CN113013492B - Organic electrolyte with wide working temperature area and sodium ion battery - Google Patents
Organic electrolyte with wide working temperature area and sodium ion battery Download PDFInfo
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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
- H01M10/0569—Liquid materials characterised by the solvents
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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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
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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 provides an organic electrolyte with a wide working temperature range and a sodium ion battery, wherein the organic electrolyte comprises electrolyte sodium salt and an organic solvent, and the organic solvent comprises one or more of a cyclic ether solvent, a chain ether solvent and a nitrile solvent. The organic electrolyte provided by the invention has the advantages of low viscosity and melting point and high ionic conductivity, and can work at the temperature of-50-60 ℃; the organic electrolyte with wide working temperature area is used for constructing the sodium ion battery, so that the working temperature of the sodium ion battery can be effectively widened, and the safety and the cycling stability of the battery are improved.
Description
Technical Field
The invention relates to the field of sodium ion batteries, in particular to an organic electrolyte with a wide working temperature range and a sodium ion battery.
Background
The electrolyte is an ion conductor which plays a role in conduction between the anode and the cathode of the battery, and greatly influences the capacity, the cycle life and the safety performance of the ion battery. Sodium ion batteries are expected to become a potential next-generation energy storage system because of the advantages of abundant sodium reserves, low cost, wide working temperature range, environmental friendliness and the like, and the sodium ion batteries are widely concerned by researchers. In recent years, in order to meet certain special use environments, such as aerospace and deep sea exploration fields, batteries are required to be capable of operating within a wide temperature range (-50-60 ℃), and thus batteries are required to have higher low-temperature charge and discharge resistance or high-temperature charge and discharge resistance.
However, similar to lithium ion battery electrolyte, sodium ion battery electrolyte also faces the problems of easy crystallization at low temperature, greatly reduced conductivity, increased charge transfer resistance and the like, thereby greatly reducing the cycle performance of the battery, increasing concentration polarization, and seriously causing dendrite to pierce through a diaphragm to cause short circuit or fire. In addition, commercial low temperature lithium ion battery electrolyte solvent compositions are typically mixtures of ethylene carbonate, propylene carbonate, methyl ethyl carbonate, and carboxylic esters, but prior studies have shown that lithium ion battery electrolytes are not necessarily suitable for use in sodium ion batteries.
Therefore, developing a sodium ion battery electrolyte that can operate in a wide temperature range is a currently urgent problem to be solved.
Disclosure of Invention
In view of the above, the present invention is directed to an organic electrolyte and a sodium ion battery with a wide working temperature range, so as to solve the problems of discomfort of the existing sodium ion battery electrolyte and a non-wide working temperature range.
In order to achieve the above purpose, the technical scheme of the invention is realized as follows:
an organic electrolyte having a wide working temperature range, the organic electrolyte comprising an electrolyte sodium salt and an organic solvent comprising one or more of a cyclic ether solvent, a chain ether solvent, and a nitrile solvent.
Optionally, the electrolyte sodium salt includes one or more of sodium triflate, sodium bis (trifluoromethylsulfonate) imide, sodium hexafluorophosphate, sodium tetrafluoroborate, and sodium perchlorate.
Alternatively, the molar concentration of the electrolyte sodium salt is 0.1-5M.
Optionally, the cyclic ether solvent is a cyclic organic substance with at least one oxygen atom and carbon number in the range of 2-10, and the melting point of the cyclic organic substance is in the range of-20 ℃ to-150 ℃; the structural formula of the chain ether solvent comprises one or more [ -CH 2 OCH 2 -]A structural unit, wherein the number of carbon atoms contained in the chain ether solvent is in the range of 3-20, and the melting point of the chain ether solvent is in the range of-20 ℃ (-150); the nitrile solvent contains at least one nitrile group, and the melting point of the nitrile solvent is in the range of-0 ℃ to-150 ℃.
Optionally, the cyclic ether solvent comprises one or more of ethylene oxide, tetrahydrofuran, tetrahydropyran, 2-methyltetrahydrofuran, 1, 3-dioxolane, 1, 3-dioxane, and 2, 2-dimethyltetrahydrofuran.
