CN116264323B - Sodium ion battery electrolyte and sodium ion battery - Google Patents
Sodium ion battery electrolyte and sodium ion battery Download PDFInfo
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- CN116264323B CN116264323B CN202111531953.7A CN202111531953A CN116264323B CN 116264323 B CN116264323 B CN 116264323B CN 202111531953 A CN202111531953 A CN 202111531953A CN 116264323 B CN116264323 B CN 116264323B
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- sodium ion
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 67
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 60
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 42
- 239000000654 additive Substances 0.000 claims abstract description 41
- 230000000996 additive effect Effects 0.000 claims abstract description 39
- 239000011734 sodium Substances 0.000 claims abstract description 27
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 19
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 19
- 239000011356 non-aqueous organic solvent Substances 0.000 claims abstract description 9
- 239000002000 Electrolyte additive Substances 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- -1 sodium hexafluorophosphate Chemical compound 0.000 claims description 10
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 9
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 9
- 239000011888 foil Substances 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical group FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000006262 metallic foam Substances 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
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 claims description 3
- KBVUALKOHTZCGR-UHFFFAOYSA-M sodium;difluorophosphinate Chemical group [Na+].[O-]P(F)(F)=O KBVUALKOHTZCGR-UHFFFAOYSA-M 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 229920001774 Perfluoroether Polymers 0.000 claims description 2
- DWYMPOCYEZONEA-UHFFFAOYSA-L fluoridophosphate Chemical compound [O-]P([O-])(F)=O DWYMPOCYEZONEA-UHFFFAOYSA-L 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 50
- 229910052799 carbon Inorganic materials 0.000 abstract description 27
- 239000002086 nanomaterial Substances 0.000 abstract description 20
- 238000000034 method Methods 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 7
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 abstract description 5
- 210000001787 dendrite Anatomy 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 229910002804 graphite Inorganic materials 0.000 description 10
- 239000010439 graphite Substances 0.000 description 10
- 229910021389 graphene Inorganic materials 0.000 description 9
- 239000003575 carbonaceous material Substances 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000002096 quantum dot Substances 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000002113 nanodiamond Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000011852 carbon nanoparticle Substances 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 241000234282 Allium Species 0.000 description 1
- 235000002732 Allium cepa var. cepa Nutrition 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910021201 NaFSI Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- VCCATSJUUVERFU-UHFFFAOYSA-N sodium bis(fluorosulfonyl)azanide Chemical compound FS(=O)(=O)N([Na])S(F)(=O)=O VCCATSJUUVERFU-UHFFFAOYSA-N 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000011882 ultra-fine particle Substances 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a sodium ion battery electrolyte and a sodium ion battery. In order to solve the problems that the existing sodium ion battery is easy to generate short circuit phenomenon caused by sodium dendrite, and the electrical property and the safety property of the sodium ion battery are poor, the sodium ion battery electrolyte provided by the invention comprises a nonaqueous organic solvent, sodium salt and electrolyte additives, wherein the electrolyte additives comprise an additive A, the additive A is a zero-dimensional carbon nano material and/or a quasi-zero-dimensional carbon nano material, and the concentration of the sodium salt is more than 1mol/L. The electrolyte of the sodium ion battery can effectively inhibit dendrite formation of sodium metal in the electrochemical circulation process, and improve the initial discharge capacity, the circulation performance and the rate capability of the sodium ion battery.
Description
Technical Field
The invention belongs to the technical field of sodium batteries, and particularly relates to a sodium ion battery electrolyte and a sodium ion battery.
Background
Along with the wide application of lithium ion batteries, the demand of lithium is rapidly increased, and because lithium belongs to rare metals, the production and recovery technologies are not mature enough, and the lithium ion batteries are limited to be further applied in large scale, so that the development of a novel high-performance secondary battery system is particularly important. Sodium ion batteries using sodium instead of lithium have high potential economic and environmental benefits.
