CN117766874A - Aqueous electrolyte and application thereof - Google Patents
Aqueous electrolyte and application thereof Download PDFInfo
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- CN117766874A CN117766874A CN202311786713.0A CN202311786713A CN117766874A CN 117766874 A CN117766874 A CN 117766874A CN 202311786713 A CN202311786713 A CN 202311786713A CN 117766874 A CN117766874 A CN 117766874A
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- aqueous electrolyte
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 73
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 23
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 4
- 239000007774 positive electrode material Substances 0.000 claims abstract description 4
- 239000007773 negative electrode material Substances 0.000 claims abstract 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 9
- 150000003751 zinc Chemical class 0.000 claims description 9
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 8
- 159000000003 magnesium salts Chemical class 0.000 claims description 8
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 claims description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 4
- 159000000007 calcium salts Chemical class 0.000 claims description 4
- 229910003002 lithium salt Inorganic materials 0.000 claims description 4
- 159000000002 lithium salts Chemical class 0.000 claims description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 4
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 4
- 159000000000 sodium salts Chemical class 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- DMFBPGIDUUNBRU-UHFFFAOYSA-N magnesium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Mg+2].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 DMFBPGIDUUNBRU-UHFFFAOYSA-N 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- MPCRDALPQLDDFX-UHFFFAOYSA-L Magnesium perchlorate Chemical compound [Mg+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O MPCRDALPQLDDFX-UHFFFAOYSA-L 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 239000008151 electrolyte solution Substances 0.000 claims description 2
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 2
- 229940069446 magnesium acetate Drugs 0.000 claims description 2
- 239000011654 magnesium acetate Substances 0.000 claims description 2
- 235000011285 magnesium acetate Nutrition 0.000 claims description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- NNNSKJSUQWKSAM-UHFFFAOYSA-L magnesium;dichlorate Chemical compound [Mg+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O NNNSKJSUQWKSAM-UHFFFAOYSA-L 0.000 claims description 2
- BZQRBEVTLZHKEA-UHFFFAOYSA-L magnesium;trifluoromethanesulfonate Chemical compound [Mg+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F BZQRBEVTLZHKEA-UHFFFAOYSA-L 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- GTQFPPIXGLYKCZ-UHFFFAOYSA-L zinc chlorate Chemical compound [Zn+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O GTQFPPIXGLYKCZ-UHFFFAOYSA-L 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- CITILBVTAYEWKR-UHFFFAOYSA-L zinc trifluoromethanesulfonate Substances [Zn+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F CITILBVTAYEWKR-UHFFFAOYSA-L 0.000 claims description 2
- RXBXBWBHKPGHIB-UHFFFAOYSA-L zinc;diperchlorate Chemical compound [Zn+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O RXBXBWBHKPGHIB-UHFFFAOYSA-L 0.000 claims description 2
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 claims 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- 239000011701 zinc Substances 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- ZMLPZCGHASSGEA-UHFFFAOYSA-M zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F ZMLPZCGHASSGEA-UHFFFAOYSA-M 0.000 claims 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- 229910001425 magnesium ion Inorganic materials 0.000 description 14
- 239000007772 electrode material Substances 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 238000009830 intercalation Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical group CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerol group Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 230000002687 intercalation Effects 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000009831 deintercalation Methods 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000010405 anode material Substances 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 238000004807 desolvation Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 229960002337 magnesium chloride Drugs 0.000 description 3
- 229940091250 magnesium supplement Drugs 0.000 description 3
- 238000001075 voltammogram Methods 0.000 description 3
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical group COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000006259 organic additive Substances 0.000 description 2
- 239000005486 organic electrolyte Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- QEORIOGPVTWFMH-UHFFFAOYSA-N zinc;bis(trifluoromethylsulfonyl)azanide Chemical compound [Zn+2].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 QEORIOGPVTWFMH-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- -1 alcohol ethers Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229940050906 magnesium chloride hexahydrate Drugs 0.000 description 1
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 description 1
- 229960003390 magnesium sulfate Drugs 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000000954 titration curve Methods 0.000 description 1
Classifications
-
- 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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- Secondary Cells (AREA)
Abstract
The invention relates to the technical field of water-based secondary batteries, and discloses a water-based electrolyte, which comprises electrolyte, water and an organic compound; the organic compound is an alcohol ether small molecular compound. The invention also discloses application of the aqueous electrolyte in the aqueous secondary battery, and the negative electrode material of the aqueous secondary battery comprises TiO 2 The positive electrode material comprises V 2 O 5 . The invention solves the technical problem that the existing water-based electrolyte has a narrower electrochemical stability window.
