CN115995598A - Multifunctional sodium battery electrolyte additive and application thereof - Google Patents

Multifunctional sodium battery electrolyte additive and application thereof Download PDF

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Publication number
CN115995598A
CN115995598A CN202111222620.6A CN202111222620A CN115995598A CN 115995598 A CN115995598 A CN 115995598A CN 202111222620 A CN202111222620 A CN 202111222620A CN 115995598 A CN115995598 A CN 115995598A
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sodium
electrolyte
battery
additive
boron trifluoride
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薛巍然
李泉
禹习谦
李泓
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Institute of Physics of CAS
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    • 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 multifunctional sodium battery electrolyte additive and application thereof. The multifunctional sodium battery electrolyte additive comprises: a compound or mixture containing both fluorine and boron; the fluorine element exists in the form of fluorine-containing groups; the boron element in the additive is coordinated with the oxygen element in trace water of the electrolyte, trace water is removed, the chemical stability and electrochemical stability of the electrolyte are improved, and the interface impedance of the sodium battery is reduced; and the boron element is coordinated with anions of sodium salt in the sodium battery electrolyte, so that the solubility and dissociation degree of the sodium salt are improved, and the ionic conductivity of the electrolyte is improved; the fluorine-containing group in the additive is used for regulating and controlling the components of an electrode-electrolyte interface, reducing interface impedance, improving the wettability of the electrolyte to an electrode, passivating the aluminum foil of a current collector of a sodium battery and inhibiting the corrosion of sodium salt to the aluminum foil.

Description

Multifunctional sodium battery electrolyte additive and application thereof
Technical Field
The invention relates to the technical field of materials, in particular to a multifunctional sodium battery electrolyte additive and application thereof.
Background
The lithium ion battery is widely applied to the fields of production and life, such as consumer electronics, electric automobiles, medical electronics, unmanned aerial vehicles and the like. However, with the rapid increase in demand for lithium ion batteries, the supply of lithium resources is becoming increasingly intense. In order to find alternative or alternative energy storage technologies for lithium ion batteries, sodium ion batteries having similar principles of operation as lithium ion batteries are receiving increasing attention from researchers. Sodium is abundant in resource, occupies about 2.64 percent of the storage of crust elements, and has low price and wide distribution. Sodium ion batteries therefore have the potential for large-scale application.
The electrolyte in the sodium battery plays a vital role, is a carrier for ion transmission in the battery, and is a guarantee that the sodium battery has the advantages of high safety, high voltage, high multiplying power, high specific energy, low cost and the like. However, the traditional nonaqueous liquid electrolyte and solid electrolyte are difficult to realize the performances of good SEI construction, high stability, high ionic conductivity, good wettability and the like, so that the use of the electrolyte additive is considered to be the most feasible, economical and effective method for assisting in improving the comprehensive performance of the electrolyte.
In order to improve the cycle life of the battery, che Hai discloses a sultone compound which is taken as an electrolyte additive to be added into the electrolyte, wherein the additive can form a stable and compact passivation protection layer on the surface of the anode and the cathode, inhibit the subsequent decomposition reaction of the electrolyte at the interface of the anode active material and the cathode, improve the cycle stability of the sodium ion battery and prolong the service life of the battery. Liu Jing et al developed a sodium ion battery electrolyte additive containing rubidium and/or cesium cations which acted on the negative electrode to change the structure and composition of the negative electrode SEI film, improve the stability of the negative electrode SEI film of the sodium ion battery, reduce the impedance, thereby reducing the polarization of the sodium ion battery, improving the cycling stability of the sodium ion battery, and prolonging the life of the sodium ion battery. In order to inhibit the alkalinity of the surface of the sodium-electricity positive electrode material and trace moisture in the electrolyte, zhou Quan et al developed an anhydride additive that can neutralize the alkalinity of the surface of the positive electrode material and inhibit the decomposition of carbonate by the alkalinity of the metal oxide. Meanwhile, the anhydride is also used as a competing agent of trace moisture, and preferentially reacts with water to inhibit the hydrolysis of the electrolyte. Therefore, the storage performance of the sodium ion battery is improved, the generation of gas in the charging and discharging process of the battery is inhibited, and the cycle performance of the battery is improved.
Although the above research ideas can improve part of the performance of the sodium ion battery under certain specific conditions, all of the research ideas cannot comprehensively improve the energy efficiency, cycle life and rate capability of the battery, and part of the additives are expensive. Therefore, there is a continuous search and research to develop an electrolyte additive that can comprehensively improve battery performance, is inexpensive, and is applicable to mass production.
Disclosure of Invention
The embodiment of the invention provides a multifunctional sodium battery electrolyte additive and application thereof, and the multifunctional sodium battery electrolyte additive provided by the invention can effectively improve the cycle life, power density, rate capability and energy efficiency of a sodium battery.
In a first aspect, embodiments of the present invention provide a multi-functional sodium battery electrolyte additive comprising: a compound or mixture containing both fluorine and boron; the fluorine element exists in the form of fluorine-containing groups;
the boron element in the additive is coordinated with the oxygen element in trace water of the electrolyte, trace water is removed, the chemical stability and electrochemical stability of the electrolyte are improved, and the interface impedance of the sodium battery is reduced; and the boron element is coordinated with anions of sodium salt in the sodium battery electrolyte, so that the solubility and dissociation degree of the sodium salt are improved, and the ionic conductivity of the electrolyte is improved;
The fluorine-containing group in the additive is used for regulating and controlling the components of an electrode-electrolyte interface, reducing interface impedance, improving the wettability of the electrolyte to an electrode, passivating the aluminum foil of a current collector of a sodium battery and inhibiting the corrosion of sodium salt to the aluminum foil.
Preferably, the total concentration of the additive in the electrolyte is in the range of 0.0001mol/L to 1mol/L.
Preferably, the compound or mixture containing both fluorine element and boron element specifically includes: fluoroborates and complexes thereof, fluoroboric acid, inorganic fluoroborates, organofluoroborates, polyfluoroarene borides, fluoroorganoboranes, fluoroboric acid nitro or other organofluoroboric compounds;
the state of the multifunctional sodium battery electrolyte additive comprises a gaseous state, a liquid state or a solid state.
Further preferably, the fluoroborate has the formula B a F b Or BF c X d The method comprises the steps of carrying out a first treatment on the surface of the Wherein a is more than or equal to 0.5 and less than or equal to 2,1.5 and b is more than or equal to 3; c is more than or equal to 0.5 and less than or equal to 3,0.5, d is more than or equal to 3, and X is halogen element; the substances forming the complex with the fluoroborate compound include: one or more of water, ammonia, argon, alcohol, carboxylic acid, amine, nitrile, ester, aldehyde, ketone, ether, phenol, sulfone;
the chemical formula of the fluoroboric acid is HBF 4 ；
The chemical formula of the inorganic fluoborate is M n (BF 4 ) m The method comprises the steps of carrying out a first treatment on the surface of the Wherein M comprises one or more of aluminum, copper, lead, tin, nickel, zinc, cadmium, beryllium, magnesium, calcium, strontium, barium, cesium, rubidium, manganese, iron, cobalt, silver, indium and thallium; n is more than or equal to 0.2 and less than or equal to 5,0.2, m is more than or equal to 8; the inorganic fluoroborate is dissociable;
the chemical formula of the organofluorine boron compound comprises: R-BF 3 M、F-R-BH x 、R-BF 3 、BF 4 NO、BF 4 NO 2 One of the following; wherein R is an organic group comprising: any of hydrocarbyl, alcohol, ether, ester, ketone, carboxylic acid, phenolic, or other organic groups; x is more than or equal to 0.5 and less than or equal to 3; the organofluoroborate is dissociable.
Further preferably, the fluoro boride complex specifically includes: one or more of boron trifluoride dihydrate, boron trifluoride methanol, boron trifluoride ethanol, boron trifluoride acetic acid, boron trifluoride propionic acid, boron trifluoride phosphoric acid, boron trifluoride dimethyl carbonate, boron trifluoride ethyl acetate, boron trifluoride butyl acetate, boron trifluoride ethyl chloroacetate, boron trifluoride acetonitrile, boron trifluoride tetrahydrofuran, boron trifluoride methyl ether, boron trifluoride ethyl ether, boron trifluoride butyl ether, boron trifluoride sulfolane, boron trifluoride monoethyl amine, boron trifluoride ethylamine, boron trifluoride benzylamine, boron trifluoride phenol, phenol formaldehyde resin boron trifluoride phenol, boron trifluoride dimethyl ether;
The inorganic fluoroborate comprises: one or more of rubidium tetrafluoroborate, cesium tetrafluoroborate, ammonium tetrafluoroborate, copper tetrafluoroborate, tin tetrafluoroborate, zinc tetrafluoroborate, nickel tetrafluoroborate, iron tetrafluoroborate, cobalt tetrafluoroborate, manganese tetrafluoroborate, silver tetrafluoroborate, cadmium tetrafluoroborate, aluminum tetrafluoroborate, magnesium tetrafluoroborate, calcium tetrafluoroborate, strontium tetrafluoroborate, and barium tetrafluoroborate;
the organofluoroborate comprises: cesium organic trifluoroborate, rubidium organic trifluoroborate, potassium organic trifluoroborate, sodium organic trifluoroborate, lithium organic trifluoroborate, ammonium organic trifluoroborate, copper organic trifluoroborate, tin organic trifluoroborate, zinc organic trifluoroborate, nickel organic trifluoroborate, iron organic trifluoroborate, cobalt organic trifluoroborate, manganese organic trifluoroborate, silver organic trifluoroborate, cadmium organic trifluoroborate, aluminum organic trifluoroborate, magnesium organic trifluoroborate, calcium organic trifluoroborate, strontium organic trifluoroborate, and barium organic trifluoroborate.
