CN114899486A - Pyridine-containing non-aqueous electrolyte, preparation method thereof and sodium battery - Google Patents
Pyridine-containing non-aqueous electrolyte, preparation method thereof and sodium battery Download PDFInfo
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- CN114899486A CN114899486A CN202210543565.9A CN202210543565A CN114899486A CN 114899486 A CN114899486 A CN 114899486A CN 202210543565 A CN202210543565 A CN 202210543565A CN 114899486 A CN114899486 A CN 114899486A
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- sodium
- pyridine
- electrolyte
- acetylpyridine
- carbonate
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- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 239000011734 sodium Substances 0.000 title claims abstract description 89
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 82
- 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 title claims abstract description 74
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title abstract description 21
- WEGYGNROSJDEIW-UHFFFAOYSA-N 3-Acetylpyridine Chemical compound CC(=O)C1=CC=CN=C1 WEGYGNROSJDEIW-UHFFFAOYSA-N 0.000 claims abstract description 26
- 230000000996 additive effect Effects 0.000 claims abstract description 24
- 239000000654 additive Substances 0.000 claims abstract description 23
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 21
- AJKVQEKCUACUMD-UHFFFAOYSA-N 2-Acetylpyridine Chemical compound CC(=O)C1=CC=CC=N1 AJKVQEKCUACUMD-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- WMQUKDQWMMOHSA-UHFFFAOYSA-N 1-pyridin-4-ylethanone Chemical group CC(=O)C1=CC=NC=C1 WMQUKDQWMMOHSA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011356 non-aqueous organic solvent Substances 0.000 claims abstract description 9
- 239000003792 electrolyte Substances 0.000 claims description 69
- 239000008151 electrolyte solution Substances 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 13
- 239000007774 positive electrode material Substances 0.000 claims description 13
- 150000005678 chain carbonates Chemical class 0.000 claims description 10
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 10
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 9
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 239000007784 solid electrolyte Substances 0.000 claims description 5
- 239000007773 negative electrode material Substances 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910018908 NaN(SO2C2F5)2 Inorganic materials 0.000 claims description 3
- ADKPKEZZYOUGBZ-UHFFFAOYSA-N [C].[O].[Si] Chemical compound [C].[O].[Si] ADKPKEZZYOUGBZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 238000005524 ceramic coating Methods 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910021385 hard carbon Inorganic materials 0.000 claims description 3
- 229910003480 inorganic solid Inorganic materials 0.000 claims description 3
- 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 3
- 239000012528 membrane Substances 0.000 claims description 3
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004745 nonwoven fabric Substances 0.000 claims description 3
- 229920000098 polyolefin Polymers 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 3
- 229960003351 prussian blue Drugs 0.000 claims description 3
- 239000013225 prussian blue Substances 0.000 claims description 3
- 239000002153 silicon-carbon composite material Substances 0.000 claims description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 3
- 229910021384 soft carbon Inorganic materials 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 239000006259 organic additive Substances 0.000 claims 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 abstract description 14
- 210000001787 dendrite Anatomy 0.000 abstract description 6
- 238000007599 discharging Methods 0.000 abstract description 2
- 210000004027 cell Anatomy 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 9
- 238000010586 diagram Methods 0.000 description 8
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 8
- 230000010287 polarization Effects 0.000 description 6
- 230000002035 prolonged effect Effects 0.000 description 4
- 235000013024 sodium fluoride Nutrition 0.000 description 4
- 239000011775 sodium fluoride Substances 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- -1 sodium hexafluorophosphate Chemical compound 0.000 description 2
- 238000007614 solvation Methods 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 239000002152 aqueous-organic solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Images
Classifications
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- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- 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 nonaqueous electrolyte containing pyridine, which comprises a sodium salt, a nonaqueous organic solvent and an additive, wherein the additive is pyridine or acetylpyridine, and the weight percentage content of the additive is 0.5-2.0 wt%. The acetylpyridine is 4-acetylpyridine or 3-acetylpyridine, and the concentration of sodium salt is 1M. The non-aqueous electrolyte containing pyridine, the preparation method thereof and the sodium battery can solve the problems of low coulombic efficiency and few charging and discharging times caused by the fact that metal sodium in the existing sodium metal battery is easy to form dendrites.
