000 claims description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 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 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 150000001555 benzenes Chemical class 0.000 claims description 9
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 claims description 9
- 125000001424 substituent group Chemical group 0.000 claims description 9
- ZXTHWIZHGLNEPG-UHFFFAOYSA-N 2-phenyl-4,5-dihydro-1,3-oxazole Chemical class O1CCN=C1C1=CC=CC=C1 ZXTHWIZHGLNEPG-UHFFFAOYSA-N 0.000 claims description 8
- VCUVETGKTILCLC-UHFFFAOYSA-N 5,5-dimethyl-1-pyrroline N-oxide Chemical class CC1(C)CCC=[N+]1[O-] VCUVETGKTILCLC-UHFFFAOYSA-N 0.000 claims description 8
- LUQZKEZPFQRRRK-UHFFFAOYSA-N 2-methyl-2-nitrosopropane Chemical class CC(C)(C)N=O LUQZKEZPFQRRRK-UHFFFAOYSA-N 0.000 claims description 7
- 239000000010 aprotic solvent Substances 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims description 6
- 125000004122 cyclic group Chemical group 0.000 claims description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 3
- 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
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- 230000002708 enhancing effect Effects 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 46
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 24
- 238000012360 testing method Methods 0.000 description 16
- 229910021389 graphene Inorganic materials 0.000 description 12
- 239000011259 mixed solution Substances 0.000 description 12
- 238000011056 performance test Methods 0.000 description 11
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 10
- 229910052808 lithium carbonate Inorganic materials 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 8
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000011267 electrode slurry Substances 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 239000006230 acetylene black Substances 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 239000006256 anode slurry Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 229940021013 electrolyte solution Drugs 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000004435 EPR spectroscopy Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000013319 spin trapping Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
-
- 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
Abstract
The embodiment of the application provides an electrolyte additive for a lithium carbon dioxide battery, an electrolyte and the battery, wherein the electrolyte additive comprises the following components: a nitrone-based additive comprising at least one of an open-chain nitrone, an open-chain nitrone derivative, a cyclic nitrone derivative, and an imidazole derivative. The nitrone-based additive provided by the embodiment of the application can effectively improve the solubility of carbon dioxide in electrolyte, thereby obviously enhancing the discharge capacity of the battery; and can promote Li 2 CO 3 Is of (1) and accelerate Li 2 CO 3 The decomposition efficiency of the lithium carbon dioxide battery is reduced, and the cycle life of the battery is prolonged.
Description
Technical Field
The application relates to the technical field of lithium carbon dioxide batteries, in particular to an electrolyte additive for a lithium carbon dioxide battery, an electrolyte and a battery.
Background
The lithium carbon dioxide battery has ultrahigh specific energy density, and carbon dioxide is adopted as an active substance, so that the greenhouse effect can be effectively relieved, and the dependence on traditional fossil fuels can be reduced. Due to the ultra-high theoretical specific energy density (1876 Wh/kg), lithium carbon dioxide batteries have great potential for development in electric automobiles, smart grids, and spark detection. However, lithium carbon dioxide batteries suffer from lower energy efficiency, higher charge overpotential, low practical specific capacity, poor cycling stability, etc., which greatly limit their practical application and future development.
Redox mediators are believed to enhance the kinetics of lithium carbon dioxide battery reactions, reducing the polarization of the positive electrode, to improve electrochemical performance. However, the current redox additive cannot greatly improve the discharge capacity of the lithium carbon dioxide battery, and cannot effectively reduce the battery charging overpotential, so that reliable and stable circulation of the lithium carbon dioxide battery cannot be realized. Therefore, a new redox additive is needed to improve the energy efficiency and cycle life of lithium carbon dioxide batteries.
Disclosure of Invention
In view of the above, the present application provides an electrolyte additive, an electrolyte and a battery for a lithium carbon dioxide battery, so as to solve the problems of low energy efficiency and short cycle life of the lithium carbon dioxide battery in the prior art.
In a first aspect, embodiments of the present application provide an electrolyte additive for a lithium carbon dioxide battery, comprising:
a nitrone-based additive comprising at least one of an open-chain nitrone, an open-chain nitrone derivative, a cyclic nitrone derivative, and an imidazole derivative.
