CN117254101A - Sodium ion battery gel electrolyte, preparation method and sodium ion battery - Google Patents
Sodium ion battery gel electrolyte, preparation method and sodium ion battery Download PDFInfo
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- CN117254101A CN117254101A CN202311202389.3A CN202311202389A CN117254101A CN 117254101 A CN117254101 A CN 117254101A CN 202311202389 A CN202311202389 A CN 202311202389A CN 117254101 A CN117254101 A CN 117254101A
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- electrolyte
- ion battery
- sodium ion
- gel
- additive
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- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 52
- 239000011245 gel electrolyte Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000003792 electrolyte Substances 0.000 claims abstract description 72
- 239000000654 additive Substances 0.000 claims abstract description 44
- 230000000996 additive effect Effects 0.000 claims abstract description 44
- 229920000642 polymer Polymers 0.000 claims abstract description 32
- -1 fluoro-sulfonyl Chemical group 0.000 claims abstract description 31
- 239000003960 organic solvent Substances 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 6
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims abstract description 4
- 125000004765 (C1-C4) haloalkyl group Chemical group 0.000 claims abstract description 4
- 125000006656 (C2-C4) alkenyl group Chemical group 0.000 claims abstract description 4
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 4
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 4
- 150000002367 halogens Chemical class 0.000 claims abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- 150000002825 nitriles Chemical class 0.000 claims abstract description 3
- 239000010408 film Substances 0.000 claims description 27
- 229920005597 polymer membrane Polymers 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 16
- 239000011159 matrix material Substances 0.000 claims description 12
- UUBPGZYXFMTMFR-UHFFFAOYSA-N N=[S+]F Chemical compound N=[S+]F UUBPGZYXFMTMFR-UHFFFAOYSA-N 0.000 claims description 11
- 239000002105 nanoparticle Substances 0.000 claims description 11
- 239000002033 PVDF binder Substances 0.000 claims description 9
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 9
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 8
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 7
- 239000004745 nonwoven fabric Substances 0.000 claims description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000007773 negative electrode material Substances 0.000 claims description 6
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 6
- 239000004926 polymethyl methacrylate 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
- 150000005678 chain carbonates Chemical class 0.000 claims description 5
- 239000007774 positive electrode material Substances 0.000 claims description 4
- 159000000000 sodium salts Chemical group 0.000 claims description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- 229910010093 LiAlO Inorganic materials 0.000 claims description 3
- 229910021201 NaFSI Inorganic materials 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 239000004642 Polyimide Substances 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- QXZNUMVOKMLCEX-UHFFFAOYSA-N [Na].FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F Chemical compound [Na].FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F QXZNUMVOKMLCEX-UHFFFAOYSA-N 0.000 claims description 3
- 239000004760 aramid Substances 0.000 claims description 3
- 229920003235 aromatic polyamide Polymers 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 239000004927 clay Substances 0.000 claims description 3
- 229910052570 clay Inorganic materials 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 3
- 150000002910 rare earth metals Chemical class 0.000 claims description 3
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 3
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 3
- 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 3
- 239000010457 zeolite Substances 0.000 claims description 3
- 239000011152 fibreglass Substances 0.000 claims description 2
- 125000005059 halophenyl group Chemical group 0.000 claims description 2
- 230000001351 cycling effect Effects 0.000 abstract description 5
- 238000000354 decomposition reaction Methods 0.000 abstract description 5
- 239000010406 cathode material Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 150000003949 imides Chemical class 0.000 description 6
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 4
- 238000005345 coagulation Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000010041 electrostatic spinning Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 229910021385 hard carbon Inorganic materials 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000863 Ferronickel Inorganic materials 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
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000009461 vacuum packaging Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62C—FIRE-FIGHTING
- A62C3/00—Fire prevention, containment or extinguishing specially adapted for particular objects or places
- A62C3/16—Fire prevention, containment or extinguishing specially adapted for particular objects or places in electrical installations, e.g. cableways
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Dispersion Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Public Health (AREA)
- Business, Economics & Management (AREA)
- Emergency Management (AREA)
- Secondary Cells (AREA)
Abstract
In order to solve the problems of large electrolyte interface film thickness and high impedance caused by sodium ion battery cathode materials in the prior art, the gel electrolyte of the sodium ion battery comprises a gel polymer diaphragm and functional electrolyte, wherein the functional electrolyte is adsorbed in the gel polymer diaphragm, the functional electrolyte comprises electrolyte salt, an organic solvent and an additive, the additive comprises a fluoro-sulfonyl imide additive, and the structure of the fluoro-sulfonyl imide additive is as follows:wherein R is 1 ‑R 3 Each independently selected from hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl, nitrile, C1-C3 alkylnitrile, C2-C4 alkenyl, alkoxy, carboxyl, phenyl, halogenated phenyl. Meanwhile, the invention also discloses a preparation method of the gel electrolyte. The gel electrolyte provided by the invention forms an excellent interface film on the surface of the electrode, inhibits electrolyte decomposition, relieves the thickness of the interface film, improves the interface impedance between the pole piece and the electrolyte, and improves the cycling stability of the sodium ion battery.
