CN118156612A - Electrolyte for improving electrochemical performance of oxide layered anode and application of electrolyte in sodium ion battery - Google Patents
Electrolyte for improving electrochemical performance of oxide layered anode and application of electrolyte in sodium ion battery Download PDFInfo
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- CN118156612A CN118156612A CN202410282320.4A CN202410282320A CN118156612A CN 118156612 A CN118156612 A CN 118156612A CN 202410282320 A CN202410282320 A CN 202410282320A CN 118156612 A CN118156612 A CN 118156612A
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- electrolyte
- carbonate
- sodium
- ion battery
- sodium ion
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 58
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 26
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 25
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 claims description 16
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 15
- -1 sodium hexafluorophosphate Chemical group 0.000 claims description 12
- 239000002000 Electrolyte additive Substances 0.000 claims description 8
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 7
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 7
- 159000000000 sodium salts Chemical class 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 2
- 150000005678 chain carbonates Chemical class 0.000 claims 1
- 150000005676 cyclic carbonates Chemical class 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 230000000153 supplemental effect Effects 0.000 claims 1
- 230000001351 cycling effect Effects 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001291 vacuum drying 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 belongs to the technical field of sodium ion batteries, and mainly relates to an electrolyte for improving electrochemical performance of an oxide layered anode. The invention aims to design and develop an electrolyte system capable of forming a more stable CEI film on the surface of an oxide layered anode aiming at poor cycling stability of the existing sodium ion battery, so as to improve the electrochemical performance of the sodium ion battery.
Description
Technical Field
The invention relates to electrolyte for improving the electrochemical performance of an oxide layered anode of a sodium ion battery and application of the electrolyte in the sodium ion battery, and belongs to the technical field of sodium ion batteries.
Background
The widespread use of lithium ion batteries has raised concerns about lithium resources due to the low abundance of lithium and the uneven distribution in the crust. In contrast, sodium content is very rich and electrochemical behavior in electrochemical energy storage devices is similar to lithium. Sodium ion batteries are therefore considered a promising alternative to lithium ion batteries, particularly in large-scale energy storage systems where energy density requirements are not as high as in electric car power systems.
Among the positive electrode candidate materials of sodium ion batteries, O3 type layered transition metal oxides have been widely studied due to their superior specific capacity and similar synthetic processes to lithium counterparts, but long cycle performance is still a great impediment to their realization of large-scale industrialization.
The stable positive electrode-electrolyte interface (CEI) film can maintain the structural stability of the positive electrode material while allowing sodium ions to freely shuttle, and inhibit and prevent the reduction of the cycling stability caused by structural transformation. The CEI film generated on the surface of the layered positive electrode by the existing electrolyte has poor stability, and the damage and reformation of the CEI film can aggravate the deterioration of the electrochemical performance of the positive electrode material.
Aiming at the problems, the invention discloses a novel sodium ion battery electrolyte which improves the electrochemical performance of an oxide layered anode material.
Disclosure of Invention
Aiming at the defects of the existing sodium ion battery electrolyte system, the invention provides the electrolyte for enhancing the circulation performance of the oxide layered anode, and a stable CEI film can be formed on the surface of the anode, so that the electrochemical performance of the battery is improved.
The invention is realized by the following technical scheme: an electrolyte for improving the electrochemical performance of an oxide layered anode comprises an organic solvent, sodium salt, an auxiliary electrolyte additive fluoroethylene carbonate and an electrolyte additive glutaric anhydride shown in a structure I. The auxiliary additive fluoroethylene carbonate accounts for 1-10% of the total volume of the electrolyte, the mass of the electrolyte additive glutaric anhydride with the structural formula I accounts for 0.1-10% of the total mass of the electrolyte, and the concentration of sodium salt in the electrolyte is 0.5-1.5 mol/L.
Preferably, the organic solvent is a cyclic carbonate compound.
Preferably, the organic solvent is a chain carbonate compound.
Preferably, the cyclic carbonate compound is one or more compounds of ethylene carbonate and propylene carbonate.
Preferably, the chain carbonate compound is one or more of dimethyl carbonate, diethyl carbonate and ethylmethyl carbonate.
Preferably, the sodium salt is sodium hexafluorophosphate and/or sodium perchlorate.
Preferably, a sodium ion battery contains any of the above electrolytes.