Description
Technical Field
The invention relates to the technical field of water-based secondary batteries, in particular to a water-based electrolyte and application thereof.
Background
Secondary batteries, such as rechargeable lithium ion batteries, aqueous magnesium ion batteries, and the like, have been hot spots for research and application due to their high energy density, long cycle life, high voltage, and the like. Rechargeable lithium ion batteries have been commercialized and have taken up a large share in the market of rechargeable and discharge energy storage devices. However, in recent years, the use of lithium ion batteries in large-scale energy storage devices has been limited by factors such as the frequent occurrence of safety accidents caused by lithium ion batteries due to the flammability of organic electrolytes in lithium ion batteries and the high production environments (e.g., water oxygen content below 0.1ppm, etc.) required.
The aqueous magnesium ion battery uses the aqueous electrolyte, and meanwhile, the aqueous magnesium ion battery can avoid using flammable organic electrolyte, so that the aqueous magnesium ion battery has higher safety and good ion conductivity. However, the electrochemical stability window of water molecules is narrow, which is only 1.23V theoretically, and the electrochemical stability window of the water-based electrolyte is limited. The aqueous electrolyte can be widened to about 1.8V after the electrolyte is added, but is still far away from 4V of the current lithium ion battery. The narrow electrochemical stability window of aqueous electrolytes has become an important factor limiting the energy density of aqueous metal ion batteries.
The narrow electrochemical stability window of aqueous electrolytes not only limits the energy density of aqueous ionic cells, but also limits the choice of electrode materials. In the electrochemical stability window of 1.8V, most electrode materials do not work properly, but rather serious hydrogen evolution and oxygen evolution side reactions occur. It is therefore important to develop an aqueous electrolyte that can be used stably in an electrochemical stability window of 1.8V.
Disclosure of Invention
The invention aims to provide a water-based electrolyte and application thereof, so as to solve the technical problem that the existing water-based electrolyte has a narrow electrochemical stability window.
In order to achieve the above purpose, the invention adopts the following technical scheme: an aqueous electrolyte comprises electrolyte, water and organic compound; the organic compound is an alcohol ether small molecular compound.
The invention also provides application of the aqueous electrolyte in an aqueous secondary battery, wherein the aqueous secondary battery comprises a positive electrode, a negative electrode and the aqueous electrolyte.
The principle and the advantages of the scheme are as follows: as described in the background art, the existing aqueous secondary battery has the problem of narrower electrochemical stability window, and the limit electrochemical stability window after the electrolyte is added is about 1.8V, but in the electrochemical stability window, most electrode materials and electrolyte cannot be adapted to normal work, so that the practical application of the aqueous secondary battery is limited.
The inventor of the application aims at the problems, creatively uses alcohol ether micromolecular compounds as organic additives in the electrolyte, and can form the electrolyte in a homogeneous phase miscible state with water due to hydrophilic groups in the compounds, so that the electrolyte can be fully miscible with the electrolyte. Meanwhile, O atoms in the alcohol ether type micromolecule compound are combined with H atoms in free water in the electrolyte, so that the activity of the free water is limited, the contact between the free water and the electrode surface is reduced, and the dissolution of the electrode material is reduced. Meanwhile, as the same as a common organic additive, the alcohol ether type small molecular compound liquid can inhibit the occurrence of hydrogen precipitation and oxygen precipitation side reaction, widens the electrochemical stability window of the water-based electrolyte, increases the selection range of electrode materials, and reduces the activity of water molecules and the dissolution of the electrode materials due to the addition of the organic compound. Meanwhile, the organic compound forms coordination with magnesium ions or zinc ions, so that water molecules in a solvated sheath structure of the magnesium ions or the zinc ions are reduced, the water molecule content at an electrode/electrolyte interface is reduced, and the voltage stability and the cycle life stability of the battery are improved.