Description
Technical Field
The invention belongs to the technical field of sodium ion batteries, and particularly relates to a sodium ion battery gel electrolyte, a preparation method and a sodium ion battery thereof.
Background
The hard carbon of the negative electrode material of the sodium ion battery has large specific surface area, so that electrolyte is easy to continuously reduce and decompose on the negative electrode to generate thick and compact decomposition products, the impedance between the electrode material and the electrolyte or the diaphragm is increased, and the cycle performance of the battery is influenced. The conventional method is to add an additive into a liquid electrolyte for improvement, for example, 1, 3-Propane Sultone (PS) is widely used as the additive in sodium ion electrolyte, however, the formed electrode/electrolyte interface film has larger thickness and higher impedance, the using amount of the electrode/electrolyte interface film needs to be strictly controlled, and PS is added into a high-attention substance list in 2015 of European Union, so that the development of a novel functional film forming additive is urgently needed; in addition, the liquid electrolyte has fluidity, and the battery is easy to burn under extreme conditions, so that great potential safety hazards exist.
Disclosure of Invention
Aiming at the problems of large electrolyte interface film thickness and high impedance caused by the negative electrode material of the sodium ion battery in the prior art, the gel electrolyte of the sodium ion battery, the preparation method and the sodium ion battery thereof are provided.
The technical scheme adopted by the invention for solving the technical problems is as follows:
in one aspect, the invention provides a sodium ion battery gel electrolyte, which comprises a gel polymer membrane and a functional electrolyte, wherein the functional electrolyte is adsorbed in the gel polymer membrane, the functional electrolyte comprises electrolyte salt, an organic solvent and an additive, the additive comprises a fluoro-sulfonyl imide additive, and the structure of the fluoro-sulfonyl imide additive is as follows:
wherein R is 1 -R 3 Each independently selecting one or more of hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl, nitrile group, C1-C3 alkylnitrile, C2-C4 alkenyl, alkoxy, carboxyl, phenyl and halogenated phenyl.
Optionally, the fluorosulfonyl imide additive is selected from one or more of the following compounds:
optionally, the mass ratio of the gel polymer diaphragm to the functional electrolyte is 1-9: 9-1, wherein the mass percentage of the fluoro-sulfimide additive is 1-5% based on 100% of the total mass of the functional electrolyte.
Optionally, the gel polymer membrane comprises a matrix membrane and a polymer attached to the matrix membrane, wherein the mass ratio of the matrix membrane to the polymer is 4-9: 6 to 1.
Optionally, the matrix film comprises one or more of non-woven fabrics, polyethylene, polypropylene-polyethylene-polypropylene three-layer composite film, polyimide, aramid, cellulose and glass fiber; the polymer includes one or more of polyvinylidene fluoride (PVdF), polyacrylonitrile (PAN), polyethylene oxide (PEO), polymethyl methacrylate (PMMA), polyhexafluoropropylene (HFP), and polystyrene oxide (PPO).
