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CN116646602A - Electrolyte based on phosphorus-oxygen-group nitrogen-containing heterocyclic compound and sodium ion battery - Google Patents

Electrolyte based on phosphorus-oxygen-group nitrogen-containing heterocyclic compound and sodium ion battery Download PDF

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Publication number
CN116646602A
CN116646602A CN202310776112.5A CN202310776112A CN116646602A CN 116646602 A CN116646602 A CN 116646602A CN 202310776112 A CN202310776112 A CN 202310776112A CN 116646602 A CN116646602 A CN 116646602A
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unsubstituted
substituted
phosphorus
oxygen
ion battery
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Inventor
孔东波
邵俊华
韩飞
王亚洲
宋东亮
李渠成
施艳霞
司雅楠
张利娟
李海杰
龚国斌
郭飞
闫志卫
王郝为
闫国锋
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Henan Faenlaite New Energy Technology Co ltd
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Henan Faenlaite New Energy Technology Co ltd
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Priority to CN202310776112.5A priority Critical patent/CN116646602A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Secondary Cells (AREA)

Abstract

The application discloses electrolyte based on phosphorus-oxygen-based nitrogen-containing heterocyclic compound and a sodium ion battery, and relates to the field of sodium ion batteries. The application comprises an organic solvent, an electrolyte and an additive; the additive comprises phosphorus-oxygen-containing nitrogen heterocyclic compound, sodium bis-fluorosulfonyl imide and vinyl sulfate; so as to realize that the property of the negative electrode interface film can be improved after the electrolyte is applied to the sodium ion battery, and the purposes of improving the initial charge-discharge coulomb efficiency and the cycle performance of the battery are achieved.

Description

Electrolyte based on phosphorus-oxygen-group nitrogen-containing heterocyclic compound and sodium ion battery
Technical Field
The application relates to the field of sodium ion batteries, in particular to electrolyte based on phosphorus-oxygen-based nitrogen-containing heterocyclic compounds and a sodium ion battery.
Background
In recent years, new energy automobiles have received increasing attention. As a core component, a power battery is one of the keys for the development of new energy automobiles. Along with the development of the problems of price rising, limited resource reserves and the like of the lithium ion battery, the sodium ion battery with wide resource distribution gradually enters the field of vision of people.
The fittings of sodium ion batteries are correspondingly cheaper than lithium ion batteries, and in addition sodium compounds can be used as electrode materials, which is also an important direction for cost reduction. The sodium salt raw material has rich reserves and low price, and compared with the ternary positive electrode material of the lithium ion battery, the iron-manganese-nickel-based positive electrode material has half of the raw material cost.
The sodium-ion battery is allowed to discharge to zero volts due to its non-overdischarge characteristics. The energy density of the sodium ion battery is more than 100Wh/kg, which is comparable with that of the lithium iron phosphate battery, but the sodium ion battery has obvious cost advantage and is expected to replace the traditional lead-acid battery in large-scale energy storage.
However, since the ionic radius (r=0.113 nm) of sodium ions is about 3.3 times that of lithium ions (r=0.076 nm), there is a corresponding technical problem that the regular graphite structure, the high-temperature graphitized carbon mesophase microspheres (MCMB) have almost no sodium intercalation capacity, and reversible sodium intercalation capacity of nearly 280mAh/g and circularity can be obtained by partially pyrolyzing hard carbon, but the initial irreversible capacity is high and the kinetic performance is poor.
Disclosure of Invention
The application aims to provide an electrolyte based on phosphorus-oxygen-based nitrogen-containing heterocyclic compounds; so as to realize that the property of the negative electrode interface film can be improved after the electrolyte is applied to the sodium ion battery, and the purposes of improving the initial charge-discharge coulomb efficiency and the cycle performance of the battery are achieved.
In order to achieve the above purpose, the present application adopts the following technical means:
a sodium ion battery electrolyte based on phosphorus-oxygen nitrogen heterocyclic compound comprises an organic solvent, an electrolyte and an additive;
the additive comprises phosphorus-oxygen-containing nitrogen heterocyclic compound, sodium bis-fluorosulfonyl imide and vinyl sulfate.