In a second aspect, an embodiment of the present invention provides a sodium battery electrolyte, including a solvent, a sodium salt, and the multifunctional sodium battery electrolyte additive described in the first aspect above;
The solvent comprises: ethylene Carbonate (EC), propylene Carbonate (PC), butylene Carbonate (BC), ethylene carbonate (VC), ethylene Sulfite (ES), dimethyl sulfite (DMS), diethyl sulfite (DES), dibutyl carbonate (DBC), dibutyl carbonate (GBL), methyl butyl carbonate (BMC), dipropyl carbonate (DPC), methyl ester (PA), propylene Sulfite (PS), gamma-butyrolactone (gamma BL), gamma-valerolactone (gamma VL), ethylene carbonate (VEC), dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC) fluoroethylene carbonate (FEC), dimethyl pyrocarbonate (DMPC), dioxolane (DOL), ethylene glycol dimethyl ether (DME), dimethoxymethane (DMM), ethylene glycol diethyl ether (DEE), tetraethylene glycol dimethyl ether (TEGDME), methyl Propyl Carbonate (MPC), methyl isopropyl carbonate (MiPC), methyl Formate (MF), ethyl Formate (EF), methyl Acetate (MA), ethyl Acetate (EA), methyl Propionate (MP), ethyl Propionate (EP), ethyl Butyrate (EB), fluorobenzene (FB), tetrahydrofuran (THF), 2-methyltetrahydrofuran (2 Me-THF), tetrahydropyran (THP), methyl ethyl acetate (MA), ethyl Acetate (EA) and Ethyl Propionate (EP), ethyl Butyrate (EB), fluorobenzene (FB), tetrahydrofuran (THF), methyl-ethyl-methyl-carbonate (TMP), one or more of diethylene glycol dimethyl ether/Diglyme (DG), acetonitrile (AN), dimethyl sulfoxide (DMSO), N-Dimethylformamide (DMF), sulfolane (SL), dimethyl sulfone (MSM), methyl ethyl sulfone (EMS), 3-trifluoropropyl methyl sulfone (FPMS), 1, 3-dioxolane (1, 3-DL), 4-methyl-1, 3-dioxolane (4-Me-1, 3-DL), 2-methyl-1, 3-dioxolane (2 Me-1, 3-DL) or acetone;
The sodium salt comprises: sodium fluoride (NaF), sodium carbonate (Na) 2 CO 3 ) Sodium nitrate (NaNO) 3 ) Sodium perchlorate (NaClO) 4 ) Sodium sulfide (Na) 2 S), sodium sulfite (Na) 2 SO 3 ) Sodium sulfate (Na) 2 SO 4 ) Sodium hexafluorophosphate (NaPF) 6 ) Sodium tetrafluoroborate (NaBF) 4 ) Sodium hexafluoroarsenate (NaAsF) 6 ) Sodium hexafluorotantalate (NaTaF) 6 ) Sodium hexafluorostannate (NaSnF) 6 ) Sodium hexafluorogermanate (NaGeF) 6 ) Sodium tetrahaloaluminate NaAlX 4 Sodium tri-titanate (Na) 2 Ti 3 O 7 ) Sodium bismuth (NaBiO) 3 ) Sodium ureate (Na) 2 C 5 H 2 N 4 O 3 ) Sodium uranyl acetate (NaZn (UO) 2 ) 3 ·(CH 3 COO) 9 ·9H 2 O), sodium hexahydroxy antimonic (V) acid (Na [ Sb (OH) 6 ]) Sodium uranyl arsenate (NaUO) 2 AsO 4 ) Sodium ammonium hexanitro cobalt (III) acid (Na (NH 4) 2 [Co(NO 2 ) 6 ]) Sodium bis (trimethylsilyl) amide (LiHMDS), sodium bis (trifluoromethylsulfonyl) imide (NaTFSI), sodium bis (fluorosulfonyl) imide (NaFSI), sodium trifluoromethylsulfonate (NaCF) 3 SO 3 ) Sodium tris (trifluoromethylsulfonyl) methyl (NaC (SO) 2 CF 3 ) 3 ) Sodium bis (perfluoroethylsulfonyl) imide (NaBETI), sodium thioglycolate (NaSCN), sodium bisoxalato borate (NaBOB), sodium difluorooxalato borate (NaDFOB), disodium ethylenediamine tetraacetate (C) 10 H 14 N 2 Na 2 O 8 ) Trisodium citrate (C) 6 H 5 Na 3 O 7 ) Mono sodium 4-chlorophthalic acid (C) 8 H 4 ClNaO 4 ) Sodium bis (catechol) borate (NaBBB).
In a third aspect, an embodiment of the present invention provides a sodium battery, including the sodium battery electrolyte of the second aspect.
In a fourth aspect, embodiments of the present invention provide a solid electrolyte comprising the multifunctional sodium battery electrolyte additive of the first aspect.
In a fifth aspect, an embodiment of the present invention provides a solid-liquid mixed electrolyte, including the multifunctional sodium battery electrolyte additive described in the first aspect.
In a sixth aspect, embodiments of the present invention provide a solid-state sodium battery comprising the solid-state electrolyte according to the fourth aspect or comprising the solid-liquid mixed electrolyte according to the fifth aspect.
The boron element contained in the multifunctional sodium battery electrolyte additive can be effectively coordinated with oxygen element in trace water of the electrolyte to remove trace water, so that the chemical/electrochemical stability of the electrolyte is improved, the interface impedance of a sodium battery is reduced, and meanwhile, the boron element contained in the multifunctional sodium battery electrolyte additive can be coordinated with anions of sodium salt to improve the solubility and dissociation degree of the sodium salt, so that the ionic conductivity of the electrolyte is improved, and the cycle life and the multiplying power performance of the sodium battery can be remarkably improved. The fluorine-containing group can regulate and control the components of the electrode/electrolyte interface, effectively reduce interface impedance, increase the wettability of the electrolyte to the porous electrode, simultaneously effectively passivate the aluminum foil, and inhibit the corrosion of sodium salt to the aluminum foil under high voltage, thereby improving the stability of the electrode and the charge and discharge kinetics, and improving the safety, the storage life and the rate capability of the sodium battery. The electrolyte additive is easy to obtain, and has cheap raw materials and mass production. By applying the multifunctional sodium battery electrolyte additive disclosed by the invention to liquid electrolyte, solid-liquid mixed electrolyte or solid electrolyte, excellent comprehensive properties such as passivation of aluminum foil, trace water removal, electrode wettability improvement, sodium salt solubility improvement, electrode dynamics improvement and the like can be achieved by matching different anode and cathode materials.
Drawings
The technical scheme of the embodiment of the invention is further described in detail through the drawings and the embodiments.
FIG. 1 is a graph comparing the discharge performance at 1C rate of a battery provided with the additive for electrolyte of a multi-functional sodium battery according to example 1 of the present invention with a battery provided with no additive according to comparative example 1;
FIG. 2 is a graph showing the rate performance of the battery with the additive for the electrolyte of the sodium battery according to example 2 of the present invention compared to the battery without the additive according to comparative example 2 under different discharge conditions;
fig. 3 is a graph comparing electrochemical impedance spectra of a battery provided with the additive for electrolyte of a multi-functional sodium battery according to example 2 of the present invention and a battery provided with no additive according to comparative example 2.
Detailed Description
The invention is further illustrated by the drawings and the specific examples, which are to be understood as being for the purpose of more detailed description only and are not to be construed as limiting the invention in any way, i.e. not intended to limit the scope of the invention.
The embodiment of the invention provides a multifunctional sodium battery electrolyte additive, which comprises the following components: a compound or mixture containing both fluorine and boron; the total concentration of the additive in the electrolyte is in the range of 0.0001mol/L to 1mol/L. Preferably 0.001 to 0.1mol/L, more preferably 0.001 to 0.05mol/L.
The boron element in the additive is coordinated with the oxygen element in trace water of the electrolyte, trace water is removed, the chemical stability and electrochemical stability of the electrolyte are improved, and the interface impedance of the sodium battery is reduced; and the boron element is coordinated with anions of sodium salt in the sodium battery electrolyte, so that the solubility and dissociation degree of the sodium salt are improved, and the ionic conductivity of the electrolyte is improved;
the fluorine element in the additive exists in the form of fluorine-containing groups, and the fluorine-containing groups are used for regulating and controlling the components of an electrode-electrolyte interface, reducing interface impedance, improving the wettability of the electrolyte to an electrode, passivating the aluminum foil of a current collector of a sodium battery and inhibiting the corrosion of sodium salt to the aluminum foil.