Optionally, also includeNanoparticles uniformly dispersed in the gel polymer membrane, wherein the mass percentage of the nanoparticles is 0.1-20% based on 100% of the total mass of the gel polymer membrane, and the nanoparticles are SiO 2 、Al 2 O 3 、SnO 2 、TiO 2 、LiAlO 2 、CeO 2 、Fe 2 O 3 One or more of rare earth, clay or zeolite.
Optionally, the organic solvent comprises 40-90% by mass of the total mass of the functional electrolyte is 100%, and the organic solvent comprises one or more of a cyclic carbonate solvent and a chain carbonate solvent.
Optionally, the electrolyte salt is selected from sodium salt, and the mass percentage of the electrolyte salt is 5% -25% based on 100% of the total mass of the functional electrolyte.
Optionally, the sodium salt comprises one or more of sodium hexafluorophosphate, sodium perchlorate, sodium bis (trifluoromethylsulfonyl) imide (NaTFSI) and sodium bis (fluorosulfonyl) imide (NaFSI).
In another aspect, the invention provides a method for preparing a gel electrolyte of a sodium ion battery, comprising the following steps:
obtaining a gel polymer membrane;
mixing electrolyte salt with an organic solvent to obtain a reference electrolyte;
adding the fluoro-sulfimide additive into a reference electrolyte to obtain a functional electrolyte;
and adding the functional electrolyte into the gel polymer membrane to absorb and saturate to obtain the gel electrolyte.
In another aspect, the invention provides a sodium ion battery, comprising a positive plate, a diaphragm, a negative plate and the sodium ion battery gel electrolyte, wherein the positive plate comprises a positive electrode active material, the negative plate comprises a negative electrode active material, and the diaphragm is arranged between the positive plate and the negative plate.
The sodium ion battery gel electrolyte provided by the invention comprises the fluoro-sulfimide additive, and the fluoro-sulfimide additive introduced into the electrolyte can form an excellent interface film on the surface of an electrode, inhibit the decomposition of electrolyte and the pulverization and diffusion of material particles to relieve the thickness of the interface film, so that the interface impedance of a pole piece and the electrolyte is improved, and the cycling stability of the sodium ion battery is improved.
Drawings
Fig. 1 is a graph showing the high and low temperature discharge capacity retention rate of examples 1, 5, 7 and comparative example 1 according to the present invention.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects solved by the invention more clear, the invention is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The specific meaning of the above terms in the present invention will be understood in specific cases by those of ordinary skill in the art.
The invention provides a sodium ion battery gel electrolyte, which comprises a gel polymer membrane and a functional electrolyte, wherein the functional electrolyte is adsorbed in the gel polymer membrane, the functional electrolyte comprises electrolyte salt, an organic solvent and an additive, the additive comprises a fluoro-sulfonyl imide additive, and the structure of the fluoro-sulfonyl imide additive is shown as follows:
wherein R is 1 -R 3 Each independently selected from one or more of hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl, nitrile, C1-C3 alkylnitrile, C2-C4 alkenyl, alkoxy, carboxyl, phenyl, halophenyl.
Specifically, the fluoro-sulfimide additive is introduced into the electrolyte, so that an excellent interface film can be formed on the surface of the electrode, the decomposition of the electrolyte and the pulverization and diffusion of material particles are inhibited, the thickness of the interface film is relieved, the interface impedance between a pole piece and the electrolyte is further improved, the cycling stability of the sodium ion battery is improved, and the sodium ion battery still has good high-temperature performance and low-temperature performance under the condition of large environmental temperature span.
In some embodiments, the fluorosulfonyl imide additive is selected from one or more of the following compounds:
in particular, in a preferred embodiment, the fluorosulfonyl imide additive is selected from one or more of N-p-fluorophenyl bis (trifluoromethanesulfonyl) imide (1-2), N-pentafluorophenyl bis (trifluoromethanesulfonyl) imide (1-3), and N-trifluoromethanesulfonyl) imide (1-4); the fluoro-sulfimide additive is added into the electrolyte, so that an excellent interfacial film can be formed on the surface of the electrode, the decomposition of the electrolyte and the pulverization and diffusion effects of material particles are inhibited, the interfacial impedance is improved, and the cycling stability of the sodium ion battery is improved.
