CN118136958A - Double-additive sodium ion battery electrolyte and sodium ion battery - Google Patents
Double-additive sodium ion battery electrolyte and sodium ion battery Download PDFInfo
- Publication number
- CN118136958A CN118136958A CN202410199174.9A CN202410199174A CN118136958A CN 118136958 A CN118136958 A CN 118136958A CN 202410199174 A CN202410199174 A CN 202410199174A CN 118136958 A CN118136958 A CN 118136958A
- Authority
- CN
- China
- Prior art keywords
- electrolyte
- additive
- sodium ion
- ion battery
- sodium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003792 electrolyte Substances 0.000 title claims abstract description 93
- 239000000654 additive Substances 0.000 title claims abstract description 56
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 49
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 48
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims abstract description 12
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims abstract description 12
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract 5
- -1 cyclotriphosphazene compound Chemical class 0.000 claims abstract 5
- 229910052731 fluorine Inorganic materials 0.000 claims abstract 5
- 239000011737 fluorine Substances 0.000 claims abstract 5
- 230000000996 additive effect Effects 0.000 claims description 41
- 229910021385 hard carbon Inorganic materials 0.000 claims description 35
- 239000002904 solvent Substances 0.000 claims description 15
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 14
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 14
- 230000009977 dual effect Effects 0.000 claims description 14
- 239000007774 positive electrode material Substances 0.000 claims description 14
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 11
- 239000003365 glass fiber Substances 0.000 claims description 11
- 239000007773 negative electrode material Substances 0.000 claims description 8
- 239000000919 ceramic Substances 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-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
- 239000004210 ether based solvent Substances 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 claims description 2
- 229920000447 polyanionic polymer Polymers 0.000 claims description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 2
- 229960003351 prussian blue Drugs 0.000 claims description 2
- 239000013225 prussian blue Substances 0.000 claims description 2
- 229910021384 soft carbon Inorganic materials 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 claims description 2
- 229910019398 NaPF6 Inorganic materials 0.000 claims 1
- 239000003660 carbonate based solvent Substances 0.000 claims 1
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 5
- 239000007772 electrode material Substances 0.000 abstract description 4
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 239000003063 flame retardant Substances 0.000 abstract description 3
- 239000007784 solid electrolyte Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 26
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 20
- 239000000463 material Substances 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 12
- 239000002033 PVDF binder Substances 0.000 description 12
- 239000006230 acetylene black Substances 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 12
- 238000000576 coating method Methods 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 12
- 239000002002 slurry Substances 0.000 description 12
- 229910052786 argon Inorganic materials 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 239000011888 foil Substances 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 239000006257 cathode slurry Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000011889 copper foil Substances 0.000 description 6
- 239000011267 electrode slurry Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- CBTAIOOTRCAMBD-UHFFFAOYSA-N 2-ethoxy-2,4,4,6,6-pentafluoro-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound CCOP1(F)=NP(F)(F)=NP(F)(F)=N1 CBTAIOOTRCAMBD-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- DFFDSQBEGQFJJU-UHFFFAOYSA-N butyl hydrogen carbonate Chemical compound CCCCOC(O)=O DFFDSQBEGQFJJU-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 description 1
- 238000007614 solvation 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
- 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
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
-
- 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)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a dual-additive sodium ion battery electrolyte and a sodium ion battery, which are prepared by uniformly mixing a certain amount of sodium salt and an organic solvent to form a basic electrolyte, and then introducing sodium perchlorate and a fluorine-containing cyclotriphosphazene compound with different mass fractions into the basic electrolyte to form the dual-additive electrolyte, wherein the mass fraction of the sodium salt is 10-15%, the mass fraction of the sodium perchlorate is 0.3-0.7%, and the combined mass fraction of the fluorine-containing cyclotriphosphazene compound is 1-8%; the synergistic effect of the double additives can simultaneously improve the interface stability of the cathode and anode solid electrolyte of the battery, and form stable SEI and CEI on the surface of an electrode material, so that the electrochemical performances of battery circulation, multiplying power, capacity and the like are improved, and the double-additive sodium ion battery electrolyte has good flame retardant effect and can improve the safety performance of the battery.