The state of the multifunctional sodium battery electrolyte additive comprises a gaseous state, a liquid state or a solid state; the method specifically comprises the following steps: fluoroborates and complexes thereof, fluoroboric acid, inorganic fluoroborates, organofluoroborates, polyfluoroarene borides, fluoroorganoboranes, nitro fluoroborates or other organofluoroboric compounds.
The chemical formula of the fluoroborate is B a F b Or BF c X d The method comprises the steps of carrying out a first treatment on the surface of the Wherein a is more than or equal to 0.5 and less than or equal to 2,1.5 and b is more than or equal to 3; c is more than or equal to 0.5 and less than or equal to 3,0.5, d is more than or equal to 3, and X is halogen element;
the substances forming the complex with the fluoroborate compound include: one or more of water, ammonia, argon, alcohol, carboxylic acid, amine, nitrile, ester, aldehyde, ketone, ether, phenol, sulfone; the fluoroborate complex specifically includes: one or more of boron trifluoride dihydrate, boron trifluoride methanol, boron trifluoride ethanol, boron trifluoride acetic acid, boron trifluoride propionic acid, boron trifluoride phosphoric acid, boron trifluoride dimethyl carbonate, boron trifluoride ethyl acetate, boron trifluoride butyl acetate, boron trifluoride ethyl chloroacetate, boron trifluoride acetonitrile, boron trifluoride tetrahydrofuran, boron trifluoride methyl ether, boron trifluoride ethyl ether, boron trifluoride butyl ether, boron trifluoride sulfolane, boron trifluoride monoethyl amine, boron trifluoride ethylamine, boron trifluoride benzylamine, boron trifluoride phenol, phenol formaldehyde resin boron trifluoride phenol, boron trifluoride dimethyl ether;
The fluoboric acid has a chemical formula of HBF 4 ；
The chemical formula of the inorganic fluoborate is M n (BF 4 ) m The method comprises the steps of carrying out a first treatment on the surface of the N is more than or equal to 0.2 and less than or equal to 5,0.2, m is more than or equal to 8; wherein M comprises one or more of aluminum, copper, lead, tin, nickel, zinc, cadmium, beryllium, magnesium, calcium, strontium, barium, cesium, rubidium, manganese, iron, cobalt, silver, indium and thallium; the inorganic fluoroborate is dissociable; the inorganic fluoroborates may include in particular: rubidium tetrafluoroborate, cesium tetrafluoroborate, ammonium tetrafluoroborate, copper tetrafluoroborate, tin tetrafluoroborate, zinc tetrafluoroborate, nickel tetrafluoroborateOne or more of iron tetrafluoroborate, cobalt tetrafluoroborate, manganese tetrafluoroborate, silver tetrafluoroborate, cadmium tetrafluoroborate, aluminum tetrafluoroborate, magnesium tetrafluoroborate, calcium tetrafluoroborate, strontium tetrafluoroborate and barium tetrafluoroborate;
the chemical formula of the organofluorine boron compound includes: R-BF 3 M、F-R-BH x 、R-BF 3 、BF 4 NO、BF 4 NO 2 One of the following; x is more than or equal to 0.5 and less than or equal to 3; wherein R is an organic group comprising: any of hydrocarbyl, alcohol, ether, ester, ketone, carboxylic acid, phenolic, or other organic groups; the method specifically comprises the following steps: cesium organic trifluoroborate, rubidium organic trifluoroborate, potassium organic trifluoroborate, sodium organic trifluoroborate, lithium organic trifluoroborate, ammonium organic trifluoroborate, copper organic trifluoroborate, tin organic trifluoroborate, zinc organic trifluoroborate, nickel organic trifluoroborate, iron organic trifluoroborate, cobalt organic trifluoroborate, manganese organic trifluoroborate, silver organic trifluoroborate, cadmium organic trifluoroborate, aluminum organic trifluoroborate, magnesium organic trifluoroborate, calcium organic trifluoroborate, strontium organic trifluoroborate, and barium organic trifluoroborate. The organofluoroborate can dissociate.
The multifunctional sodium battery electrolyte additive can be used for sodium battery electrolyte, solid electrolyte or solid-liquid mixed electrolyte.
When used in sodium battery electrolyte, the sodium battery electrolyte also comprises solvent and sodium salt; the solvent comprises: ethylene Carbonate (EC), propylene Carbonate (PC), butylene Carbonate (BC), ethylene carbonate (VC), ethylene Sulfite (ES), dimethyl sulfite (DMS), diethyl sulfite (DES), dibutyl carbonate (DBC), dibutyl carbonate (GBL), methyl butyl carbonate (BMC), dipropyl carbonate (DPC), methyl ester (PA), propylene Sulfite (PS), gamma-butyrolactone (ybl), gamma-valerolactone (γvl), ethylene carbonate (VEC), dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), fluoroethylene carbonate (FEC), dimethyl pyrocarbonate (DMPC), dioxolane (DOL), ethylene glycol dimethyl ether (DME), dimethoxymethane (DMM), ethylene glycol diethyl ether (DEE), tetraethylene glycol dimethyl ether (teggme), methyl Propyl Carbonate (MPC), methyl isopropyl carbonate (micc), methyl isopropyl carbonate (DMC),Methyl Formate (MF), ethyl Formate (EF), methyl Acetate (MA), ethyl Acetate (EA), methyl Propionate (MP), ethyl Propionate (EP), ethyl Butyrate (EB), fluorobenzene (FB), tetrahydrofuran (THF), 2-methyltetrahydrofuran (2 Me-THF), tetrahydropyran (THP), diglyme/Diglyme (DG), acetonitrile (AN), dimethylsulfoxide (DMSO), N-Dimethylformamide (DMF), sulfolane (SL), dimethylsulfone (MSM), methylsulfone (EMS), 3-trifluoropropylmethylsulfone (FPMS), 1, 3-dioxolane (1, 3-DL), 4-methyl-1, 3-dioxolane (4-Me-1, 3-DL), 2-methyl-1, 3-dioxolane (2 Me-1, 3-DL) or acetone; the sodium salt includes: sodium fluoride (NaF), sodium carbonate (Na) 2 CO 3 ) Sodium nitrate (NaNO) 3 ) Sodium perchlorate (NaClO) 4 ) Sodium sulfide (Na) 2 S), sodium sulfite (Na) 2 SO 3 ) Sodium sulfate (Na) 2 SO 4 ) Sodium hexafluorophosphate (NaPF) 6 ) Sodium tetrafluoroborate (NaBF) 4 ) Sodium hexafluoroarsenate (NaAsF) 6 ) Sodium hexafluorotantalate (NaTaF) 6 ) Sodium hexafluorostannate (NaSnF) 6 ) Sodium hexafluorogermanate (NaGeF) 6 ) Sodium tetrahaloaluminate NaAlX 4 Sodium tri-titanate (Na) 2 Ti 3 O 7 ) Sodium bismuth (NaBiO) 3 ) Sodium ureate (Na) 2 C 5 H 2 N 4 O 3 ) Sodium uranyl acetate (NaZn (UO) 2 ) 3 ·(CH 3 COO) 9 ·9H 2 O), sodium hexahydroxy antimonic (V) acid (Na [ Sb (OH) 6 ]) Sodium uranyl arsenate (NaUO) 2 AsO 4 ) Sodium ammonium hexanitro cobalt (III) acid (Na (NH 4) 2 [Co(NO 2 ) 6 ]) Sodium bis (trimethylsilyl) amide (LiHMDS), sodium bis (trifluoromethylsulfonyl) imide (NaTFSI), sodium bis (fluorosulfonyl) imide (NaFSI), sodium trifluoromethylsulfonate (NaCF) 3 SO 3 ) Sodium tris (trifluoromethylsulfonyl) methyl (NaC (SO) 2 CF 3 ) 3 ) Sodium bis (perfluoroethylsulfonyl) imide (NaBETI), sodium thioglycolate (NaSCN), sodium bisoxalato borate (NaBOB), sodium difluorooxalato borate (NaDFOB), disodium ethylenediamine tetraacetate (C) 10 H 14 N 2 Na 2 O 8 ) Trisodium citrate (C) 6 H 5 Na 3 O 7 ) Mono sodium 4-chlorophthalic acid (C) 8 H 4 ClNaO 4 ) Sodium bis (catechol) borate (NaBBB).