In one possible implementation, the open-chain nitrone and open-chain nitrone derivative comprise:
derivatives of 2-methyl-2-nitrosopropane MNP, N-t-butyl-alpha-phenylnitrone PBN and N-t-butyl-alpha-phenylnitrone PBN in which t-butyl group is substituted with a substituent comprising at least one of alkyl, cyano, benzene and benzene derivatives.
In one possible implementation, the cyclic nitrone and cyclic nitrone derivative include:
derivatives of 5, 5-dimethyl-1-pyrroline-N-oxide DMPO and 5, 5-dimethyl-1-pyrroline-N-oxide DMPO in which the methyl group is substituted with a substituent comprising at least one of alkyl, cyano, benzene and benzene derivatives.
In one possible implementation, the imidazole derivative comprises:
derivatives of 2-phenyl-4, 5-tetramethylimidazolin-3-oxo-1-oxoPTIO and 2-phenyl-4, 5-tetramethylimidazolin-3-oxo-1-oxoPTIO in which the methyl group is substituted with a substituent comprising at least one of alkyl, cyano, benzene and benzene derivatives.
In a second aspect, an embodiment of the present application provides an electrolyte for a lithium carbon dioxide battery, including:
a lithium salt, an aprotic solvent, and an electrolyte additive of any one of the first aspects.
In one possible implementation, the electrolyte additive is present in the electrolyte at a concentration of 0.001mol/L to a saturation concentration.
In one possible implementation, the lithium salt includes at least one of lithium bistrifluoromethane sulfonimide, lithium perchlorate, lithium hexafluorophosphate, and lithium difluorooxalato borate.
In one possible implementation, the concentration of the lithium salt in the electrolyte is 0.1-10mol/L.
In one possible implementation, the aprotic solvent includes at least one of tetraethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and dimethyl sulfoxide.
In a third aspect, an embodiment of the present application provides a lithium carbon dioxide battery, including a porous carbon dioxide positive electrode, a lithium metal negative electrode, a separator, and the electrolyte of any one of the second aspects.
The nitrone-based additive provided by the embodiment of the application can effectively improve the solubility of carbon dioxide in electrolyte, thereby obviously enhancing the discharge capacity of the battery; and can promote Li 2 CO 3 Is of (1) and accelerate Li 2 CO 3 The decomposition efficiency of the lithium carbon dioxide battery is reduced, and the cycle life of the battery is prolonged.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a CV scan of the electrolyte of example 1 and comparative example 1 of the present application;
FIG. 2 is a constant current full discharge graph of the battery obtained in application example 1 of the present application and comparative application example 1;
FIG. 3 is a graph showing the cycle performance test of the batteries obtained in application example 1 of the present application and comparative application example 1;
FIG. 4 is a CV scan of the electrolyte of example 2 and comparative example 2 of the present application;
FIG. 5 is an electron spin resonance wave pattern of the electrolyte of example 2 and comparative example 2 of the present application;
FIG. 6 is a scanning electron microscope image of the product of example 2 of the present application after discharging the battery obtained in comparative example 2;
FIG. 7 is a graph showing the cycle performance test of the batteries obtained in application example 3 of the present application and comparative application example 3;
fig. 8 is a graph showing the rate performance test of the batteries obtained in application example 3 of the present application and comparative application example 3.
Detailed Description
For a better understanding of the technical solution of the present application, the following detailed description of the embodiments of the present application refers to the accompanying drawings.
It should be understood that the described embodiments are merely some, but not all, embodiments of the application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
The terminology used in the embodiments of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in this application and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
It should be understood that the term "and/or" as used herein is merely one way of describing an association of associated objects, meaning that there may be three relationships, e.g., a and/or b, which may represent: the first and second cases exist separately, and the first and second cases exist separately. In addition, the character "/" herein generally indicates that the front and rear associated objects are an "or" relationship.
Aiming at the problem of low energy efficiency and short cycle life of a lithium carbon dioxide battery in the prior art, the embodiment of the application provides an electrolyte additive for the lithium carbon dioxide battery, which comprises the following components: a nitrone-based additive comprising at least one of an open-chain nitrone, an open-chain nitrone derivative, a cyclic nitrone derivative, and an imidazole derivative.