However, the method is limited by the low gram capacity and voltage platform of the anode and cathode materials of the sodium ion battery at present, and the energy density of the sodium ion battery is always in a large gap compared with that of the lithium ion battery, so that the method cannot realize the actual commercial application. Under the background that the energy density of the positive electrode material can not be broken through all the time, the direct adoption of sodium metal (theoretical specific capacity 1166 mAh/g) as the negative electrode becomes an effective method for greatly improving the energy density of the battery. However, sodium metal has the characteristics of poor chemical stability in air, low melting point (98 ℃), easiness in generating dendrites in the electrochemical cycle process and the like, and is also a reason that commercial application of sodium ion batteries is difficult to realize.
Sodium ions are provided in CN113437254AA negative electrode tab of a battery, an electrochemical device, and an electronic apparatus. In the patent, a negative electrode sheet comprises a negative electrode current collector and a carbon material coating formed on at least part of the surface of the negative electrode current collector, wherein the thickness of the carbon material coating is less than or equal to 10 mu m, the carbon material coating comprises a carbon material and a polymer binder, the carbon material comprises mesophase carbon microspheres, graphite, natural graphite, expanded graphite, artificial graphite, glassy carbon, carbon-carbon composite materials, carbon fibers, hard carbon, porous carbon, highly oriented graphite, three-dimensional graphite, carbon black, carbon nanotubes and graphene, but the discharge curves of the graphite and the graphene are all 1 slope, na + Is difficult to be embedded in the layer, and graphene is not accumulated and Na cannot be embedded + Therefore Na + Only on the surface of these carbon materials. On the premise that graphite can be charged and discharged normally in sodium ion, na is adopted + Mechanism of intercalation between graphite layers together with solvent molecules to form a graphite film composed of Na + And a ternary graphite intercalation compound composed of solvent molecules and graphite. In this patent, the ether solvent ethylene glycol dimethyl ether (DME) must be used as an organic solvent to enable the normal charge and discharge of graphite and graphene-based sodium ion batteries. However, the poor stability of ether solvents at high voltages limits their use in sodium ion batteries. Meanwhile, the carbon material mentioned in the patent is settled while being left in the electrolyte, so that it cannot be used as a uniform solution in a sodium ion battery.
Disclosure of Invention
The invention aims to provide the sodium ion battery electrolyte which can effectively inhibit dendrite formation of sodium metal in the electrochemical cycle process and improve the initial discharge capacity, cycle performance and rate capability of a sodium ion battery.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the electrolyte comprises a nonaqueous organic solvent, sodium salt and an electrolyte additive, wherein the electrolyte additive comprises an additive A, the additive A is a zero-dimensional carbon nanomaterial and/or a quasi-zero-dimensional carbon nanomaterial, and the concentration of the sodium salt is more than 1mol/L.
Preferably, the electrolyte is free of polymer.
Preferably, the zero-dimensional carbon nanomaterial is one or more of fullerene, nanodiamond or carbon nano onion; the quasi-zero-dimensional carbon nanomaterial graphene quantum dot or carbon dot.
Preferably, the feeding mass of the additive A is 0.1-10 mol/L of the total mass of the sodium ion battery electrolyte.
Further preferably, the feeding mass of the additive A is 0.1-8 mol/L of the total mass of the sodium ion battery electrolyte.
Preferably, the additive further comprises an additive B, wherein the additive B is fluoroethylene carbonate.
Preferably, the feeding mass of the additive B is 1-15% of the total mass of the sodium ion battery electrolyte.
Preferably, the additive further comprises a sodium salt type additive, wherein the sodium salt type additive is sodium difluorophosphate and/or sodium difluorooxalato borate.
Further preferably, the concentration of the sodium salt type additive is 0.01 to 0.1mol/L.
Still more preferably, the concentration of the sodium salt type additive is 0.02 to 0.08mol/L.
