CN116014249A - Electrolyte, sodium ion battery and electricity utilization device - Google Patents
Electrolyte, sodium ion battery and electricity utilization device Download PDFInfo
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- CN116014249A CN116014249A CN202310289538.8A CN202310289538A CN116014249A CN 116014249 A CN116014249 A CN 116014249A CN 202310289538 A CN202310289538 A CN 202310289538A CN 116014249 A CN116014249 A CN 116014249A
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Abstract
The application provides an electrolyte, a sodium ion battery and an electric device. The electrolyte comprises an S-containing anion and a B-containing anion, the S-containing anion comprising N (FSO) 2 ) 2 ‑ And N (CF) 3 SO 2 ) 2 ‑ At least one of which contains B anions comprising B (F 2 C 2 O 4 ) ‑ And BF 4 ‑ At least one of the elements is an electrolyte, and the molar ratio of the S element to the B element is (2-20): 1. When the electrolyte is applied to a sodium ion battery, a solid electrolyte interface film (SEI film) containing S element and B element is formed on the surface of the negative electrode of the battery, and the SEI film can achieve high-efficiency sodium ion transmission rate and high toughness, and is beneficial to improving the storage capacity retention rate of the sodium ion battery.
Description
Technical Field
The application relates to the technical field of secondary batteries, in particular to an electrolyte, a sodium ion battery and an electric device.
Background
The statements herein merely provide background information related to the present application and may not necessarily constitute prior art.
Sodium ion batteries operate as a secondary battery mainly by means of movement of sodium ions between a positive electrode and a negative electrode. In the field of secondary batteries, sodium ion batteries have a better cost advantage, which is advantageous in widening the range of use of sodium ion batteries, however, the storage capacity retention rate of sodium ion batteries is to be further improved.
Disclosure of Invention
The application provides an electrolyte. The electrolyte includes an S-containing anion and a B-containing anion, the S-containing anion including N (FSO 2 ) 2 - And N (CF) 3 SO 2 ) 2 - At least one of the B-containing anions comprising B (F 2 C 2 O 4 ) - And BF 4 - At least one of the elements S and B in the electrolyte is (2-20): 1.
The electrolyte comprises corresponding S-containing anions, B-containing anions and corresponding mole ratios of S element and B element, when the electrolyte is applied to a sodium ion battery, a solid electrolyte interface film (SEI film) containing the S element and the B element is formed on the surface of the negative electrode of the battery, and the SEI film can give consideration to higher efficient sodium ion transmission rate and better toughness, thereby being beneficial to improving the storage capacity retention rate of the sodium ion battery.
In some embodiments, the molar concentration of the S element in the electrolyte is 1mol/L to 4mol/L.
In some embodiments, the molar concentration of the B element in the electrolyte is 0.1mol/L to 1mol/L.
In some embodiments, the electrolyte further contains at least one of an element F and an element N.
In some embodiments, the electrolyte contains F element and N element, wherein the molar ratio of F element to N element is (2.2-10): 1.
In some embodiments, the molar concentration of the F element in the electrolyte is 1.4mol/L to 6.8mol/L.
In some embodiments, the molar concentration of the N element in the electrolyte is 0.5mol/L to 2mol/L.
In some of these embodiments, the electrolyte includes an S-containing sodium salt and a B-containing sodium salt.
In some embodiments, the S-containing sodium salt comprises at least one of sodium bis (trifluoromethylsulfonyl) imide and sodium bis (trifluoromethylsulfonyl) imide.
In some embodiments, the B-containing sodium salt comprises at least one of sodium difluorooxalato borate and sodium tetrafluoroborate.
In some of these embodiments, the electrolyte further comprises an additive comprising an alkyl sodium salt.
In some embodiments, the alkyl sodium salt comprises at least one of sodium dodecyl sulfate and sodium polydithio-dipropyl sulfonate.
In some embodiments, the molar concentration of the additive is 0.001mol/L to 0.015mol/L.
In some embodiments, the solvent in the electrolyte comprises at least one of ethylene carbonate, propylene carbonate, ethylene carbonate, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, ethyl acetate, ethyl propionate, methyl propionate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, polyethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, tetrahydrofuran, and methyltetrahydrofuran.
The application also provides a sodium ion battery comprising the electrolyte.
The application also provides an electric device comprising the sodium ion battery.
Drawings
Fig. 1 is a schematic view of a secondary battery according to an embodiment of the present application.
Fig. 2 is an exploded view of the secondary battery according to an embodiment of the present application shown in fig. 1.
Fig. 3 is a schematic view of an electric device in which the secondary battery according to an embodiment of the present application is used as a power source.
Reference numerals illustrate:
1. a secondary battery; 11. a housing; 12. an electrode assembly; 13. a top cover assembly; 2. and (5) an electric device.
Detailed Description
Hereinafter, embodiments of a battery pack, a battery cell, a secondary battery, and an electric device of the present application are specifically disclosed with reference to the accompanying drawings as appropriate. However, unnecessary detailed description may be omitted. For example, detailed descriptions of well-known matters and repeated descriptions of the actual same structure may be omitted. This is to avoid that the following description becomes unnecessarily lengthy, facilitating the understanding of those skilled in the art. Furthermore, the drawings and the following description are provided for a full understanding of the present application by those skilled in the art, and are not intended to limit the subject matter recited in the claims.