In some embodiments, the mass ratio of the gel polymer separator to the functional electrolyte is 1-9: 9-1, wherein the mass percentage of the fluoro-sulfimide additive is 1-5% based on 100% of the total mass of the functional electrolyte.
Specifically, in a preferred embodiment, the mass percentage of the fluoro-sulfimide additive is 1-3%.
In some embodiments, the gel polymer separator comprises a base film and a polymer attached to the base film, the mass ratio of the base film to the polymer being from 4 to 9:6 to 1.
In some embodiments, the matrix film comprises one or more of nonwoven fabric, polyethylene, polypropylene-polyethylene-polypropylene three-layer composite film, polyimide, aramid, cellulose, and fiberglass; the polymer comprises one or more of polyvinylidene fluoride (PVdF), polyacrylonitrile (PAN), polyethylene oxide (PEO), polymethyl methacrylate (PMMA), polyhexafluoropropylene (HFP), polystyrene oxide (PPO).
Specifically, in the preferred embodiment, the matrix film is selected from a non-woven fabric, and the non-woven fabric matrix film has the characteristics of high porosity and high thermal stability, and secondly, the three-dimensional pore structure of the non-woven fabric can ensure high electrolyte retention rate and effectively prevent the short circuit problem caused by the puncture of the separator.
In some embodiments, the gel polymer membrane further comprises nanoparticles, wherein the nanoparticles are uniformly dispersed in the gel polymer membrane, the mass percentage of the nanoparticles is 0.1-20% based on 100% of the total mass of the gel polymer membrane, and the nanoparticles are SiO 2 、Al 2 O 3 、SnO 2 、TiO 2 、LiAlO 2 、CeO 2 、Fe 2 O 3 One or more of rare earth, clay or zeolite.
In some embodiments, the organic solvent comprises 40% to 90% by mass of one or more of a cyclic carbonate solvent and a chain carbonate solvent, based on 100% by mass of the functional electrolyte.
The cyclic carbonate solvent includes Ethylene Carbonate (EC) and Propylene Carbonate (PC), and the chain carbonate solvent includes ethylmethyl carbonate (EMC) and diethyl carbonate (DEC);
the cyclic carbonate solvent has high dielectric constant and high ionic conductivity, can form a stable SEI film on the surface of the negative electrode, has lower viscosity than the cyclic carbonate solvent, has better electrochemical stability and can improve the low-temperature performance of the electrolyte; in the preparation of the electrolyte, a cyclic carbonate solvent is usually mixed with a chain carbonate solvent to form a good solvent system.
In some embodiments, the electrolyte salt is present in an amount of 5% to 25% by mass based on 100% by mass of the functional electrolyte.
In some embodiments, the sodium salt comprises one or more of sodium hexafluorophosphate, sodium perchlorate, sodium bis (trifluoromethylsulfonyl) imide (NaTFSI), and sodium bis (fluorosulfonyl) imide (NaFSI).
Another embodiment of the present invention provides a method for preparing a gel electrolyte of a sodium ion battery, comprising the steps of:
obtaining a gel polymer membrane;
mixing electrolyte salt with an organic solvent to obtain a reference electrolyte;
adding the fluoro-sulfimide additive into a reference electrolyte to obtain a functional electrolyte;
and adding the functional electrolyte into the gel polymer membrane to absorb and saturate to obtain the gel electrolyte.
In some embodiments, in the preparation of the "get gel polymer membrane", a polymer is mixed with the N-methylpyrrolidone solution to obtain a gel polymer solution, then the nanoparticles are sequentially added into the gel polymer solution to obtain a co-coagulated polymer solution, and the co-coagulated polymer solution is transferred into the matrix membrane and dried to obtain the gel polymer membrane.
It should be noted that, the mode of transferring the copolymer solution to the matrix film includes one or more of a self-phase transfer method, a soaking method, an electrostatic spinning method and a spin-coating method; specifically, in a preferred embodiment, the copolymer polymer solution is transferred into the matrix film by electrospinning; the basic principle of the electrostatic spinning is that polymer solution or melt is charged with thousands to tens of thousands of volts of high-voltage static electricity, charged polymer liquid drops are accelerated at the conical pole point of a capillary under the effect of electric field force, when the electric field force is large enough, the polymer liquid drops fight to form eruption trickles, and the trickles are evaporated or solidified by solvent in the eruption process and fall on receiving equipment to form fiber mats similar to non-woven fabrics.