Description
Technical Field
The invention relates to the technical field of sodium batteries, in particular to a pyridine-containing non-aqueous electrolyte, a preparation method thereof and a sodium battery.
Background
With the development of high-power electronic devices such as electric vehicles, it has been difficult for conventional batteries to meet the requirements for energy density thereof. The sodium metal anode battery has high theoretical capacity (1161mAh g-1), high reserves and outstanding low-temperature performance, and is considered as a next generation battery with wide application potential. However, sodium metal is easily broken by dendrite formation in repeated deposition peeling, and easily reacts with an electrolyte to form inactive sodium, thereby lowering coulombic efficiency. These problems severely limit the application of sodium metal batteries.
Disclosure of Invention
The invention aims to provide a pyridine-containing nonaqueous electrolyte, which solves the problems of low coulombic efficiency and low charge-discharge frequency caused by easy formation of dendrite of metal sodium in the conventional sodium metal battery. Another object of the present invention is to provide a method for producing a nonaqueous electrolytic solution containing pyridine and a sodium battery containing a nonaqueous electrolytic solution containing pyridine.
In order to achieve the aim, the invention provides a pyridine-containing nonaqueous electrolyte, which comprises a sodium salt, a nonaqueous organic solvent and an additive, wherein the additive is pyridine or acetylpyridine, and the weight percentage content of the additive is 0.5-2.0 wt%;
the structural formula of pyridine is
The acetylpyridine is 4-acetylpyridine or 3-acetylpyridine, and the structural formula of the 4-acetylpyridine is shown in the specification
The structural formula of the 3-acetylpyridine is shown in the specification
Preferably, the concentration of the sodium salt is 1M, and the sodium salt is NaPF 6 、NaClO 4 、NaN(SO 2 CF 3 ) 2 、NaN(SO 2 C 2 F 5 ) 2 、NaC(SO 2 CF 3 ) 3 Or NaN (SO) 2 F) 2 One or a mixture of several of them.
Preferably, the non-aqueous organic solvent is a mixture of cyclic carbonate and chain carbonate, and the volume ratio of the cyclic carbonate to the chain carbonate is 3:7-7: 3; the cyclic carbonate is one or a mixture of more of ethylene carbonate, propylene carbonate or butylene carbonate, and the chain carbonate is one or a mixture of more of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate or propyl methyl carbonate.
The preparation method of the non-aqueous electrolyte containing pyridine comprises the following steps:
s1, in a glove box, H 2 O<0.1ppm，O 2 <0.1ppm, weighing a proper amount of sodium salt, and dissolving the sodium salt in a nonaqueous organic solution, wherein the concentration of the sodium salt is 1M, so as to obtain a substrate electrolyte;
s2, adding 0.5-2.0 wt% of additive into the base electrolyte, wherein the additive is pyridine or acetylpyridine, and uniformly stirring to obtain the pyridine-containing nonaqueous electrolyte.
A sodium battery containing the pyridine-containing nonaqueous electrolyte prepared by the above preparation method comprises a battery case, and a positive electrode, a negative electrode, a separator and an electrolyte which are positioned in the battery case.
Preferably, the positive electrode comprises a positive electrode current collector and a positive electrode material positioned on the positive electrode current collector, and the positive electrode material comprises a positive electrode active material; the positive electrode active material is Na 3 V 2 (PO 4 ) 3 、Na 3 V 2 (PO 4 ) 2 O 2 F. One or a mixture of any more than one of the Prussian blue.
Preferably, the negative electrode comprises a negative electrode current collector and a negative electrode material positioned on the negative electrode current collector, wherein the negative electrode material is one or a mixture of more of graphite, hard carbon, soft carbon, a silicon-carbon composite material, a silicon-oxygen-carbon composite material, metal sodium and an alloy of the metal sodium.
Preferably, the separator is one or more of a polyolefin porous membrane, a non-woven fabric, a fiber coating, a ceramic coating, and an inorganic solid electrolyte coating.