Optionally, the nitrile solvent includes one or more of acetonitrile, propionitrile, butyronitrile, isobutyronitrile, valeronitrile, 3-methoxypropionitrile and cyclopentanecarbonitrile.
Optionally, the chain ether solvent comprises one or more of methyl ether, diethyl ether, dimethoxymethane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether.
The invention further aims to provide a sodium ion battery, so as to solve the problems of discomfort of the electrolyte of the existing sodium ion battery and the lack of a wide working temperature range.
In order to achieve the above purpose, the technical scheme of the invention is realized as follows:
a sodium ion battery comprising the organic electrolyte having a wide operating temperature range as described above.
Optionally, the sodium ion battery further comprises a positive electrode plate, a negative electrode plate and a diaphragm clamped between the positive electrode plate and the negative electrode plate, wherein the positive electrode plate comprises 80-90% of positive electrode active material by mass fraction, 5-10% of conductive agent by mass fraction and 5-10% of binder by mass fraction, and the negative electrode plate comprises negative electrode active material.
Optionally, the positive electrode active material includes a material (M includes one or more of Fe, mn, ni, co, cu and Cr) having a chemical formula of NaxMO2, a polyanion compound, or a prussian blue material; the negative electrode active material comprises graphite, hard carbon, a silicon-based negative electrode, a germanium-based negative electrode or a phosphorus-based negative electrode; the binder comprises one or more of polytetrafluoroethylene, polyvinylidene fluoride, sodium carboxymethyl cellulose and styrene-butadiene rubber.
Compared with the prior art, the organic electrolyte with the wide working temperature area and the sodium ion battery provided by the invention have the following advantages:
the organic electrolyte with wide working temperature area provided by the invention has single component, is a single or double-component solvent, does not contain additives, can greatly reduce the viscosity and melting point of the whole electrolyte system by optimizing the component proportion of the solvent, can not crystallize at the low temperature of 50 ℃ below zero, still keeps high ionic conductivity, and greatly improves the cycle life and coulombic efficiency of the sodium ion battery at the low temperature.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions of the prior art, a brief description will be given below of the drawings required for the embodiments or the prior art descriptions, and it is obvious that the drawings in the following description are some embodiments of the present invention, and that other drawings can be obtained according to these drawings without inventive effort to a person skilled in the art.
FIG. 1 is a graph showing the change of ionic conductivity with temperature of the organic electrolyte prepared in example 1 of the present invention;
FIG. 2 is a graph showing the viscosity of the organic electrolyte prepared in example 1 according to the present invention as a function of temperature;
FIG. 3 shows the current density of the organic electrolyte-matched sodium-sodium symmetric cell prepared in example 1 of the present invention at 0.5mA/cm 2 Dough kneading capacity 1mAh/cm 2 A lower long cycle curve;
FIG. 4 is a graph showing the cycle performance at low temperature of an organic electrolyte-matched hard carbon battery prepared in example 2 of the present invention;
fig. 5 is a charge-discharge curve of an organic electrolyte-matched NMC battery prepared in example 5 of the present invention;
fig. 6 is a charge-discharge curve of the organic electrolyte matched full cell prepared in example 6 of the present invention at high temperature.
Detailed Description
The principles and features of the present invention are described below in connection with specific embodiments, examples of which are provided for illustration only and are not intended to limit the scope of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other. The terms "comprising," "including," "containing," and "having" are intended to be non-limiting, as other steps and other ingredients not affecting the result may be added.
The embodiment of the invention provides an organic electrolyte with a wide working temperature range, wherein the organic electrolyte comprises electrolyte sodium salt and an organic solvent, and the organic solvent comprises one or more of a cyclic ether solvent, a chain ether solvent and a nitrile solvent. The organic solvent is selected to improve the working voltage window of the electrolyte, so that the prepared organic electrolyte can normally work in a wider voltage range.
Wherein the electrolyte sodium salt comprises one or more of sodium trifluoromethane sulfonate, sodium bis (trifluoromethane sulfonate) imide, sodium hexafluorophosphate, sodium tetrafluoroborate and sodium perchlorate. Preferably, the electrolyte sodium salt is one or more of sodium trifluoromethane sulfonate, sodium bis (trifluoromethane sulfonate) imide, and sodium hexafluorophosphate.
The molar concentration of the electrolyte sodium salt in the organic electrolyte is 0.1-5M, preferably 0.8-2.5M.
The cyclic ether solvent is a cyclic organic substance having at least one oxygen atom and having a carbon number of 2-10 (C2-C10), and the melting point of the cyclic organic substance is in the range of-20 ℃ to-150 ℃.
Further, the cyclic ether solvent includes one or more of ethylene oxide, tetrahydrofuran, tetrahydropyran, 2-methyltetrahydrofuran, 1, 3-dioxolane, 1, 3-dioxane, and 2, 2-dimethyltetrahydrofuran. In the embodiment of the present invention, preferably, the cyclic ether solvent includes one or more of 1, 3-dioxolane, 1, 3-dioxane, tetrahydrofuran, tetrahydropyran and 2-methyltetrahydrofuran having 3 to 5 carbon atoms.
The structural formula of the chain ether solvent comprises one or more [ -CH2OCH2- ] structural units, the number of carbon atoms contained in the chain ether solvent is in the range of 3-20, and the melting point of the chain ether solvent is in the range of-20-150 ℃.
Further, the chain ether solvent comprises one or more of methyl ether, diethyl ether, dimethoxymethane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether. In the embodiment of the invention, the chain ether solvent is preferably one or more of diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether or tetraethylene glycol dimethyl ether which have strong coordination complexing ability to cations.
The nitrile solvent contains at least one nitrile group and has a melting point in the range of 0 ℃ to 150 ℃, preferably, the nitrile solvent is one or more of acetonitrile, propionitrile, butyronitrile, isobutyronitrile, valeronitrile, 3-methoxy propionitrile or cyclopentane nitrile with a melting point of-40- (-120).
The organic electrolyte with the wide working temperature range provided by the embodiment of the invention has the physical properties of low viscosity and high conductivity, has weak solvation effect with sodium ions, has the advantages of low viscosity and melting point and high ion conductivity, and can work at the temperature of-50-60 ℃. The organic electrolyte is used for constructing a sodium ion battery, so that the working temperature of the battery can be effectively widened, and the safety and the cycling stability of the battery are improved.
The invention further aims to provide a sodium ion battery which comprises the organic electrolyte with a wide working temperature range, so that the problems of discomfort and non-wide working temperature range of the electrolyte of the existing sodium ion battery are solved.
The working temperature range of the organic electrolyte with a wide working temperature range is-50-60 ℃, and the ionic conductivity at the low temperature of-40 ℃ is 1.0x10 -5 -9.9×10 -4 s/cm, preferably 1.0X10 -4 -9.9×10 -3 s/cm。
The sodium ion battery also comprises a positive electrode plate, a negative electrode plate and a diaphragm clamped between the positive electrode plate and the negative electrode plate, wherein the positive electrode plate comprises 80-90% of positive electrode active material by mass fraction, 5-10% of conductive agent by mass fraction and 5-10% of binder by mass fraction, and the negative electrode plate comprises negative electrode active material.
The positive electrode active material comprises a compound of the formula NaxMO 2 (M comprises one or more of Fe, mn, ni, co, cu and Cr), a polyanionic compound or a prussian blue material; the negative electrode active material comprises graphite, hard carbon, a silicon-based negative electrode, a germanium-based negative electrode or a phosphorus-based negative electrode; the binder comprises one or more of polytetrafluoroethylene, polyvinylidene fluoride, sodium carboxymethyl cellulose and styrene-butadiene rubber.
Further, the binder is preferably one or more of polytetrafluoroethylene PTFE, polyvinylidene fluoride PVDF, and sodium carboxymethylcellulose CMC-Na.
The membrane comprises one of Celgard, GF-D (glass fiber membrane) and GF-A, preferably Celgard and GF-D membranes.
The preparation method of the sodium ion battery comprises the following steps: 1) Preparing a bare cell; 2) Preparing electrolyte; 3) And assembling the battery. The preparation method is an industry general method, and is not specifically detailed herein, and the following specific examples will be described by selecting different electrolyte sodium salts, organic solvents, and positive and negative plates.
The sodium ion battery provided by the invention comprises the organic electrolyte with a wide working temperature area, the organic electrolyte is higher in matching property when being applied to the sodium ion battery, the preferable organic solvent is matched with electrolyte sodium salt, so that the viscosity of the organic electrolyte can be kept in a more reasonable range, the conductivity of the organic electrolyte is further improved, meanwhile, the boiling point is higher, the melting point is lower, the working temperature range is wider, the stability is higher, and the sodium ion battery adopting the organic electrolyte with the wide working temperature area has the advantages of high charge and discharge efficiency, good cycle performance, high safety, wide working temperature range and low cost.
The invention is further illustrated below in connection with a method of preparing a sodium ion battery. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. The experimental methods, which do not address specific conditions in the following examples, are generally in accordance with the conditions recommended by the manufacturer. Percentages and parts are by mass unless otherwise indicated.
Example 1
The embodiment provides a sodium ion battery, which comprises the following specific steps:
1) Preparing a bare cell: sequentially stacking a sodium sheet, a diaphragm GF-D and a sodium sheet into a bare cell in a high-purity argon lower electrode shell;
2) And (3) preparing an electrolyte: preparing sodium ion battery electrolyte in a glove box filled with argon, wherein electrolyte salt is sodium hexafluorophosphate, and the concentration is 1M; the organic solvent is diethylene glycol dimethyl ether and 1, 3-dioxolane (volume ratio is 1:1), and the organic solvent is stirred and mixed uniformly to obtain the organic electrolyte of the embodiment 1;
3) Assembling a metal sodium symmetrical battery: dropwise adding the organic electrolyte obtained in the step 2) into a bare cell under high-purity argon, and completely sealing a battery shell after the cell is fully soaked to obtain a sodium ion battery;
4) Metal sodium symmetrical battery test: and carrying out constant-current charge and discharge test on the assembled metal sodium symmetrical battery on a blue electric tester at room temperature.
FIG. 1 is an ionic conductivity of the organic electrolyte prepared in example 1As can be seen from the graph of the temperature change, the ionic conductivity of the organic electrolyte decreases with increasing temperature, but the ionic conductivity can be as high as 1ms cm under the low temperature condition -1 This is one of the higher conductivity values reported so far.
Fig. 2 shows the viscosity of the organic electrolyte prepared in example 1 according to the temperature, and it can be seen from fig. 2 that the viscosity of the organic electrolyte gradually increases with the decrease in temperature. The lower the viscosity, the more favorable the ionic conduction at low temperature.
FIG. 3 shows the organic electrolyte prepared in example 1 matching sodium-sodium symmetric cells at a current density of 0.5mA/cm 2 Dough kneading capacity 1mAh/cm 2 As can be seen from FIG. 3, the current density of the sodium ion battery prepared in example 1 was 0.5mA/cm 2 The dough kneading capacity is 1mAh/cm 2 。
Example 2
The embodiment provides a sodium ion battery, which comprises the following specific steps:
1) Preparing a bare cell: weighing hard carbon, acetylene black and PVDF according to the mass ratio of 85:5:10, adding N-methyl pyrrolidone (NMP), grinding and mixing, coating on aluminum foil, drying, and stacking a hard carbon electrode, a diaphragm GF-D and a sodium sheet into a bare cell in an electrode shell at one time under high-purity argon;
2) And (3) preparing an electrolyte: preparing sodium ion battery electrolyte in a glove box filled with argon, wherein electrolyte salt is sodium hexafluorophosphate, and the concentration is 1M; the organic solvent is diethylene glycol dimethyl ether and 1, 3-dioxolane (volume ratio is 1:1), and the organic solvent is evenly stirred and mixed to obtain organic electrolyte;
3) Assembling a hard carbon battery: dropwise adding the organic electrolyte obtained in the step 2) into a bare cell under high-purity argon, and completely sealing a battery shell after the cell is fully soaked to obtain a sodium ion battery;
4) Cell electrochemical performance test: and carrying out charge and discharge test on the assembled sodium ion battery on a blue electric tester.
The test voltage interval is 0-2V, and the battery capacity and the charge-discharge multiplying power are calculated according to the mass of active substance hard carbon. Battery poweredThe flow density was 100mA g -1 The charge and discharge cycles were carried out at normal temperature, high temperature and low temperature, respectively, and the test performance results are shown in tables 1 to 3.
Fig. 4 the cycle performance diagram of the organic electrolyte-matched hard carbon battery prepared in example 2 at low temperature, and it can be seen from fig. 4 that the organic electrolyte prepared in example 2 has higher specific capacity at both-40 ℃ and-50 ℃ and good cycle stability.
Example 3
This embodiment provides a sodium ion battery, and the difference between this embodiment and embodiment 2 is that:
in the step 2), the organic solvent is 2-methyltetrahydrofuran; other parameters and steps were the same as in example 2.
The sodium ion battery prepared in example 3 was subjected to charge and discharge tests on a blue electric tester, the test voltage interval was 0-2V, and the battery capacity and charge and discharge rate were calculated by the mass of the active substance hard carbon. The current density of the battery is 100mA g -1 The charge and discharge cycles were carried out at normal temperature, high temperature and low temperature, respectively, and the test performance results are shown in tables 1 to 3.
Example 4
This embodiment provides a sodium ion battery, and the difference between this embodiment and embodiment 2 is that:
in step 2), the concentration of the electrolyte salt is 2M; other parameters and steps were the same as in example 2.
The sodium ion battery prepared in example 4 was subjected to charge and discharge test on a blue electricity tester, the test voltage interval was 0-2V, and the battery capacity and charge and discharge rate were calculated by the mass of the active substance hard carbon. The current density of the battery is 100mA g -1 The charge and discharge cycles were carried out at normal temperature, high temperature and low temperature, respectively, and the test performance results are shown in tables 1 to 3.
Example 5
The embodiment provides a sodium ion battery, which comprises the following specific steps:
1) Preparing a bare cell: weighing Na according to the mass ratio of 80:10:10 2/3 Mn 2/3 Ni 1/4 Cu 1/12 O 2 (NMC), acetylene black and PVDF, with addition of N-methylpyrroleGrinding and mixing alkanone (NMP), coating an aluminum foil into a positive electrode film, drying, and stacking the positive electrode film, the diaphragm GF-D and the sodium sheet into a bare cell in an electrode shell for one time under high-purity argon;
2) And (3) preparing an electrolyte: preparing sodium ion battery electrolyte in a glove box filled with argon, wherein electrolyte salt is sodium hexafluorophosphate, and the concentration is 1M; the organic solvent is diethylene glycol dimethyl ether and 1, 3-dioxolane (volume ratio is 1:1), and the organic solvent is evenly stirred and mixed to obtain organic electrolyte;
3) Assembling a sodium ion battery: dropwise adding the organic electrolyte obtained in the step 2) into a bare cell under high-purity argon, and completely sealing a battery shell after the cell is fully soaked to obtain a sodium ion battery;
4) And (3) testing electrochemical performance of the battery, namely, carrying out charge and discharge testing on the assembled sodium ion battery at room temperature on a blue electric tester. The test voltage interval is 2.5-4.2V. The battery capacity and the charge-discharge rate are calculated from the mass of the active material NMC. The current density of the battery is 20mAg -1 And (5) performing charge and discharge circulation at normal temperature.
Fig. 5 shows that the organic electrolyte prepared in example 5 matches the charge-discharge curve of NMC battery, and as can be seen from fig. 5, the organic electrolyte prepared in example 5 has good compatibility with positive electrode NMC, and the capacity of 10 cycles of cycle is not significantly attenuated.
Example 6
The embodiment provides a sodium ion battery, which comprises the following specific steps:
1) Preparing a bare cell, and weighing Na according to the mass ratio of 80:10:10 2/3 Mn 2/3 Ni 1/4 Cu 1/12 O 2 (NMC), acetylene black and PVDF, adding N-methyl pyrrolidone (NMP), grinding and mixing, and coating on aluminum foil to form a positive electrode film; weighing hard carbon, acetylene black and PVDF according to the mass ratio of 85:5:10, adding N-methyl pyrrolidone, grinding and mixing, coating an aluminum foil into a negative electrode film, drying, and stacking the positive electrode film, the diaphragm GF-D and the negative electrode film into a bare cell in an electrode shell at one time under high-purity argon;
2) And (3) preparing an electrolyte: preparing sodium ion battery electrolyte in a glove box filled with argon, wherein electrolyte salt is sodium hexafluorophosphate, and the concentration is 1M; the organic solvent is diethylene glycol dimethyl ether and 1, 3-dioxolane (volume ratio is 1:1), and the organic solvent is evenly stirred and mixed to obtain organic electrolyte;
3) Assembling a sodium ion battery: dropwise adding the organic electrolyte obtained in the step 2) into a bare cell under high-purity argon, and completely sealing a battery shell after the cell is fully soaked to obtain a sodium ion battery;
4) Cell electrochemical performance test: and carrying out charge and discharge test on the assembled sodium ion battery at high temperature on a blue electric tester. The test voltage interval is 2-4V, and the battery capacity and the charge-discharge multiplying power are calculated according to the mass of the active substance NMC. The battery was rated at 0.5C (corresponding to a current density of 40mA g -1 ) And (3) carrying out charge and discharge circulation at a low temperature and a high temperature.
Fig. 6 is a charge-discharge curve of the organic electrolyte-matched full cell prepared in example 6 at high temperature, and it can be seen from fig. 6 that the prepared organic electrolyte has good electrochemical properties at high temperature.
Comparative example 1
The difference between this comparative example and example 2 is that:
in the step 2), the organic solvent is ethylene carbonate and dimethyl carbonate (volume ratio 1:1);
other parameters and steps were the same as in example 2.
The sodium ion battery prepared in comparative example 1 was subjected to charge and discharge tests on a blue electric tester, the test voltage interval was 0-2V, and the battery capacity and charge and discharge rate were calculated by the mass of the active substance hard carbon. The current density of the battery is 100mA g -1 The charge and discharge cycles were carried out at normal temperature, high temperature and low temperature, respectively, and the test performance results are shown in tables 1 to 3.
Comparative example 2
The difference between this comparative example and example 2 is that:
in the step 2), the organic solvent is ethylene carbonate and propylene carbonate (volume ratio is 1:1);
other parameters and steps were the same as in example 2.
The sodium ion battery prepared in comparative example 2 was charged and discharged on a blue electric testerAnd (3) electrically testing, wherein the test voltage interval is 0-2V, and the battery capacity and the charge-discharge multiplying power are calculated according to the mass of the active substance hard carbon. The current density of the battery is 100mA g -1 The charge and discharge cycles were carried out at normal temperature, high temperature and low temperature, respectively, and the test performance results are shown in tables 1 to 3.
Table 1 room temperature electrochemical performance test of various examples
Table 2 high temperature electrochemical performance test of various examples
Table 3 low temperature electrochemical performance test of various examples
From tables 1-3, the above examples and comparative examples show that the organic electrolyte with a wide working temperature range provided by the invention has a wider temperature use range, higher ionic conductivity and lower viscosity than the conventional ester organic electrolyte, and maintains good low-temperature cycle performance while improving the normal-temperature cycle and high-temperature stability of the battery.
In summary, the invention utilizes the selection of electrolyte salt and organic solvent to prepare the sodium ion battery electrolyte solution with wide working temperature range, high ionic conductivity and low viscosity, and the assembled sodium ion battery has higher charge-discharge specific capacity and coulombic efficiency both at high temperature and low temperature, and has obvious advantages compared with the traditional ester electrolyte solution. Therefore, the invention provides the organic electrolyte capable of working in a wide temperature range, and the assembled battery has excellent electrochemical performance at-50 to 60 ℃ and has excellent application prospect.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.
Claims (4)
1. An organic electrolyte with a wide working temperature range, which is characterized by comprising electrolyte sodium salt and an organic solvent, wherein the organic solvent comprises the following components in percentage by volume: 1 and 1, 3-dioxolane, wherein the electrolyte sodium salt is sodium hexafluorophosphate, and the molar concentration of the sodium hexafluorophosphate is 1M.
2. A sodium ion battery comprising the organic electrolyte of claim 1 having a broad operating temperature range.
3. The sodium ion battery of claim 2, further comprising a positive electrode sheet, a negative electrode sheet, and a separator sandwiched between the positive electrode sheet and the negative electrode sheet, wherein the positive electrode sheet comprises 80-90% by mass of a positive electrode active material, 5-10% by mass of a conductive agent, and 5-10% by mass of a binder, and the negative electrode sheet comprises a negative electrode active material.
4. A sodium ion battery according to claim 3, wherein the positive electrode active material comprises a compound of the formula Na x MO 2 M comprises one or more of Fe, mn, ni, co, cu and Cr, a polyanionic compound or a prussian blue material;
the negative electrode active material comprises graphite, hard carbon, a silicon-based negative electrode, a germanium-based negative electrode or a phosphorus-based negative electrode;
the binder comprises one or more of polytetrafluoroethylene, polyvinylidene fluoride, sodium carboxymethyl cellulose and styrene-butadiene rubber.
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| CN113937342A (en) * | 2021-09-20 | 2022-01-14 | 复旦大学 | Wide-temperature-range sodium ion battery based on iron-based polyanionic anode and tin-carbon cathode |
| CN113964376A (en) * | 2021-10-18 | 2022-01-21 | 南京大学 | Preparation and application of novel low eutectic agent |
| CN114464885A (en) * | 2022-02-16 | 2022-05-10 | 温州大学碳中和技术创新研究院 | Flame-retardant sodium-ion battery electrolyte and preparation method of safe sodium-ion battery |
| CN114784381A (en) * | 2022-06-07 | 2022-07-22 | 湖北万润新能源科技股份有限公司 | Electrolyte, preparation method thereof and lithium ion battery |
| CN115051034A (en) * | 2022-07-15 | 2022-09-13 | 南开大学 | Wide-temperature-range sodium ion battery electrolyte |
| CN115799645B (en) * | 2023-02-06 | 2023-10-27 | 宁德时代新能源科技股份有限公司 | Electrolyte for sodium secondary battery, sodium secondary battery and electricity utilization device |
Citations (1)
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| CN105810997A (en) * | 2014-12-31 | 2016-07-27 | 龙能科技（苏州）有限公司 | Lithium ion battery electrolyte solution and preparation method thereof, and lithium ion battery |
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| CN109103489B (en) * | 2017-06-21 | 2020-05-05 | 宁德时代新能源科技股份有限公司 | Electrolyte and battery |
| JP7223221B2 (en) * | 2017-09-12 | 2023-02-16 | セントラル硝子株式会社 | Additive for non-aqueous electrolyte, non-aqueous electrolyte, and non-aqueous electrolyte battery |
| CN108172903B (en) * | 2017-12-26 | 2020-11-03 | 深圳先进技术研究院 | Electrolyte, sodium ion secondary battery and preparation method thereof |
| CN108232161A (en) * | 2018-01-12 | 2018-06-29 | 南开大学 | A kind of full battery of sodium ion |
| CN113140723A (en) * | 2021-03-02 | 2021-07-20 | 复旦大学 | Wide-temperature-range sodium ion battery based on metal bismuth cathode |
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