The "range" disclosed herein is defined in terms of lower and upper limits, with a given range being defined by the selection of a lower and an upper limit, the selected lower and upper limits defining the boundaries of the particular range. Ranges that are defined in this way can be inclusive or exclusive of the endpoints, and any combination can be made, i.e., any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a particular parameter, it is understood that ranges of 60-110 and 80-120 are also contemplated. Furthermore, if the minimum range values 1 and 2 are listed, and if the maximum range values 3,4 and 5 are listed, the following ranges are all contemplated: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5. In this application, unless otherwise indicated, the numerical range "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, the numerical range "0-5" indicates that all real numbers between "0-5" have been listed throughout, and "0-5" is a shorthand representation of only a combination of these values. When a certain parameter is expressed as an integer of 2 or more, it is disclosed that the parameter is, for example, an integer of 2, 3,4, 5, 6, 7, 8, 9, 10, 11, 12 or the like.
All embodiments and alternative embodiments of the present application may be combined with each other to form new solutions, unless specifically stated otherwise.
All technical features and optional technical features of the present application may be combined with each other to form new technical solutions, unless specified otherwise.
All steps of the present application may be performed sequentially or randomly, preferably sequentially, unless otherwise indicated. For example, the method comprises steps (a) and (b), meaning that the method may comprise steps (a) and (b) performed sequentially, or may comprise steps (b) and (a) performed sequentially. For example, the method may further include step (c), which means that step (c) may be added to the method in any order, for example, the method may include steps (a), (b) and (c), may include steps (a), (c) and (b), may include steps (c), (a) and (b), and the like.
Reference herein to "comprising" and "including" means open ended, as well as closed ended, unless otherwise noted. For example, the terms "comprising" and "comprises" may mean that other components not listed may be included or included, or that only listed components may be included or included.
The term "or" is inclusive in this application, unless otherwise specified. For example, the phrase "a or B" means "a, B, or both a and B. More specifically, either of the following conditions satisfies the condition "a or B": a is true or present, and B is false or absent; a is false or absent and B is true or present; or both A and B are true, or both A and B are present.
Unless otherwise indicated, the terms "positive electrode sheet" and "positive electrode sheet" are used interchangeably in this application. The terms "negative electrode sheet" and "negative electrode sheet" have the same meaning and are used interchangeably. The terms "separator membrane" and "separator membrane" have the same meaning and are used interchangeably.
An embodiment of the present application provides an electrolyte. The electrolyte comprises an S-containing anion and a B-containing anion, the S-containing anion comprising N (FSO 2 ) 2 - And N (CF) 3 SO 2 ) 2 - At least one of which contains B anions comprising B (F 2 C 2 O 4 ) - And BF 4 - At least one of the elements is an electrolyte, and the molar ratio of the S element to the B element is (2-20): 1. The electrolyte comprises corresponding S-containing anions and B-containing anions, and corresponding mole ratios of S element and B element, and when the electrolyte is applied to a sodium ion battery, the electrolyte is shaped on the surface of the negative electrode of the batteryThe solid electrolyte interface film (SEI film) containing S element and B element is formed, and the SEI film can give consideration to high-efficiency sodium ion transmission rate and high toughness, and is beneficial to improving the storage capacity retention rate of a sodium ion battery. When the molar ratio of the S element to the B element is excessively large, the toughness of the SEI film may be poor, and cracking damage may easily occur during cycling, resulting in deterioration of electrical properties. When the molar ratio of the S element to the B element is too small, it may cause deterioration in the transmission rate of sodium ions in the SEI film, resulting in an increase in impedance, an increase in polarization, and thus a decrease in electrical properties.
It is understood that the S element and the B element in the electrolyte may be provided by an S anion and a B anion. Further alternatively, the S anion is a source of the S element and the B anion is a source of the B element. It will also be appreciated that other S-and/or B-containing species may be present in the electrolyte, which species may also provide a certain amount of S-and B-elements.
As some optional examples of the molar ratio of the S element and the B element, the molar ratio of the S element and the B element may be, but is not limited to, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, 12:1, 13:1, 14:1, 15:1, 16:1, 17:1, 18:1, 19:1, 20:1, and the like. It is understood that the molar ratio of the S element to the B element may be selected within the range of (2-20): 1. Further, the molar ratio of the S element and the B element may be selected from the molar ratios of the S element and the B element described in examples below in the present application.
As an example of the molar concentration of the S element in the electrolyte, the molar concentration of the S element in the electrolyte is 1mol/L to 4mol/L. Alternatively, in the electrolyte, the molar concentration of the S element is 1mol/L, 1.2mol/L, 1.5mol/L, 1.8mol/L, 2mol/L, 2.2mol/L, 2.5mol/L, 2.8mol/L, 3mol/L, 3.2mol/L, 3.5mol/L, 3.8mol/L, 4mol/L, or the like.
As an example of the molar concentration of the B element in the electrolyte, the molar concentration of the B element in the electrolyte is 0.1mol/L to 1mol/L. Alternatively, in the electrolyte, the molar concentration of the B element is 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L, 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L, 1mol/L, or the like.