Preferably, as a modification, the organic compound comprises one or more of diethylene glycol, triethylene glycol and tripropylene glycol, and the mass percentage of the organic compound to water is 1% -99.5%.
In the application, diethylene glycol, triethylene glycol and tripropylene glycol are all small molecular compounds of alcohol ethers, the electrolyte formed by the small molecular compounds has high desolvation energy, desolvation is not needed in the magnesium intercalation process, and the intercalation/deintercalation process of magnesium is completed by a solvent co-intercalation/deintercalation mechanism, so that the influence of the slow desolvation process on the magnesium intercalation dynamics can be reduced, and the stability of the secondary battery is improved.
Preferably, as an improvement, the electrolyte may be a magnesium salt, wherein the magnesium salt includes one or more of magnesium sulfate, magnesium chloride, magnesium perchlorate, magnesium acetate, magnesium chlorate, magnesium triflate, and magnesium bis (trifluoromethylsulfonyl) imide.
In this application, most of the magnesium salts used in the secondary battery can be used as the electrolyte in the present embodiment, and among them, magnesium chloride and magnesium bis (trifluoromethylsulfonyl) imide are preferable.
Preferably, as an improvement, the electrolyte may be zinc salt, wherein the zinc salt includes one or more of zinc sulfate, zinc nitrate, zinc chloride, zinc perchlorate, zinc acetate, zinc chlorate, zinc triflate, and zinc bis (trifluoromethylsulfonyl) imide.
In this application, zinc salts used in most secondary batteries can be used as the electrolyte in the present embodiment, and among them, zinc chloride and zinc bis (trifluoromethylsulfonyl) imide are preferable.
Preferably, as a modification, the concentration of the zinc salt or magnesium salt is 0.01 to 10 mol.kg -1 。
In the application, the higher concentration of zinc salt or magnesium salt can lead to the resistance in the electrolyte to become large, so that the electrolyte cannot work normally.
Preferably, as a modification, the electrolyte further comprises one or more of potassium salt, sodium salt, lithium salt, calcium salt and aluminum salt.
In this application, most of the zinc salts used in secondary batteries can be used as the electrolyte in the present scheme.
Preferably, as a modification, the concentration of the potassium salt, sodium salt, lithium salt, calcium salt or aluminum salt is 0.01 to 12 mol.kg -1 。
In this application, it is necessary to ensure that the concentration of the electrolyte is in a suitable working range, and the above range is a preferable application range in practical use of this application.
Preferably, as an improvement, the anode material comprises TiO 2 The positive electrode material includes V 2 O 5 。
In the present application, tiO 2 When used as a cathode material, the charge-discharge voltage platform in the magnesium ion battery is relatively low, and the requirement on electrolyte is extremely high, so TiO can be used 2 The electrolyte used as the anode material in the scheme can meet the use requirements of most anode materials.
Drawings
Fig. 1 is a constant current charge-discharge curve of a secondary battery in example 1 of the present invention;
fig. 2 is a cycle chart of the secondary battery in example 1 of the present invention;
fig. 3 is a cyclic voltammogram of the secondary battery in example 1 of the present invention;
fig. 4 is a cyclic voltammogram of the secondary battery in example 2 of the present invention;
fig. 5 is a linear sweep voltammogram of the secondary battery of comparative example 1 of the present invention;
FIG. 6 is a linear sweep voltammogram of Experimental example 1 of the present invention;
FIG. 7 is a graph showing the constant current intermittent titration curve and the variation of the magnesium ion diffusion rate in experimental example 2 of the present invention.