Compared with redox mediators in the prior art, the nitrone-based additive is applied to a lithium carbon dioxide battery and has at least the following advantages:
1) The nitrone group additive has the function of adsorbing carbon dioxide, can be used as a spin trapping agent to capture carbon dioxide anion free radicals, promotes the physical adsorption of carbon dioxide gas, provides more reactants for redox reaction, and can also promote the redox kinetics process to a great extent, so that the carbon dioxide anion is directly converted into the product lithium carbonate in a mode of intramolecular disproportionation.
2) The nitrone-based additive can change the redox mechanism of carbon dioxide, convert four-electron reaction into reversible two-electron reaction, and enable the battery to have ultrahigh specific capacity and energy efficiency.
3) The nitrone-based additive can promote the decomposition of the product lithium carbonate, can obviously regulate and control the morphology of the product, and converts granular lithium carbonate into flaky lithium carbonate, so that a charging platform is greatly reduced, and the rate performance and the cycle life are improved.
In one possible implementation, the open-chain nitrone and open-chain nitrone derivative comprise:
derivatives of 2-methyl-2-nitrosopropane (MNP), N-t-butyl-alpha-Phenylnitrone (PBN) and N-t-butyl-alpha-Phenylnitrone (PBN) in which t-butyl is substituted with a substituent comprising at least one of alkyl, cyano, benzene and benzene derivatives.
In one possible implementation, the cyclic nitrone and cyclic nitrone derivative include:
derivatives of 5, 5-dimethyl-1-pyrroline-N-oxide (DMPO) and 5, 5-dimethyl-1-pyrroline-N-oxide (DMPO) in which the methyl group is substituted with a substituent comprising at least one of alkyl, cyano, benzene and benzene derivatives.
In one possible implementation, the imidazole derivative comprises:
derivatives of 2-phenyl-4, 5-tetramethylimidazolin-3-oxo-1-oxide (PTIO) and 2-phenyl-4, 5-tetramethylimidazolin-3-oxo-1-oxide (PTIO) in which the methyl group is substituted with a substituent comprising at least one of alkyl, cyano, benzene and benzene derivatives.
Corresponding to the above embodiments, the embodiment of the present application further provides an electrolyte for a lithium carbon dioxide battery, including: lithium salt, aprotic solvent and electrolyte additives as described in the above examples.
In one possible implementation, the concentration of electrolyte additive in the electrolyte is from 0.001mol/L to the saturation concentration. For example, 0.001mol/L, 0.5mol/L, 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L, etc., and those skilled in the art can adaptively select within this range according to actual needs, and the present application is not particularly limited thereto. In a preferred embodiment, the concentration of the electrolyte additive in the electrolyte is a saturated concentration.
In one possible implementation, the lithium salt includes at least one of lithium bistrifluoromethane sulfonimide, lithium perchlorate, lithium hexafluorophosphate, and lithium difluorooxalato borate.
In one possible implementation, the concentration of lithium salt in the electrolyte is 0.1-10mol/L. For example, 0.1mol/L, 1mol/L, 2mol/L, 3mol/L, 4mol/L, 4.8mol/L, etc., and those skilled in the art can adaptively select within this range according to actual needs, and the present application is not particularly limited thereto. In a preferred embodiment, the concentration of lithium salt in the electrolyte is 1mol/L.
In one possible implementation, the aprotic solvent includes at least one of tetraethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and dimethyl sulfoxide.
Corresponding to the embodiment, the embodiment of the application also provides a lithium carbon dioxide battery, which comprises a porous carbon dioxide positive electrode, a lithium metal negative electrode, a diaphragm and the electrolyte.
In order to facilitate understanding, the technical scheme provided by the application is described in detail below in connection with specific embodiments.
Example 1:
the structural formula of the nitrone-based additive in this example is:
LiTFSI and TEGDME are uniformly mixed to obtain an organic mixed solution with a lithium salt concentration of 1mol/L, and then 2-phenyl-4, 5-tetramethylimidazoline-3-oxo-1-oxygen (PTIO) of the embodiment is added into the obtained mixed solution and stirred for 48 hours to obtain an electrolyte, wherein the concentration of a nitrone-based additive in the electrolyte is 0.1mol/L.