Description
Technical Field
The invention belongs to the technical field of sodium ion batteries, and particularly relates to a double-additive sodium ion battery electrolyte and a sodium ion battery.
Background
As sodium ion batteries are intensively studied, more and more potential advantages of sodium ion batteries are explored, so that the sodium ion batteries are expected to occupy a favorable position in the future battery market. Compared with a lithium ion battery, the sodium ion battery has a similar working principle as the lithium ion battery, has rich sodium resources, wide distribution range, low cost, capability of using cheaper aluminum foil negative electrode current collector and the like, and is widely focused by people. However, the poor compatibility of the electrolyte with the electrode interface of sodium-ion batteries severely hampers the development of sodium-ion batteries. Therefore, there is a need for an electrolyte that improves battery electrode interface stability, thereby improving battery cycling, rate, capacity, and other electrochemical properties.
Disclosure of Invention
Based on the problems, the invention provides a dual-additive sodium ion battery electrolyte and a sodium ion battery, which aim to solve the related problems in the background technology.
The invention realizes the above purpose through the following technical scheme:
it is an object of this embodiment to provide a dual additive sodium ion battery electrolyte comprising a sodium salt, an organic solvent, a sodium perchlorate additive, and a fluorocyclotriphosphazene compound additive.
The structural formulas of the sodium perchlorate additive and the fluorocyclotriphosphazene compound additive are shown in the following formulas I and II respectively:
In the invention, the sodium perchlorate additive and the fluorocyclotriphosphazene compound additive are matched to be used as dual additives, and the synergistic effect of the two additives can simultaneously improve the interface stability of the cathode and anode solid electrolyte of the battery, and form stable SEI and CEI on the surface of the electrode material, thereby improving the electrochemical performances of the sodium ion battery, such as circulation, multiplying power, capacity and the like.
Preferably, the sodium perchlorate additive is present in the electrolyte in a mass percentage of 0.3 to 0.7%, for example 0.3%, 0.4%, 0.5%, 0.6% or 0.7%.
Preferably, the fluorocyclotriphosphazene compound additive is present in the electrolyte in an amount of 1% to 8% by mass, for example 1%, 2%, 3%, 4%, 5%, 6%, 7% or 8%.
Preferably, the organic solvent is any one or a combination of at least two of carbonate solvents and ether solvents.
Preferably, the carbonate solvent comprises any one or a combination of at least two of ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate and propylmethyl carbonate.
Preferably, the ether solvent comprises any one or at least two of tetrahydrofuran, 1, 3-dioxolane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether.
Preferably, the sodium salt is any one or at least two of NaPF 6、NaBF4, naOTf, naFSI, naTFSI.
Preferably, the mass fraction of the sodium salt in the electrolyte is 10-15%.
The second purpose of the embodiment is that the invention also provides a sodium ion battery, which comprises a positive electrode, a negative electrode, a diaphragm and the sodium ion battery electrolyte.
In the present invention, the positive electrode and the negative electrode are immersed in the dual additive sodium ion battery electrolyte and separated by a separator.
Preferably, the positive electrode material is any one of an oxide positive electrode material, a polyanion positive electrode material and a Prussian blue positive electrode material.
Preferably, the negative electrode material is any one of hard carbon, soft carbon and sodium metal sheet.
Preferably, the diaphragm is any one of a glass fiber diaphragm and a ceramic diaphragm.