Specifically, the drying temperature is 60 ℃, and the drying time is 12 hours.
The invention further provides a sodium ion battery, which comprises a positive plate, a diaphragm, a negative plate and the sodium ion battery gel electrolyte, wherein the positive plate comprises a positive electrode active material, the negative plate comprises a negative electrode active material, and the diaphragm is arranged between the positive plate and the negative plate.
The positive plate further comprises a positive current collector, the negative plate further comprises a negative current collector, the positive current collector and the negative current collector are used for leading out current, the positive active material covers the positive current collector, and the negative active material covers the negative current collector.
The electrolyte salt is mixed with an organic solvent and carried out in an inert atmosphere.
The invention is further illustrated by the following examples.
Example 1
The embodiment is used for explaining the gel electrolyte of the sodium ion battery and the preparation method thereof, and comprises the following operation steps:
mixing polyvinylidene fluoride (PVDF) and Polyacrylonitrile (PAN) according to a mass ratio of 1:1 with N-methylpyrrolidone (NMP), and stirring for 2 hours at a stirring speed of 250r/min to fully dissolve the mixture, thereby obtaining a gel polymer solution with a mass fraction of 12%;
adding 10% wt of nano particles into the gel polymer solution successively and stirring for 4 hours to obtain a co-coagulation gel polymer solution;
transferring the co-coagulation polymer solution into a matrix film by using electrostatic spinning equipment, volatilizing a solvent in the co-coagulation polymer solution under natural conditions, and continuously drying in a vacuum oven at 60 ℃ for 12 hours to obtain a gel polymer diaphragm;
1.0M NaPF in inert atmosphere 6 5.0wt% fec was mixed with organic solvent PC, EC, EMC (PC, EC, EMC =2:1:7) to form a base electrolyte at a concentration of 1 mol/L;
adding 1.0wt% of N-p-fluorophenyl bis (trifluoromethanesulfonyl) imine into a reference electrolyte to obtain a functional electrolyte;
and adding the functional electrolyte into the gel polymer membrane in inert atmosphere to absorb and saturate to obtain the gel electrolyte.
Example 2
This example is for illustrating a sodium ion battery gel electrolyte and a method for preparing the same disclosed in the present invention, and comprises most of the operations in the examples, which are different in that:
the fluorosulfonyl imide additive was 2.0wt% of N-p-fluorophenyl bis (trifluoromethanesulfonyl) imide, and the other components were added in the amounts shown in example 2 of Table 1.
Example 3
This example is for illustrating a sodium ion battery gel electrolyte and a method for preparing the same disclosed in the present invention, and comprises most of the operations in the examples, which are different in that:
the fluorosulfonyl imide additive was 3.0wt% of N-p-fluorophenyl bis (trifluoromethanesulfonyl) imide, and the other components were added in the amounts shown in example 3 of Table 1.
Example 4
This example is for illustrating a sodium ion battery gel electrolyte and a method for preparing the same disclosed in the present invention, and comprises most of the operations in the examples, which are different in that:
the fluorosulfonyl imide additive was 0.5wt% of N-pentafluorophenyl bis (trifluoromethanesulfonyl) imide, and the other components were added in the amounts shown in example 4 of Table 1.
Example 5
This example is for illustrating a sodium ion battery gel electrolyte and a method for preparing the same disclosed in the present invention, and comprises most of the operations in the examples, which are different in that:
the fluorosulfonyl imide additive was 1.0wt% of N-pentafluorophenyl bis (trifluoromethanesulfonyl) imide, and the other components were added in the amounts shown in example 5 of Table 1.
Example 6
This example is for illustrating a sodium ion battery gel electrolyte and a method for preparing the same disclosed in the present invention, and comprises most of the operations in the examples, which are different in that:
the fluorosulfonyl imide additive was 1.5wt% of N-pentafluorophenyl bis (trifluoromethanesulfonyl) imide, and the other components were added in the amounts shown in example 6 of Table 1.