According to the non-aqueous electrolyte containing pyridine, the preparation method thereof and the sodium battery, the additive contains acetyl groups with electron absorption, the cation solvation structure can be adjusted in the electrolyte, and the energy barrier of anions participating in a solid electrolyte interface phase (SEI) is reduced, so that the salt is promoted to degrade on the surface of a metal anode to generate the SEI rich in sodium fluoride NaF, the SEI has high mechanical strength and high surface energy, the growth of sodium dendrite is favorably inhibited, and the cycle efficiency of the battery is improved. The acetylpyridine additive can also form a high-stability cathode electrolyte interface phase (CEI), and the performances of the battery such as stability, multiplying power and the like are improved, so that the overall performance of the battery is improved.
The technical solution of the present invention is further described in detail by the accompanying drawings and embodiments.
Drawings
FIG. 1 is a graph of cycle life of a sodium symmetric cell prepared using a pyridine-containing nonaqueous electrolyte and a method of preparing the same, and electrolyte 1 of a sodium cell according to the present invention;
FIG. 2 is a graph of cycle life of a sodium symmetric cell prepared using a pyridine-containing nonaqueous electrolyte and a method of preparing the same, and electrolyte 2 of a sodium cell according to the present invention;
FIG. 3 is a graph of cycle life of a sodium symmetric cell prepared using a pyridine-containing nonaqueous electrolyte and a method of preparing the same and electrolyte 3 of a sodium cell according to the present invention;
FIG. 4 is a graph of cycle life of a sodium symmetric cell prepared using a pyridine-containing nonaqueous electrolyte and a method of preparing the same and electrolyte 4 of a sodium cell in accordance with the present invention;
FIG. 5 is a graph of cycle life of a sodium symmetric cell prepared using a pyridine-containing nonaqueous electrolyte and a method of preparing the same, and electrolyte 5 of a sodium cell in accordance with the present invention;
FIG. 6 is a graph of cycle life of a sodium symmetric cell prepared using a pyridine-containing nonaqueous electrolyte and a method of preparing the same and electrolyte 6 of a sodium cell according to the present invention;
FIG. 7 is a graph of cycle life of a sodium symmetric cell prepared using electrolyte 7 of a pyridine-containing nonaqueous electrolyte and a method of preparing the same and a sodium cell of the present invention;
FIG. 8 is a graph of cycle life of a sodium symmetric cell prepared using a pyridine-containing nonaqueous electrolyte of the present invention, a method of preparing the same, and a comparative electrolyte 1 for a sodium cell;
fig. 9 is a graph showing cycle performance of all-cell batteries prepared using the non-aqueous electrolyte solution containing pyridine of the present invention and the preparation method thereof, and the electrolyte solution 1 of sodium battery and the comparative electrolyte solution 1.
Detailed Description
A non-aqueous electrolyte containing pyridine comprises a sodium salt, a non-aqueous organic solvent and an additive, wherein the additive is pyridine or acetylpyridine, and the weight percentage of the additive is 0.5-2.0 wt%.
The structural formula of pyridine is
The acetylpyridine is 4-acetylpyridine or 3-acetylpyridine, and the structural formula of the 4-acetylpyridine is shown in the specification
The structural formula of the 3-acetylpyridine is shown in the specification
The additive contains acetyl groups with electron absorption, can adjust a cation solvation structure in electrolyte, and reduces the energy barrier of anions participating in a solid electrolyte interface phase (SEI), thereby promoting the salt to be degraded on the surface of a metal anode to generate the SEI rich in sodium fluoride NaF, having high mechanical strength and high surface energy, being beneficial to inhibiting the growth of sodium dendrite and improving the cycle efficiency of the battery. The acetylpyridine additive can also form a high-stability cathode electrolyte interface phase (CEI), and the performances of the battery such as stability, multiplying power and the like are improved, so that the overall performance of the battery is improved.
The concentration of sodium salt is 1M, and the sodium salt is NaPF 6 、NaClO 4 、NaN(SO 2 CF 3 ) 2 、NaN(SO 2 C 2 F 5 ) 2 、NaC(SO 2 CF 3 ) 3 Or NaN (SO) 2 F) 2 One or a mixture of several of them.
