CN117423899A - Sodium ion battery electrolyte additive, electrolyte and sodium ion battery - Google Patents
Sodium ion battery electrolyte additive, electrolyte and sodium ion battery Download PDFInfo
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- CN117423899A CN117423899A CN202310735267.4A CN202310735267A CN117423899A CN 117423899 A CN117423899 A CN 117423899A CN 202310735267 A CN202310735267 A CN 202310735267A CN 117423899 A CN117423899 A CN 117423899A
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- additive
- electrolyte
- ion battery
- sodium ion
- sodium
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- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 50
- 239000002000 Electrolyte additive Substances 0.000 title claims abstract description 43
- 239000003792 electrolyte Substances 0.000 title claims abstract description 33
- 239000000654 additive Substances 0.000 claims abstract description 45
- 230000000996 additive effect Effects 0.000 claims abstract description 41
- -1 diester compound Chemical class 0.000 claims abstract description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 8
- 239000010703 silicon Substances 0.000 claims abstract description 8
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 7
- 239000011734 sodium Substances 0.000 claims abstract description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 33
- 125000002252 acyl group Chemical group 0.000 claims description 15
- 125000003545 alkoxy group Chemical group 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 14
- 125000005843 halogen group Chemical group 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 125000004417 unsaturated alkyl group Chemical group 0.000 claims description 10
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 6
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 6
- 239000011356 non-aqueous organic solvent Substances 0.000 claims description 6
- 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 6
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 6
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 6
- 159000000000 sodium salts Chemical class 0.000 claims description 6
- YLKTWKVVQDCJFL-UHFFFAOYSA-N sodium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Na+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F YLKTWKVVQDCJFL-UHFFFAOYSA-N 0.000 claims description 5
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 4
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 4
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims description 3
- HFZLSTDPRQSZCQ-UHFFFAOYSA-N 1-pyrrolidin-3-ylpyrrolidine Chemical compound C1CCCN1C1CNCC1 HFZLSTDPRQSZCQ-UHFFFAOYSA-N 0.000 claims description 3
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 claims description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 3
- 229910021201 NaFSI Inorganic materials 0.000 claims description 3
- 229910019398 NaPF6 Inorganic materials 0.000 claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 150000005690 diesters Chemical class 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 3
- 150000003949 imides Chemical class 0.000 claims description 3
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 3
- 229940090181 propyl acetate Drugs 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 3
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 claims description 3
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 3
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 2
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 claims 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 abstract description 8
- 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 abstract description 4
- 238000007086 side reaction Methods 0.000 abstract description 4
- 229910001428 transition metal ion Inorganic materials 0.000 abstract description 4
- 125000004989 dicarbonyl group Chemical group 0.000 abstract description 3
- 239000007774 positive electrode material Substances 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 2
- 230000007797 corrosion Effects 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 230000007062 hydrolysis Effects 0.000 abstract description 2
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- OBCUTHMOOONNBS-UHFFFAOYSA-N phosphorus pentafluoride Chemical compound FP(F)(F)(F)F OBCUTHMOOONNBS-UHFFFAOYSA-N 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 125000004093 cyano group Chemical group *C#N 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000006245 Carbon black Super-P Substances 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000006256 anode slurry Substances 0.000 description 2
- DFFDSQBEGQFJJU-UHFFFAOYSA-N butyl hydrogen carbonate Chemical compound CCCCOC(O)=O DFFDSQBEGQFJJU-UHFFFAOYSA-N 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 229910004838 Na2/3Ni1/3Mn2/3O2 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000003756 stirring 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
- H01M10/0566—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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a sodium ion battery electrolyte additive, electrolyte and a sodium ion battery, wherein the additive comprises a first additive and a second additive, the first additive contains an unsaturated bond diester compound, and the second additive is a silicon-based phosphoryl diamine compound. The first additive can form a low-impedance interfacial film with stable sodium-rich salt on the surface of the negative electrode, and the interface film has a dicarbonyl structure, can complex divalent transition metal ions, reduces transition metal ions from being transferred to the negative electrode to damage the SEI film, and reduces side reactions of a battery to prolong the service life of a battery core; the second additive spontaneously reacts with trace water and hydrofluoric acid in the electrolyte to inhibit hydrolysis of sodium hexafluorophosphate, prevent corrosion of products such as hydrofluoric acid and phosphorus pentafluoride on the positive electrode material, improve stability of the material and the electrolyte, combine hydrogen free radicals in thermal runaway, and reduce combustibility of the battery cell.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a sodium ion battery electrolyte additive, an electrolyte and a sodium ion battery.