Preferably, the phosphorus-oxygen-containing nitrogen-containing heterocyclic compound is selected from at least one of compounds shown in formulas I to V:
further, the R 11 、R 12 、R 13 、R 21 、R 22 、R 23 、R 24 、R 31 、R 32 、R 33 、R 41 、R 42 、R 43 、R 44 、R 51 、R 52 、R 53 、R 54 、R 55 Each independently selected from hydrogen atom, halogen atom, amino group, sulfonic group, substituted or unsubstituted C 1 -C 20 Alkyl, substituted or unsubstituted C 2 -C 20 Alkenyl, substituted or unsubstituted C 6 -C 26 Aryl, substituted or unsubstituted C 1 -C 20 Sulfonylalkyl, substituted or unsubstituted C 2 -C 20 Sulfonylalkenyl, substituted or unsubstituted C 6 -C 26 One of the sulfonylaryl groups.
Further, the phosphorus-oxygen-containing nitrogen-containing heterocyclic compound is selected from at least one of compounds represented by formulas IA to VA:
further, the R 61 、R 62 、R 63 、R 64 、R 65 、R 66 、R 71 、R 72 、R 73 、R 74 、R 75 、R 76 、R 77 、R 78 、R 81 、R 82 、R 83 、R 84 、R 85 、R 86 、R 91 、R 92 、R 93 、R 94 、R 95 、R 96 、R 97 、R 98 、R 101 、R 102 、R 103 、R 104 、R 105 、R 106 、R 107 、R 108 、R 109 、R 110 Each independently selected from hydrogen atom, halogen atom, amino group, sulfonic group, substituted or unsubstituted C 1 -C 20 Alkyl, substituted or unsubstituted C 2 -C 20 Alkenyl, substituted or unsubstituted C 6 -C 26 Aryl, substituted or unsubstituted C 1 -C 20 Sulfonylalkyl, substituted or unsubstituted C 2 -C 20 Sulfonylalkenyl, substituted or unsubstituted C 6 -C 26 One of the sulfonylaryl groups.
Further, the R 67 、R 79 、R 87 、R 99 、R 111 Each independently selected from the group consisting of a hydrogen atom, a halogen atom, an amino group, a sulfonic group, a pyrrolinyl group, a pyrazolyl group, a pyrrolidinyl group, an imidazolyl group, a pyridyl group, a piperidyl group, a substituted or unsubstituted C 1 -C 20 Alkyl, substituted or unsubstituted C 2 -C 20 Alkenyl, substituted or unsubstituted C 6 -C 26 Aryl, substituted or unsubstituted C 1 -C 20 Sulfonylalkyl, substituted or unsubstituted C 2 -C 20 Sulfonylalkenyl, substituted or unsubstituted C 6 -C 26 Sulfonyl aryl.
Further, the phosphorus-oxygen-containing nitrogen-containing heterocyclic compound is selected from at least one of the compounds shown as the compounds 1 to 5:
still further, the additive further comprises at least one of cyclic sultone, double bond-containing cyclic carbonate, fluorine-containing carbonate, boron-containing sodium salt, and phosphorus-containing sodium salt.
The electrolyte provided by the application has the following beneficial effects:
in the high-temperature formation process of the sodium ion battery, a SE I film is formed on the surface of the positive electrode by utilizing phosphorus-oxygen-group nitrogen-containing heterocyclic compound in preference to consumption of sodium ions; and forming an SE I film on the surface of the negative electrode material by utilizing sodium bis (fluorosulfonyl) imide and vinyl sulfate in preference to consumption of phosphorus-oxygen-containing nitrogen heterocyclic compounds and sodium ions. And further improves the initial charge-discharge coulombic efficiency of the battery by reducing the consumption of sodium ions in the formation process.
When the phosphorus-oxygen-containing nitrogen heterocyclic compound of the electrolyte can be subjected to ring-opening polymerization on the surface of the positive electrode to form a passivation film, but because the phosphorus-oxygen-containing nitrogen heterocyclic compound can also form a SE I film with larger impedance on the interface of the negative electrode, for a sodium ion battery, the intercalation and deintercalation of sodium ions in the negative electrode can be prevented, and the loss of active sodium and battery capacity is caused. According to the electrolyte disclosed by the application, the phosphorus-oxygen nitrogen-containing heterocyclic compound is used together with the sodium bis-fluorosulfonyl imide and the vinyl sulfate, the sodium bis-fluorosulfonyl imide and the vinyl sulfate can form a stable SE I film with high ion conductivity on the surface of the negative electrode preferentially, and synergistic effect can be generated between the sodium bis-fluorosulfonyl imide and the vinyl sulfate, so that adverse influence of the phosphorus-oxygen nitrogen-containing heterocyclic compound on the interface impedance of the negative electrode is further inhibited, the polarization of the battery is reduced, the discharge capacity is improved, and the initial charge-discharge coulomb efficiency and the cycle performance of the battery can be obviously improved.