The non-aqueous organic solvent is a mixture of cyclic carbonate and chain carbonate, and the volume ratio of the cyclic carbonate to the chain carbonate is 3:7-7: 3; the cyclic carbonate is one or a mixture of more of ethylene carbonate, propylene carbonate or butylene carbonate, and the chain carbonate is one or a mixture of more of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate or propyl methyl carbonate. The mixed solution of the cyclic carbonate organic solvent with high dielectric constant and the chain carbonate organic solvent with low viscosity is used as the solvent of the sodium ion battery electrolyte, so that the mixed solution of the organic solvents simultaneously has high ionic conductivity, high dielectric constant and low viscosity.
The preparation method of the non-aqueous electrolyte containing pyridine comprises the following steps:
s1, in a glove box, H 2 O<0.1ppm，O 2 <0.1ppm, weighing a proper amount of sodium salt, and dissolving the sodium salt in a nonaqueous organic solution, wherein the concentration of the sodium salt is 1M, so as to obtain a substrate electrolyte;
s2, adding 0.5-2.0 wt% of additive into the base electrolyte, wherein the additive is pyridine or acetylpyridine, and uniformly stirring to obtain the pyridine-containing nonaqueous electrolyte.
A sodium battery containing the pyridine-containing nonaqueous electrolyte prepared by the above preparation method comprises a battery case, and a positive electrode, a negative electrode, a separator and an electrolyte which are positioned in the battery case.
The positive electrode comprises a positive electrode current collector and a positive electrode material positioned on the positive electrode current collector, wherein the positive electrode material comprises a positive electrode active material; the positive electrode active material is Na 3 V 2 (PO 4 ) 3 、Na 3 V 2 (PO 4 ) 2 O 2 F. One or a mixture of any more than one of the Prussian blue.
The negative electrode comprises a negative current collector and a negative material positioned on the negative current collector, wherein the negative material is one or a mixture of more of graphite, hard carbon, soft carbon, a silicon-carbon composite material, a silicon-oxygen-carbon composite material, metal sodium and an alloy of the metal sodium.
The separator is one or more of polyolefin porous membrane, non-woven fabric, fiber coating, ceramic coating and inorganic solid electrolyte coating.
The technical solution of the present invention is further illustrated by the accompanying drawings and examples.
Example 1
In a glove box (H) 2 O<0.1ppm，O 2 <0.1ppm), an appropriate amount of sodium hexafluorophosphate (NaPF) was weighed 6 ) And dissolving the electrolyte in a non-aqueous organic solution to obtain a base electrolyte.
Sodium salt concentration: 1M sodium hexafluorophosphate;
non-aqueous organic solvent: ethylene Carbonate (EC), a mixed solvent of diethyl carbonate (DEC) 1:1(v: v);
a compound represented by 3-acetylpyridine with a mass fraction of 1.0 wt% was added to the base electrolyte, and the mixture was stirred uniformly to obtain an electrolyte solution 1.
Example 2
An electrolyte was prepared as described in example 1, except that pyridine was added to the base electrolyte in a mass fraction of 1.0 wt%, to give a working electrolyte 2.
Example 3
An electrolyte was prepared as described in example 1, except that 1.0 wt% of 4-acetylpyridine was added to the base electrolyte to give example electrolyte 3.
Example 4
An electrolyte was prepared as described in example 1, except that 3-acetylpyridine was added to the base electrolyte in a mass fraction of 0.5 wt%, to give a working electrolyte 4.
Example 5
An electrolyte was prepared as described in example 1, except that 3-acetylpyridine was added to the base electrolyte in a mass fraction of 2.0 wt% to give a working electrolyte 5.
Example 6
An electrolyte was prepared by the method described in example 1 except that the mixed solvent ratio of Ethylene Carbonate (EC) to diethyl carbonate (DEC) in the base electrolyte was 3:7(v: v), to obtain a working electrolyte 6.
Example 7
An electrolyte was prepared by the method described in example 1 except that the mixed solvent ratio of Ethylene Carbonate (EC) to diethyl carbonate (DEC) in the base electrolyte was 7:3(v: v), to obtain a working electrolyte 7.
Comparative example 1
Comparative example a base electrolyte prepared by the method described in example 1 was used as comparative electrolyte 1.
Sodium batteries were prepared using the above-described example electrolytes 1 to 7 and the comparative electrolyte 1.