Preferably, the nonaqueous organic solvent is one or more of carbonate, phosphate, fluorophosphate or fluoroether.
Further preferably, the nonaqueous organic solvent is a combination of ethylene carbonate and propylene carbonate.
Further preferably, the volume ratio of the ethylene carbonate to the propylene carbonate is 0.5 to 1.5:1, still further preferably 0.8 to 1.2:1.
Preferably, the sodium salt is one or more of sodium hexafluorophosphate, sodium perchlorate, sodium tetrafluoroborate, sodium bistrifluoromethylsulfonylimide and sodium bistrifluorosulfonylimide.
Preferably, the concentration of the sodium salt is 1.1mol/L to 10mol/L.
Further preferably, the concentration of the sodium salt is 1.1mol/L to 8mol/L.
The invention also provides a sodium ion battery, which comprises an anode, a cathode and electrolyte, wherein the electrolyte is the sodium ion battery electrolyte.
Preferably, the negative electrode comprises a negative electrode current collector, and the negative electrode current collector is one or more of a metal foil, a metal foam current collector, a metal mesh current collector and a composite current collector.
Preferably, the positive electrode is Na 0.62 [Fe 0.5 Mn 0.5 ]O 2 And/or the negative electrode is a metal aluminum foil with a porous structure.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
according to the invention, the zero-dimensional carbon nano material and/or the quasi-zero-dimensional carbon nano material are/is matched with the sodium salt with high concentration in the electrolyte to form the uniform and stable electrolyte, and when the electrolyte is charged for the first time, the zero-dimensional or quasi-zero-dimensional carbon nano particles are uniformly distributed on the surface of the negative electrode current collector to form nucleation points of sodium ions, so that the kinetic performance of sodium metal nucleation in the sodium ion battery is improved, lithium ions and the zero-dimensional or quasi-zero-dimensional carbon nano material are co-deposited on the negative electrode current collector, uniform dendrite-free sodium deposition is generated, and the cycle performance of the battery is improved. In the discharging process, the metal sodium can be more easily converted into sodium ions to return to the positive electrode, so that the cyclic charging and discharging are realized. The sodium ion battery can be stored for a long time and does not generate self-discharge, and even if the battery is short-circuited, the sodium ion battery does not generate current, so that the safety is extremely high; the zero-dimensional or quasi-zero-dimensional carbon nano particles can also solve the problems of high viscosity and poor ion conductivity of the sodium salt electrolyte with high concentration; the high-concentration composite sodium salt, FEC, sodium salt type additive and zero-dimensional or zero-dimensional-like carbon nano particles can improve the cycle stability performance and the rate capability of the sodium ion battery.
Detailed Description
The invention is further described below with reference to examples. The present invention is not limited to the following examples. The implementation conditions adopted in the embodiments can be further adjusted according to different requirements of specific use, and the implementation conditions which are not noted are conventional conditions in the industry. The technical features of the various embodiments of the present invention may be combined with each other as long as they do not collide with each other.
Because the sodium ion battery in the prior art is easy to have the short circuit phenomenon caused by sodium dendrite, and the problems of poor electrical property and safety performance of the sodium battery, the inventor provides the sodium ion battery electrolyte through a great deal of researches and experiments.
According to the invention, the sodium ion battery electrolyte comprises a nonaqueous organic solvent, sodium salt and an electrolyte additive, wherein the electrolyte additive comprises an additive A, the additive A is a zero-dimensional carbon nanomaterial and/or a quasi-zero-dimensional carbon nanomaterial, and the concentration of the sodium salt is more than 1mol/L.
In the invention, the zero-dimensional carbon nanomaterial comprises clusters and nanoparticles. Clusters refer to aggregates of several to several hundred atoms with a particle size of less than or equal to 1nm, which are neither atoms nor molecules, a transition state, such as fullerenes C 60 . Nanoparticles refer to ultrafine particles with particle dimensions on the order of nanometers, larger than atomic clusters, within 100nm, such as nanodiamond and carbon nano-onions.