Meanwhile, the application also provides a sodium ion battery comprising the electrolyte;
the lithium ion battery also comprises an anode pole piece and a cathode pole piece, wherein the electrolyte is arranged between the anode pole piece and the cathode pole piece.
Preferably, the positive electrode plate contains sodium manganese iron cobalt nickel titanium, and the structural formula of the sodium manganese iron cobalt nickel titanium is NaMn X Fe Y Co Z Ni U T i V O2, wherein 0<x<1，0<y<1，0<z<1，0<u<1，0<v<1，x+y+z+u+v＝1；
The negative electrode plate contains hard carbon.
The sodium ion battery provided by the application has the advantages that the initial charge and discharge coulomb efficiency is obviously improved, the capacity retention rate after circulation and the high-temperature storage gas production performance are also obviously improved, and the high-temperature storage performance can be improved.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present application more apparent, the technical solutions in the embodiments of the present application will be clearly and completely described in the following in conjunction with the embodiments of the present application, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments.
Thus, the following detailed description of the embodiments of the application is not intended to limit the scope of the application, as claimed, but is merely representative of selected embodiments of the application. All other embodiments, based on the embodiments of the application, which are apparent to those of ordinary skill in the art without inventive faculty, are intended to be within the scope of the application.
In addition, the embodiments of the present application and the features of the embodiments may be combined with each other without collision.
Firstly, preparing a positive plate of the sodium ion battery:
(1) Preparation of positive plate of sodium ion battery
The positive electrode active material of ferromanganese cobalt nickel sodium titanate (NaMn 0.2 Fe 0.2 Co 0.2 Ni 0.2 Ti 0.2 O 2 ) The conductive agent Super-P and the binder polyvinylidene fluoride (PVDF) are dissolved in a solvent N-methyl pyrrolidone (NMP) according to the mass ratio of 95.5:2.25:2.25 to prepare positive electrode slurry, and the solid content of the positive electrode slurry is 76 wt%. And uniformly coating the positive electrode slurry on a current collector aluminum foil, wherein the coating weight is 0.0105g/cm < 2 >, drying at 80 ℃, then carrying out cold pressing, trimming, cutting and slitting, drying at 80 ℃ under vacuum for 3 hours, and welding the tab to prepare the positive electrode plate of the sodium ion battery.
(2) Preparation of negative plate of sodium ion battery
The preparation method comprises the following steps of (1) mixing hard carbon serving as a cathode active material, super-P serving as a conductive agent, CMC serving as a thickening agent and styrene-butadiene rubber (SBR) serving as an adhesive according to a mass ratio of 96:2:1:1, dissolving the mixture in deionized water serving as a solvent, uniformly mixing to prepare negative electrode slurry, uniformly coating the negative electrode slurry on the front and back surfaces of a current collector copper foil, wherein the coating weight is 0.0070g/cm < 2 >, drying at 86 ℃, then carrying out cold pressing, trimming, cutting pieces and slitting, drying at 105 ℃ under vacuum for 4.5 hours, and welding tabs to prepare the negative electrode piece of the lithium ion battery.
(3) Preparation of electrolyte for sodium ion battery
In a glove box filled with argon, ethylene Carbonate (EC), ethylmethyl carbonate (EMC) and 1, 3-Dioxolane (DOL) were mixed in mass ratio EC: EMC: dol=20:60:20 as nonaqueous organic solvents. Adding sodium hexafluorophosphate with the concentration of sodium salt of 1.0 mol/L into a nonaqueous organic solvent, adding an additive into the solution, and uniformly mixing to obtain the electrolyte.