Compared with the prior art, the invention has the beneficial effects that:
According to the dual-additive sodium ion battery electrolyte provided by the invention, the sodium perchlorate additive and the fluorocyclotriphosphazene compound additive are introduced to realize synergistic effect, so that a solvation structure of sodium ions in the electrolyte is reconstructed, and stable SEI and CEI are formed on the surface of an electrode material, thereby inhibiting decomposition of the electrolyte, improving the cycle, multiplying power, capacity, electrochemical performances of a sodium ion battery and the like, and the dual-additive sodium ion battery electrolyte has a good flame retardant effect and can improve the safety performance of the battery.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a graph showing the cycling profile at 1C of an NFP button cell assembled from the electrolyte in example 1 of the present invention and an NFP button cell assembled from the electrolyte in comparative example 1;
FIG. 2 is a graph showing the rate capability of the NFP button cell assembled from the electrolyte in example 2 of the present invention at different current densities than the NFP button cell assembled from the electrolyte in comparative example 2;
FIG. 3 is a graph showing the cycle of the assembled HC button cell of the electrolyte in example 3 of the present invention and the assembled HC button cell of the electrolyte in comparative example 3 at a current density of 100mA g -1;
FIG. 4 is a graph showing the rate capability of the assembled HC button cell of example 4 of the present invention at different current densities than the assembled HC button cell of the electrolyte of comparative example 4;
Fig. 5 is a cycle curve at 1C of the NFP HC pouch cell assembled with the electrolyte in example 5 of the present invention and the NFP HC pouch cell assembled with the electrolyte in comparative example 5;
FIG. 6 is a graph showing the flammability test of the electrolyte in example 1 of the present invention and the electrolyte in comparative example 1.
Detailed Description
The present invention is further described below in conjunction with embodiments, which are merely some, but not all embodiments of the present invention. Based on the embodiments of the present invention, other embodiments that may be used by those of ordinary skill in the art without making any inventive effort are within the scope of the present invention.
In the embodiment and the comparative example of the invention, the main materials used for preparing the dual-additive sodium ion battery electrolyte and the sodium ion battery are as follows:
Additive A, sodium perchlorate (formula I); additive B: ethoxy (pentafluoro) cyclotriphosphazene (formula II-1);
organic solvent: ethylene Carbonate (EC), diethyl carbonate (DEC);
Sodium salt: naPF 6;
Positive electrode of sodium ion battery: na 3Fe2(PO4)P2O7 (NFP);
negative electrode of sodium ion battery: hard Carbon (HC), sodium metal flakes;
Sodium ion battery separator: glass fiber diaphragm and ceramic diaphragm.
Example 1:
The electrolyte was prepared in an argon filled glove box (H 2O,O2 <0.01 ppm). Solvents EC, DEC were mixed in a volume ratio of 1:1, then dissolving NaPF 6 salt which is slowly dissolved in the solution, cooling the solution to room temperature in a container, adding 0.5 mass percent of additive A and 5 mass percent of additive B, and fully stirring for 24 hours.
NFP, acetylene black, PVDF according to 8:1:1 in the mass ratio of N-methyl pyrrolidone to obtain positive electrode slurry. And uniformly coating the slurry on an aluminum foil, and drying to obtain the NFP positive electrode material. The material is used as an anode, a sodium metal sheet is used as a cathode, the electrolyte is prepared by the electrolyte in the embodiment 1, the diaphragm is a glass fiber diaphragm, and the button type NFP half battery is assembled, and a new-wire battery test system is used for charge and discharge test under the 1C multiplying power, wherein the voltage interval is 1.5-3.5V.
Example 2:
The electrolyte was prepared in an argon filled glove box (H 2O,O2 <0.01 ppm). Solvents EC, DEC were mixed in a volume ratio of 1:1, then dissolving NaPF 6 salt which is slowly dissolved in the solution, cooling the solution to room temperature in a container, adding 0.5 mass percent of additive A and 5 mass percent of additive B, and fully stirring for 24 hours.
NFP, acetylene black, PVDF according to 8:1:1 in the mass ratio of N-methyl pyrrolidone to obtain positive electrode slurry. And uniformly coating the slurry on an aluminum foil, and drying to obtain the NFP positive electrode material. The material is used as an anode, a sodium metal sheet is used as a cathode, the electrolyte is prepared by the electrolyte in the embodiment 2, the diaphragm is a glass fiber diaphragm, and the button type NFP half battery is assembled, and a new-wire battery test system is used for multiplying power charge and discharge tests under different current densities, wherein the voltage interval is 1.5-3.5V.
Example 3:
The electrolyte was prepared in an argon filled glove box (H 2O,O2 <0.01 ppm). Solvents EC, DEC were mixed in a volume ratio of 1:1, then dissolving NaPF 6 salt which is slowly dissolved in the solution, cooling the solution to room temperature in a container, adding 0.5 mass percent of additive A and 5 mass percent of additive B, and fully stirring for 24 hours.