It is understood that the molar concentration of the S element in the electrolyte may be selected within the range of 1mol/L to 4mol/L. In the electrolyte, the molar concentration of the B element can be selected from the range of 0.1mol/L to 1mol/L. Further, in the electrolyte, the molar concentration of the S element may be selected from the molar concentrations of the S element described in examples below in the present application. In the electrolyte, the molar concentration of the B element may also be selected from the molar concentrations of the B element described in examples below in the present application.
It is understood that the species and molar concentrations of the elements herein may be measured with reference to inductively coupled plasma atomic emission spectroscopy (EPA 6010D-2018), inductively coupled plasma atomic emission spectroscopy general (JY/T0567-2020), or lithium hexafluorophosphate product analysis method (GBT 19282-2014). For example, after the sample is pretreated, the inductively coupled plasma atomic emission spectrometer is used for testing the types and the molar concentrations of the elements, and optionally, the testing method comprises the following steps: (1) Accurately measuring 5mL of fresh electrolyte sample in the digestion tank, and recording the weight of the sample after the balance is digitally stabilized; (2) Slowly add 10mL of concentrated HNO 3 The sample on the inner wall is flushed into the bottom of the digestion tank and slightly shakes the digestion tank; (3) putting the digestion tank into an acid expelling instrument to be digested for about 30min at 180 ℃; (4) When the solution is steamed to 1-2 mL, taking down the digestion tank, cooling to room temperature, flushing the tank with ultrapure water for 3 times, pouring the flushing liquid into a 50mL plastic volumetric flask for constant volume and shaking uniformly; (5) And testing the solution with the constant volume by adopting an inductively coupled plasma atomic emission spectrometer.
It is understood that reference is made in this application to standards JY/T020-1996 and GB/T36240-2018 for the type and molar concentration of ions, and the quantitative analysis of the ionic components in the electrolyte is carried out by means of ion chromatography.
Further, the electrolyte also contains at least one of F element and N element. Optionally, the mol ratio of F element to N element is (2.2-10): 1. For example, the molar ratio of F element to N element may be, but is not limited to, 2.2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, 5.5:1, 6:1, 6.5:1, 7:1, 7.5:1, 8:1, 8.5:1, 9:1, 9.5:1, 10:1, etc. It is understood that the molar ratio of F element to N element may be selected within the range of (2.2-10): 1. Optionally, the mol ratio of F element to N element is (2.2-6.8): 1. Further, the molar ratio of the F element and the N element may be selected among the molar ratios of the F element and the N element described in the examples below in the present application.
Specifically, in the electrolyte, the molar concentration of the F element is 1.4mol/L to 6.8mol/L. Alternatively, in the electrolyte, the molar concentration of the F element is 1.4mol/L, 1.5mol/L, 1.8mol/L, 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, 6.8mol/L, or the like. Of course, the molar concentration of the F element in the electrolyte may be selected from the molar concentrations of the F element described in examples below in the present application.
Optionally, the molar concentration of the N element is 0.5 mol/L-2 mol/L. Alternatively, in the electrolyte, the molar concentration of the N element is 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L, 1mol/L, 1.1mol/L, 1.2mol/L, 1.3mol/L, 1.4mol/L, 1.5mol/L, 1.6mol/L, 1.7mol/L, 1.8mol/L, 1.9mol/L, 2mol/L, or the like. It is understood that the molar concentration of the N element in the electrolyte may be selected from the range of 0.5mol/L to 2mol/L. Of course, the molar concentration of the N element in the electrolyte may be selected from the molar concentrations of the N element described in examples below in the present application.
In some embodiments, the electrolyte includes an S-containing sodium salt and a B-containing sodium salt. Alternatively, the S-containing sodium salt includes sodium bis-fluorosulfonyl imide (N (FSO) 2 ) 2 Na) and sodium bis (trifluoromethylsulfonyl) imide (N (CF) 3 SO 2 ) 2 At least one of Na) and the sodium salt B-containing salt comprises sodium difluorooxalato borate (B (F) 2 C 2 O 4 ) Na) and sodium tetrafluoroborate (BF 4 Na).
Optionally, in the electrolyte, the molar ratio of the S-containing sodium salt to the B-containing sodium salt is (1-10): 1. Further alternatively, in the electrolyte, the molar ratio of the S-containing sodium salt to the B-containing sodium salt is 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, 5.5:1, 6:1, 6.5:1, 7:1, 7.5:1, 8:1, 8.5:1, 9:1, 9.5:1, 10:1, etc. It is understood that the molar ratio of the sodium salt containing S to the sodium salt containing B in the electrolyte may be selected within the range of (1 to 10): 1. Of course, the molar ratio of the S-containing sodium salt to the B-containing sodium salt may be selected among the molar ratios of the S-containing sodium salt to the B-containing sodium salt described in the examples below in the present application.
Optionally, in the electrolyte, the molar concentration of the S-containing sodium salt is 0.5 mol/L-2 mol/L. Alternatively, the molar concentration of the S-containing sodium salt is 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L, 1mol/L, 1.1mol/L, 1.2mol/L, 1.3mol/L, 1.4mol/L, 1.5mol/L, 1.6mol/L, 1.7mol/L, 1.8mol/L, 1.9mol/L, 2mol/L, etc.