In the invention, the quasi-zero-dimensional carbon nanomaterial refers to quantum dots formed by a small number of atoms. The three dimensions of the quantum dot are all below 100 nanometers, and the appearance is just like a tiny dot like carbon dots and graphene quantum dots.
According to the invention, the zero-dimensional carbon nano material and/or the quasi-zero-dimensional carbon nano material can be uniformly dispersed by formula adjustment, and the electrolyte is kept stable and uniform before the first charge, so that sedimentation hardly occurs. The electrolyte of the present invention does not require the additional use of additives capable of stabilizing the electrolyte, such as polymer-based additives (PEO), which, although improving the uniformity of the electrolyte, hinder the transport of ions within the battery and thus deteriorate the performance of the battery.
In the invention, the sodium salt is one or more of sodium hexafluorophosphate, sodium perchlorate, sodium tetrafluoroborate, sodium bistrifluoromethylsulfonylimide and sodium bistrifluorosulfonyllimide.
Preferably, the concentration of the sodium salt is 1.1mol/L to 10mol/L, for example 1.1mol/L, 1.5mol/L, 1.8mol/L, 2mol/L, 2.2mol/L, 2.5mol/L, 3mol/L, 3.5mol/L, 4mol/L, 4.5mol/L, 5mol/L, 5.5mol/L, 6mol/L, 6.5mol/L, 7mol/L, 7.5mol/L, 8mol/L, 8.5mol/L, 9mol/L, 9.5mol/L, 10mol/L. Practice proves that in the invention, the concentration of sodium salt in the electrolyte is improved, so that irreversible loss of sodium in the initial cathode-free cell can be counteracted, and meanwhile, the uniformity of the electrolyte in the long-time storage process can be improved.
Preferably, the additive a is added in an amount of 0.1% -10% by mass, such as 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10% by mass of the total mass of the sodium ion battery electrolyte.
In the invention, the additive also comprises an additive B, wherein the additive B is fluoroethylene carbonate.
Preferably, the additive B is added in an amount of 1% -15% of the total mass of the sodium ion battery electrolyte, for example 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5%, 15%.
In the invention, the additive also comprises a sodium salt type additive, wherein the sodium salt type additive is sodium difluorophosphate and/or sodium difluorooxalato borate.
Further preferably, the concentration of the sodium salt type additive is 0.01 to 0.1mol/L, for example, 0.02mol/L, 0.03mol/L, 0.04mol/L, 0.05mol/L, 0.06mol/L, 0.07mol/L, 0.08mol/L, 0.09mol/L, 0.1mol/L.
In the invention, the nonaqueous organic solvent is one or more of carbonic ester, phosphoric ester, fluorinated phosphoric ester or fluorinated ether.
A combination of ethylene carbonate and propylene carbonate is preferred.
Further preferred, the volume ratio of ethylene carbonate to propylene carbonate is from 0.5 to 1.5:1, e.g. 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1.
In the invention, the sodium ion battery comprises a positive electrode, a negative electrode and electrolyte, wherein the electrolyte is the sodium ion battery electrolyte.
Preferably, the negative electrode comprises a negative electrode current collector, and the negative electrode current collector is one or more of a metal foil, a metal foam current collector, a metal mesh current collector and a composite current collector.
Preferably, the positive electrode is Na 0.62 [Fe 0.5 Mn 0.5 ]O 2 。
The invention is further described below with reference to examples. The present invention is not limited to the following examples. The implementation conditions adopted in the embodiments can be further adjusted according to different requirements of specific use, and the implementation conditions which are not noted are conventional conditions in the industry. The technical features of the various embodiments of the present invention may be combined with each other as long as they do not collide with each other.