The invention has the beneficial effects that: (1) The glutaric anhydride electrolyte additive added in the invention can be preferentially oxidized and decomposed on the surface of the oxide layered anode to form an anode-electrolyte interface film with a protective effect, so that the material structure damage caused by overlarge volume expansion-contraction of the anode material in the charge and discharge process is inhibited, and the capacity retention capacity of the battery in the circulation process is improved; (2) The added glutaric anhydride electrolyte additive can generate a protective film on the surface of the positive electrode, which can inhibit oxidative decomposition side reaction of the electrolyte at the interface, thereby improving the coulomb efficiency of the battery; (3) The protection film generated on the surface of the positive electrode by the glutaric anhydride electrolyte additive provided by the invention is rich in organic components (sodium alkyl carbonate), and is complementary with the interfacial film generated by the auxiliary additive fluoroethylene carbonate and rich in inorganic components (sodium fluoride), so that the structure protection effect and the higher ionic conductivity are both considered, and the electrochemical performance of the battery is improved at multiple angles.
Drawings
Fig. 1 is a schematic view of capacity retention ratios of the assembled batteries of the electrolytes of example 1, example 2, example 3 and comparative example 1.
Fig. 2 is a schematic view of capacity retention rates of the electrolyte assembled batteries of example 6, example 7 and comparative example 2.
Fig. 3 is a schematic diagram of coulombic efficiency of the electrolyte assembled batteries of example 6, example 7, and comparative example 2.
Detailed Description
The following detailed description of the present invention is provided in connection with specific embodiments, and it is apparent that the described embodiments are merely some, but not all embodiments of the present invention.
All examples or comparative examples:
(1) Preparing an electrolyte: the raw materials required for preparing the electrolyte were weighed according to the mass and proportion in the following examples in a glove box filled with argon atmosphere at room temperature, all the raw materials were mixed in a glass bottle, stirred using a magnetic stirrer until the solution was clear, and then transferred to an aluminum bottle for storage for use.
(2) Button cell assembly and electrochemical performance test: electrochemical performance testing was performed by CR2032 button cell at room temperature. The positive electrode material uses transition metal layered oxide NaNi 1/3Fe1/3Mn1/3O2, and the working electrode preparation process is as follows: first, the active material, the conductive agent Super P and the binder PVDF were mixed according to 8:1:1 in N-methyl pyrrolidone to prepare uniform slurry; then, the obtained slurry is uniformly scraped and coated on an aluminum foil by a scraper, the thickness of the slurry is 200 micrometers, and the slurry is kept at 100 ℃ for vacuum drying for 12 hours; finally, the aluminum foil coated with the sample was pressed into a small disk having a diameter of 1.1cm by a sheet punching machine as the positive electrode. The negative electrode material used was a metallic sodium sheet. The electrolyte was used in any of the following examples. The battery was assembled in a glove box filled with an argon atmosphere at room temperature. The charge and discharge test was completed under a new battery test system with a test voltage range of 2-4V, a test temperature of 30 ℃ at room temperature and a test current density of 0.5C (1c=130 mA/g).
Example 1
An electrolyte for improving the electrochemical performance of an oxide layered anode comprises the following components in percentage by weight: 1.224g sodium perchlorate, 9.5mL EC 0.5:DEC0.5, 0.5mL fluoroethylene carbonate, 0.128g glutaric anhydride; and uniformly mixing the components to obtain the sodium ion battery electrolyte.
Example 2
An electrolyte for improving the electrochemical performance of an oxide layered anode comprises the following components in percentage by weight: 1.224g sodium perchlorate, 9.5mL EC 0.5:DEC0.5, 0.5mL fluoroethylene carbonate, 0.393g glutaric anhydride; and uniformly mixing the components to obtain the sodium ion battery electrolyte.
Example 3
An electrolyte for improving the electrochemical performance of an oxide layered anode comprises the following components in percentage by weight: 1.224g sodium perchlorate, 9.5mL EC 0.5:DEC0.5, 0.5mL fluoroethylene carbonate, 0.669g glutaric anhydride; and uniformly mixing the components to obtain the sodium ion battery electrolyte.
Example 4
An electrolyte for improving the electrochemical performance of an oxide layered anode comprises the following components in percentage by weight: 1.224g sodium perchlorate, 9.5mL EC 0.5:DEC0.5, 0.5mL fluoroethylene carbonate, 1.412g glutaric anhydride; and uniformly mixing the components to obtain the sodium ion battery electrolyte.