Comparative example 1:
and uniformly mixing LiTFSI and TEGDME to obtain a mixed solution with the lithium salt concentration of 1mol/L, thereby obtaining the electrolyte.
In an argon atmosphere, the electrolytes of example 1 and comparative example 1 were respectively subjected to CV scanning using a three-electrode system under the following CV scanning conditions: the working electrode is a carbon electrode, the reference electrode is a silver electrode, the counter electrode is a lithium metal electrode, the scanning speed is 50mV/S, and the voltage range is 2.0-4.0 Vvs. Li/Li + The resulting CV scan is shown in FIG. 1. As can be seen from fig. 1, the electrolyte system provided in example 1 exhibits a redox peak; whereas comparative example 1 has no redox peak.
Application example 1:
according to the mass ratio of 8:1:1 taking graphene oxide, PVDF and acetylene black and adding N-methylpyrrolidineKetone to obtain positive electrode slurry; coating the obtained positive electrode slurry on the surface of carbon paper, and drying for 12 hours at 110 ℃ to obtain a porous carbon dioxide positive electrode, wherein the total load amount of graphene oxide on the surface of the porous carbon dioxide positive electrode is 0.2-0.3 mg/cm 2 ；
Adopting glass fiber diaphragm GF/D as battery diaphragm, wherein the aperture of the diaphragm is 2.7 mu m, and the diameter is 19mm;
in the order of assembling the lithium metal anode, separator and porous oxygen cathode, the lithium metal anode was assembled in a glove box (H 2 O<0.1ppm，O 2 <0.1 ppm) of the assembled Swagelok type battery, the electrolyte of example 1 was dropped in an amount of 60 to 120 μl after the battery was assembled.
Performance test: and adopting a Land battery test system to perform constant current charge and discharge test on the obtained Swagelok battery, wherein the test conditions are as follows: constant temperature 25 ℃, current density of 100-1000mA/g, specific capacity limit of 500mAh/g (calculated based on the mass of graphene oxide in carbon dioxide anode) and potential range of 2.2-5.0Vvs Li/Li + 。
Comparative application example 1:
the electrolyte of comparative example 1 was used instead of the electrolyte of example 1, and the other technical means were the same as those of application example 1, to obtain a Swagelok type battery.
Constant current full discharge tests were performed on the Swagelok batteries obtained in application example 1 and comparative application example 1, respectively, and the obtained constant current full discharge map was shown in fig. 2. As can be seen from FIG. 2, the discharge capacity of application example 1 was 74.6Ah/g, and the discharge capacity of comparative application example 1 was 4.6Ah/g, and it can be seen that the Swagelok type battery provided in application example 1 of the present application exhibited a higher discharge capacity. The reason for this analysis is that the formation of lithium carbonate is efficiently promoted by the n—o bond contained in the nitrone group additive in the electrolyte.
The Swagelok type batteries obtained in application example 1 and comparative application example 1 were respectively subjected to cycle performance test, and the obtained cycle performance test chart is shown in fig. 3, wherein the Swagelok type battery provided in application example 1 of the present application shows higher cycle stability.
Example 2:
the structural formula of the nitrone-based additive in this example is:
LiTFSI and TEGDME were uniformly mixed to obtain an organic mixed solution having a lithium salt concentration of 1mol/L, and then N-t-butyl-alpha-Phenylnitrone (PBN) of the present example was added to the obtained mixed solution, followed by stirring for 48 hours, to obtain an electrolyte. Wherein the concentration of the nitrone-based additive in the electrolyte is 0.5mol/L.
Comparative example 2:
and uniformly mixing LiTFSI and TEGDME to obtain a mixed solution with the lithium salt concentration of 1mol/L, thereby obtaining the electrolyte.
In an argon atmosphere, the electrolyte solutions of example 2 and comparative example 2 were respectively subjected to CV scanning under the following CV scanning conditions: the working electrode is a carbon electrode, the reference electrode is a silver electrode, the counter electrode is a lithium metal electrode, the scanning speed is 50mV/S, and the voltage range is 2.0-4.0 Vvs. Li/Li + The resulting CV scan is shown in FIG. 4. As can be seen from fig. 4, the electrolyte system provided in example 2 exhibited a redox peak and had a significant increase in current density; whereas comparative example 2 has no redox peak and a lower current density.