Example 7
This example is for illustrating a sodium ion battery gel electrolyte and a method for preparing the same disclosed in the present invention, and comprises most of the operations in the examples, which are different in that:
the fluorosulfonyl imide additive was 1.0wt% of N-trifluoromethylbis (trifluoromethanesulfonyl) imide, and the other components were added in the amounts shown in example 7 of Table 1.
Example 8
This example is for illustrating a sodium ion battery gel electrolyte and a method for preparing the same disclosed in the present invention, and comprises most of the operations in the examples, which are different in that:
the fluorosulfonyl imide additive was 3.0wt% of N-trifluoromethylbis (trifluoromethanesulfonyl) imide, and the other components were added in the amounts shown in example 8 of Table 1.
Comparative example 1
This comparative example is used to compare and illustrate a sodium ion battery gel electrolyte and a method for preparing the same disclosed in the present invention, including most of the operations in the examples, which are different in that:
excluding the fluorosulfonyl imide additive.
Preparing an electrode: adding sodium ferronickel manganate, a conductive agent and polyvinylidene fluoride into an N-methyl pyrrolidone solvent according to a ratio of 94.5:3.0:2.5, fully stirring and mixing, and obtaining a 59 x 79mm positive plate after coating, drying, rolling and slitting;
adding hard carbon, conductive agent acetylene black, binder styrene-butadiene rubber and thickener sodium carboxymethyl cellulose into deionized water according to a mass ratio of 95:2:2:1, fully stirring and mixing, and obtaining the 60 x 80mm negative plate after coating, drying, rolling and slitting.
Preparing a sodium ion battery: the gel electrolytes prepared in examples 1 to 8 and comparative example 1 are used as a separation film, a positive electrode plate, a separation film and a negative electrode plate are sequentially stacked, the separation film is positioned between the positive electrode plate and the negative electrode plate, a bare cell is prepared by adopting a lamination process, the bare cell is placed in an aluminum plastic film for packaging, and the sodium ion battery is prepared through the procedures of vacuum packaging, standing, formation, shaping and the like.
Performance testing
The sodium ion batteries prepared using the gel electrolytes of examples 1 to 8 and comparative example 1 were subjected to the relevant performance test:
the test results obtained are filled in tables 1 to 2.
TABLE 1
TABLE 2
| Test group | Discharge at-20 DEG C | Discharge at-10 DEG C | Discharge at 0 DEG C | Discharge at 5 DEG C | Discharging at 45 DEG C | Discharge at 60 DEG C |
| Example 1 | 86.22％ | 91.60％ | 95.96％ | 97.29％ | 100.43％ | 101.20％ |
| Example 5 | 89.26％ | 92.40％ | 95.51％ | 96.66％ | 99.36％ | 100.11％ |
| Example 7 | 90.23％ | 93.46％ | 96.33％ | 97.14％ | 98.85％ | 98.35％ |
| Comparative example 1 | 83.20％ | 86.43％ | 91.61％ | 91.13％ | 93.79％ | 93.25％ |
As can be seen from the test results in Table 1, the capacity retention rates of examples 1 to 7 were all 80% or more, which is greater than that of comparative example 1; the functional additives of examples 1 to 3 are all N-p-fluorophenyl bis (trifluoromethanesulfonyl) imine, the addition amounts are different, and the test result of example 1 is optimal under the condition that the addition amount reaches 92.7%; examples 4 to 6 were added with different amounts of N-pentafluorophenyl bis (trifluoromethanesulfonyl) imide, respectively, and the effect of example 5 was best, while the amounts of N-trifluoromethanebis (trifluoromethanesulfonyl) imide added in examples 7 to 8 were 1.0wt% and 3.0wt% respectively, and the effect of example 7 was superior to that of example 8, so that it was found that the optimum amount of the fluorosulfonyl imide additive was 1.0wt% under the gel electrolyte preparation conditions of the present application, and the test results of example 8 were smaller than those of the comparative example because the amount of N-trifluoromethanebis (trifluoromethanesulfonyl) imide added in example 8 was too high.