When the above multifunctional sodium battery electrolyte additive is used in sodium battery electrolyte of sodium battery, or in solid electrolyte or solid-liquid mixed electrolyte of solid sodium battery, the mateable positive electrode material includes but is not limited to transition metal oxide Na x MO 2 (wherein M is a transition group metal element), sodium iron phosphate, sodium vanadium phosphate, sodium fluorophosphate, sodium iron fluorophosphate, sodium cobalt fluorophosphate, sodium iron pyrophosphate, sodium cobalt pyrophosphate, sodium manganese pyrophosphate, prussian blue homolog (Na) x MFe(CN) 6 Wherein M is a transition group metal element), disodium rhodizonate, tetrasodium dihydroxyterephthalate, titanium disulfide, graphite fluoride, mnO 2 、FeS 2 、FeF 3 、S、H 2 O、CO 2 、O 2 One or more of the following. The negative electrode material includes, but is not limited to, high-phase pyrolytic graphite, artificial graphite, natural graphite, hollow carbon nanowires, graphitized carbon fibers, graphitized mesocarbon microbeads, hard carbon, soft carbon, carbon nanotubes, sodium metal, graphene and graphene composite negative electrodes, na 2 Ti 3 O 7 、Na 2 Ti 6 O 13 、Na 4 Ti 5 O 12 Silicon anode, sb-based anode, sn-based anode, ge-based anode, in-based anode, P-based anode, sb-C composite anode, metal oxide (MO x ) Sulfide (MS) x ) One or more of the following.
The boron element contained in the multifunctional sodium battery electrolyte additive can be effectively coordinated with oxygen element in trace water of the electrolyte to remove trace water, so that the chemical/electrochemical stability of the electrolyte is improved, the interface impedance of a sodium battery is reduced, and meanwhile, the boron element contained in the multifunctional sodium battery electrolyte additive can be coordinated with anions of sodium salt to improve the solubility and dissociation degree of the sodium salt, so that the ionic conductivity of the electrolyte is improved, and the cycle life and the multiplying power performance of the sodium battery can be remarkably improved. The fluorine-containing group can regulate and control the components of the electrode/electrolyte interface, effectively reduce interface impedance, increase the wettability of the electrolyte to the porous electrode, simultaneously effectively passivate the aluminum foil, and inhibit the corrosion of sodium salt to the aluminum foil under high voltage, thereby improving the stability of the electrode and the charge and discharge kinetics, and improving the safety, the storage life and the rate capability of the sodium battery. The electrolyte additive is easy to obtain, and has cheap raw materials and mass production. By applying the multifunctional sodium battery electrolyte additive disclosed by the invention to liquid electrolyte, solid-liquid mixed electrolyte or solid electrolyte, excellent comprehensive properties such as passivation of aluminum foil, trace water removal, electrode wettability improvement, sodium salt solubility improvement, electrode dynamics improvement and the like can be achieved by matching different anode and cathode materials.
For better understanding of the technical scheme provided by the invention, the following specific examples are used for respectively describing the specific application and characteristics of the multifunctional sodium battery electrolyte additive.
Example 1
The present example uses a boron fluoride compound HBF 4 And the ester electrolyte is added to improve the battery performance.
1. Firstly, preparing an electrolyte in a glove box protected by argon: 1M NaClO 4 EC-DMC (the volume ratio of EC to DMC is 1:1). Then weighing a certain mass of boron fluoride compound HBF 4 Adding into the electrolyte to obtain 1M NaClO containing 0.005mol/L fluorine boron compound additive 4 EC-DMC electrolyte.
2. The battery was assembled in an argon-protected glove box, and the battery specifically used was a CR2032 button cell structure in which sodium sheets were used as the negative electrode and sodium vanadium phosphate as the positive electrode, respectively, and the electrolyte containing 0.005mol/L of the boron fluoride compound additive prepared in step 1 was used to complete the assembly of the battery of this example.
3. The assembled battery was tested on a marchand blue electrical test system (LANHE) and the battery was cycled at 0.5C at 25 degrees celsius and the results are shown in fig. 1.
4. After the battery is disassembled, the surfaces of the positive electrode and the negative electrode are respectively observed through a Hitachi S8600 scanning electron microscope, and the comparison shows that the stability of the electrode active material is obviously improved after the battery containing the fluorine boron compound additive is circulated. In addition, the anode aluminum current collector shows fewer corrosion behaviors in an electrolyte system containing the fluorine-boron compound additive, which indicates that the fluorine-boron compound additive has the effect of passivating the aluminum foil, so that the stability of the current collector in the circulating process is improved, the contact resistance is reduced, and the battery performance is further remarkably improved.
Example 2
In this example, boron trifluoride dihydrate as a boron trifluoride compound was added to an ester electrolyte to improve battery performance.
1. Firstly, preparing an electrolyte in a glove box protected by argon: 1M NaPF 6 EC-DMC (the volume ratio of EC to DMC is 1:1). Then weighing a certain mass of boron trifluoride dihydrate as a fluorine boron compound, adding the boron trifluoride dihydrate into the prepared electrolyte to obtain 1MNAPF containing 0.01mol/L fluorine boron compound additive 6 EC-DMC electrolyte.
2. The assembly of the cells was performed in an argon-protected glove box, and a specific cell used a CR2032 button cell structure in which Na was used for each of 2 Ti 3 O 7 The electrolyte prepared in step 1 and containing 0.01mol/L of the boron fluoride compound additive was used as a negative electrode, and the assembly of the comparative battery and the example was completed.
3. The assembled battery was tested on a marchand blue electrical test system (LANHE), cycling and rate testing was performed on the battery at 0.2C-3C rates, at a temperature of 25 degrees celsius, and the results are shown in fig. 2. The electrochemical impedance spectrum of the cell to which the 0.01mol/L additive for the fluorine boron compound was added was tested, and the test results are shown in FIG. 3.
4. After the battery is disassembled, the surfaces of the positive electrode and the negative electrode are respectively observed through a Hitachi S8600 scanning electron microscope, and the comparison shows that the stability of the electrode active material is obviously improved after the battery containing the fluorine boron compound additive is circulated, and the corrosion of the current collector is inhibited, so that the battery performance is obviously improved.
Example 3
In the embodiment, the fluorine boron compound zinc tetrafluoroborate is adopted to add the ester electrolyte, so that the battery performance is improved.
1. Firstly, preparing an electrolyte in a glove box protected by argon: 1M NaPF 6 EC-DMC (the volume ratio of EC to DMC is 1:1). Then weighing a certain mass of boron fluoride compound, adding the boron fluoride compound into the prepared electrolyte to obtain 1M NaPF containing 0.001mol/L boron fluoride compound additive 6 EC-DMC electrolyte. Meanwhile, an electrolyte containing no additive of the fluorine-boron compound is used as a comparative electrolyte. Trace water test is carried out on the prepared electrolyte, and the trace water content in the electrolyte containing the fluorine-boron compound additive is obviously reduced, so that the improvement of the battery performance is facilitated.
2. The battery was assembled in an argon-protected glove box using a CR2032 button cell structure in which sodium sheets were used as the negative electrode and sodium cobalt fluoride phosphate as the positive electrode, respectively, and the electrolyte containing 0.001mol/L of the additive of the fluorine-boron compound and the additive of the fluorine-boron compound prepared in step 1 was used to complete the assembly of the batteries for comparison and example, respectively.
3. The assembled battery was tested on a marchand blue electrical test system (LANHE) and cycled at a rate of 0.2C-20C at a temperature of 25 degrees celsius. The test results show that the battery containing 0.001mol/L of the boron fluoride compound additive has higher coulombic efficiency and longer cycle life. And releases higher specific capacity under high multiplying power, and shows excellent multiplying power performance.
4. After the battery is disassembled, the surfaces of the positive electrode and the negative electrode are respectively observed through a Hitachi S8600 scanning electron microscope, and the comparison shows that the stability of the electrode active material is obviously improved after the battery containing the fluorine-boron compound additive is circulated, and the corrosion of the current collector is inhibited.
Example 4
In the embodiment, the fluorine boron compound organic sodium trifluoroborate is adopted to add the ester electrolyte, so that the battery performance is improved.
1. Firstly, preparing an electrolyte in a glove box protected by argon: 1M NaBF 4 EC-PC (the volume ratio of EC to PC is 1:1). Then weighing a certain mass of organic sodium trifluoroborate which is a fluoboric compound, and adding the organic sodium trifluoroborate into the prepared electricityIn the solution, 1M NaBF containing 0.01mol/L fluorine boron compound additive is obtained 4 EC-PC electrolyte. Meanwhile, an electrolyte containing no additive of the fluorine-boron compound is used as a comparative electrolyte.
2. The battery was assembled in an argon-protected glove box using a CR2032 button cell structure in which sodium sheets were used as the negative electrode and sodium ferric pyrophosphate as the positive electrode, respectively, and the electrolyte prepared in step 1 and containing 0.02mol/L of the additive of the fluoroboric compound and the additive of the non-fluoroboric compound was used to complete the assembly of the batteries for comparison and example, respectively.
3. The assembled battery was tested on a marchand blue electrical test system (LANHE) and cycled at a rate of 0.01C-20C at a temperature of 25 degrees celsius. From comparison of the cyclic coulombic efficiencies, it can be seen that the test results show that the battery containing 0.02mol/L of the boron fluoride compound additive has higher coulombic efficiency and longer cycle life, and thus the boron fluoride compound additive increases the stability of the interface layer.
4. After the battery is disassembled, the surfaces of the positive electrode and the negative electrode are respectively observed through a Hitachi S8600 scanning electron microscope, and the comparison shows that the stability of the electrode active material is obviously improved after the battery containing the fluorine boron compound additive is circulated. In addition, the anode aluminum current collector shows fewer corrosion behaviors in an electrolyte system containing the fluorine-boron compound additive, which indicates that the fluorine-boron compound additive has the effect of passivating the aluminum foil, so that the stability of the current collector in the circulating process is improved, the contact resistance is reduced, and the battery performance is further remarkably improved.