(4) Preparation of lithium ion batteries
A16 μm polyethylene film (PE) was used as a separator. And sequentially stacking the prepared positive plate, the isolating film and the negative plate, enabling the isolating film to be positioned between the positive plate and the negative plate, winding to obtain a bare cell, welding a tab, placing the bare cell in an outer package, injecting the prepared electrolyte into the dried cell, packaging, standing, then charging to 3.3V by using 0.02C constant current, and then charging to 3.6V by using 0.1C constant current, shaping and testing capacity to complete the preparation of the sodium ion battery. The thickness of the prepared soft-package sodium ion battery is 4.0mm, the width is 60mm, and the length is 140mm.
In the following examples, the components of the different additives were specifically implemented, and the addition amounts of the respective additives were calculated as mass percentages based on the total mass of the electrolyte.
Example 1
In this example, the additive consisted of 1% compound 1 and 1% sodium bis-fluorosulfonyl imide.
Example 2
In this example, the additive consisted of 1% compound 1 and 0.1% sodium bis-fluorosulfonyl imide.
Example 3
In this example, the additive consisted of 1% compound 1 and 11% sodium bis-fluorosulfonyl imide.
Example 4
In this example, the additive consisted of 1% compound 1 and 1% vinyl sulfate.
Example 5
In this example, the additive consisted of 1% compound 1 and 0.5% vinyl sulfate.
Example 6
In this example, the additive consisted of 1% compound 1 and 3.5% vinyl sulfate.
Example 7
In this example, the additive consisted of 1% of compound 1 and 1% of 1, 3-Propane Sultone (PS).
Example 8
In this example, the additive consisted of 1% compound 1 and 1% Vinylene Carbonate (VC).
Example 9
In this example, the additive consisted of 1% compound 1 and 1% fluoroethylene carbonate (FEC).
Example 10
In the present embodiment, addThe agent consists of 1% of compound 1 and 1% of NaBF 4 Composition is prepared.
Example 11
In this example, the additive consisted of 1% of compound 1 and 1% sodium difluorophosphate.
Example 12
In this example, the additive consisted of 1% compound 1, 1% sodium bis-fluorosulfonyl imide, and 1% vinyl sulfate.
Example 13
In this example, the additive consisted of 1% compound 1, 1% sodium bis-fluorosulfonamide, 1% vinyl sulfate, and 1% 1, 3-Propane Sultone (PS).
Example 14
In this example, the additive consisted of 1% compound 1, 1% sodium bis-fluorosulfonyl imide, 1% vinyl sulfate, and 1% Vinylene Carbonate (VC).
Example 15
In this example, the additive consisted of 1% compound 1, 1% sodium bis-fluorosulfonyl imide, 1% vinyl sulfate, and 1% fluoroethylene carbonate (FEC).
Example 16
In this example, the additive consists of 1% of compound 1, 1% of sodium bisfluorosulfonyl imide, 1% of vinyl sulfate and 1% of NaBF 4 Composition is prepared.
Example 17
In this example, the additive consisted of 1% compound 1, 1% sodium bis-fluorosulfonyl imide, 1% vinyl sulfate, and 1% sodium difluorophosphate.
Example 18
In this example, the additive consists of 1% of compound 1, 1% of sodium difluorosulfimide, 1% of vinyl sulfate, 1% of 1, 3-Propane Sultone (PS), 1% of Vinylene Carbonate (VC), 1% of fluoroethylene carbonate (FEC), 1% of NaBF 4 And 1% sodium difluorophosphate.
Example 19
In the present embodiment, addThe additive consists of 1% of compound 2, 1% of sodium bis-fluorosulfonyl imide, 1% of vinyl sulfate, 1% of 1, 3-Propane Sultone (PS), 1% of Vinylene Carbonate (VC), 1% of fluoroethylene carbonate (FEC), 1% of NaBF 4 And 1% sodium difluorophosphate.
Example 20
In this example, the additive consists of 1% of Compound 3, 1% of sodium difluorosulfimide, 1% of vinyl sulfate, 1% of 1, 3-Propane Sultone (PS), 1% of Vinylene Carbonate (VC), 1% of fluoroethylene carbonate (FEC), 1% of NaBF 4 And 1% sodium difluorophosphate.
Example 21
In this example, the additive consists of 1% of Compound 4, 1% of sodium difluorosulfimide, 1% of vinyl sulfate, 1% of 1, 3-Propane Sultone (PS), 1% of Vinylene Carbonate (VC), 1% of fluoroethylene carbonate (FEC), 1% of NaBF 4 And 1% sodium difluorophosphate.