HC, acetylene black, PVDF according to 8:1:1 in the mass ratio of N-methyl pyrrolidone to obtain the cathode slurry. And uniformly coating the slurry on a copper foil, and drying to obtain the HC negative electrode material. The material is used as an anode, a sodium metal sheet is used as a cathode, the electrolyte is prepared by the electrolyte in the embodiment 3, the diaphragm is a glass fiber diaphragm, and the button HC half-cell is assembled, and a new-Wei cell test system is used for charge and discharge test under the current density of 100mA g -1, wherein the voltage interval is 0.01-2.5V.
Example 4:
The electrolyte was prepared in an argon filled glove box (H 2O,O2 <0.01 ppm). Solvents EC, DEC were mixed in a volume ratio of 1:1, then dissolving NaPF 6 salt which is slowly dissolved in the solution, cooling the solution to room temperature in a container, adding 0.5 mass percent of additive A and 5 mass percent of additive B, and fully stirring for 24 hours.
HC, acetylene black, PVDF according to 8:1:1 in the mass ratio of N-methyl pyrrolidone to obtain the cathode slurry. And uniformly coating the slurry on a copper foil, and drying to obtain the HC negative electrode material. The material is used as an anode, a sodium metal sheet is used as a cathode, the electrolyte is prepared by the electrolyte in the embodiment 4, the diaphragm is a glass fiber diaphragm, and the button HC half-cell is assembled, and a new-Wei cell test system is used for carrying out multiplying power charge and discharge test under different current densities, wherein the voltage interval is 0.01-2.5V.
Example 5:
The electrolyte was prepared in an argon filled glove box (H 2O,O2 <0.01 ppm). Solvents EC, DEC were mixed in a volume ratio of 1:1, then dissolving NaPF 6 salt which is slowly dissolved in the solution, cooling the solution to room temperature in a container, adding 0.5 mass percent of additive A and 5 mass percent of additive B, and fully stirring for 24 hours.
NFP, acetylene black, PVDF according to 93:3.5: and (3.5) fully mixing the materials in N-methyl pyrrolidone to obtain positive electrode slurry. And uniformly coating the slurry on an aluminum foil, and drying to obtain the NFP positive electrode material. HC, acetylene black, PVDF according to 93:3.5: and 3.5, fully mixing the materials in N-methyl pyrrolidone to obtain the cathode slurry. And uniformly coating the slurry on a copper foil, and drying to obtain the HC negative electrode material. The NFP electrode plate is used as a positive electrode, the HC electrode plate is used as a negative electrode, the electrolyte is prepared by the electrolyte prepared in the embodiment 5, the diaphragm is a ceramic diaphragm, and the soft-packed battery is assembled, and the charge and discharge test is carried out by using a Xinwei battery test system under the 1C multiplying power, wherein the voltage interval is 1.5-3.5V.
Comparative example 1:
The electrolyte was prepared in an argon filled glove box (H 2O,O2 <0.01 ppm). Solvents EC, DEC were mixed in a volume ratio of 1:1, then dissolving and slowly dissolving 1.0mol/L NaPF 6 salt therein, and stirring thoroughly for 24h.
NFP, acetylene black, PVDF according to 8:1:1 in the mass ratio of N-methyl pyrrolidone to obtain positive electrode slurry. And uniformly coating the slurry on an aluminum foil, and drying to obtain the NFP positive electrode material. The material is used as an anode, a sodium metal sheet is used as a cathode, electrolyte is prepared by using the electrolyte of the comparative example 1, a button type NFP half cell is assembled by using a glass fiber diaphragm as a diaphragm, a new wire cell test system is used for charge and discharge test under the 1C multiplying power, and the voltage interval is 1.5-3.5V.
Comparative example 2:
The electrolyte was prepared in an argon filled glove box (H 2O,O2 <0.01 ppm). Solvents EC, DEC were mixed in a volume ratio of 1:1, then dissolving and slowly dissolving 1.0mol/L NaPF 6 salt therein, and stirring thoroughly for 24h.