Example 5
In the embodiment, the fluorine boron compound boron trifluoride ethyl acetate is adopted to add the ether electrolyte, so that the battery performance is improved.
1. Firstly, preparing an electrolyte in a glove box protected by argon: 1M NaClO 4 EC-PC (volume ratio of EC to PC is 1:1), then weighing boron trifluoride ethyl acetate as a fluorine boron compound with a certain mass, adding into the prepared electrolyte to obtain 1MNaClO containing 0.01mol/L fluorine boron compound additive 4 EC-PC electrolyte. At the same time, will not contain fluorine boron compoundThe electrolyte of the additive was used as a comparative electrolyte.
2. The battery was assembled in an argon-protected glove box using a CR2032 button cell structure in which sodium sheets were used as the negative electrode and sodium iron phosphate as the positive electrode, respectively, and the electrolyte prepared in step 1 and containing 0.01mol/L of the additive of the fluoroboric compound and the additive of the non-fluoroboric compound was used to complete the assembly of the battery for comparison and the example, respectively.
3. The assembled battery was tested on a marchand blue electrical test system (LANHE) at a rate of 0.5C-20C at a temperature of 25 degrees celsius. The test result shows that the rate performance and the power density of the battery are obviously improved, and the electrode dynamics are improved by adding the fluorine boron compound additive.
4. After the battery is disassembled, the surfaces of the positive electrode and the negative electrode are respectively observed through a Hitachi S8600 scanning electron microscope, and the comparison shows that the size of electrode particles of the battery containing the fluorine boron compound additive is smaller, so that the polarization is reduced, the migration rate of sodium ions is increased, and the electrode dynamics is further improved. Meanwhile, the aluminum current collector is further passivated by the fluorine boron compound additive, so that the contact resistance is reduced, and the battery performance is further improved obviously.
5. The composition of the positive electrode is characterized by adopting photoelectron spectroscopy (XPS), and the result shows that the fluorine content in the film layer is obviously improved, which indicates that the capacity of the electrode active material is fully released, and the energy efficiency of the battery is improved.
Example 6
In the embodiment, boron trifluoride ethylamine as a fluorine boron compound is adopted to add the ether electrolyte, so that the battery performance is improved.
1. Firstly, preparing an electrolyte in a glove box protected by argon: 1M NaBF 4 EC-PC (the volume ratio of EC to PC is 1:1). Then weighing boron trifluoride ethylamine as a fluorine boron compound with a certain mass, adding into the prepared electrolyte to obtain 1M NaBF containing 0.01mol/L fluorine boron compound additive 4 EC-PC electrolyte. Meanwhile, an electrolyte containing no additive of the fluorine-boron compound is used as a comparative electrolyte.
2. The battery was assembled in an argon-protected glove box using a CR2032 button cell structure in which sodium sheets were used as the negative electrode and graphite fluoride was used as the positive electrode, and the electrolyte containing 0.01mol/L of the fluorine-boron compound additive and the electrolyte containing no fluorine-boron compound additive prepared in step 1 were used to complete the assembly of the batteries for example and comparative example, respectively.
3. The assembled battery was tested on a marchand blue electrical test system (LANHE) and cycled at a rate of 0.2C-20C at a temperature of 25 degrees celsius. The test results show that the battery containing 0.01mol/L of the boron fluoride compound additive has higher coulombic efficiency and longer cycle life. And releases higher specific capacity under high multiplying power, and shows excellent multiplying power performance.
4. After the battery is disassembled, the surfaces of the positive electrode and the negative electrode are respectively observed through a Hitachi S8600 scanning electron microscope, and the comparison shows that the stability of the electrode active material is obviously improved after the battery containing the fluorine boron compound additive is circulated. It follows that the boron fluoride compound additive increases the stability of the interfacial layer. Meanwhile, the aluminum current collector is further passivated by the fluorine boron compound additive, so that the contact resistance is reduced, and the battery performance is further improved obviously.
Example 7
In the embodiment, the fluorine boron compound zinc tetrafluoroborate is adopted to add the ether electrolyte, so that the battery performance is improved.
1. Firstly, preparing an electrolyte in a glove box protected by argon: 1M NaClO 4 DME-DOL (volume ratio of DME to DOL is 1:1). Then weighing a certain mass of boron fluoride compound zinc tetrafluoroborate, adding into the prepared electrolyte to obtain 1MNaClO containing 0.01mol/L boron fluoride compound additive 4 DME-DOL electrolyte. Meanwhile, an electrolyte containing no additive of the fluorine-boron compound is used as a comparative electrolyte.
2. The battery was assembled in an argon-protected glove box using a CR2032 button cell structure in which sodium sheets were used as the negative electrode and titanium disulfide as the positive electrode, and the electrolyte containing 0.01mol/L of the fluorine-boron compound additive and the electrolyte containing no fluorine-boron compound additive prepared in step 1 were used to complete the assembly of the battery for comparison and the battery for comparison, respectively.
3. The assembled battery was tested on a marchand blue electrical test system (LANHE) and the battery was cycled at 0.5C at 25 degrees celsius. The test result shows that the cycle efficiency of the battery containing 0.1mol/L of the fluoboric compound additive is obviously improved, the battery can reach more than 1000 weeks under the condition of 80 percent capacity retention rate, and the polarization is reduced from 0.12V to 0.06V.
4. After the battery is disassembled, the surfaces of the positive electrode and the negative electrode are respectively observed through a Hitachi S8600 scanning electron microscope, and the comparison shows that the stability of the electrode active material is obviously improved after the battery containing the fluorine boron compound additive is circulated. It follows that the boron fluoride compound additive increases the stability of the interfacial layer. Meanwhile, the aluminum current collector is further passivated by the fluorine boron compound additive, so that the contact resistance is reduced, and the battery performance is further improved obviously.
Example 8
In the embodiment, the fluorine boron compound magnesium tetrafluoroborate is adopted to add the ether electrolyte, so that the battery performance is improved.
1. Firstly, preparing an electrolyte in a glove box protected by argon: 1M NaPF 6 DME-DOL (volume ratio of DME to DOL is 1:1). Then weighing a certain mass of tetrafluoroboric compound magnesium fluoroborate, adding into the prepared electrolyte to obtain 1MNAPF containing 0.5mol/L fluoroboric compound additive 6 DME-DOL electrolyte. Meanwhile, an electrolyte containing no additive of the fluorine-boron compound is used as a comparative electrolyte.
2. The battery was assembled in an argon-protected glove box using CR2032 button cell structures, with sodium plates as the negative electrode, and NaNiFe (CN) 6 The electrolyte prepared in step 1 and containing 0.5mol/L of the fluorine boron compound additive and the electrolyte containing no fluorine boron compound additive were used as a positive electrode, and the batteries for comparison and example were assembled, respectively.
3. The assembled battery was tested on a marchand blue electrical test system (LANHE) at a 5C rate at 25 degrees celsius. The test result shows that the cycle performance, the multiplying power performance and the power density of the battery are obviously improved.
4. After the battery is disassembled, the surfaces of the positive electrode and the negative electrode are respectively observed through a Hitachi S8600 scanning electron microscope, and the comparison shows that the battery containing the fluorine-boron compound additive has the advantages of increasing the wettability of the electrode, improving the solubility of sodium salt and further improving the dynamics of the electrode. Meanwhile, the aluminum current collector is further passivated by the fluorine boron compound additive, so that the contact resistance is reduced, and the battery performance is further improved obviously.
5. The composition of the positive electrode is characterized by adopting photoelectron spectroscopy (XPS), and the result shows that the stability of an electrode interface is enhanced, thereby improving the performance of the battery.
Example 9
In the embodiment, the fluorine boron compound copper trifluoride is adopted to add the ether electrolyte, so that the battery performance is improved.
1. Firstly, preparing an electrolyte in a glove box protected by argon: 1M Na 2 SO 4 DME-DOL (volume ratio of DME to DOL is 1:1). Then weighing a certain mass of organic copper trifluoroborate of the fluoboric compound, adding the organic copper trifluoroborate into the prepared electrolyte to obtain 1MNA containing 1mol/L fluoboric compound additive 2 SO 4 DME-DOL electrolyte. Meanwhile, an electrolyte containing no additive of the fluorine-boron compound is used as a comparative electrolyte.
2. The battery was assembled in an argon-protected glove box using a CR2032 button cell configuration with sodium plates as the negative electrode, mnO 2 The electrolyte prepared in step 1 and containing 1mol/L of the fluorine boron compound additive and the electrolyte containing no fluorine boron compound additive were used as a positive electrode, and the assembly of the comparative battery was completed in each of the examples.
3. The assembled battery was tested on a marchand blue electrical test system (LANHE) at a rate of 0.01C-15C at a temperature of 25 degrees celsius. The test result shows that the rate performance and the power density of the battery are obviously improved.