Optionally, in the electrolyte, the molar concentration of the sodium salt containing B is 0.1mol/L to 1mol/L. Alternatively, in the electrolyte, the molar concentration of the B-containing sodium salt is 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L, 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L, 1mol/L, or the like.
In some embodiments, the electrolyte further comprises an additive comprising an alkyl sodium salt. The alkyl sodium salt additive can promote the electrolyte to infiltrate the surface of the negative electrode, thereby reducing the content of the battery and further improving the storage capacity retention rate of the battery. Optionally, the alkyl sodium salt comprises at least one of sodium dodecyl sulfate and sodium polydithio-dipropyl sulfonate. Further alternatively, the molar concentration of the additive is 0.001mol/L to 0.015mol/L. For example, the molar concentration of the additive may be, but is not limited to, 0.001mol/L, 0.0015mol/L, 0.0018 mol/L, 0.002 mol/L, 0.0025mol/L, 0.003mol/L, 0.0035mol/L, 0.004 mol/L, 0.0045 mol/L, 0.005 mol/L, 0.0055 mol/L, 0.006 mol/L, 0.0065 mol/L, 0.007 mol/L, 0.0075mol/L, 0.008mol/L, 0.0085mol/L, 0.009 mol/L, 0.0095 mol/L, 0.01 mol/L, 0.012 mol/L, 0.015mol/L, etc. It is understood that the molar concentration of the additive may be selected within the range of 0.0015mol/L to 0.015mol/L. Of course, the molar concentration of the additive may be selected from the molar concentrations of the additives described in the examples below in the present application.
In some embodiments, the electrolyte further includes a solvent including at least one of ethylene carbonate, propylene carbonate, ethylene carbonate, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, ethyl acetate, ethyl propionate, methyl propionate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, polyethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, tetrahydrofuran, and methyltetrahydrofuran. Alternatively, the solvent includes propylene carbonate and dimethyl carbonate. Further alternatively, the volume ratio of propylene carbonate to dimethyl carbonate is (0.5-1.5): 1. For example, the volume ratio of propylene carbonate to dimethyl carbonate may be, but is not limited to, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1. Optionally, the molecular weight of the polyethylene glycol dimethyl ether is 250-320.
Yet another embodiment of the present application provides a sodium ion battery. The sodium ion battery comprises the electrolyte.
Yet another embodiment of the present application provides an electrical device. The power utilization device comprises the sodium ion battery.
The secondary battery will be described below with reference to the related drawings.
In general, a secondary battery includes a positive electrode tab, a negative electrode tab, an electrolyte, and a separator. During the charge and discharge of the battery, active ions are inserted and extracted back and forth between the positive electrode plate and the negative electrode plate. The electrolyte plays a role in ion conduction between the positive electrode plate and the negative electrode plate. The isolating film is arranged between the positive pole piece and the negative pole piece, and mainly plays a role in preventing the positive pole piece and the negative pole piece from being short-circuited, and meanwhile ions can pass through the isolating film.
[ Positive electrode sheet ]
The positive pole piece comprises a positive current collector and a positive film layer arranged on at least one surface of the positive current collector, wherein the positive film layer comprises a positive active material.
As an example, the positive electrode current collector has two surfaces opposing in its own thickness direction, and the positive electrode film layer is provided on either one or both of the two surfaces opposing the positive electrode current collector.
In some embodiments, the positive current collector may employ a metal foil or a composite current collector. For example, as the metal foil, aluminum foil may be used. The composite current collector may include a polymeric material base layer and a metal layer formed on at least one surface of the polymeric material base layer. The composite current collector may be formed by forming a metal material on a polymeric material substrate. Alternatively, the metallic material may include, but is not limited to, one or more of aluminum, aluminum alloys, nickel alloys, titanium alloys, silver, and silver alloys. Alternatively, the polymer material substrate may include, but is not limited to, one or more of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), and Polyethylene (PE).