Background
As 80% of sodium resources in China are imported in a dependent manner, the supply condition of sodium resources becomes more and more tense along with the rapid increase of the demand for lithium ion batteries. Recently, the price of battery-grade lithium carbonate has been increased to 60 ten thousand/ton or more, and the price of sodium carbonate is only several thousand yuan/ton, so that the development of a sodium ion battery with lower cost has become urgent. At present, the sodium ion battery also has the problems of poor high-temperature performance, low initial efficiency, poor cycle performance and the like. The electrolyte has critical influence on the cycle performance, high-temperature performance and the like of the sodium ion battery, and the commercial sodium ion battery electrolyte additive is still a lithium ion battery electrolyte additive, so that the matching degree with a sodium ion battery system is not high. According to the invention, by adding the novel additive, the side reaction of the sodium ion battery can be reduced, and the stability of the sodium ion battery can be improved, so that the service life of the sodium ion battery can be prolonged, and the high-temperature performance of the sodium ion battery can be improved.
Disclosure of Invention
Based on the above, it is necessary to provide a sodium ion battery electrolyte additive, an electrolyte and a sodium ion battery aiming at the problems of the traditional positive electrode materials, so as to reduce side reactions of the sodium ion battery, improve the stability of the sodium ion battery, prolong the service life of the sodium ion battery and improve the high temperature performance of the sodium ion battery.
In order to solve the technical problems, the invention is realized by the following technical scheme:
an electrolyte additive of a sodium ion battery, wherein the electrolyte additive is an unsaturated bond-containing diester compound with a dicarbonyl structure, and the chemical structural formula 1 of the unsaturated bond-containing diester compound is as follows:
wherein R1 is selected from any one of unsaturated hydrocarbon groups with 2-10 carbon atoms, alkoxy groups with 1-10 carbon atoms and alkanoyl groups with 2-10 carbon atoms; r2 and R3 are each independently selected from any one of H, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an unsaturated alkyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms and an alkanoyl group having 2 to 10 carbon atoms.
In one embodiment, H in the alkyl group, the unsaturated alkyl group, the alkoxy group, and the alkanoyl group of the electrolyte additive may be partially or fully substituted with one or more of a halogen atom, a cyano group, a carboxyl group, and a sulfonic group.
In one embodiment, the electrolyte additive has the chemical formula 3 as follows:
the electrolyte additive is a silicon-based phosphoryl diamine compound, and the chemical structural formula 2 of the silicon-based phosphoryl diamine compound is as follows:
r4, R5, R6, R7, R8, R9 and R10 are each independently selected from any one of H, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an unsaturated alkyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms and an alkanoyl group having 2 to 10 carbon atoms.
In one embodiment, H in the alkyl group, the unsaturated alkyl group, the alkoxy group, and the alkanoyl group of the electrolyte additive may be partially or fully substituted with one or more of a halogen atom, a cyano group, a carboxyl group, and a sulfonic group.
In one embodiment, the electrolyte additive has the chemical formula 4 as follows:
an electrolyte comprising an electrolyte sodium salt, a nonaqueous organic solvent and an additive, the additive comprising a first additive and a second additive, the first additive being the electrolyte additive of any one of claims 1-3, the second additive being the electrolyte additive of any one of claims 4-6.
In one embodiment, the nonaqueous organic solvent includes one or a combination of several of ethylene carbonate EC, propylene carbonate, butylene carbonate BC, dimethyl carbonate DMC, diethyl carbonate DEC, ethylmethyl carbonate EMC, propylmethyl carbonate, γ -butyrolactone GBL, methyl acetate MA, ethyl acetate EA, propyl acetate EP, butyl acetate, ethyl propionate, propyl propionate, and butyl propionate. The electrolyte additive of claim 3 is adopted as the first additive, and the addition amount of the first additive is 0.5% -2% of the total weight of the electrolyte; the second additive is the electrolyte additive of claim 6, and the addition amount of the second additive is 0.1% -1% of the total weight of the electrolyte.
In one embodiment, the sodium salt comprises one or a combination of sodium hexafluorophosphate NaPF6, sodium perchlorate NaClO4, sodium bis (trifluoromethanesulfonyl) imide NaTFSI, sodium fluorosulfonyl (trifluoromethanesulfonyl) imide NaFTFSI, sodium bis (fluorosulfonyl) imide NaFSI.