Example 22
In this example, the additive consists of 1% of compound 5, 1% of sodium difluorosulfimide, 1% of vinyl sulfate, 1% of 1, 3-Propane Sultone (PS), 1% of Vinylene Carbonate (VC), 1% of fluoroethylene carbonate (FEC), 1% of NaBF 4 And 1% sodium difluorophosphate.
Comparative example 1
In this comparative example, no additive was added to the electrolyte.
Comparative example 2
In this comparative example, the additive consisted of only 1% of compound 1.
Comparative example 3
In this comparative example, the additive consisted of only 1% of compound 2.
Comparative example 4
In this comparative example, the additive consisted of only 1% of compound 3.
Comparative example 5
In this comparative example, the additive consisted of only 1% of compound 4.
Comparative example 6
In this comparative example, the additive consisted of only 1% of compound 5.
Comparative example 7
In this comparative example, the additive consisted of only 1% sodium bis-fluorosulfonyl imide.
Comparative example 8
In this comparative example, the additive consisted of only 1% vinyl sulfate.
Comparative example 9
In this comparative example, the additive consisted of 1% only of 1, 3-Propane Sultone (PS).
Comparative example 10
In this comparative example, the additive consisted of only 1% Vinylene Carbonate (VC).
Comparative example 11
In this comparative example, the additive consisted of only 1% fluoroethylene carbonate (FEC).
Comparative example 12
In this comparative example, the additive consisted of only 1% NaBF 4 Composition is prepared.
Comparative example 13
In this comparative example, the additive consisted of only 1% sodium difluorophosphate.
Comparative example 14
In this comparative example, the additive consisted of only 0.1% of compound 1.
Comparative example 15
In this comparative example, the additive consisted of only 0.1% of compound 2.
Comparative example 16
In this comparative example, the additive consisted of only 0.1% of compound 3.
Comparative example 17
In this comparative example, the additive consisted of only 0.1% of compound 4.
Comparative example 18
In this comparative example, the additive consisted of only 0.1% of compound 5.
Comparative example 19
In this comparative example, the additive consisted of only 2.5% of compound 1.
Comparative example 20
In this comparative example, the additive consisted of only 2.5% of compound 2.
Comparative example 21
In this comparative example, the additive consisted of only 2.5% of compound 3.
Comparative example 22
In this comparative example, the additive consisted of only 2.5% of compound 4.
Comparative example 23
In this comparative example, the additive consisted of only 2.5% of compound 5.
Comparative example 24
In this comparative example, the additive consisted of only 0.1% sodium bis-fluorosulfonamide.
Comparative example 25
In this comparative example, the additive consisted of only 11% sodium bis-fluorosulfonyl imide.
Comparative example 26
In this comparative example, the additive consisted of only 0.5% vinyl sulfate.
Comparative example 27
In this comparative example, the additive consisted of only 3.5% vinyl sulfate.
The batteries prepared in examples 1 to 22 and comparative examples 1 to 27 were each tested in the following manner:
(1) First efficiency test of sodium ion battery.
The sodium ion battery is packaged, is static, is charged to 3.3V by 0.02C constant current, is charged to 3.6V by 0.1C constant current, is placed for 24 hours at the temperature of 2.5 ℃, is charged to 4.1V by 1C constant current, is charged to 0.05C by 4.1V constant voltage, is placed for 1 hour, and is discharged to 2.5V by 1C constant current. First efficiency (%) =first discharge capacity/total charge capacity×100% of the sodium ion battery.
(2) Cycling performance test of sodium ion cell (25 ℃ and 45 ℃ C.)
The sodium ion battery was charged to 4.1V at a constant current of 1C, then charged to 0.05C at a constant voltage of 4.1V, and then discharged to 2.5V at a constant current of 1C, which is one charge-discharge cycle. The capacity retention rate of the sodium ion battery after 500 cycles was calculated with the capacity of the first discharge being 100%. Capacity retention (%) after 500 cycles of the sodium ion battery=discharge capacity of 500 th cycle/capacity of first discharge×100%.