Examples 1 to 7 and comparative examples 1 to 7
Electrolyte solution: the sodium salt is sodium hexafluorophosphate, and the solvent is ethylene carbonate: propylene carbonate = 1:1 (volume ratio), the other components and amounts in the electrolyte (based on the total mass of the electrolyte) are shown in table 1. In the preparation process, sodium hexafluorophosphate and zero-dimensional carbon nano material or quasi-zero-dimensional carbon nano material are added into an organic solvent, stirred at normal temperature until a uniformly dispersed solution is formed, and the electrolyte is observed after standing for 24 hours, and the result is shown in table 1.
Uniformity of electrolyte: the electrolyte was allowed to stand for 24 hours after preparation, and whether or not there was sedimentation of the carbon material at the bottom of the electrolyte was visually observed.
TABLE 1
Table 1 shows that nanodiamond (zero-dimensional carbon nanomaterial), carbon dot (quasi-zero-dimensional carbon nanomaterial) or graphene quantum dot (quasi-zero-dimensional carbon nanomaterial) is added to a conventional electrolyte, and when the sodium salt concentration is 1.0M (comparative example 1, comparative example 2), there is a small amount of precipitation, after the sodium salt concentration is increased, the electrolyte is still a uniform and stable solution after standing, and when the sodium salt is increased to 1.5M, the electrolyte is still a uniform and stable solution after standing, which indicates that the electrolyte is suitable for preparing a high-concentration sodium salt electrolyte. And graphene or carbon nano tubes are added into conventional electrolyte, the concentration of sodium salt is 1.5-2.5M (comparative examples 3-7), the electrolyte is layered after standing, and precipitation occurs at the bottom of the electrolyte, which indicates that the graphene or carbon nano tubes are not suitable to be directly added into the sodium salt electrolyte as an additive for use.
Examples 8 to 19 and comparative example 8
Electrolyte solution: the sodium salt is sodium hexafluorophosphate, the molar concentration of the sodium salt is 2.0mol/L, and the solvent is ethylene carbonate: propylene carbonate = 1:1 (volume ratio), the other components and amounts in the electrolyte (based on the total mass of the electrolyte) are shown in table 2. The uniformity of the electrolyte was observed and the results are shown in table 2.
And (3) a positive electrode: na (Na) 0.62 [Fe 0.5 Mn 0.5 ]O 2 。
And (3) a negative electrode: porous aluminum foil.
The electrolyte, the positive electrode and the negative electrode were assembled into a sodium ion battery according to a conventional process, and the sodium ion battery prepared in each example was tested for a first 0C discharge capacity (25 ℃) between 1.5 and 4.3V, a battery capacity percentage (25 ℃) after 100 weeks of 1C cycle charge and discharge, and a 2C discharge capacity retention rate (25 ℃), and the results are shown in table 1.
100Z cycle capacity percentage= (average value of 100 th week discharge capacity/5 first weeks discharge capacity) ×100.
2C discharge capacity retention rate (%) = (discharge capacity of sodium battery 2C to 1.5V/discharge capacity of lithium battery 1C to 1.5V) ×100.
TABLE 2
Table 2 shows that, adding nano diamond, carbon dot or graphene quantum dot with different contents into the electrolyte of 2M sodium salt can obviously improve the initial discharge capacity, the cycle performance and the rate performance of the sodium ion battery.
Examples 20 to 25 and comparative examples 9 to 10
Electrolyte solution: the solvent is ethylene carbonate: propylene carbonate = 1:1 (volume ratio), sodium salt in the electrolyte, other ingredients and amounts (based on the total mass of the electrolyte) are shown in table 3. The uniformity of the electrolyte was observed and the results are shown in table 3.
And (3) a positive electrode: na (Na) 0.62 [Fe 0.5 Mn 0.5 ]O 2 。
And (3) a negative electrode: porous aluminum foil.
The electrolyte, the positive electrode and the negative electrode were assembled into a lithium battery according to a conventional process, and the sodium battery prepared in each example was tested for a battery capacity percentage (25 ℃) and a 3C discharge capacity retention rate (25 ℃) after 300 weeks of 1C cycle charge and discharge, and the results are shown in table 1.