As can be seen from the high-low temperature discharge capacity retention test results of table 2, the capacity retention rates at each stage of examples 1, 5 and 7 are all greater than those of comparative example 1, i.e., the high-low temperature discharge performance is good;
as can be seen from the test results of tables 1 and 2, the fluorosulfonyl imide additive described in the present application can form an excellent interfacial film on the electrode surface, improving the cycling performance and stability of the sodium ion 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. The sodium ion battery gel electrolyte is characterized by comprising a gel polymer membrane and a functional electrolyte, wherein the functional electrolyte is adsorbed in the gel polymer membrane, the functional electrolyte comprises electrolyte salt, an organic solvent and an additive, the additive comprises a fluoro-sulfonyl imide additive, and the structure of the fluoro-sulfonyl imide additive is shown as follows:
wherein R is 1 -R 3 Each independently selected from one or more of hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl, nitrile, C1-C3 alkylnitrile, C2-C4 alkenyl, alkoxy, carboxyl, phenyl, halophenyl。
2. A sodium ion battery gel electrolyte according to claim 1, wherein the fluorosulfonyl imide additive is selected from one or more of the following compounds:
3. the sodium ion battery gel electrolyte according to claim 1, wherein the mass ratio of the gel polymer membrane to the functional electrolyte is 1-9: 9-1, wherein the mass percentage of the fluoro-sulfimide additive is 1-5% based on 100% of the total mass of the functional electrolyte.
4. The gel electrolyte of a sodium ion battery according to claim 1, wherein the gel polymer separator comprises a base film and a polymer attached to the base film, and the mass ratio of the base film to the polymer is 4-9: 6 to 1.
5. The sodium ion battery gel electrolyte of claim 4, wherein the matrix film comprises one or more of nonwoven fabric, polyethylene, polypropylene-polyethylene-polypropylene three-layer composite film, polyimide, aramid, cellulose, and fiberglass; the polymer comprises one or more of polyvinylidene fluoride (PVdF), polyacrylonitrile (PAN), polyethylene oxide (PEO), polymethyl methacrylate (PMMA), polyhexafluoropropylene (HFP), polystyrene oxide (PPO).
6. The sodium ion battery gel electrolyte of claim 1, further comprising nanoparticles uniformly dispersed in the gel polymer separator, the nanoparticles being 100% of the total mass of the gel polymer separatorThe mass percentage of the seed is 0.1-20%, and the nano particles are SiO 2 、Al 2 O 3 、SnO 2 、TiO 2 、LiAlO 2 、CeO 2 、Fe 2 O 3 One or more of rare earth, clay or zeolite.
7. The gel electrolyte of a sodium ion battery according to claim 1, wherein the mass percentage of the electrolyte salt is 5% -25% based on 100% of the total mass of the functional electrolyte; the mass percentage of the organic solvent is 40% -90%, and the organic solvent comprises one or more of cyclic carbonate solvent and chain carbonate solvent.
8. A sodium ion battery gel electrolyte according to claim 1 wherein the electrolyte salt is selected from sodium salts including one or more of sodium hexafluorophosphate, sodium perchlorate, sodium bis (trifluoromethylsulfonyl) imide (NaTFSI) and sodium bis (fluorosulfonyl) imide (NaFSI).
9. The method for preparing a gel electrolyte for a sodium ion battery according to any one of claims 1 to 8, comprising the steps of:
obtaining a gel polymer membrane;
mixing electrolyte salt with an organic solvent to obtain a reference electrolyte;
adding the fluoro-sulfimide additive into a reference electrolyte to obtain a functional electrolyte;
and adding the functional electrolyte into the gel polymer membrane to absorb and saturate to obtain the gel electrolyte.
10. A sodium ion battery comprising a positive electrode sheet comprising a positive electrode active material, a separator, a negative electrode sheet comprising a negative electrode active material, and a sodium ion battery gel electrolyte as claimed in any one of claims 1 to 8, the separator being interposed between the positive electrode sheet and the negative electrode sheet.
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