The sodium battery preparation method comprises the following steps:
sodium symmetric cell: in a glove box (H) 2 O<0.1ppm，O 2 <0.1ppm), sequentially assembling the positive electrode shell → the sodium sheet → the electrolyte → the diaphragm → the electrolyte → the sodium sheet → the stainless steel gasket → the negative electrode shell from bottom to top, and then transferring to a tablet press for punching and packaging to obtain the finished sodium symmetric battery.
All-battery: in a glove box (H) 2 O<0.1ppm，O 2 <0.1ppm), sequentially assembling the positive electrode shell → FNVP pole piece → electrolyte → diaphragm → sodium piece → stainless steel gasket → spring piece → negative electrode shell from bottom to top, and then transferring to a tablet press for punching and packaging to obtain the finished full cell.
Electrochemical performance tests were performed on the assembled cells using novalr test equipment. The specific experimental process is as follows: sodium sheets are used as positive and negative electrodes to assemble a sodium symmetrical battery to carry out constant current charge and discharge test; sodium sheet as negative electrode, FNVP (Na) 3 V 2 (PO 4 ) 2 O 2 F) Is a positive active material, and is matched and assembled into a full cell for constant current charge and discharge test.
Fig. 1 is a cycle life diagram of a sodium symmetric battery prepared using a pyridine-containing nonaqueous electrolytic solution and a preparation method thereof and an electrolyte 1 of a sodium battery according to the present invention, fig. 2 is a cycle life diagram of a sodium symmetric battery prepared using a pyridine-containing nonaqueous electrolytic solution and a preparation method thereof and an electrolyte 2 of a sodium battery according to the present invention, fig. 3 is a cycle life diagram of a sodium symmetric battery prepared using a pyridine-containing nonaqueous electrolytic solution and a preparation method thereof and an electrolyte 3 of a sodium battery according to the present invention, and fig. 8 is a cycle life diagram of a sodium symmetric battery prepared using a pyridine-containing nonaqueous electrolytic solution and a preparation method thereof according to the present invention and a comparative electrolyte 1 of a sodium battery. As shown in the figure, the polarization degree of the sodium symmetric battery prepared by using the electrolyte 1 is still small after the battery is cycled for more than 360 hours, the polarization degree of the sodium symmetric battery prepared by using the electrolyte 2 is still small after the battery is cycled for more than 120 hours, and the polarization degree of the sodium symmetric battery prepared by using the electrolyte 3 is still small after the battery is cycled for more than 150 hours. The sodium symmetric cell prepared with comparative electrolyte 1 exhibited severe polarization after 100 hours of cycling. Therefore, 3-acetylpyridine is added into the electrolyte, so that the cycle life of the sodium symmetric battery can be effectively prolonged. The cycle life of the sodium symmetrical battery is slightly prolonged by adding 4-acetylpyridine or pyridine into the electrolyte.
Fig. 4 is a cycle life diagram of a sodium symmetric battery prepared using a pyridine-containing nonaqueous electrolytic solution and a preparation method thereof and an electrolyte 4 of a sodium battery according to the present invention, and fig. 5 is a cycle life diagram of a sodium symmetric battery prepared using a pyridine-containing nonaqueous electrolytic solution and a preparation method thereof and an electrolyte 5 of a sodium battery according to the present invention. As shown, the polarization was still small after cycling the sodium symmetric cell in electrolyte 4 for more than 180 hours, and the cycle life of the sodium symmetric cell was increased. After the sodium symmetrical battery in the electrolyte 5 is circulated for over 380 hours, the polarization degree is still small, and the cycle life of the sodium symmetrical battery is greatly prolonged. The concentration of the 3-acetylpyridine additive in the electrolyte is changed, and the cycle life of the obtained sodium symmetric battery is better prolonged.
Fig. 6 is a cycle life diagram of a sodium symmetric battery prepared using a pyridine-containing nonaqueous electrolytic solution and a preparation method thereof and an electrolyte 6 of a sodium battery according to the present invention, and fig. 7 is a cycle life diagram of a sodium symmetric battery prepared using a pyridine-containing nonaqueous electrolytic solution and a preparation method thereof and an electrolyte 7 of a sodium battery according to the present invention. As shown in the figure, under the condition of non-aqueous organic solvents with different proportions, the 3-acetylpyridine additive can still obviously prolong the cycle life of the sodium symmetric battery.