In some embodiments, when the secondary battery is a lithium ion battery, the positive electrode active material may be a positive electrode active material for a lithium ion battery, which is well known in the art. As an example, the positive electrode active material may include at least one of the following materials: olivine structured lithium-containing phosphates, lithium transition metal oxides and their respective modified compounds. However, the present application is not limited to these materials, and other conventional materials that can be used as a battery positive electrode active material may be used. These positive electrode active materials may be used alone or in combination of two or more. Examples of the lithium transition metal oxide may include, but are not limited to, at least one of lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium nickel cobalt oxide, lithium manganese cobalt oxide, lithium nickel manganese oxide, lithium nickel cobalt aluminum oxide, modified compounds thereof, and the like. Alternatively, the lithium cobalt oxide comprises LiCoO 2 . The lithium nickel oxide includes LiNiO 2 . The lithium manganese oxide comprises LiMnO 2 And LiMn 2 O 4 At least one of them. The lithium nickel cobalt manganese oxide comprises LiNi 1/3 Co 1/3 Mn 1/3 O 2 （NCM 333 ）、LiNi 0.5 Co 0.2 Mn 0.3 O 2 （NCM 523 ）、LiNi 0.5 Co 0.25 Mn 0.25 O 2 （NCM 211 ）、LiNi 0.6 Co 0.2 Mn 0.2 O 2 （NCM 622 ) LiNi 0.8 Co 0.1 Mn 0.1 O 2 （NCM 811 ) At least one of them. The lithium nickel cobalt aluminum oxide includes LiNi 0.85 Co 0.15 Al 0.05 O 2 . Examples of the olivine structured lithium-containing phosphate may include, but are not limited to, at least one of lithium iron phosphate, a composite of lithium iron phosphate and carbon, lithium manganese phosphate, a composite of lithium manganese phosphate and carbon. Optionally, the lithium iron phosphate comprises LiFePO 4 (LFP). The lithium manganese phosphate comprises LiMnPO 4 。
In some embodiments, when the secondary battery is a sodium-ion battery, the positive electrode active material may employ a positive electrode active material for a sodium-ion battery, which is well known in the art. As an example, the positive electrode active material may be used alone, or two or more kinds may be combined. The positive electrode active material may be selected from sodium-iron composite oxide, sodium-cobalt composite oxide, sodium-chromium composite oxide, sodium-manganese composite oxide, sodium-nickel-titanium composite oxide, sodium-nickel-manganese composite oxide, sodium-iron-manganese composite oxide, sodium-nickel-cobalt-manganese composite oxide, sodium-iron-phosphate compound, sodium-manganese-phosphate compound, sodium-cobalt-phosphate compound, sodium-nickel-iron-manganese composite oxide, prussian blue material, polyanion material, etc., but the present application is not limited to these materials, and other conventionally known materials that can be used as positive electrode active materials of sodium-ion batteries may be used. Alternatively, the sodium iron composite oxide includes NaFeO 2 . The sodium cobalt composite oxide comprises NaCoO 2 . The sodium-chromium composite oxide comprises NaCrO 2 . The sodium-manganese composite oxide comprises NaMnO 2 . The sodium-nickel composite oxide comprises NaNiO 2 . The sodium nickel titanium composite oxide comprises NaNi 1/2 Ti 1/ 2 O 2 . The sodium nickel manganese composite oxide comprises NaNi 1/2 Mn 1/2 O 2 . The Na-Fe-Mn composite oxide comprises Na 2/3 Fe 1/3 Mn 2/3 O 2 . The sodium nickel cobalt manganese composite oxide comprises NaNi 1/3 Co 1/3 Mn 1/3 O 2 . The sodium iron phosphate compound comprises NaFePO 4 . The sodium manganese phosphate compound comprises NaMnPO 4 . Sodium cobalt phosphate compounds include NaCoPO 4 . The polyanionic material includes at least one of phosphate, fluorophosphate, pyrophosphate, and sulfate.
In some embodiments, the positive electrode film layer further optionally includes a binder. As an example, the binder may include at least one of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), a vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, a vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, a tetrafluoroethylene-hexafluoropropylene copolymer, and a fluoroacrylate resin.
In some embodiments, the positive electrode film layer further optionally includes a conductive agent. As an example, the conductive agent may include at least one of superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
In some embodiments, the positive electrode sheet may be prepared by: dispersing the above components for preparing the positive electrode sheet, such as the positive electrode active material, the conductive agent, the binder and any other components, in a solvent to form a positive electrode slurry; and (3) coating the positive electrode slurry on a positive electrode current collector, and obtaining a positive electrode plate after the procedures of drying, cold pressing and the like. Alternatively, the solvent comprises N-methylpyrrolidone.
[ negative electrode sheet ]
The negative electrode plate comprises a negative electrode current collector and a negative electrode film layer arranged on at least one surface of the negative electrode current collector, wherein the negative electrode film layer comprises a negative electrode active material.
As an example, the anode current collector has two surfaces opposing in its own thickness direction, and the anode film layer is provided on either one or both of the two surfaces opposing the anode current collector.
In some embodiments, the negative electrode current collector may employ a metal foil or a composite current collector. For example, as the metal foil, copper foil may be used. The composite current collector may include a polymeric material base layer and a metal layer formed on at least one surface of the polymeric material base material. The composite current collector may be formed by forming a metal material on a polymeric material substrate. Optionally, the metallic material comprises at least one of copper, copper alloy, nickel alloy, titanium alloy, silver, and silver alloy. The polymer material comprises at least one of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS) and Polyethylene (PE).
In some embodiments, the anode active material may employ an anode active material for a battery, which is well known in the art. As an example, the anode active material may include at least one of the following materials: artificial graphite, natural graphite, soft carbon, hard carbon, silicon-based materials, tin-based materials, lithium titanate, and the like. The silicon-based material may be at least one selected from elemental silicon, silicon oxygen compounds, silicon carbon composites, silicon nitrogen composites, and silicon alloys. The tin-based material may be at least one selected from elemental tin, tin oxide, and tin alloys. However, the present application is not limited to these materials, and other conventional materials that can be used as a battery anode active material may be used. These negative electrode active materials may be used alone or in combination of two or more.
In some embodiments, the negative electrode film layer further optionally includes a binder. The binder may be at least one selected from styrene-butadiene rubber (SBR), polyacrylic acid (PAA), sodium Polyacrylate (PAAs), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium Alginate (SA), polymethacrylic acid (PMAA), carboxymethyl chitosan (CMCS), polyamideimide (PAI), polyethylenimine (PEI), polyimide (PI), and poly-t-butyl acrylate-triethoxyvinylsilane (TBATEVS).