Detailed Description
The following is a further detailed description of the embodiments:
example 1
An aqueous electrolyte comprises electrolyte, water and organic compound. In this embodiment, 2mol kg of electrolyte is selected -1 Magnesium chloride, the organic compound is triethylene glycol, and the weight percentage of the triethylene glycol to water is 90%. Specifically, 0.2mol of magnesium chloride hexahydrate was added to a mixed solvent composed of 10g of water and 90g of triethylene glycol, and stirred for 8 hours to prepare an electrolytic solution.
The embodiment also discloses an application of the aqueous electrolyte in the secondary battery, wherein the anode material of the secondary battery is TiO 2 The positive electrode material is V 2 O 5 The electrolyte is the electrolyte, carbon cloth is adopted as a positive and negative current collector, and the positive electrode, the electrolyte and the negative electrode are assembled into a secondary battery in a lamination mode for performance test. The test results are shown in figures 1-4。
As can be seen from fig. 1, there are a plurality of voltage plateaus during charge and discharge, and the voltage values at the plateaus are consistent with the peak positions of the redox peaks in fig. 3, which correspond to intercalation and deintercalation of magnesium ions in the electrode material.
As can be seen from fig. 2, the upper graph shows the change in the coulomb efficiency of the secondary battery, which remains close to 100% after 100 cycles, with little decay. The curve located below the graph shows the change in specific capacity of the secondary battery, which after 100 cycles still approaches 60mAh g -1 . Therefore, after 100 cycles, the specific capacity and the coulombic efficiency of the secondary battery are hardly attenuated, and the practical application value of the secondary battery is improved.
As can be seen from FIG. 3, there are multiple pairs of redox peaks in the cyclic voltammogram, corresponding to the intercalation and deintercalation of magnesium ions into the electrode material. Meanwhile, no hydrogen precipitation and oxygen precipitation side reaction occur in the whole charge and discharge process.
Example 2
The difference between this example and example 1 is that the organic compound in the electrolyte is tripropylene glycol, and the other is the same as in example. The experimental results are shown in fig. 4, and the cyclic voltammogram has a plurality of pairs of redox peaks corresponding to the intercalation and deintercalation process of magnesium ions in the electrode material. Meanwhile, no hydrogen precipitation and oxygen precipitation side reaction occur in the whole charge and discharge process.
Comparative example 1
The comparative example is different from example 1 in that the organic compound in the electrolyte is ethylene glycol, the weight percentage of ethylene glycol and water is 83%, and the other components are the same as the examples.
Comparative example 2
The comparative example differs from example 1 in that the organic compound in the electrolyte is glycerol, and the other is the same as in example.
Comparative example 3
The comparative example differs from example 1 in that the organic compound in the electrolyte is diethylene glycol monomethyl ether, and the other is the same as in example.
Comparative example 4
This comparative example differs from example 1 in that the organic compound in the electrolyte is propylene glycol, and the other is the same as in example.
The electrochemical stability windows of the above examples and comparative examples were tested and the tests are recorded in the following table.
| Numbering device | Organic compound name | Electrochemical stability window/V |
| Example 1 | Triethylene glycol | 3.6 |
| Example 2 | Tripropylene glycol | 3.6 |
| Comparative example 1 | Ethylene glycol | 2.6 |
| Comparative example 2 | Glycerol | 2 |
| Comparative example 3 | Diethylene glycol monomethyl ether | 2.2 |
| Comparative example 4 | Propylene glycol | 2 |
Summary of test results: from test results, the alcohol ether small molecular compound is selected to effectively widen the chemical stability window of the electrolyte, wherein hydrophilic groups existing in the alcohol ether small molecular compound and O atoms in the structure play a key role, so that the solubility of the organic compound in water is increased, the activity of free water in the electrolyte is also improved, the dissolution of electrode materials and the occurrence of side reactions are reduced, and the electrochemical stability window of the electrolyte is widened.