(3) Storage gas production performance test of sodium ion battery
The initial volume of the battery was measured in deionized water at 25C by charging the battery to 4.1V at a constant current of 0.5C, further to 0.05C at a constant voltage of 4.1V, then the initial volume of the battery was measured in deionized water by a drainage method, and then the battery was left to stand at 85℃ for 24 hours each, left to stand at room temperature for 60 min, cooled to room temperature for 1 hour, and the volume after storage was measured by the drainage method, and the volume expansion rate= (volume after storage/initial volume-1) ×100% and the number of days when the volume expansion rate reached 30% was recorded as a time that can endure gas production at 85℃.
The test results are shown in the following table.
As can be seen from the test results of the table, compared with comparative examples 1-27, in example 1, which contains both the phosphorus-oxygen-containing nitrogen-containing heterocyclic compound and sodium bis-fluorosulfonyl imide, the initial charge-discharge coulomb efficiency of the sodium ion battery is remarkably improved, and the capacity retention rate and the high-temperature storage gas production performance after circulation are also remarkably improved.
From the experimental data of example 4, it was found that the initial charge-discharge coulombic efficiency, the capacity retention after the cycle, and the high-temperature storage gas production performance were further improved by further adding vinyl sulfate.
In examples 7 to 11, PS, VC, FEC, naBF was added 4 Sodium difluorophosphate can improve high temperature storage performance. In examples 18 to 22, a phosphorus-oxygen-containing nitrogen-containing heterocyclic compound, sodium difluorosulfimide and vinyl sulfate were used in combination, and PS, VC, FEC, naBF was further added 4 Sodium difluorophosphate, the initial charge-discharge coulombic efficiency, capacity retention rate after circulation and high-temperature storage gas production performance of the battery are further improved.
In addition, in the foregoing examples and comparative examples, the content of the phosphorus-oxygen-based nitrogen-containing heterocyclic compound in the electrolyte is 0.01% to 2% by mass. If the content of the phosphorus-oxygen-group nitrogen-containing heterocyclic compound is too large, a compact and thick passivation film is formed on the surfaces of the anode and the cathode, and the interface impedance of the anode and the cathode is increased, so that the cycle performance of the battery is deteriorated to a certain extent; if the content of the phosphorus-oxygen-group nitrogen-containing heterocyclic compound is too small, the coulombic efficiency and the cycle performance of the first charge and discharge are not obviously improved.
The upper limit of the mass percentage content range of the phosphorus-oxygen-containing nitrogen-containing heterocyclic compound in the electrolyte is optionally from 2%, 1%, 0.8%, 0.7%, and the lower limit is optionally from 0.01%, 0.05%, 0.1%, 0.3%, 0.5%, 0.6%. The mass percentage of the phosphorus-oxygen-group nitrogen-containing heterocyclic compound in the electrolyte is 0.1-1.5%.
The mass percentage of the sodium bis (fluorosulfonyl) imide in the electrolyte is 0.01-10%. If the content of sodium bis (fluorosulfonyl) imide is too large, the viscosity of the electrolyte is increased and the conductivity is reduced; if the sodium difluorosulfimide content is too small, no obvious effect is achieved on reducing the film forming resistance of the negative electrode.
Specifically, the upper limit of the mass percentage content range of the sodium difluorosulfimide in the electrolyte is optionally 10%, 9.5%, 9%, 8.5%, 8%, 7.5%, 7%, 6.5%, 6%, 5.5%, 5%, 4.5%, 4%, 3.5%, 3%, 2.5%, 2%, 1%, 0.8%, 0.7%, and the lower limit is optionally 0.01%, 0.05%, 0.1%, 0.3%, 0.5%, 0.6%. More preferably, the mass percentage of the sodium bis-fluorosulfonyl imide in the electrolyte is 0.1-5%.
The mass percentage of the vinyl sulfate in the electrolyte is 0.01-3%. If the content of the vinyl sulfate is too large, gas is produced by oxidation of the positive electrode at high temperature, so that the performance of the battery is deteriorated to a certain extent; if the content of the vinyl sulfate is too small, the film forming efficiency is not high, and the cycle performance of the battery is not obviously improved.
Specifically, the upper limit of the mass percentage content range of the vinyl sulfate in the electrolyte is optionally 3%, 2.5%, 2%, 1%, 0.8%, 0.7%, and the lower limit is optionally 0.01%, 0.05%, 0.1%, 0.3%, 0.5%, 0.6%. More preferably, the mass percentage of the vinyl sulfate in the electrolyte is 0.5% -2%.
The electrolyte used in the present application may be suitably exemplified by the following sodium salts.