The sodium ion battery comprises a positive electrode plate, a negative electrode plate and a diaphragm, and further comprises the electrolyte.
The advantages and effects:
the additive for the sodium ion battery electrolyte adopted by the invention comprises at least two additives. The first additive can form a low-impedance interfacial film with stable sodium-rich salt on the surface of the negative electrode, and the divalent transition metal ions can be complexed by the double carbonyl structure, so that the transition metal ions are reduced to be transferred to the negative electrode to damage the SEI film, and the side reaction of the battery is reduced, and the service life of the battery core is prolonged; the second additive spontaneously reacts with trace water and hydrofluoric acid in the electrolyte to inhibit hydrolysis of sodium hexafluorophosphate, prevent corrosion of products such as hydrofluoric acid and phosphorus pentafluoride on the positive electrode material, improve stability of the material and the electrolyte, combine hydrogen free radicals in thermal runaway, and reduce combustibility of the battery cell.
Detailed Description
In order to better understand the technical solutions in the present application, the following description of the technical solutions in the embodiments of the present application will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present application, not all embodiments. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the present disclosure, are within the scope of the present disclosure.
It will be understood that when an element is referred to as being "fixed" or "disposed" on another element, it can be directly on the other element or be indirectly on the other element; when an element is referred to as being "connected to" another element, it can be directly connected to the other element or be indirectly connected to the other element.
It is to be understood that the terms "length," "width," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," and the like indicate directional or positional relationships, merely to facilitate describing the present application and simplify the description, and do not indicate or imply that the devices or elements referred to must have a particular orientation, be configured and operated in a particular orientation, and thus are not to be construed as limiting the present application.
Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature. In the description of the present application, the meaning of "a plurality" or "a number" is two or more, unless explicitly defined otherwise.
It should be understood that the disclosure of the present application is not intended to limit the applicable scope of the present application, but is not intended to limit the scope of the present application to the details of the modification of the structure, the variation of the scale or the adjustment of the size of the structures, the effects of the present application and the objects achieved, which are not to be limited by the scope of the present application.
An electrolyte additive of a sodium ion battery, wherein the electrolyte additive is an unsaturated bond-containing diester compound with a dicarbonyl structure, and the chemical structural formula 1 of the unsaturated bond-containing diester compound is as follows:
wherein R1 is selected from any one of unsaturated hydrocarbon groups with 2-10 carbon atoms, alkoxy groups with 1-10 carbon atoms and alkanoyl groups with 2-10 carbon atoms; r2 and R3 are each independently selected from any one of H, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an unsaturated alkyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms and an alkanoyl group having 2 to 10 carbon atoms.
In one embodiment, wherein H in the alkanyl, unsaturated hydrocarbyl, alkoxy and alkanoyl groups may be partially or fully substituted with one or more of halogen atoms, cyano groups, carboxyl groups and sulfonic acid groups.
In one embodiment, the electrolyte additive has the chemical formula 2 as follows:
a sodium ion battery electrolyte additive, wherein the electrolyte additive is a silicon-based phosphoryl diamine compound, and the chemical structural formula 4 of the silicon-based phosphoryl diamine compound is as follows:
r4, R5, R6, R7, R8, R9 and R10 are each independently selected from any one of H, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an unsaturated alkyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms and an alkanoyl group having 2 to 10 carbon atoms.
In one embodiment, wherein H in the alkanyl, unsaturated hydrocarbyl, alkoxy and alkanoyl groups may be partially or fully substituted with one or more of halogen atoms, cyano groups, carboxyl groups and sulfonic acid groups.
In one embodiment, the electrolyte additive has the chemical formula 4 as follows:
an electrolyte comprises electrolyte sodium salt, a nonaqueous organic solvent and an additive, wherein the additive comprises a first additive and a second additive, the first additive is an electrolyte additive of the diester-based compound containing unsaturated bonds, and the second additive is an electrolyte additive of the silicon-based phosphoryl diamine compound.
In one embodiment, the nonaqueous organic solvent comprises one or a combination of several of ethylene carbonate EC, propylene carbonate, butylene carbonate BC, dimethyl carbonate DMC, diethyl carbonate DEC, ethylmethyl carbonate EMC, propylmethyl carbonate, gamma-butyrolactone GBL, methyl acetate MA, ethyl acetate EA, propyl acetate EP, butyl acetate, ethyl propionate, propyl propionate and butyl propionate. Wherein the first additive adopts a chemical structural formula 2 of an electrolyte additive, and the addition amount of the first additive is 0.5% -2% of the total weight of the electrolyte; the second additive adopts a chemical structural formula 4 of the electrolyte additive, wherein the addition amount of the second additive is 0.1% -1% of the total weight of the electrolyte.