4. After the battery is disassembled, the surfaces of the positive electrode and the negative electrode are respectively observed through a Hitachi S8600 scanning electron microscope, and the comparison shows that the battery containing the fluorine-boron compound additive has the advantages of increasing the wettability of the electrode, improving the solubility of sodium salt and further improving the dynamics of the electrode. Meanwhile, the aluminum current collector is further passivated by the fluorine boron compound additive, so that the contact resistance is reduced, and the battery performance is further improved obviously.
5. The composition of the positive electrode is characterized by adopting photoelectron spectroscopy (XPS), and the result shows that the stability of an electrode interface is enhanced, thereby improving the performance of the battery.
Example 10
In the embodiment, the ether electrolyte is added into the boron fluoride compound organic barium trifluoroborate, so that the battery performance is improved.
1. Firstly, preparing an electrolyte in a glove box protected by argon: 1M NaAsF 6 DME-DOL (volume ratio of DME to DOL is 1:1). Then, a certain volume of organic barium trifluoroborate of the fluoboric compound is measured and added into the prepared electrolyte to obtain the 1MLiTFSI/DME-DOL electrolyte containing 0.02mol/L fluoboric compound additive. Meanwhile, an electrolyte containing no additive of the fluorine-boron compound is used as a comparative electrolyte.
2. The battery was assembled in an argon-protected glove box using a CR2032 button cell structure in which sodium sheets were used as the negative electrode and S as the positive electrode, and the electrolyte containing 0.02mol/L of the fluorine-boron compound additive and the electrolyte containing no fluorine-boron compound additive prepared in step 1 were used to complete the assembly of the battery for comparison and the battery for comparison, respectively.
3. The assembled battery was tested on a marchand blue electrical test system (LANHE) at a rate of 0.5C at a temperature of 25 degrees celsius. The test result shows that the cycle performance and the energy efficiency of the battery are obviously improved.
4. After the battery is disassembled, the surfaces of the positive electrode and the negative electrode are respectively observed through a Hitachi S8600 scanning electron microscope, and the comparison shows that the stability of the electrode active material is obviously improved after the battery containing the fluorine boron compound additive is circulated. In addition, the anode aluminum current collector shows fewer corrosion behaviors in an electrolyte system containing the fluorine-boron compound additive, which indicates that the fluorine-boron compound additive has the effect of passivating the aluminum foil, so that the stability of the current collector in the circulating process is improved, the contact resistance is reduced, and the battery performance is further remarkably improved.
Example 11
In the embodiment, the boron fluoride compound copper tetrafluoroborate is adopted to add the polyethylene oxide solid electrolyte, so that the battery performance is improved.
1. First, 0.5 g of sodium hexafluoroarsenate (NaAsF) was weighed out 6 ) A certain mass of boron fluoride compound copper tetrafluoroborate and 5 ml of acetonitrile solvent are placed in the same container for ultrasonic treatment for at least 15 minutes to be completely dispersed. Then 10 g of Polyimide (PI) from Sigma was weighed out and dissolved in the dispersed solution and stirred for 6 hours, wherein the ratio of sodium to oxygen of PI polymer and sodium salt was kept in the range of 20:1. The evenly stirred solution is coated on the surface of a silicon substrate, dried at 50 ℃ to prepare a polyimide solid electrolyte sheet with proper size and thickness of 60 mu M and porosity of 10 percent and containing 0.05M fluorine boron compound additive.
2. The battery was assembled in an argon-protected glove box using a CR2032 button cell structure in which sodium sheets were used as the negative electrode and sodium vanadium fluorophosphate as the positive electrode, respectively, and the solid electrolyte containing 0.05M of the additive of the fluoroboric compound and the additive of the non-fluoroboric compound prepared in step 1 was used to complete the assembly of the battery for comparison and the example, respectively.
3. The assembled battery was tested on a marchand blue electrical test system (LANHE) at a 1C rate at 60 degrees celsius. The test result shows that the cycle performance and the energy efficiency of the battery are obviously improved.
4. After the battery is disassembled, the surfaces of the positive electrode and the negative electrode are respectively observed through a Hitachi S8600 scanning electron microscope, and the comparison shows that the stability of the electrode active material is obviously improved after the battery containing the fluorine boron compound additive is circulated. And the wettability and the sodium salt solubility of the electrode are also improved, so that the electrode dynamics are improved. Meanwhile, the aluminum current collector is further passivated by the fluorine boron compound additive, so that the contact resistance is reduced, and the battery performance is further improved obviously.
Example 12
The present example uses a boron fluoride compound HBF 4 For polyethylene oxide solidThe addition of the electrolyte improves the battery performance.
1. First, 0.5 g of sodium hexafluoroarsenate (NaAsF) was weighed out 6 ) A certain mass of boron fluoride compound HBF 4 And 5 ml of acetonitrile solvent, and placing the mixture in the same container for ultrasonic treatment for at least 15 minutes to completely disperse. Then 10 g of Polyimide (PI) from Sigma was weighed out and dissolved in the dispersed solution and stirred for 6 hours, wherein the ratio of sodium to oxygen of PI polymer and sodium salt was kept in the range of 20:1. The evenly stirred solution is coated on the surface of a silicon substrate, dried at 50 ℃ to prepare a polyimide solid electrolyte sheet with proper size and thickness of 60 mu M and porosity of 10 percent and containing 0.05M fluorine boron compound additive.
2. The battery was assembled in an argon-protected glove box using a CR2032 button cell structure in which sodium sheets were used as the negative electrode and sodium phosphate fluoride as the positive electrode, respectively, and the electrolyte containing 0.07M of the additive of the fluoroboric acid compound and the additive of the non-fluoroboric acid compound prepared in step 1 was used to complete the assembly of the battery for comparison and example, respectively.
3. The assembled battery was tested on a marchand blue electrical test system (LANHE) at a 3C rate at 60 degrees celsius. The test result shows that the cycle performance and the energy efficiency of the battery are obviously improved.
4. After the battery is disassembled, the surfaces of the positive electrode and the negative electrode are respectively observed through a Hitachi S8600 scanning electron microscope, and the comparison shows that the stability of the electrode active material is obviously improved after the battery containing the fluorine boron compound additive is circulated. And the wettability and the sodium salt solubility of the electrode are also improved, so that the electrode dynamics are improved. Meanwhile, the aluminum current collector is further passivated by the fluorine boron compound additive, so that the contact resistance is reduced, and the battery performance is further improved obviously.
Example 13
This example uses the boron fluoride compound zinc tetrafluoroborate vs Na 3 Zr 2 (SiO 4 ) 2 (PO 4 ) And polyimide composite solid electrolyte are added to improve the battery performance.
To inorganic solid electrolyte Na 3 Zr 2 (SiO 4 ) 2 (PO 4 ) Dispersing powder and boron tetrafluoro compound zinc tetrafluoroborate into polyimide solid electrolyte, oven drying at 50deg.C to obtain proper size, and stripping to obtain Na with thickness of 60 μm and porosity of 10% containing boron tetrafluoro compound additive 3 Zr 2 (SiO 4 ) 2 (PO 4 ) Polyimide composite solid electrolyte sheet.
2. The symmetrical battery system of Na-Na is adopted to represent the properties of circulation performance, multiplying power performance, polarization and the like. The battery is assembled in a glove box protected by argon, and the specific battery uses a CR2032 button cell structure, specifically, a sodium sheet is adopted as a negative electrode and a counter electrode, and the electrolyte sheet containing the fluorine-boron compound additive and the electrolyte sheet not containing the fluorine-boron compound additive prepared in the step 1 are adopted respectively.
3. The assembled battery was tested on a marchand blue electrical test system (LANHE), and the battery was cycled at a rate of 0.2C at a temperature of 60 degrees celsius. The results show that the polarization of the cell containing the fluorine-containing boron compound additive is greatly reduced and the cycle life is greatly improved compared with the cell without the fluorine-containing boron compound additive.
4. After the battery is disassembled, the surfaces of the positive electrode and the negative electrode are respectively observed through a Hitachi S8600 scanning electron microscope, and the comparison shows that the stability of the electrode active material is obviously improved after the battery containing the fluorine boron compound additive is circulated.
Example 14
This example uses a boron fluoride compound organic aluminum trifluoroborate to an inorganic solid electrolyte Na 3 PS 4 The addition is performed to improve the battery performance.
1. To inorganic solid electrolyte Na 3 PS 4 And a certain mass of organic aluminum trifluoroborate powder tablet of the fluoboric compound, and sintering for 8 hours at 1100 ℃ to ensure that the conductivity reaches the optimal value, thus obtaining Na added with the fluoboric compound 3 PS 4 Electrolyte sheet.
2. The battery was assembled in an argon-protected glove box using a CR2032 button cell structure in which sodium sheets were used as the negative electrode and sodium ferric fluoride phosphate as the positive electrode, respectively, and the fluorine-containing boron compound additive and the electrolyte containing no fluorine-containing boron compound additive prepared in step 1 were used to complete the assembly of the battery for comparison and example, respectively.