NaPF 6 、NaBF 4 、NaPO 2 F 2 、NaFS I。
The concentration of sodium salt in the electrolyte was 0.5M-2M (m=mol·l) -1 ) Preferably, the concentration of sodium salt in the electrolyte is 0.8M to 1.2M.
In the above electrolyte, the organic solvent is at least one selected from the group consisting of carbonate compounds and ether compounds, wherein the carbonate compounds may be chain carbonates or cyclic carbonates.
As examples of the organic solvent, there may be mentioned: at least one of ethylene carbonate, propylene carbonate, butylene carbonate, fluoroethylene carbonate, methylethyl carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methylpropyl carbonate, ethylpropyl carbonate, propylene oxide, xylene, tetrahydrofuran, 2-methyltetrahydrofuran, 1, 3-dioxolane, dimethoxymethane, 1, 2-dimethoxyethane, and diglyme.
The electrolyte according to the embodiment of the application can be obtained by, for example, the following method: the above-mentioned organic solvent is mixed, and the electrolyte and the phosphorus-oxygen-containing nitrogen-containing heterocyclic compound and sodium difluorosulfimide of the present application are added thereto, and further, vinyl sulfate may be added, and further, at least one of cyclic sultone, double bond-containing cyclic carbonate, fluorine-containing carbonate, boron-containing sodium salt, and phosphorus-containing sodium salt may be further added.
Meanwhile, the aforementioned compound 1 was prepared by the following route:
(CAS No. 68593-85-1) methane gas was introduced, and after the reaction was completed, the mixture was placed in an oven to bake moisture, and then fluorine gas was introduced to obtain Compound 1.
The aforementioned compound 2 was prepared using the following route:
(phosphorylimidazole, CAS No. 15496-31-8) oxygen was introduced and reacted at 50℃for 3 hours to obtain Compound 2.
The aforementioned compound 3 was prepared using the following route:
(CAS No.: 89982-87-6) and +.>(imidazole, CAS: 288-32-4), and methane gas was introduced thereto and reacted at 50℃for three hours to obtain Compound 3.
The aforementioned compound 4 was prepared using the following route:
(methylphenyl-oxyphosphorusCAS 19315-13-0) and +.>(Benzimidazole derivativesCAS 51-17-2), introducing oxygen after mixing, reacting for three hours at 50 ℃, and distilling to remove water to obtain the compound 4.
The aforementioned compound 5 was prepared using the following route:
(methylphenyl-oxyphosphorusCAS 19315-13-0) and +.>(2-methylimidazoleCAS 693-98-1), introducing oxygen, reacting at 50 deg.C for three hours, distilling to remove water to obtain compound 5.
Although the present application has been described with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments described, or equivalents may be substituted for elements thereof, and any modifications, equivalents, improvements and changes may be made without departing from the spirit and principles of the present application.

Claims (10)

1. A sodium ion battery electrolyte based on phosphorus-oxygen-containing nitrogen heterocyclic compound is characterized in that: comprises an organic solvent, an electrolyte and an additive;
the additive comprises phosphorus-oxygen-containing nitrogen heterocyclic compound, sodium bis-fluorosulfonyl imide and vinyl sulfate.
2. The sodium ion battery electrolyte based on phosphorus-oxygen-containing nitrogen heterocyclic compound according to claim 1, wherein the electrolyte comprises the following components: the phosphorus-oxygen-containing nitrogen-containing heterocyclic compound is selected from at least one of compounds shown in the formulas I to V:
3. the sodium ion battery electrolyte based on phosphorus-oxygen-containing nitrogen heterocyclic compound according to claim 2, wherein the electrolyte is characterized in that: the R is 11 、R 12 、R 13 、R 21 、R 22 、R 23 、R 24 、R 31 、R 32 、R 33 、R 41 、R 42 、R 43 、R 44 、R 51 、R 52 、R 53 、R 54 、R 55 Each independently selected from hydrogen atom, halogen atom, amino group, sulfonic group, substituted or unsubstituted C 1 -C 20 Alkyl, substituted or unsubstituted C 2 -C 20 Alkenyl, substituted or unsubstituted C 6 -C 26 Aryl, substituted or unsubstituted C 1 -C 20 Sulfonylalkyl, substituted or unsubstituted C 2 -C 20 Sulfonylalkenyl, substituted or unsubstituted C 6 -C 26 One of the sulfonylaryl groups.