In some embodiments, the negative electrode film layer further optionally includes a conductive agent. The conductive agent is at least one selected from superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene and carbon nanofibers.
In some embodiments, the negative electrode film layer may also optionally include other adjuvants, such as thickening agents. Optionally, the thickener comprises sodium carboxymethylcellulose (CMC-Na).
In some embodiments, the negative electrode sheet may be prepared by: dispersing the above components for preparing the negative electrode sheet, such as a negative electrode active material, a conductive agent, a binder and any other components, in a solvent to form a negative electrode slurry; and coating the negative electrode slurry on a negative electrode current collector, and obtaining a negative electrode plate after the procedures of drying, cold pressing and the like. Optionally, the solvent comprises deionized water.
[ electrolyte ]
The electrolyte plays a role in ion conduction between the positive electrode plate and the negative electrode plate. The type of electrolyte is not particularly limited in this application, and may be selected according to the need. For example, the electrolyte may be liquid, gel, or all solid.
In some embodiments, the electrolyte is an electrolyte.
In some embodiments, the electrolyte further optionally includes an additive. For example, the additives may include negative electrode film-forming additives, positive electrode film-forming additives, and may also include additives capable of improving certain properties of the battery, such as additives that improve the overcharge performance of the battery, additives that improve the high or low temperature performance of the battery, and the like.
[ isolation Membrane ]
In some embodiments, a separator is further included in the secondary battery. The type of the separator is not particularly limited, and any known porous separator having good chemical stability and mechanical stability may be used.
In some embodiments, the material of the isolating film may be at least one selected from glass fiber, non-woven fabric, polyethylene, polypropylene and polyvinylidene fluoride. The separator may be a single-layer film or a multilayer composite film, and is not particularly limited. When the separator is a multilayer composite film, the materials of the respective layers may be the same or different, and are not particularly limited.
In some embodiments, the positive electrode tab, the negative electrode tab, and the separator may be manufactured into an electrode assembly through a winding process or a lamination process.
In some embodiments, the secondary battery may include an outer package. The outer package may be used to encapsulate the electrode assembly and electrolyte as described above.
In some embodiments, the outer package of the secondary battery may be a hard case, such as a hard plastic case, an aluminum case, a steel case, or the like. The exterior package of the secondary battery may also be a pouch type pouch, for example. The material of the flexible bag may be plastic, and examples of the plastic include polypropylene, polybutylene terephthalate, and polybutylene succinate.
The shape of the secondary battery is not particularly limited in the present application, and may be cylindrical, square, or any other shape. For example, fig. 1 is a secondary battery 1 of a square structure as one example. It is understood that the secondary battery 1 may be a sodium ion battery.
In some embodiments, referring to fig. 2, the overpack may include a housing 11 and a cap assembly 13. The housing 11 may include a bottom plate and a side plate connected to the bottom plate, where the bottom plate and the side plate enclose a receiving chamber. The housing 11 has an opening communicating with the accommodation chamber, and the cap assembly 13 can be cap-provided to the opening to close the accommodation chamber. The positive electrode sheet, the negative electrode sheet, and the separator may be formed into the electrode assembly 12 through a winding process or a lamination process. The electrode assembly 12 is enclosed in the accommodating chamber. The electrolyte is impregnated in the electrode assembly 12. The number of electrode assemblies 12 included in the secondary battery 1 may be one or more, and those skilled in the art may select according to specific practical requirements.
In some embodiments, the secondary batteries may be assembled into a battery module, and the number of secondary batteries included in the battery module may be one or more, and the specific number may be selected by one skilled in the art according to the application and capacity of the battery module.
In addition, the application also provides an electric device, which comprises the secondary battery provided by the application. The secondary battery may be used as a power source of the power consumption device, and may also be used as an energy storage unit of the power consumption device. The power utilization device may include, but is not limited to, mobile devices, electric vehicles, electric trains, ships and satellites, energy storage systems, and the like. For example, mobile devices include cell phones, notebook computers, and the like. Electric vehicles include all-electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, electric golf carts, electric trucks, and the like.
As the electricity consumption device, a secondary battery may be selected according to its use requirement.
Fig. 3 is an electrical device 2 as an example. The electric device is a pure electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle or the like.
As another example, the device may be a cell phone, tablet computer, notebook computer, or the like. The device is generally required to be light and thin, and a secondary battery can be used as a power source.
Examples
Example 1
In this embodiment, the electrolyte includes sodium salt S, sodium salt B and a solvent, wherein the sodium salt S is sodium difluorosulfimide (NaFSI), and the sodium salt B is sodium difluorooxalato borate (NaDFOB). Wherein, in the electrolyte, the molar concentration of the S-containing sodium salt is 0.5mol/L, the molar concentration of the B-containing sodium salt is 0.2mol/L, and the molar ratio of the S element to the B element is 5:1. The solvent is a mixed solvent of Propylene Carbonate (PC) and dimethyl carbonate (DMC) according to the volume ratio of 1:1.