Experimental example one: influence of the weight percentage of organic Compounds to Water on the stability window of the Battery
The experimental method comprises the following steps: the respective weight percentages of triethylene glycol and water were 83%, 90% and 99%, and the other components of the electrolyte were the same as in example 1, and the linear sweep voltammogram of the electrolyte was tested, and the experimental results are shown in fig. 6. The weight percentage of organic compound to water in this scheme can form a wide electrochemical stability window (3.6 v) within a range.
Experimental example two: diffusion coefficient test of magnesium ions
The testing method comprises the following steps: constant current intermittent titration technique
The calculation formula is as follows: according to a constant current intermittent titration technical curve, the diffusion coefficient of magnesium ions in the electrode material can be calculated, and the calculation formula is as follows:
wherein τ, m B 、V M 、M B And S is the constant current pulse duration, mass, molar volume, molar mass of active species in the electrode material, and electrode-electrolyte interface area, respectively; ΔEs is the static voltage difference; Δeτ is neglectedThe resistance drops and the battery voltage during the constant current pulse always varies. The experimental results are shown in fig. 7. In this embodiment, the average diffusion coefficient of magnesium ions is-2.97X10 -11 cm 2 s -1 Greater than the values reported in the prior literature.
The foregoing is merely exemplary of the present invention, and specific technical solutions and/or features that are well known in the art have not been described in detail herein. It should be noted that, for those skilled in the art, several variations and modifications can be made without departing from the technical solution of the present invention, and these should also be regarded as the protection scope of the present invention, which does not affect the effect of the implementation of the present invention and the practical applicability of the patent. The protection scope of the present application shall be subject to the content of the claims, and the description of the specific embodiments and the like in the specification can be used for explaining the content of the claims.
Claims (10)
1. An aqueous electrolyte solution, characterized in that: comprising electrolyte, water and organic compound; the organic compound is an alcohol ether small molecular compound.
2. The aqueous electrolyte according to claim 1, wherein: the organic compound comprises one or more of diethylene glycol, triethylene glycol and tripropylene glycol.
3. The aqueous electrolyte according to claim 2, wherein: the mass percentage of the organic compound and the water is 1-99.5%.
4. The aqueous electrolyte according to claim 1, wherein: the electrolyte can be magnesium salt, wherein the magnesium salt comprises one or more of magnesium sulfate, magnesium chloride, magnesium perchlorate, magnesium acetate, magnesium chlorate, magnesium triflate and magnesium bis (trifluoromethyl sulfonyl) imide.
5. The aqueous electrolyte according to claim 1, wherein: the electrolyte can be zinc salt, wherein the zinc salt comprises one or more of zinc sulfate, zinc nitrate, zinc chloride, zinc perchlorate, zinc acetate, zinc chlorate, zinc trifluoromethane sulfonate and bis (trifluoromethane sulfonyl) imide zinc.
6. The aqueous electrolyte according to claim 4 or 5, wherein: the concentration of the zinc salt or magnesium salt is 0.01-10mol.kg -1 。
7. The aqueous electrolyte according to claim 1, wherein: the electrolyte also comprises one or more of potassium salt, sodium salt, lithium salt, calcium salt and aluminum salt.
8. The aqueous electrolyte according to claim 7, wherein: the concentration of the potassium salt, the sodium salt, the lithium salt, the calcium salt or the aluminum salt is 0.01 to 12 mol.kg -1 。
9. Use of an aqueous electrolyte according to any one of claims 1 to 8, characterized in that: a secondary battery is prepared using an aqueous electrolyte, and further includes a positive electrode and a negative electrode.
10. Use of an aqueous electrolyte according to claim 9, characterized in that: the negative electrode material comprises TiO 2 The positive electrode material includes V 2 O 5 。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311786713.0A CN117766874A (en) | 2023-12-22 | 2023-12-22 | Aqueous electrolyte and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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