4. The sodium ion battery electrolyte based on phosphorus-oxygen-containing nitrogen heterocyclic compound according to claim 1, wherein the electrolyte comprises the following components: the phosphorus-oxygen-containing nitrogen-containing heterocyclic compound is selected from at least one of compounds shown in formulas IA to VA:
5. the sodium ion battery electrolyte based on phosphorus-oxygen-containing nitrogen heterocyclic compounds as described in claim 4, wherein: the R is 61 、R 62 、R 63 、R 64 、R 65 、R 66 、R 71 、R 72 、R 73 、R 74 、R 75 、R 76 、R 77 、R 78 、R 81 、R 82 、R 83 、R 84 、R 85 、R 86 、R 91 、R 92 、R 93 、R 94 、R 95 、R 96 、R 97 、R 98 、R 101 、R 102 、R 103 、R 104 、R 105 、R 106 、R 107 、R 108 、R 109 、R 110 Each independently selected from hydrogen atom, halogen atom, amino group, sulfonic group, substituted or unsubstituted C 1 -C 20 Alkyl, substituted or unsubstituted C 2 -C 20 Alkenyl, substituted or unsubstituted C 6 -C 26 Aryl, substituted or unsubstituted C 1 -C 20 Sulfonylalkyl, substituted or unsubstituted C 2 -C 20 Sulfonylalkenyl, substituted or unsubstituted C 6 -C 26 One of the sulfonylaryl groups.
6. A sodium ion battery electrolyte based on a phosphorus-oxygen-containing nitrogen heterocyclic compound according to claim 4 or 5, wherein: the R is 67 、R 79 、R 87 、R 99 、R 111 Each independently selected from the group consisting of a hydrogen atom, a halogen atom, an amino group, a sulfonic group, a pyrrolinyl group, a pyrazolyl group, a pyrrolidinyl group, an imidazolyl group, a pyridyl group, a piperidyl group, a substituted or unsubstituted C 1 -C 20 Alkyl, substituted or unsubstituted C 2 -C 20 Alkenyl, substituted or unsubstituted C 6 -C 26 Aryl, substituted or unsubstituted C 1 -C 20 Sulfonylalkyl, substituted or unsubstituted C 2 -C 20 Sulfonylalkenyl, substituted or unsubstituted C 6 -C 26 Sulfonyl aryl.
7. The sodium ion battery electrolyte based on phosphorus-oxygen-containing nitrogen heterocyclic compound according to claim 1, wherein the electrolyte comprises the following components: the phosphorus-oxygen-containing nitrogen-containing heterocyclic compound is selected from at least one of the compounds shown as the compounds 1 to 5:
8. a sodium ion battery electrolyte based on a phosphorus-oxygen-containing nitrogen-containing heterocyclic compound according to any one of claims 1-7, wherein: the additive also comprises at least one of cyclic sultone, cyclic carbonate containing double bonds, fluorine-containing carbonate, boron-containing sodium salt and phosphorus-containing sodium salt.
9. A sodium ion battery characterized by: comprising an electrolyte as claimed in any one of claims 1 to 8;
the lithium ion battery also comprises an anode pole piece and a cathode pole piece, wherein the electrolyte is arranged between the anode pole piece and the cathode pole piece.
10. A sodium ion battery according to claim 9, wherein: the positive pole piece contains sodium manganese iron cobalt nickel titanium, and the structural formula of the sodium manganese iron cobalt nickel titanium is NaMn X Fe Y Co Z Ni U Ti V O 2 Wherein 0 is<x<1，0<y<1，0<z<1，0<u<1，0<v<1，x+y+z+u+v＝1；
The negative electrode plate contains hard carbon.
CN202310776112.5A 2023-06-28 2023-06-28 Electrolyte based on phosphorus-oxygen-group nitrogen-containing heterocyclic compound and sodium ion battery Pending CN116646602A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118497504A (en) * 2024-07-18 2024-08-16 新乡市中天新能源科技股份有限公司 Method for recycling lithium battery recycling solution and waste ternary battery anode material

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118497504A (en) * 2024-07-18 2024-08-16 新乡市中天新能源科技股份有限公司 Method for recycling lithium battery recycling solution and waste ternary battery anode material

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