In one embodiment, wherein the sodium salt comprises one or a combination of sodium hexafluorophosphate NaPF6, sodium perchlorate NaClO4, sodium bis (trifluoromethanesulfonyl) imide NaTFSI, sodium fluorosulfonyl (trifluoromethanesulfonyl) imide NaFTFSI, sodium bis (fluorosulfonyl) imide NaFSI.
The sodium ion battery comprises a positive electrode plate, a negative electrode plate and a diaphragm, wherein the sodium ion battery further comprises the electrolyte.
1) Preparation of electrolyte
The electrolytes of examples 1 to 4 and comparative examples 1 to 4 were prepared as follows:
ethylene carbonate EC and diethyl carbonate DEC were mixed in a mass ratio EC: dec=3:7, and then sodium hexafluorophosphate was added to a molar concentration of 1mol/L, and the types of additives and the contents thereof in the electrolytes of examples and comparative examples are shown in table 1, wherein the proportion of the additives is a proportion of the total weight of the electrolytes.
TABLE 1 additives of examples 1-10 and comparative examples 1-4 and their contents
2) Preparation of positive plate
Mixing transition metal oxide Na2/3Ni1/3Mn2/3O2, super-P (Carbon nano tube), CNT (Carbon nano tube) and PVDF (polyvinylidene fluoride) according to the mass ratio of 95.5:2:1:1.5, and then dispersing the mixture in NMP (N-methylpyrrolidone), and stirring the mixture to be stable and uniform under the action of a vacuum stirrer to obtain anode slurry; uniformly coating the anode slurry on an aluminum foil with the thickness of 16 mu m; and (3) airing the aluminum foil at room temperature, transferring the aluminum foil into a blast oven at 120 ℃ for drying for 2 hours, and then carrying out cold pressing and die cutting to obtain the positive plate.
3) Preparation of negative electrode sheet
Mixing hard carbon, super-P (small particle conductive carbon black), SBR (styrene butadiene rubber) and CMC (carboxymethyl cellulose) according to the mass ratio of 95.5:1.5:1:2, and dispersing the mixture in deionized water to obtain negative electrode slurry; coating the negative electrode slurry and copper foil with the thickness of 8 mu m; and (3) airing the copper foil at room temperature, transferring the copper foil into a blast oven at 120 ℃ for drying for 2 hours, and then carrying out cold pressing and die cutting to obtain the negative plate.
4) Preparation of sodium ion batteries
And (3) obtaining a bare cell through a lamination process by the positive plate, the negative plate and the diaphragm, putting the cell into a packaging shell, injecting electrolyte, sequentially sealing, and carrying out processes such as standing, hot and cold pressing, formation, capacity division and the like to obtain the sodium ion battery.
The performance test procedure and test results of the sodium ion battery are described below:
(1) Normal temperature cycle performance test
The sodium ion battery is charged to 4V at 25 ℃ under a constant current of 1C, then charged to a cut-off current of 0.05C under a constant voltage, and then discharged to 2V under a constant current of 1C, which is recorded as a charge-discharge cycle. Then 1000 cycles were performed according to the above conditions. The capacity retention (%) = (discharge capacity of 1000 th cycle/first discharge capacity) ×100% after 1000 cycles of the sodium ion battery.
(2) High temperature cycle performance test
The sodium ion battery is charged to 4V at the constant current of 1C at 45 ℃, then charged to the cut-off current of 0.05C at a constant voltage, and then discharged to 2V at the constant current of 1C, which is recorded as a charge-discharge cycle. Then 800 cycles were performed according to the above conditions. The capacity retention (%) = (discharge capacity of 800 th cycle/first discharge capacity) ×100% after 800 cycles of the sodium ion battery.