Application example 2:
according to the mass ratio of 8:1: taking graphene oxide, PVDF and acetylene black, and adding N-methyl pyrrolidone to obtain anode slurry; coating the obtained positive electrode slurry on the surface of carbon paper, and drying for 12 hours at 110 ℃ to obtain a porous carbon dioxide positive electrode, wherein the total load amount of graphene oxide on the surface of the porous carbon dioxide positive electrode is 0.2-0.3 mg/cm 2 ；
Adopting glass fiber diaphragm GF/D as battery diaphragm, wherein the aperture of the diaphragm is 2.7 mu m, and the diameter is 19mm;
in the order of assembling the lithium metal anode, separator and porous oxygen cathode, the lithium metal anode was assembled in a glove box (H 2 O<0.1ppm，O 2 <0.1 ppm) of an assembled Swagelok type battery, the electrolyte of example 2 was dropped in an amount of 60 to 120 μl after the battery was assembled.
Performance test: and adopting a Land battery test system to perform constant current charge and discharge test on the obtained Swagelok battery, wherein the test conditions are as follows: constant temperature 25 ℃, current density of 100-500mA/g, specific capacity limit of 500mAh/g (calculated based on the mass of graphene oxide in carbon dioxide anode) and potential range of 2.2-5.0V vs Li/Li + 。
Comparative application example 2:
the electrolyte of comparative example 2 was used instead of the electrolyte of example 2, and the other technical means were the same as those of application example 2, to obtain a Swagelok type battery.
Carbon dioxide radical trapping tests were performed on the Swagelok type batteries obtained in application example 2 and comparative application example 2, respectively, and the obtained spin compound spectra were shown in fig. 5. As can be seen from fig. 5, the electrolyte of application example 2 can effectively capture carbon dioxide anion free radicals to form a stable carbon dioxide spin compound; however, comparative example 2 did not show a characteristic peak, indicating that it was difficult for comparative example 2 to capture carbon dioxide radicals.
The product obtained after discharging the Swagelok type batteries obtained in application example 2 and comparative application example 2 is compared, and the morphology of the obtained product lithium carbonate is shown in fig. 6, wherein the left graph is comparative application example 2, and the right graph is application example 2. As can be seen from fig. 6, after the Swagelok type battery provided in application example 2 of the present application is disassembled, the morphology of lithium carbonate on the positive electrode is in the shape of leaves or sheets, and the morphology of lithium carbonate in comparative application example 2 is in the shape of particles. The lithium carbonate in application example 2 of the present application was significantly smaller in diameter than the comparative application example, comparing the sizes of both.
Example 3:
the structural formula of the nitrone-based additive in this example is:
(H 3 C) 3 C-NO
LiTFSI and TEGDME were uniformly mixed to obtain an organic mixed solution having a lithium salt concentration of 1mol/L, and then 2-methyl-2-nitrosopropane (MNP) of the present example was added to the obtained mixed solution, followed by stirring for 48 hours, to obtain an electrolyte. Wherein the concentration of the nitrone-based additive in the electrolyte is 0.3mol/L.
Comparative example 3
And uniformly mixing LiTFSI and TEGDME to obtain a mixed solution with the lithium salt concentration of 1mol/L, thereby obtaining the electrolyte.
In an argon atmosphere, the electrolyte solutions of example 3 and comparative example 3 were respectively subjected to CV scanning by using a three-electrode system, and CV scanning conditions were: the working electrode is a carbon electrode, the reference electrode is a silver electrode, the counter electrode is a lithium metal electrode, the scanning speed is 50mV/S, and the voltage range is 2.0-4.0 Vvs. Li/Li + . The electrolyte system provided in example 3 exhibited a redox peak; whereas comparative example 3 has no redox peak.