3. The assembled battery was tested on a marchand blue electrical test system (LANHE), and the battery was cycled at a rate of 0.2C at a temperature of 60 degrees celsius. The results show that the cell cycle efficiency of the fluorine-containing boron compound additive was stabilized at 99% or more and was able to be cycled for 500 weeks or more, while the cell without the fluorine-containing boron compound additive was maintained for 200 weeks only. And polarization of the cell containing the fluorine boron compound additive is greatly reduced compared to the cell without the fluorine boron compound additive.
4. After the battery is disassembled, the surfaces of the positive electrode and the negative electrode are respectively observed through a Hitachi S8600 scanning electron microscope, and the comparison shows that the stability of the electrode active material is obviously improved after the battery containing the fluorine boron compound additive is circulated.
Example 15
This example uses a boron fluoride compound, organomagnesium trifluoroborate vs Na 3 SbS 4 And polyimide composite solid electrolyte are added to improve the battery performance.
1. To inorganic solid electrolyte Na 3 SbS 4 Dispersing powder and organic magnesium trifluoroborate into polyimide solid electrolyte, oven drying at 50deg.C, preparing into proper size, and stripping to obtain Na with thickness of 60 μm 3 SbS 4 Polyimide composite solid electrolyte sheet.
2. The battery was assembled in an argon-protected glove box using a CR2032 button cell structure in which sodium sheets were used as the negative electrode and cobalt sodium pyrophosphate as the positive electrode, respectively, and the fluorine-containing boron compound additive and the solid electrolyte containing no fluorine-containing boron compound additive prepared in step 1 were used to complete the assembly of the battery for comparison and the example, respectively.
3. The assembled battery was tested on a marchand blue electrical test system (LANHE), and the battery was cycled at a rate of 0.1C at a temperature of 60 degrees celsius. The results show that the polarization of the cell containing the fluorine-containing boron compound additive is greatly reduced and the cycle life is greatly improved compared with the cell without the fluorine-containing boron compound additive.
4. After the battery is disassembled, the surfaces of the positive electrode and the negative electrode are respectively observed through a Hitachi S8600 scanning electron microscope, and the comparison shows that the stability of the electrode active material is obviously improved after the battery containing the fluorine boron compound additive is circulated.
5. Impedance spectroscopy tests were performed on the cell containing the additive of the boron fluoride compound and the cell without the additive of the boron fluoride compound using an IM6 type impedance spectroscopy tester available from Zahner, germany, and the result shows that the impedance of the cell with the additive is significantly lower than that of the cell without the additive.
Comparative example 1
Comparative example 1 the battery performance was tested using a conventional carbonate electrolyte.
1. Preparation of electrolyte: at room temperature, in a glove box, the solvent was taken up as Ethylene Carbonate (EC): propylene Carbonate (PC): diethyl carbonate (DEC) =1:1:2 (volume ratio), 100mL of the mixture was mixed, and 16.8g of sodium hexafluorophosphate (NaPF) was added thereto 6 ) Preparing a solution, and uniformly stirring to obtain the electrolyte of the comparative example.
2. Preparation of a positive plate: 1000g N-methylpyrrolidone (NMP), 30g of polyvinylidene fluoride (PVDF) as a binder, was added to the stirrer, and stirred for 2 hours at revolution of 30 rpm and rotation of 3000 rpm; then adding 30g of conductive agent acetylene black, and stirring for 1 hour; then 940g of positive electrode active material Na [ Cu ] is added 1/3 Fe 1/3 Mn 1/3 ]O 2 Stirring for 2 hours, defoaming, and sieving with a 200-mesh sieve to prepare the sodium ion battery anode slurry. The slurry is uniformly coated on aluminum foil with the thickness of 20 microns, and then dried, pressed and cut into positive plates with the thickness of 78 multiplied by 48 mm, wherein each positive plate contains 1.2 g of active substances.
3. Preparing a negative plate: 500g of a negative electrode active material soft carbon, 30g of a binder styrene-butadiene rubber (SBR), 30g of carboxymethyl cellulose (CMC) were added to 500g of water, and then stirred in a vacuum stirrer to form a stable, uniform negative electrode slurry. The negative electrode slurry was uniformly coated on a 20 μm thick copper foil, dried, rolled, and cut into 80×50 mm negative electrode sheets each containing 0.72 g of a negative electrode active material.
4. Preparation of sodium ion battery: and sequentially stacking the positive plate, the polypropylene diaphragm with the thickness of 20 micrometers and the negative plate into an electrode group, filling the electrode group into a pit punching aluminum-plastic film (containing an air pocket pit), injecting electrolyte into a battery shell according to the amount of 9g/Ah, and sealing to prepare the soft package sodium ion battery.
5. And (3) testing normal temperature multiplying power performance: the cells were charged to 4.0 volts at 25 ℃ with 0.1C current, respectively, and then left to stand for 5 minutes; and (5) completing battery activation. The current is then discharged to 1.5 volts at 1C, with the discharge curve shown in fig. 1. As can be seen from the comparison of fig. 1, fig. 1 shows that the battery employing the 0.005mol/L fluorine boron compound additive of example 1 of the present invention has a higher discharge voltage and discharge capacity at normal temperature 1C rate than the battery using the electrolyte of comparative example 1, indicating that the fluorine boron compound additive can effectively improve the rate performance of the sodium ion battery.
Comparative example 2
Comparative example 2 the battery performance was tested using a conventional ether electrolyte.
1. Electrolyte additive preparation: at room temperature, in a glove box, the solvent was taken up as Propylene Carbonate (PC): 1, 3-Dioxolane (DOL): ethylene glycol dimethyl ether (DME) =1:2:2 (volume ratio), 100mL of the mixture was mixed, and 16.8g of sodium hexafluorophosphate (NaPF) was added thereto 6 ) Preparing a solution, and uniformly stirring to obtain the electrolyte of the comparative example.
2. Characterization of battery performance: and (2) assembling a sodium ion battery by adopting a ternary material for the positive electrode and adopting metal sodium for the negative electrode and using the conventional ether electrolyte prepared in the step (1), testing the assembled battery on a Wuhan blue electric testing system (LANHE), and performing cycle and multiplying power testing on the battery at a multiplying power of 0.2-3C, wherein the testing temperature is 25 ℃, and the result is shown in figure 2. The electrochemical impedance spectrum of the battery using the conventional ether electrolyte was tested, and the test results are shown in fig. 3. As can be seen from the comparison of fig. 2, fig. 2 shows that the battery using the 0.01mol/L fluoroboric compound additive of example 2 of the present invention has a higher specific capacity at normal temperature of 0.2C-3C than the battery using the conventional ether electrolyte of comparative example 2, indicating that the fluoroboric compound additive can effectively improve the reaction kinetics and rate performance of the sodium ion battery. As can be seen from comparison of electrochemical impedance spectra of fig. 3, the battery added with 0.01mol/L of the fluoroboric compound additive has lower charge transfer impedance than the battery using the conventional ether electrolyte in comparative example 2, which suggests that the fluoroboric compound additive can accelerate ion diffusion kinetics and electrochemical reaction kinetics, thereby improving charge-discharge kinetics of the electrode and enhancing rate capability of the sodium battery.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the invention, and is not meant to limit the scope of the invention, but to limit the invention to the particular embodiments, and any modifications, equivalents, improvements, etc. that fall within the spirit and principles of the invention are intended to be included within the scope of the invention.

Claims (10)

1. A multifunctional sodium battery electrolyte additive, characterized in that the multifunctional sodium battery electrolyte additive comprises: a compound or mixture containing both fluorine and boron; the fluorine element exists in the form of fluorine-containing groups;
the boron element in the additive is coordinated with the oxygen element in trace water of the electrolyte, trace water is removed, the chemical stability and electrochemical stability of the electrolyte are improved, and the interface impedance of the sodium battery is reduced; and the boron element is coordinated with anions of sodium salt in the sodium battery electrolyte, so that the solubility and dissociation degree of the sodium salt are improved, and the ionic conductivity of the electrolyte is improved;
the fluorine-containing group in the additive is used for regulating and controlling the components of an electrode-electrolyte interface, reducing interface impedance, improving the wettability of the electrolyte to an electrode, passivating the aluminum foil of a current collector of a sodium battery and inhibiting the corrosion of sodium salt to the aluminum foil.
2. The multifunctional sodium battery electrolyte additive of claim 1, wherein the total concentration of the additive in the electrolyte is in the range of 0.0001mol/L to 1mol/L.
3. The multifunctional sodium battery electrolyte additive according to claim 1, wherein the compound or mixture containing both fluorine element and boron element specifically comprises: fluoroborates and complexes thereof, fluoroboric acid, inorganic fluoroborates, organofluoroborates, polyfluoroarene borides, fluoroorganoboranes, fluoroboric acid nitro or other organofluoroboric compounds;
the state of the multifunctional sodium battery electrolyte additive comprises a gaseous state, a liquid state or a solid state.