Examples 2 to 11
Examples 2 to 4 are different from example 1 in that one or more of the molar concentration of the S-containing sodium salt, the molar concentration of the B-containing sodium salt, and the molar ratio of the corresponding S element to the B element are different in the electrolyte. As shown in table 1.
Examples 12 to 13
Examples 12 to 13 are different from example 2 in that the solvent in the electrolyte is different.
Example 14
In this embodiment, the electrolyte includes sodium salt S, sodium salt B, an additive and a solvent, wherein the sodium salt S is sodium difluorosulfimide (NaFSI), and the sodium salt B is sodium difluorooxalato borate (NaDFOB). Wherein, in the electrolyte, the molar concentration of the S-containing sodium salt is 0.5mol/L, the molar concentration of the B-containing sodium salt is 0.2mol/L, and the molar ratio of the S element to the B element is 5:1. The solvent is a mixed solvent of propylene carbonate and dimethyl carbonate in a volume ratio of 1:1. The additive is sodium polydithio-dipropyl sulfonate, and the molar concentration of the additive in the electrolyte is 0.003mol/L.
Examples 15 to 33
Examples 15 to 33 are different from example 14 in that one or more of the molar concentration of the S-containing sodium salt, the molar concentration of the B-containing sodium salt, the molar ratio of the S element to the B element, the additive and the molar concentration thereof, and the kind of the solvent are different. As shown in table 1.
Comparative examples 1 to 2
Comparative examples 1 to 2 are different from example 1 in the molar concentration of the sodium salt containing S, the molar concentration of the sodium salt containing B, and the molar ratio of the element S and the element B.
Comparative examples 3 to 4
Comparative examples 3 to 4 are different from example 14 in that the molar concentration of the sodium salt containing S, the molar concentration of the sodium salt containing B, and the molar ratio of the element S and the element B are different.
Comparative example 5
Comparative example 5 differs from example 1 in that the sodium salt containing S was replaced with sodium salt containing B in equimolar concentration in the electrolyte.
Comparative example 6
Comparative example 6 differs from example 1 in that the B-containing sodium salt was replaced with an equimolar concentration of S-containing sodium salt in the electrolyte.
Comparative example 7
Comparative example 7 differs from example 14 in that the sodium salt containing S was replaced with sodium salt containing B in equimolar concentration in the electrolyte.
Comparative example 8
Comparative example 8 differs from example 14 in that the B-containing sodium salt was replaced with an equimolar concentration of S-containing sodium salt in the electrolyte.
Comparative example 9
Comparative example 9 differs from example 1 in that sodium salt containing S and sodium salt containing B are replaced with sodium hexafluorophosphate of equimolar concentration in the electrolyte.
Comparative example 10
Comparative example 10 differs from example 11 in that sodium salt containing S and sodium salt containing B were replaced with sodium hexafluorophosphate of equimolar concentration in the electrolyte.
In Table 1, the unit of molar concentration is mol/L, and represents the molar concentration in the electrolyte.
Test case
(1) And (3) preparing a positive electrode plate.
10wt% of polyvinylidene fluoride binder is fully dissolved in N-methyl pyrrolidone, and 10wt% of carbon black conductive agent and 80wt% of sodium nickel iron manganese oxide positive electrode active material are added to prepare uniformly dispersed slurry. The slurry was uniformly coated on the surface of a 60 μm aluminum foil, and then transferred to a vacuum drying oven to be completely dried. And rolling the obtained pole piece, and punching to obtain the positive pole piece.
(2) And (3) preparing a negative electrode plate.
Dissolving a negative electrode active material hard carbon, a conductive agent acetylene black, a binder SBR and a thickener CMC-Na in a weight ratio of 94:2:2.8:1.2 in deionized water, uniformly stirring to prepare a negative electrode slurry, preparing the slurry after ultrasonic dispersion, coating the slurry on the surface of a copper foil with the thickness of 12 mu m, and then transferring the coated slurry into a vacuum drying oven for complete drying to prepare the negative electrode plate.
(3) And (3) preparing an electrolyte.
At H 2 O<0.1ppm，O 2 <In a glove box with an argon atmosphere of 0.1ppm, the preparation raw materials of the electrolyte in the examples and the comparative examples were mixed and stirred uniformly to prepare the electrolyte.
(4) And a separation film.
A polypropylene film was used as the separator film.
(5) And (3) preparing a sodium ion battery.
And (3) sequentially stacking the positive electrode plate in (1), the isolating film in (4) and the negative electrode plate in (2), so that the isolating film is positioned between the positive electrode plate and the negative electrode plate to play a role of isolation, and assembling the laminated battery by adding the electrolyte in (3).
(6) Storage capacity retention test.
Charging the sodium ion battery prepared in the step (5) to 4V at 25 ℃ with a constant current of 0.2C, then charging to 0.05C with a constant voltage of 4V, and then discharging to 2.5V with a constant current of 0.2C to obtain a discharge capacity (Cd 1) before storage; the cell was then charged again to 4V at a constant current of 0.2C, after which the current was reduced to 0.05C at a constant voltage of 4V. Then the battery was stored in a 60 ℃ incubator for 30 days, after taking out, the battery was charged to 4V at 25 ℃ with a constant current of 0.2C, then charged to 0.05C with a constant voltage of 4V, and then discharged to 2.5V with a constant current of 0.2C, to obtain a discharge capacity (Cd 2) after storage, and the sodium ion battery capacity retention rate was calculated according to the following formula:
storage capacity retention=discharge capacity after storage (Cd 2)/discharge capacity before storage (Cd 1) ×100%. The results are shown in Table 1.
