CN114976237A - Electrolyte for improving cycle performance of sodium ion battery - Google Patents
Electrolyte for improving cycle performance of sodium ion battery Download PDFInfo
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- CN114976237A CN114976237A CN202210847599.7A CN202210847599A CN114976237A CN 114976237 A CN114976237 A CN 114976237A CN 202210847599 A CN202210847599 A CN 202210847599A CN 114976237 A CN114976237 A CN 114976237A
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- Prior art keywords
- electrolyte
- sodium
- ion battery
- cycle performance
- improving
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 53
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 39
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 38
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims abstract description 34
- 235000010344 sodium nitrate Nutrition 0.000 claims abstract description 17
- 239000004317 sodium nitrate Substances 0.000 claims abstract description 17
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 6
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 4
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims description 17
- -1 ether compound Chemical class 0.000 claims description 14
- 239000011734 sodium Substances 0.000 claims description 6
- 159000000000 sodium salts Chemical class 0.000 claims description 6
- 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 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 2
- 229910021201 NaFSI Inorganic materials 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 230000002829 reductive effect Effects 0.000 claims description 2
- VCCATSJUUVERFU-UHFFFAOYSA-N sodium bis(fluorosulfonyl)azanide Chemical compound FS(=O)(=O)N([Na])S(F)(=O)=O VCCATSJUUVERFU-UHFFFAOYSA-N 0.000 claims description 2
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 claims description 2
- 238000004146 energy storage Methods 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Dispersion Chemistry (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
An electrolyte for improving the circulation performance of a sodium-ion battery is prepared by adding sodium nitrate into the electrolyte, wherein the molecular formula is NaNO 3 The added sodium nitrate can form a thin and continuous solid electrolyte film (SEI film) on the surface of the negative electrode in preference to the electrolyte solvent in the battery, and the reduction and decomposition of the negative electrode on the electrolyte are inhibited.
Description
Technical Field
The invention belongs to the technical field of battery electrolyte, and particularly relates to electrolyte for improving the cycle performance of a sodium-ion battery.
Background
Lithium ion batteries have gained a leading position in many areas of the energy storage market due to their advantages of high energy density, long life, no memory effect, etc. In recent years, the price of the raw materials related to the lithium ion battery is on the trend of increasing year by year, and therefore, the popularization of the lithium ion battery in the aspect of large-scale energy storage faces huge cost disadvantage. Therefore, the novel battery with abundant resource reserves and low cost is researched and developed, and the development challenge of the large-scale energy storage market can be well met. Sodium has the advantages of abundant reserves and low refining cost compared with lithium, and the sodium and the lithium are in the same main group, show similar chemical characteristics and have similar electrode potentials. If a novel sodium ion battery can be researched and developed, the working performance of the battery is enhanced, and the sodium ion battery has a cost advantage over a lithium ion battery in the development of the large-scale energy storage field.
For this reason, the research on sodium ion batteries having high capacity and long cycle life has been a hot spot in the field. The working principle of the sodium ion battery is the same as that of the lithium ion battery, and the system mainly comprises three aspects of a positive electrode, electrolyte and a negative electrode. The electrolyte, which acts as the "blood" of the cell, has an important role in conducting ions. The excellent electrolyte can form a stable interface film on the positive and negative electrode interfaces, and the cycling stability of the battery is improved. Sodium ion batteries are the first choice for the next generation of energy storage batteries, and long cycle performance is the first characteristic of large-scale energy storage.
However, the negative electrode of the sodium ion battery is severely decomposed by reduction of the electrolyte during charge and discharge, and the working performance of the battery is adversely affected.
Disclosure of Invention
The invention aims to provide an electrolyte for improving the cycle performance of a sodium-ion battery, which can form an interface film (SEI film) on the surface of a negative electrode of the sodium-ion battery so as to improve the cycle performance of the battery.