4. The multi-functional sodium battery electrolyte additive of claim 3, wherein,
the chemical formula of the fluoroborate is B a F b Or BF c X d The method comprises the steps of carrying out a first treatment on the surface of the Wherein a is more than or equal to 0.5 and less than or equal to 2,1.5 and b is more than or equal to 3; c is more than or equal to 0.5 and less than or equal to 3,0.5, d is more than or equal to 3, and X is halogen element; the substances forming the complex with the fluoroborate compound include: one or more of water, ammonia, argon, alcohol, carboxylic acid, amine, nitrile, ester, aldehyde, ketone, ether, phenol, sulfone;
the chemical formula of the fluoroboric acid is HBF 4 ；
The chemical formula of the inorganic fluoborate is M n (BF 4 ) m The method comprises the steps of carrying out a first treatment on the surface of the Wherein M comprises one or more of aluminum, copper, lead, tin, nickel, zinc, cadmium, beryllium, magnesium, calcium, strontium, barium, cesium, rubidium, manganese, iron, cobalt, silver, indium and thallium; n is more than or equal to 0.2 and less than or equal to 5,0.2, m is more than or equal to 8; the inorganic fluoroborate is dissociable;
the chemical formula of the organofluorine boron compound comprises: R-BF 3 M、F-R-BH x 、R-BF 3 、BF 4 NO、BF 4 NO 2 One of the following; wherein R is an organic group comprising: any of hydrocarbyl, alcohol, ether, ester, ketone, carboxylic acid, phenolic, or other organic groups; x is more than or equal to 0.5 and less than or equal to 3; the organofluoroborate is dissociable.
5. A multifunctional sodium battery electrolyte additive according to claim 3, characterized in that the fluoro boride complex specifically comprises: one or more of boron trifluoride dihydrate, boron trifluoride methanol, boron trifluoride ethanol, boron trifluoride acetic acid, boron trifluoride propionic acid, boron trifluoride phosphoric acid, boron trifluoride dimethyl carbonate, boron trifluoride ethyl acetate, boron trifluoride butyl acetate, boron trifluoride ethyl chloroacetate, boron trifluoride acetonitrile, boron trifluoride tetrahydrofuran, boron trifluoride methyl ether, boron trifluoride ethyl ether, boron trifluoride butyl ether, boron trifluoride sulfolane, boron trifluoride monoethyl amine, boron trifluoride ethylamine, boron trifluoride benzylamine, boron trifluoride phenol, phenol formaldehyde resin boron trifluoride phenol, boron trifluoride dimethyl ether;
The inorganic fluoroborate comprises: one or more of rubidium tetrafluoroborate, cesium tetrafluoroborate, ammonium tetrafluoroborate, copper tetrafluoroborate, tin tetrafluoroborate, zinc tetrafluoroborate, nickel tetrafluoroborate, iron tetrafluoroborate, cobalt tetrafluoroborate, manganese tetrafluoroborate, silver tetrafluoroborate, cadmium tetrafluoroborate, aluminum tetrafluoroborate, magnesium tetrafluoroborate, calcium tetrafluoroborate, strontium tetrafluoroborate, and barium tetrafluoroborate;
the organofluoroborate comprises: cesium organic trifluoroborate, rubidium organic trifluoroborate, potassium organic trifluoroborate, sodium organic trifluoroborate, lithium organic trifluoroborate, ammonium organic trifluoroborate, copper organic trifluoroborate, tin organic trifluoroborate, zinc organic trifluoroborate, nickel organic trifluoroborate, iron organic trifluoroborate, cobalt organic trifluoroborate, manganese organic trifluoroborate, silver organic trifluoroborate, cadmium organic trifluoroborate, aluminum organic trifluoroborate, magnesium organic trifluoroborate, calcium organic trifluoroborate, strontium organic trifluoroborate, and barium organic trifluoroborate.
6. A sodium battery electrolyte, characterized in that the sodium battery electrolyte comprises: a solvent, a sodium salt and the multifunctional sodium battery electrolyte additive of any one of claims 1-5;
The solvent comprises: ethylene Carbonate (EC), propylene Carbonate (PC), butylene Carbonate (BC), ethylene carbonate (VC), ethylene Sulfite (ES), dimethyl sulfite (DMS), diethyl sulfite (DES), dibutyl carbonate (DBC), dibutyl carbonate (GBL), methyl butyl carbonate (BMC), dipropyl carbonate (DPC), methyl ester (PA), propylene Sulfite (PS), gamma-butyrolactone (gamma BL), gamma-valerolactone (gamma VL), ethylene carbonate (VEC), dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC) fluoroethylene carbonate (FEC), dimethyl pyrocarbonate (DMPC), dioxolane (DOL), ethylene glycol dimethyl ether (DME), dimethoxymethane (DMM), ethylene glycol diethyl ether (DEE), tetraethylene glycol dimethyl ether (TEGDME), methyl Propyl Carbonate (MPC), methyl isopropyl carbonate (MiPC), methyl Formate (MF), ethyl Formate (EF), methyl Acetate (MA), ethyl Acetate (EA), methyl Propionate (MP), ethyl Propionate (EP), ethyl Butyrate (EB), fluorobenzene (FB), tetrahydrofuran (THF), 2-methyltetrahydrofuran (2 Me-THF), tetrahydropyran (THP), methyl ethyl acetate (MA), ethyl Acetate (EA) and Ethyl Propionate (EP), ethyl Butyrate (EB), fluorobenzene (FB), tetrahydrofuran (THF), methyl-ethyl-methyl-carbonate (TMP), one or more of diethylene glycol dimethyl ether/Diglyme (DG), acetonitrile (AN), dimethyl sulfoxide (DMSO), N-Dimethylformamide (DMF), sulfolane (SL), dimethyl sulfone (MSM), methyl ethyl sulfone (EMS), 3-trifluoropropyl methyl sulfone (FPMS), 1, 3-dioxolane (1, 3-DL), 4-methyl-1, 3-dioxolane (4-Me-1, 3-DL), 2-methyl-1, 3-dioxolane (2 Me-1, 3-DL) or acetone;
The sodium salt comprises: sodium fluoride (NaF), sodium carbonate (Na) 2 CO 3 ) Sodium nitrate (NaNO) 3 ) Sodium perchlorate (NaClO) 4 ) Sodium sulfide (Na) 2 S), sodium sulfite (Na) 2 SO 3 ) Sodium sulfate (Na) 2 SO 4 ) Sodium hexafluorophosphate (NaPF) 6 ) Sodium tetrafluoroborate (NaBF) 4 ) Sodium hexafluoroarsenate (NaAsF) 6 ) Sodium hexafluorotantalate (NaTaF) 6 ) Sodium hexafluorostannate (NaSnF) 6 ) Sodium hexafluorogermanate (NaGeF) 6 ) Sodium tetrahaloaluminate NaAlX 4 Sodium tri-titanate (Na) 2 Ti 3 O 7 ) Sodium bismuth (NaBiO) 3 ) Sodium ureate (Na) 2 C 5 H 2 N 4 O 3 ) Sodium uranyl acetate (NaZn (UO) 2 ) 3 ·(CH 3 COO) 9 ·9H 2 O), sodium hexahydroxy antimonic (V) acid (Na [ S ]b(OH) 6 ]) Sodium uranyl arsenate (NaUO) 2 AsO 4 ) Sodium ammonium hexanitro cobalt (III) acid (Na (NH 4) 2 [Co(NO 2 ) 6 ]) Sodium bis (trimethylsilyl) amide (LiHMDS), sodium bis (trifluoromethylsulfonyl) imide (NaTFSI), sodium bis (fluorosulfonyl) imide (NaFSI), sodium trifluoromethylsulfonate (NaCF) 3 SO 3 ) Sodium tris (trifluoromethylsulfonyl) methyl (NaC (SO) 2 CF 3 ) 3 ) Sodium bis (perfluoroethylsulfonyl) imide (NaBETI), sodium thioglycolate (NaSCN), sodium bisoxalato borate (NaBOB), sodium difluorooxalato borate (NaDFOB), disodium ethylenediamine tetraacetate (C) 10 H 14 N 2 Na 2 O 8 ) Trisodium citrate (C) 6 H 5 Na 3 O 7 ) Mono sodium 4-chlorophthalic acid (C) 8 H 4 ClNaO 4 ) Sodium bis (catechol) borate (NaBBB).
7. A sodium battery comprising the sodium battery electrolyte of claim 6.
8. A solid state electrolyte comprising the multi-functional sodium battery electrolyte additive of any one of claims 1-5.
9. A solid-liquid mixed electrolyte, characterized in that the solid-liquid mixed electrolyte comprises the multifunctional sodium battery electrolyte additive according to any one of the preceding claims 1-5.
10. A solid state sodium battery comprising the solid state electrolyte of claim 8 or comprising the mixed solid-liquid electrolyte of claim 9.
CN202111222620.6A 2021-10-20 2021-10-20 Multifunctional sodium battery electrolyte additive and application thereof Pending CN115995598A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116706252A (en) * 2023-07-28 2023-09-05 宁德时代新能源科技股份有限公司 Battery monomer, battery, electricity utilization device and preparation method

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116706252A (en) * 2023-07-28 2023-09-05 宁德时代新能源科技股份有限公司 Battery monomer, battery, electricity utilization device and preparation method
CN116706252B (en) * 2023-07-28 2023-12-26 宁德时代新能源科技股份有限公司 Secondary battery, electricity utilization device and preparation method

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