(3) High temperature storage performance test
The constant-current and constant-voltage charge is carried out at room temperature and 1C until the constant-current and constant-voltage charge reaches 4V, the constant-current discharge is carried out at 1C, the constant-current discharge is carried out at 2V, the average capacity is calculated to be the initial capacity C0 three times, and the volume of the sodium ion battery is tested to be V0; constant-current and constant-voltage charging at room temperature 1C until 4V is reached, cutting off at 0.05C, then placing the battery in a high-temperature test cabinet, storing at 60 ℃ for 15 days, taking out the volume of the tested sodium ion battery and recording the volume as Vn, wherein the volume expansion rate (%) = (Vn-V0)/V0;
after 5h at room temperature, 1C was discharged to 2V at constant current, and the discharge capacity C1, percent charged=c1/C0 was recorded; the constant-current and constant-voltage charge is carried out at room temperature of 1C until the constant-current and constant-voltage charge reaches 4V, the constant-current discharge is carried out at 1C until the constant-voltage charge reaches 0.05C, the constant-current discharge is carried out at 2V, and the recovery capacity C2 is recorded; percent recovery = C2/C0.
TABLE 2 test results for examples 1-4 and comparative examples 1-4
According to the results shown in table 2: compared with comparative examples 1-4, the sodium ion batteries of examples 1-4 are greatly improved in normal temperature cycle, high temperature storage and the like.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (10)
1. The electrolyte additive for the sodium ion battery is characterized in that the electrolyte additive is an unsaturated bond-containing diester-based compound, and the chemical structural formula 1 of the unsaturated bond-containing diester-based compound is as follows:
wherein R1 is selected from any one of unsaturated hydrocarbon groups with 2-10 carbon atoms, alkoxy groups with 1-10 carbon atoms and alkanoyl groups with 2-10 carbon atoms; r2 and R3 are each independently selected from any one of H, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an unsaturated alkyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms and an alkanoyl group having 2 to 10 carbon atoms.
2. The sodium ion battery electrolyte additive of claim 1, wherein H in the alkyl, unsaturated alkyl, alkoxy, and alkanoyl groups of the electrolyte additive may be partially or fully substituted with one or more of a halogen atom, cyano, carboxyl, and sulfonic acid group.
3. The sodium ion battery electrolyte additive of claim 1, wherein the electrolyte additive has a chemical structure of formula 3:
4. the electrolyte additive for the sodium ion battery is characterized by being a silicon-based phosphoric acid diamine compound, wherein the chemical structural formula 2 of the silicon-based phosphoric acid diamine compound is as follows:
r4, R5, R6, R7, R8, R9 and R10 are each independently selected from any one of H, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an unsaturated alkyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms and an alkanoyl group having 2 to 10 carbon atoms.
5. The sodium ion battery electrolyte additive of claim 4, wherein H in the alkyl, unsaturated alkyl, alkoxy, and alkanoyl groups of the electrolyte additive may be partially or fully substituted with one or more of a halogen atom, cyano, carboxyl, and sulfonic acid group.
6. The sodium ion battery electrolyte additive of claim 4, wherein the electrolyte additive has a chemical formula 4 as follows:
7. an electrolyte comprising electrolyte sodium salt, a nonaqueous organic solvent and an additive, wherein the additive is a first additive and a second additive, the first additive is the sodium ion battery electrolyte additive according to any one of claims 1-3, and the second additive is the sodium ion battery electrolyte additive according to any one of claims 4-6.
8. The electrolyte according to claim 7, wherein the nonaqueous organic solvent comprises one or a combination of several of ethylene carbonate EC, propylene carbonate, butylene carbonate BC, dimethyl carbonate DMC, diethyl carbonate DEC, ethylmethyl carbonate EMC, methylpropyl carbonate, γ -butyrolactone GBL, methyl acetate MA, ethyl acetate EA, propyl acetate EP, butyl acetate, ethyl propionate, propyl propionate, and butyl propionate; the electrolyte additive of claim 3 is adopted as the first additive, and the addition amount of the first additive is 0.5% -2% of the total weight of the electrolyte; the second additive is the electrolyte additive of claim 6, and the addition amount of the second additive is 0.1% -1% of the total weight of the electrolyte.
9. The electrolyte of claim 7 wherein the sodium salt comprises one or a combination of sodium hexafluorophosphate NaPF6, sodium perchlorate NaClO4, sodium bis (trifluoromethanesulfonyl) imide naffsi, sodium fluorosulfonyl (trifluoromethanesulfonyl) imide naffsi, sodium bis (fluorosulfonyl) imide NaFSI.
10. A sodium ion battery comprising a positive electrode sheet, a negative electrode sheet and a separator, wherein the sodium ion battery further comprises the electrolyte of any one of claims 7-9.
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