NFP, acetylene black, PVDF according to 8:1:1 in the mass ratio of N-methyl pyrrolidone to obtain positive electrode slurry. And uniformly coating the slurry on an aluminum foil, and drying to obtain the NFP positive electrode material. The material is used as an anode, a sodium metal sheet is used as a cathode, electrolyte is prepared by using the electrolyte of the comparative example 2, a button type NFP half cell is assembled by using a glass fiber diaphragm as a diaphragm, a new-Wei cell test system is used for carrying out multiplying power charge and discharge tests under different current densities, and the voltage interval is 1.5-3.5V.
Comparative example 3:
The electrolyte was prepared in an argon filled glove box (H 2O,O2 <0.01 ppm). Solvents EC, DEC were mixed in a volume ratio of 1:1, then dissolving and slowly dissolving 1.0mol/L NaPF 6 salt therein, and stirring thoroughly for 24h.
HC, acetylene black, PVDF according to 8:1:1 in the mass ratio of N-methyl pyrrolidone to obtain the cathode slurry. And uniformly coating the slurry on a copper foil, and drying to obtain the HC negative electrode material. The material is used as an anode, a sodium metal sheet is used as a cathode, the electrolyte is prepared by using the electrolyte of the comparative example 3, the diaphragm is a glass fiber diaphragm, and the button HC half-cell is assembled, and a new Wei cell test system is used for charge and discharge test under the current density of 100mA g -1, wherein the voltage interval is 0.01-2.5V.
Comparative example 4:
The electrolyte was prepared in an argon filled glove box (H 2O,O2 <0.01 ppm). Solvents EC, DEC were mixed in a volume ratio of 1:1, then dissolving and slowly dissolving 1.0mol/L NaPF 6 salt therein, and stirring thoroughly for 24h.
HC, acetylene black, PVDF according to 8:1:1 in the mass ratio of N-methyl pyrrolidone to obtain the cathode slurry. And uniformly coating the slurry on a copper foil, and drying to obtain the HC negative electrode material. The material is used as an anode, a sodium metal sheet is used as a cathode, electrolyte is prepared by using the electrolyte of the comparative example 4, a buckle type HC half cell is assembled by using a glass fiber diaphragm as a diaphragm, a new-Wei cell test system is used for carrying out multiplying power charge and discharge tests under different current densities, and the voltage interval is 0.01-2.5V.
Comparative example 5:
The electrolyte was prepared in an argon filled glove box (H 2O,O2 <0.01 ppm). Solvents EC, DEC were mixed in a volume ratio of 1:1, then dissolving and slowly dissolving 1.0mol/L NaPF 6 salt therein, and stirring thoroughly for 24h.
NFP, acetylene black, PVDF according to 93:3.5: and (3.5) fully mixing the materials in N-methyl pyrrolidone to obtain positive electrode slurry. And uniformly coating the slurry on an aluminum foil, and drying to obtain the NFP positive electrode material. HC, acetylene black, PVDF according to 93:3.5: and 3.5, fully mixing the materials in N-methyl pyrrolidone to obtain the cathode slurry. And uniformly coating the slurry on a copper foil, and drying to obtain the HC negative electrode material. The NFP electrode plate is used as a positive electrode, the HC electrode plate is used as a negative electrode, the electrolyte is prepared by using the electrolyte prepared in the comparative example 5, the diaphragm is a ceramic diaphragm, and a soft-packed battery is assembled, and a new-Wei battery test system is used for charge and discharge test under the 1C multiplying power, wherein the voltage interval is 1.5-3.5V.
The NFP half cell assembled by the electrolyte of the present example 1 and the NFP half cell assembled by the electrolyte of the comparative example 1 circulate for 50 circles at a 1C rate, as shown in fig. 1, the capacity retention rate of the example 1 is approximately 95%, and the comparative example 1 is only 75%, which shows that the electrolyte of the present invention forms a stable CEI and significantly improves the circulation performance of the NFP half cell.
The NFP half cell assembled by the electrolyte of the present example 2 and the NFP half cell assembled by the electrolyte of the comparative example 2 are subjected to the rate test under different current densities, as shown in fig. 2, the gram capacity is higher under the same current density of the example 2 and the comparative example 2, which shows that the electrolyte of the present invention has better sodium ion transfer kinetics and better rate performance.