Example 5
An electrolyte for improving the electrochemical performance of an oxide layered anode comprises the following components in percentage by weight: 1.680g sodium hexafluorophosphate, 9.5mL EC 0.5:DEC0.5, 0.5mL fluoroethylene carbonate, 0.133g glutaric anhydride; and uniformly mixing the components to obtain the sodium ion battery electrolyte.
Example 6
An electrolyte for improving the electrochemical performance of an oxide layered anode comprises the following components in percentage by weight: 1.680g sodium hexafluorophosphate, 9.5mL EC 0.5:DEC0.5, 0.5mL fluoroethylene carbonate, 0.407g glutaric anhydride; and uniformly mixing the components to obtain the sodium ion battery electrolyte.
Example 7
An electrolyte for improving the electrochemical performance of an oxide layered anode comprises the following components in percentage by weight: 1.680g sodium hexafluorophosphate, 9.5mL EC 0.5:DEC0.5, 0.5mL fluoroethylene carbonate, 0.693g glutaric anhydride; and uniformly mixing the components to obtain the sodium ion battery electrolyte.
Example 8
An electrolyte for improving the electrochemical performance of an oxide layered anode comprises the following components in percentage by weight: 1.680g sodium hexafluorophosphate, 9.5mL EC 0.5:DEC0.5, 0.5mL fluoroethylene carbonate, 1.463g glutaric anhydride; and uniformly mixing the components to obtain the sodium ion battery electrolyte.
Comparative example 1
An electrolyte which differs from example 1 only in that no glutaric anhydride is added, the formulation of which is as follows: 1.224g sodium perchlorate, 9.5mL EC 0.5:DEC0.5, 0.5mL fluoroethylene carbonate; and uniformly mixing the components to obtain the sodium ion battery electrolyte.
Comparative example 2
An electrolyte which differs from example 5 only in that no glutaric anhydride is added, the formulation of which is as follows: 1.680g sodium hexafluorophosphate, 9.5mL EC 0.5:DEC0.5, 0.5mL fluoroethylene carbonate; and uniformly mixing the components to obtain the sodium ion battery electrolyte.
The above embodiments are merely examples of the present invention and are not intended to limit the present invention, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention are included in the scope of the present invention.
Claims (9)
1. An electrolyte for improving the electrochemical performance of an oxide layered positive electrode of a sodium ion battery is characterized by comprising an organic solvent, sodium salt, an auxiliary additive fluoroethylene carbonate and an electrolyte additive glutaric anhydride shown in a structural formula I:
2. The electrolyte of claim 1 wherein the supplemental additive fluoroethylene carbonate comprises 1% -10% of the total volume of the electrolyte.
3. The electrolyte of claim 2 wherein the electrolyte additive of formula i comprises 0.1% to 10% of the total electrolyte mass.
4. The electrolyte according to claim 3, wherein the sodium salt is sodium hexafluorophosphate and/or sodium perchlorate.
5. The electrolyte of claim 4, wherein the sodium salt is present in the electrolyte at a concentration of 0.5mol/L to 1.5mol/L.
6. The electrolyte of claim 5, wherein the solvent comprises any one or more of a chain and a cyclic carbonate compound.
7. The electrolyte of claim 6, wherein the chain carbonate comprises one or more of dimethyl carbonate, diethyl carbonate, and ethylmethyl carbonate.
8. The electrolyte of claim 7 wherein the cyclic carbonate comprises ethylene carbonate and/or propylene carbonate.
9. A sodium ion battery comprising a positive electrode made of a layered oxide and a negative electrode made of a metallic sodium sheet, characterized by further comprising the electrolyte of any one of claims 1 to 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410282320.4A CN118156612A (en) | 2024-03-13 | 2024-03-13 | Electrolyte for improving electrochemical performance of oxide layered anode and application of electrolyte in sodium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410282320.4A CN118156612A (en) | 2024-03-13 | 2024-03-13 | Electrolyte for improving electrochemical performance of oxide layered anode and application of electrolyte in sodium ion battery |
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| Publication Number | Publication Date |
|---|---|
| CN118156612A true CN118156612A (en) | 2024-06-07 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410282320.4A Pending CN118156612A (en) | 2024-03-13 | 2024-03-13 | Electrolyte for improving electrochemical performance of oxide layered anode and application of electrolyte in sodium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN118156612A (en) |
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- 2024-03-13 CN CN202410282320.4A patent/CN118156612A/en active Pending
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