(7) Cyclic capacity retention.
Charging the sodium ion battery prepared in the step (5) to 3.7V at 25 ℃ with a constant current of 0.2C, then charging to 0.05C with a constant voltage of 3.7V, and then discharging to 2.5V with a constant current of 0.2C to obtain a first-cycle discharge capacity (Cd 3); repeatedly charging and discharging until the nth turn, obtaining the discharge capacity of the sodium ion battery after the sodium ion battery circulates for n turns, marking as Cdn, and calculating the capacity retention rate of the sodium ion battery according to the following formula:
cycle capacity retention=discharge capacity after n cycles (Cdn)/first cycle discharge capacity (Cd 3). The cycle capacity retention after 20 cycles is shown in table 1.
In Table 1, naFSI represents sodium difluorosulfimide, naTFSI represents sodium bis (trifluoromethylsulfonyl) imide, naDFOB represents sodium difluorooxalato borate, naBF 4 Represents sodium tetrafluoroborate.
TABLE 1
It will be appreciated that since the additive may also have a certain amount of S element, the content of S element in the electrolyte when the additive is present may be slightly higher than the content of S element in the electrolyte in the absence of the additive.
As can be seen from examples 1 to 33 and comparative examples 5 to 8 in table 1, when the electrolyte contains both the S element and the B element, the corresponding sodium ion battery exhibits better storage capacity retention and circulation capacity retention. As can be seen from examples 1 to 33 and comparative examples 1 to 4, when the electrolyte contains both the S element and the B element at a molar ratio of (2 to 20): 1, the corresponding sodium ion battery exhibits better storage capacity retention and circulation capacity retention. It can be seen from examples 28 to 30 that when the electrolyte contains the additive, the storage capacity retention rate and the circulation capacity retention rate of the corresponding sodium ion battery are better, and when the molar concentration of the additive is 0.001mol/L to 0.015mol/L, the corresponding sodium ion battery exhibits better storage capacity retention rate and circulation capacity retention rate.
The present application is not limited to the above embodiment. The above embodiments are merely examples, and embodiments having substantially the same configuration and the same effects as those of the technical idea within the scope of the present application are included in the technical scope of the present application. Further, various modifications that can be made to the embodiments and other modes of combining some of the constituent elements in the embodiments, which are conceivable to those skilled in the art, are also included in the scope of the present application within the scope not departing from the gist of the present application.
Claims (16)
1. An electrolyte comprising an S-containing anion and a B-containing anion, wherein the S-containing anion comprises N (FSO) 2 ) 2 - And N (CF) 3 SO 2 ) 2 - At least one of the B-containing anions comprising B (F 2 C 2 O 4 ) - And BF 4 - At least one of the elements S and B in the electrolyte is (2-20): 1.
2. The electrolyte according to claim 1, wherein the molar concentration of the S element in the electrolyte is 1mol/L to 4mol/L.
3. The electrolytic solution according to claim 1, wherein the molar concentration of the B element in the electrolytic solution is 0.1mol/L to 1mol/L.
4. The electrolyte of claim 1, further comprising at least one of an element F and an element N.
5. The electrolyte according to claim 4, wherein the electrolyte contains F element and N element, and the molar ratio of F element to N element is (2.2-10): 1.
6. The electrolyte according to claim 5, wherein the molar concentration of the F element in the electrolyte is 1.4mol/L to 6.8mol/L.
7. The electrolytic solution according to claim 5, wherein the molar concentration of the N element in the electrolytic solution is 0.5mol/L to 2mol/L.
8. The electrolyte according to any one of claims 1 to 7, which comprises an S-containing sodium salt and a B-containing sodium salt.
9. The electrolyte of claim 8 wherein the S-containing sodium salt comprises at least one of sodium bis (trifluoromethylsulfonyl) imide and sodium bis (trifluoromethylsulfonyl) imide.
10. The electrolyte of claim 8 wherein the B-containing sodium salt comprises at least one of sodium difluorooxalato borate and sodium tetrafluoroborate.
11. The electrolyte of claim 8 further comprising an additive, the additive comprising an alkyl sodium salt.
12. The electrolyte of claim 11 wherein the alkyl sodium salt comprises at least one of sodium dodecyl sulfate and sodium polydithio-dipropyl sulfonate.
13. The electrolyte of claim 11, wherein the additive has a molar concentration of 0.001mol/L to 0.015mol/L.
14. The electrolyte of claim 1 wherein the solvent in the electrolyte comprises at least one of ethylene carbonate, propylene carbonate, ethylene carbonate, dimethyl carbonate, methylethyl carbonate, diethyl carbonate, ethyl acetate, ethyl propionate, methyl propionate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, polyethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, tetrahydrofuran, and methyltetrahydrofuran.
15. A sodium ion battery comprising the electrolyte of any one of claims 1 to 14.
16. An electrical device comprising the sodium ion battery of claim 15.
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