100Z cycle capacity percentage= (average value of 300 th week discharge capacity/5 first weeks discharge capacity) ×100,
3C discharge capacity retention (%) = (discharge capacity of lithium battery 3C to 1.5V/discharge capacity of lithium battery 1C to 1.5V) ×100.
TABLE 3 Table 3
Table 3 shows that high concentrations of NaFSI replace NaPF 6 Can improve the normal temperature cycle stability and the multiplying power performance of the sodium ion battery. Relative to the use of NaPF alone 6 ，NaPF 6 The sodium ion battery can further improve the normal temperature cycle stability and the multiplying power performance of the sodium ion battery by cooperating with the lithium salt additive. The synergy of carbon dots, high-concentration composite sodium salt, FEC and sodium salt additive can further improve the cycle stability and rate capability of the sodium ion battery.
The above embodiments are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the present invention and to implement the same, but are not intended to limit the scope of the present invention, and all equivalent changes or modifications made according to the spirit of the present invention should be included in the scope of the present invention.
Claims (8)
1. The sodium ion battery electrolyte comprises a nonaqueous organic solvent, sodium salt and an electrolyte additive, and is characterized in that the electrolyte additive comprises an additive A, an additive B and a sodium salt type additive, wherein the additive A is carbon dots or graphene quantum dots, the additive B is fluoroethylene carbonate, the sodium salt type additive is sodium difluorophosphate and/or sodium difluorooxalato borate, the additive A is added in an amount of 2% -10% of the total mass of the sodium ion battery electrolyte, the additive B is added in an amount of 10% -15% of the total mass of the sodium ion battery electrolyte, the concentration of the sodium salt type additive is 0.05-0.1 mol/L, and the concentration of the sodium salt is 1.5-10 mol/L.
2. The sodium ion battery electrolyte of claim 1, wherein the nonaqueous organic solvent is one or more of a carbonate, a phosphate, a fluorophosphate, or a fluoroether.
3. The sodium ion battery electrolyte of claim 2, wherein the nonaqueous organic solvent is a combination of ethylene carbonate and propylene carbonate.
4. The sodium ion battery electrolyte according to claim 1, wherein the volume ratio of the ethylene carbonate to the propylene carbonate is 0.5-1.5:1.
5. The electrolyte of a sodium ion battery of claim 1, wherein the sodium salt is one or more of sodium hexafluorophosphate, sodium perchlorate, sodium tetrafluoroborate, sodium bistrifluoromethylsulfonylimide, sodium bistrifluorosulfonylimide.
6. A sodium ion battery comprising a positive electrode, a negative electrode and an electrolyte, wherein the electrolyte is the sodium ion battery electrolyte of any one of claims 1 to 5.
7. The sodium ion battery of claim 6, wherein the negative electrode comprises a negative electrode current collector, and the negative electrode current collector is one or more of a metal foil, a metal foam current collector, a metal mesh current collector and a composite current collector.
8. The sodium ion battery of claim 7, wherein the positive electrode is Na 0.62 [Fe 0.5 Mn 0.5 ]O 2 And/or the negative electrode is a metal aluminum foil with a porous structure.
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| CN113745647A (en) * | 2021-07-30 | 2021-12-03 | 东莞力朗电池科技有限公司 | Non-negative electrode rechargeable sodium ion secondary battery and manufacturing method thereof |
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| WO2019111983A1 (en) * | 2017-12-06 | 2019-06-13 | セントラル硝子株式会社 | Electrolyte solution for nonaqueous electrolyte batteries, and nonaqueous electrolyte battery using same |
| CN110504488A (en) * | 2019-08-09 | 2019-11-26 | 电子科技大学 | A kind of electrolyte and preparation method thereof that graphene quantum dot is modified |
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