The invention is realized by the following technical scheme: an electrolyte for improving the circulation performance of a sodium-ion battery is prepared by adding sodium nitrate into the electrolyte, wherein the molecular formula is NaNO 3 The added sodium nitrate can form a thin and continuous solid electrolyte film (SEI film) on the surface of the negative electrode in preference to the electrolyte solvent in the battery, and can suppress reductive decomposition of the electrolyte by the negative electrode.
The main components of the solid electrolyte membrane comprise polyether and Na 3 And the N component can effectively inhibit the reduction and decomposition of the negative electrode to the electrolyte.
Preferably, the weight percentage of the sodium nitrate in the electrolyte is O.1wt% -2 wt%.
Preferably, the battery electrolyte further comprises an organic solvent and a sodium salt, wherein the organic solvent is an ether compound.
The ether compound is one or more than one of 1, 3-dioxolane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether.
The sodium salt is one or more compounds of sodium hexafluorophosphate and sodium bifluorosulfonimide (NaFSI).
The mass percentage of the sodium salt is 10 wt% -20 wt%.
The invention has the beneficial effects that: compared with the prior art, the additive added in the invention can form a thin and continuous Solid Electrolyte Interface (SEI) film on the surface of the negative electrode material in preference to the electrolyte solvent, and inhibit the reduction and decomposition of the negative electrode material on the electrolyte, and the sodium ion battery using the electrolyte has excellent cycle performance.
Detailed Description
The specific techniques or conditions not indicated in the examples are all conventional methods or techniques or conditions described in the literature of the field or according to the product specifications. The reagents and instruments used are conventional products which are available from normal commercial vendors, not indicated by manufacturers.
In a first embodiment, an electrolyte for improving the cycle performance of a sodium-ion battery has the following formula: 12.5g of sodium hexafluorophosphate, 87.4g of tetraethylene glycol dimethyl ether and 0.1g of sodium nitrate; the components are uniformly mixed to obtain the sodium ion battery electrolyte.
In a second embodiment, an electrolyte for improving the cycle performance of a sodium ion battery comprises the following components: 12.5g of sodium hexafluorophosphate, 87g of tetraethylene glycol dimethyl ether and 0.5g of sodium nitrate; the components are uniformly mixed to obtain the sodium ion battery electrolyte.
In a third embodiment, an electrolyte for improving the cycle performance of a sodium ion battery has the following formula: 12.5g of sodium hexafluorophosphate, 86.5g of tetraethylene glycol dimethyl ether and 1g of sodium nitrate; the components are uniformly mixed to obtain the sodium ion battery electrolyte.
In a fourth embodiment, an electrolyte for improving the cycle performance of a sodium ion battery comprises the following components: 12.5g of sodium hexafluorophosphate, 86.2g of tetraglyme, 1.3g of sodium nitrate; the components are uniformly mixed to obtain the sodium ion battery electrolyte.
Example five, an electrolyte for improving cycle performance of a sodium ion battery has the following formula: 12.5g of sodium hexafluorophosphate, 86g of tetraglyme 1.5g of sodium nitrate; the components are uniformly mixed to obtain the sodium ion battery electrolyte.
In a sixth embodiment, an electrolyte for improving cycle performance of a sodium ion battery has the following formula: 12.5g of sodium hexafluorophosphate, 85.7g of tetraethylene glycol dimethyl ether and 1.8g of sodium nitrate; the components are uniformly mixed to obtain the sodium ion battery electrolyte.
The seventh embodiment provides an electrolyte for improving the cycle performance of a sodium-ion battery, which comprises the following formula: 12.5g of sodium hexafluorophosphate, 85.5g of tetraglyme and 2g of sodium nitrate; the components are uniformly mixed to obtain the sodium ion battery electrolyte.
Comparative example one, an electrolyte, which differs from example one only in that: sodium nitrate is not added; the formula is as follows: 12.5g of sodium hexafluorophosphate, 87.5g of tetraethylene glycol dimethyl ether; the components are uniformly mixed to obtain the sodium ion battery electrolyte.
The performance was verified as follows
With a layered transition metal oxide NaCrO 2 The metal sodium sheet is used as a working electrode and a counter electrode, and is assembled with the electrolyte to form a battery as a comparison sample, and the electrochemical performance of the battery is tested.
And (4) carrying out cycle test on the prepared battery, cycling for 300 times, recording the discharge capacity of the battery at the first time and the 300 th time, and calculating the discharge retention rate. The discharge retention was 100% of the first discharge capacity/300 th discharge capacity, and the results are shown in table 1.
TABLE 1 discharge retention results
| Item | Discharge retention rate |
| Example one | 71.3％ |
| Example two | 82.4％ |
| EXAMPLE III | 85.6％ |
| Example four | 91.3％ |
| EXAMPLE five | 92.4％ |
| Example six | 93.5％ |
| EXAMPLE seven | 91.7％ |
| Comparative example 1 | 57.1％ |
The sodium nitrate was added in a proportion of 0.1 wt% to 2 wt% as seen from the first to seventh comparisons, and the sodium ion battery had the most excellent cycle performance, and the cycle life of the sodium ion battery was greatly improved as seen from the first comparison and the first to seventh comparisons.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (7)
1. The electrolyte for improving the cycle performance of the sodium-ion battery is characterized in that sodium nitrate is added into the electrolyte, and the molecular formula is NaNO 3 The added sodium nitrate can form a thin and continuous solid electrolyte film (SEI film) on the surface of the negative electrode in preference to the electrolyte solvent in the battery, and can suppress reductive decomposition of the electrolyte by the negative electrode.
2. The electrolyte for improving the cycle performance of the sodium-ion battery as recited in claim 1, wherein the weight percentage of sodium nitrate in the electrolyte is 0.1 wt% to 2 wt%.
3. The electrolyte for improving the cycle performance of the sodium-ion battery according to claim 1, wherein the electrolyte of the battery further comprises an organic solvent and a sodium salt, and the organic solvent is an ether compound.
4. The electrolyte for improving the cycle performance of the sodium-ion battery according to claim 3, wherein the ether compound is one or more compounds selected from 1, 3-dioxolane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether.
5. The electrolyte for improving the cycle performance of the sodium-ion battery as claimed in claim 3, wherein the sodium salt is one or more compounds of sodium hexafluorophosphate and sodium bifluorosulfonylimide (NaFSI).
6. The electrolyte for improving the cycle performance of the sodium-ion battery according to claim 5, wherein the mass percent of the sodium salt is 10-20 wt%.
7. The electrolyte for improving the cycle performance of the sodium-ion battery as claimed in claim 1, wherein the main component of a solid electrolyte membrane (SEI film) comprises polyether and Na3N components, the reduction decomposition of the electrolyte at the negative electrode can be effectively inhibited, and the SEI film has low impedance, so that sodium ions can more easily pass through the SEI film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210847599.7A CN114976237A (en) | 2022-07-19 | 2022-07-19 | Electrolyte for improving cycle performance of sodium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210847599.7A CN114976237A (en) | 2022-07-19 | 2022-07-19 | Electrolyte for improving cycle performance of sodium ion battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114976237A true CN114976237A (en) | 2022-08-30 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210847599.7A Pending CN114976237A (en) | 2022-07-19 | 2022-07-19 | Electrolyte for improving cycle performance of sodium ion battery |
Country Status (1)
| Country | Link |
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| CN (1) | CN114976237A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024065578A1 (en) * | 2022-09-30 | 2024-04-04 | 宁德时代新能源科技股份有限公司 | Sodium ion battery and electric apparatus comprising same |
-
2022
- 2022-07-19 CN CN202210847599.7A patent/CN114976237A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024065578A1 (en) * | 2022-09-30 | 2024-04-04 | 宁德时代新能源科技股份有限公司 | Sodium ion battery and electric apparatus comprising same |
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Application publication date: 20220830 |
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