Application example 3:
according to the mass ratio of 8:1: taking graphene oxide, PVDF and acetylene black, and adding N-methyl pyrrolidone to obtain anode slurry; coating the obtained positive electrode slurry on the surface of carbon paper, and drying for 12 hours at 110 ℃ to obtain a porous carbon dioxide positive electrode, wherein the total load amount of graphene oxide on the surface of the porous carbon dioxide positive electrode is 0.2-0.3 mg/cm 2 ；
Adopting glass fiber diaphragm GF/D as battery diaphragm, wherein the aperture of the diaphragm is 2.7 mu m, and the diameter is 19mm;
in the order of assembling the lithium metal anode, separator and porous oxygen cathode, the lithium metal anode was assembled in a glove box (H 2 O<0.1ppm，O 2 <0.1 ppm) of the assembled Swagelok type battery, the electrolyte of example 3 was dropped in an amount of 60 to 120 μl after the battery was assembled.
Performance test: and adopting a Land battery test system to perform constant current charge and discharge test on the obtained Swagelok battery, wherein the test conditions are as follows: constant temperature 25 ℃, current density of 100-500mA/g, specific capacity limit of 500mAh/g (calculated based on the mass of graphene oxide in carbon dioxide anode) and potential range of 2.2-5.0Vvs Li/Li + 。
Comparative application example 3:
the electrolyte of comparative example 3 was used instead of the electrolyte of example 3, and the other technical means were the same as those of application example 3, to obtain a Swagelok type battery.
Constant current charge and discharge tests were performed on the Swagelok type batteries obtained in application example 3 and comparative application example 3, respectively, and the obtained cycle stability diagrams are shown in fig. 7. As can be seen from fig. 7, application example 3 shows smaller cyclic polarization and higher cyclic stability, and its charging voltage is always kept below 3.7V for one hundred cycles, but that of comparative example 3 is higher than 4V.
The respective rate performance tests were carried out on the Swagelok type batteries obtained in application example 3 and comparative application example 3, and the obtained rate performance graphs are shown in fig. 8. As can be seen from fig. 8, application example 3 exhibited smaller polarization and higher stability with an increase in current, and its charge voltage was lower than that of comparative application example 3, and its discharge voltage was always higher than that of comparative application example 3.
The foregoing is merely a preferred embodiment of the present application and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present application, which are intended to be comprehended within the scope of the present application.
Example 4:
the structural formula of the nitrone-based additive in this example is:
LiTFSI and DMSO are uniformly mixed to obtain an organic mixed solution with a lithium salt concentration of 1mol/L, and then 2-phenyl-4, 5-tetramethyl imidazoline-3-oxo-1-oxygen (PTIO) of the embodiment is added into the obtained mixed solution and stirred for 48 hours to obtain an electrolyte, wherein the concentration of a nitrone-based additive in the electrolyte is 0.5mol/L.
Comparative example 4:
and uniformly mixing LiTFSI and DMSO to obtain a mixed solution with lithium salt concentration of 1mol/L, thereby obtaining the electrolyte.
In an argon atmosphere, the electrolyte solutions of example 4 and comparative example 4 were respectively subjected to CV scanning under the following CV scanning conditions: the working electrode is a carbon electrode, the reference electrode is a silver electrode, the counter electrode is a lithium metal electrode, the scanning speed is 50mV/S, and the voltage range is 2.0-4.0 Vvs. Li/Li + . The electrolyte system provided in example 4 exhibited a redox peak; while comparative example 3 does not have oxidationOriginal peak.
Application example 4:
according to the mass ratio of 8:1: taking graphene oxide, PVDF and acetylene black, and adding N-methyl pyrrolidone to obtain anode slurry; coating the obtained positive electrode slurry on the surface of carbon paper, and drying for 12 hours at 110 ℃ to obtain a porous carbon dioxide positive electrode, wherein the total load amount of graphene oxide on the surface of the porous carbon dioxide positive electrode is 0.2-0.3 mg/cm 2 ；
Adopting glass fiber diaphragm GF/D as battery diaphragm, wherein the aperture of the diaphragm is 2.7 mu m, and the diameter is 19mm;
in the order of assembling the lithium metal anode, separator and porous oxygen cathode, the lithium metal anode was assembled in a glove box (H 2 O<0.1ppm，O 2 <0.1 ppm) of the assembled Swagelok type battery, the electrolyte of example 4 was dropped in an amount of 60 to 120 μl after the battery was assembled.