The HC half cell assembled by the electrolyte of the embodiment 3 and the HC half cell assembled by the electrolyte of the comparative example 3 circulate for 50 circles at the current density of 100mA g -1, as shown in fig. 3, the capacity retention rate of the embodiment 3 is higher than that of the comparative example 3, the electrolyte of the invention forms stable SEI, and the circulation performance of the HC half cell is obviously improved.
The HC half cell assembled by the electrolyte of the embodiment 4 and the HC half cell assembled by the electrolyte of the comparative example 4 are subjected to multiplying power test under different flow densities, as shown in FIG. 4, the gram capacity of the embodiment 4 is higher under the same current density as that of the comparative example 4, and further the electrolyte provided by the invention has better sodium ion transfer kinetics and better multiplying power performance.
The NFP & lt/EN & gt HC soft package battery assembled by adopting the electrolyte of the embodiment 5 circulates 500 circles at 1C with the NFP & lt/EN & gt HC soft package battery assembled by adopting the electrolyte of the embodiment 5, as shown in fig. 5, the capacity retention rate of the embodiment 5 is obviously higher than that of the embodiment 5, the electrolyte of the invention is embodied, and the circulation performance of the battery is obviously improved under the synergistic effect of the double additives.
As can be seen from fig. 6, the electrolyte of the invention is not ignited when contacting a fire source, while the electrolyte of the invention of the control 1 is ignited, which shows that the electrolyte of the invention has good flame retardance and can improve the safety performance of the sodium ion battery.
Therefore, the dual additive electrolyte of the invention further improves the performances of circulation, multiplying power, capacity, flame retardance and the like of the battery on the basis of the comparative example.
In summary, the sodium perchlorate and the fluorocyclotriphosphazene compound are matched to serve as the dual additive, and the dual additive cooperate to improve the interface stability of the cathode and the anode solid electrolyte of the battery, and form stable SEI and CEI on the surface of the electrode material, so that the electrochemical performances of the sodium ion battery such as circulation, multiplying power and capacity are improved, and the dual additive sodium ion battery electrolyte has good flame retardant effect and can improve the safety performance of the battery.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (10)
1. A dual additive sodium ion battery electrolyte characterized by: the dual-additive sodium ion battery electrolyte comprises sodium salt, an organic solvent, a sodium perchlorate additive and a fluorine-containing cyclotriphosphazene compound additive, wherein the sodium perchlorate additive is shown as a formula I, and the fluorine-containing cyclotriphosphazene compound additive is shown as any one of a formula II:
2. the dual additive sodium ion battery electrolyte of claim 1, wherein the sodium perchlorate additive is present in the electrolyte in an amount of 0.3 to 0.7 percent by mass.
3. The dual additive sodium ion electrolyte of claim 1, wherein the fluorine-containing cyclotriphosphazene compound additive is 1-8% by mass of the electrolyte.
4. The dual additive sodium ion electrolyte of claim 1, wherein the organic solvent is any one or a combination of at least two of carbonate solvents and ether solvents.
5. The dual additive sodium ion electrolyte of claim 4, wherein the carbonate-based solvent comprises any one or a combination of at least two of ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, methylethyl carbonate, methylpropyl carbonate;
the ether solvent comprises any one or a combination of at least two of tetrahydrofuran, 1, 3-dioxolane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether.
6. The dual additive sodium ion electrolyte of claim 1, wherein the sodium salt is any one or a combination of at least two of NaPF6, naBF4, naOTf, naFSI, naTFSI.
7. A sodium ion battery comprising a positive electrode, a negative electrode, a separator and the dual additive sodium ion battery electrolyte of any one of claims 1-6.
8. The sodium ion battery of claim 7, wherein the positive electrode material is any one of an oxide positive electrode material, a polyanion positive electrode material, and a prussian blue positive electrode material.
9. The sodium ion battery of claim 7, wherein the negative electrode material is any one of hard carbon, soft carbon, sodium metal.