Fig. 9 is a graph showing cycle performance of all-cell batteries prepared using the non-aqueous electrolyte solution containing pyridine of the present invention and the preparation method thereof, and the electrolyte solution 1 of sodium battery and the comparative electrolyte solution 1. As shown in the figure, the cycle stability of the full battery assembled by using the electrolyte 1 is greatly improved, the capacity retention rate of 91.0% is still maintained after 200 cycles, the specific capacity attenuation is slow, and the average coulombic efficiency reaches 97%. .
Therefore, the non-aqueous electrolyte containing pyridine, the preparation method thereof and the sodium battery can solve the problems of low coulombic efficiency and few charging and discharging times caused by the fact that metal sodium in the existing sodium metal battery is easy to form dendrites.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting the same, and although the present invention is described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that: modifications and equivalents may be made to the invention without departing from the spirit and scope of the invention.
Claims (8)
1. A pyridine-containing nonaqueous electrolytic solution characterized in that: comprises sodium salt, non-aqueous organic solvent and additive, wherein the additive is pyridine or acetylpyridine, and the weight percentage content of the additive is 0.5-2.0 wt%;
the structural formula of pyridine is
The acetylpyridine is 4-acetylpyridine or 3-acetylpyridine, and the structural formula of the 4-acetylpyridine is shown in the specification
The structural formula of the 3-acetylpyridine is shown in the specification
2. The nonaqueous electrolytic solution containing pyridine of claim 1, wherein: the concentration of the sodium salt is 1M, and the sodium salt is NaPF 6 、NaClO 4 、NaN(SO 2 CF 3 ) 2 、NaN(SO 2 C 2 F 5 ) 2 、NaC(SO 2 CF 3 ) 3 Or NaN (SO) 2 F) 2 One or a mixture of several of them.
3. The nonaqueous electrolytic solution containing pyridine of claim 1, wherein: the non-aqueous organic solvent is a mixture of cyclic carbonate and chain carbonate, and the volume ratio of the cyclic carbonate to the chain carbonate is 3:7-7: 3; the cyclic carbonate is one or a mixture of more of ethylene carbonate, propylene carbonate or butylene carbonate, and the chain carbonate is one or a mixture of more of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate or propyl methyl carbonate.
4. The method for preparing a nonaqueous electrolytic solution containing pyridine according to any one of claims 1 to 3, characterized by comprising the steps of:
s1, in a glove box, H 2 O<0.1ppm，O 2 <0.1ppm, weighing a proper amount of sodium salt, and dissolving the sodium salt in a nonaqueous organic solution, wherein the concentration of the sodium salt is 1M, so as to obtain a substrate electrolyte;
s2, adding 0.5-2.0 wt% of additive into the base electrolyte, wherein the additive is pyridine or acetylpyridine, and uniformly stirring to obtain the pyridine-containing nonaqueous electrolyte.
5. A sodium battery containing the pyridine-containing nonaqueous electrolytic solution prepared in claim 4, characterized in that: comprises a battery shell, a positive electrode, a negative electrode, a diaphragm and electrolyte which are positioned in the battery shell.
6. The sodium battery of claim 5, wherein: the positive electrode comprises a positive electrode current collector and a positive electrode material positioned on the positive electrode current collector, wherein the positive electrode material comprises a positive electrode active material; the positive electrode active material is Na 3 V 2 (PO 4 ) 3 、Na 3 V 2 (PO 4 ) 2 O 2 F. One or a mixture of any more than one of the Prussian blue.
7. The sodium battery of claim 5, wherein: the negative electrode comprises a negative electrode current collector and a negative electrode material positioned on the negative electrode current collector, wherein the negative electrode material is one or a mixture of more of graphite, hard carbon, soft carbon, a silicon-carbon composite material, a silicon-oxygen-carbon composite material, metal sodium and an alloy of the metal sodium.
8. The sodium battery of claim 5, wherein: the diaphragm is one or more of polyolefin porous membrane, non-woven fabric, fiber coating, ceramic coating and inorganic solid electrolyte coating.
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