Performance test: and adopting a Land battery test system to perform constant current charge and discharge test on the obtained Swagelok battery, wherein the test conditions are as follows: constant temperature 25 ℃, current density of 100-1000mA/g, specific capacity limit of 500mAh/g (calculated based on the mass of graphene oxide in carbon dioxide anode) and potential range of 2.2-5.0Vvs Li/Li + 。
Comparative application example 4:
the electrolyte of comparative example 4 was used instead of the electrolyte of example 4, and the other technical means were the same as those of application example 4, to obtain a Swagelok type battery.
Constant current full discharge tests were performed on the Swagelok type batteries obtained in application example 4 and comparative application example 4, respectively. The discharge capacity of application example 4 was 56.6Ah/g, and the discharge capacity of comparative application example 4 was 3.4Ah/g, which revealed that the Swagelok type battery provided by application example 4 of the present application exhibited a higher discharge capacity. The reason for this analysis is that the formation of lithium carbonate is efficiently promoted by the n—o bond contained in the nitrone group additive in the electrolyte.
The Swagelok type batteries obtained in application example 4 and comparative application example 4 were respectively subjected to cycle performance test, and the Swagelok type battery provided in application example 4 of the present application exhibited higher cycle stability.
The foregoing is merely exemplary embodiments of the present application, and any person skilled in the art may easily conceive of changes or substitutions within the technical scope of the present application, which should be covered by the present application. The protection scope of the present application shall be subject to the protection scope of the claims.
Claims (10)
1. An electrolyte additive for a lithium carbon dioxide battery, comprising:
a nitrone-based additive comprising at least one of an open-chain nitrone, an open-chain nitrone derivative, a cyclic nitrone derivative, and an imidazole derivative.
2. The electrolyte additive of claim 1 wherein the open-chain nitrone and open-chain nitrone derivative comprise:
derivatives of 2-methyl-2-nitrosopropane MNP, N-t-butyl-alpha-phenylnitrone PBN and N-t-butyl-alpha-phenylnitrone PBN in which t-butyl group is substituted with a substituent comprising at least one of alkyl, cyano, benzene and benzene derivatives.
3. The electrolyte additive of claim 1 wherein the cyclic nitrone and cyclic nitrone derivative comprise:
derivatives of 5, 5-dimethyl-1-pyrroline-N-oxide DMPO and 5, 5-dimethyl-1-pyrroline-N-oxide DMPO in which the methyl group is substituted with a substituent comprising at least one of alkyl, cyano, benzene and benzene derivatives.
4. The electrolyte additive according to claim 1, wherein the imidazole derivative comprises:
derivatives of 2-phenyl-4, 5-tetramethylimidazolin-3-oxo-1-oxoPTIO and 2-phenyl-4, 5-tetramethylimidazolin-3-oxo-1-oxoPTIO in which the methyl group is substituted with a substituent comprising at least one of alkyl, cyano, benzene and benzene derivatives.
5. An electrolyte for a lithium carbon dioxide battery, comprising:
a lithium salt, an aprotic solvent and an electrolyte additive as claimed in any one of claims 1 to 4.
6. The electrolyte of claim 5 wherein the electrolyte additive is present in the electrolyte at a concentration of 0.001mol/L to a saturation concentration.
7. The electrolyte of claim 5 wherein the lithium salt comprises at least one of lithium bistrifluoromethane sulfonimide, lithium perchlorate, lithium hexafluorophosphate, and lithium difluorooxalato borate.
8. The electrolyte according to claim 5, wherein the concentration of the lithium salt in the electrolyte is 0.01 to 10mol/L.
9. The electrolyte of claim 5 wherein the aprotic solvent comprises at least one of tetraethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and dimethyl sulfoxide.
10. A lithium carbon dioxide battery comprising a porous carbon dioxide positive electrode, a lithium metal negative electrode, a separator, and the electrolyte of any one of claims 5-9.
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| CN202311036808.0A CN117013155A (en) | 2023-08-17 | 2023-08-17 | Electrolyte additive for lithium carbon dioxide battery, electrolyte and battery |
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| CN202311036808.0A CN117013155A (en) | 2023-08-17 | 2023-08-17 | Electrolyte additive for lithium carbon dioxide battery, electrolyte and battery |
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