10. The sodium ion battery of claim 7, wherein the separator is any one of a glass fiber separator and a ceramic separator.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410199174.9A CN118136958A (en) | 2024-02-22 | 2024-02-22 | Double-additive sodium ion battery electrolyte and sodium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410199174.9A CN118136958A (en) | 2024-02-22 | 2024-02-22 | Double-additive sodium ion battery electrolyte and sodium ion battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN118136958A true CN118136958A (en) | 2024-06-04 |
Family
ID=91238620
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410199174.9A Pending CN118136958A (en) | 2024-02-22 | 2024-02-22 | Double-additive sodium ion battery electrolyte and sodium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN118136958A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109148950A (en) * | 2017-06-15 | 2019-01-04 | 宁德时代新能源科技股份有限公司 | Electrolyte and battery |
| CN115602924A (en) * | 2022-09-01 | 2023-01-13 | 中国石油大学（华东）（Cn） | Flame-retardant sodium-ion battery electrolyte and application thereof |
| CN115954551A (en) * | 2023-03-10 | 2023-04-11 | 四川易纳能新能源科技有限公司 | Sodium ion battery electrolyte, preparation method thereof and sodium ion battery |
-
2024
- 2024-02-22 CN CN202410199174.9A patent/CN118136958A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109148950A (en) * | 2017-06-15 | 2019-01-04 | 宁德时代新能源科技股份有限公司 | Electrolyte and battery |
| CN115602924A (en) * | 2022-09-01 | 2023-01-13 | 中国石油大学（华东）（Cn） | Flame-retardant sodium-ion battery electrolyte and application thereof |
| CN115954551A (en) * | 2023-03-10 | 2023-04-11 | 四川易纳能新能源科技有限公司 | Sodium ion battery electrolyte, preparation method thereof and sodium ion battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4521525B2 (en) | Non-flammable non-aqueous electrolyte and lithium ion battery using the same | |
| KR20140138474A (en) | Magnesium hybrid battery and its fabrication method | |
| CN114447333A (en) | Sodium ion battery | |
| CN109671982B (en) | High-temperature high-safety electrolyte matched with silicon-carbon negative electrode material for lithium ion battery | |
| CN106486696A (en) | A kind of non-aqueous electrolyte for lithium ion cell and lithium ion battery | |
| JP2006216361A (en) | Electrolytic solution for lithium battery | |
| CN109830752B (en) | Non-combustible high-voltage electrolyte and preparation method and application thereof | |
| CN114421000A (en) | Lithium metal secondary battery electrolyte | |
| CN107093766B (en) | Lithium ion battery electrolyte | |
| CN110911754B (en) | Lithium ion battery electrolyte and preparation method thereof | |
| CN112186190A (en) | High-voltage lithium ion battery | |
| CN114914543A (en) | Electrolyte additive for efficiently inhibiting dendritic crystal, application thereof and lithium metal secondary battery | |
| KR880001512B1 (en) | Improved non-aqueous cell safety | |
| CN112909339A (en) | Propylene carbonate-based electrolyte and lithium ion battery containing same | |
| CN114464891A (en) | Ultralow-density electrolyte and lithium-sulfur battery | |
| CN111540954A (en) | Lithium ion battery electrolyte, preparation method and lithium ion battery | |
| CN118136958A (en) | Double-additive sodium ion battery electrolyte and sodium ion battery | |
| CN115084653A (en) | Composite electrolyte additive for improving safety and cycle performance of sodium (lithium) ion energy storage battery | |
| JPH11250933A (en) | Nonaqueous electrolyte secondary battery | |
| JP2001028272A (en) | Electrolytic solution for lithium secondary battery and lithium secondary battery using the same | |
| Ma et al. | Rechargeable Battery Electrolytes: Electrochemical Energy Storage from Liquids to Solids | |
| CN111354977A (en) | Lithium ion battery electrolyte, preparation method thereof and lithium battery comprising lithium ion battery electrolyte | |
| CN114335729B (en) | High-voltage additive for lithium battery and electrolyte | |
| CN114388889B (en) | Lithium ion battery electrolyte suitable for high-capacity micron alloy negative electrode, battery and electronic device | |
| CN116072973B (en) | High-voltage potassium ion battery ether electrolyte and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |