CN116344824B - Ferric sodium sulfate positive electrode material, and preparation method and application thereof - Google Patents
Ferric sodium sulfate positive electrode material, and preparation method and application thereof Download PDFInfo
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- CN116344824B CN116344824B CN202310489271.7A CN202310489271A CN116344824B CN 116344824 B CN116344824 B CN 116344824B CN 202310489271 A CN202310489271 A CN 202310489271A CN 116344824 B CN116344824 B CN 116344824B
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- Prior art keywords
- polyoxyethylene
- sodium
- positive electrode
- electrode material
- sulfate
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 title claims description 34
- 229910052938 sodium sulfate Inorganic materials 0.000 title claims description 33
- 235000011152 sodium sulphate Nutrition 0.000 title claims description 33
- YPPMLCHGJUMYPZ-UHFFFAOYSA-L sodium;iron(2+);sulfate Chemical compound [Na+].[Fe+2].[O-]S([O-])(=O)=O YPPMLCHGJUMYPZ-UHFFFAOYSA-L 0.000 claims abstract description 71
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- -1 polyoxypropylene Polymers 0.000 claims description 83
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- 238000010438 heat treatment Methods 0.000 claims description 46
- 229910001415 sodium ion Inorganic materials 0.000 claims description 38
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 36
- 239000002798 polar solvent Substances 0.000 claims description 23
- 239000012454 non-polar solvent Substances 0.000 claims description 22
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 20
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- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000284 resting effect Effects 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 229940035044 sorbitan monolaurate Drugs 0.000 description 1
- 239000001587 sorbitan monostearate Substances 0.000 description 1
- 235000011076 sorbitan monostearate Nutrition 0.000 description 1
- 229940035048 sorbitan monostearate Drugs 0.000 description 1
- 239000001589 sorbitan tristearate Substances 0.000 description 1
- 235000011078 sorbitan tristearate Nutrition 0.000 description 1
- 229960004129 sorbitan tristearate Drugs 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- 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 discloses a sodium iron sulfate positive electrode material and a preparation method and application thereof, wherein the positive electrode material comprises sodium iron sulfate and amphiphilic molecules for modifying the sodium iron sulfate, the hydrophilic ends of the amphiphilic molecules face towards the sodium iron sulfate, and the hydrophobic ends of the amphiphilic molecules face away from the sodium iron sulfate; the HLB of the amphipathic molecule is 10-16. According to the sodium iron sulfate positive electrode material provided by the invention, amphipathic molecules with moderate hydrophilic-hydrophobic balance (HLB) are introduced in the preparation process, so that the surface of prepared sodium iron sulfate particles is uniformly coated with a layer of amphipathic molecules, wherein the hydrophilic end of the amphipathic molecules points to sodium iron sulfate, and the hydrophobic end points to the outer side, thereby isolating the contact between the sodium iron sulfate particles and air and protecting sodium iron sulfate. The sodium ferric sulfate provided by the invention can be placed in the air for a long time, and the electrochemical performance of the sodium ferric sulfate is not obviously degraded after being placed for 12 months.
Description
Technical Field
The invention belongs to the technical field of new energy materials, and particularly relates to a sodium iron sulfate positive electrode material, a preparation method and application thereof.
Background
The sodium ion battery is used as a supplement of the lithium ion battery, and is expected to be applied to the fields of low-speed electric vehicles, communication base stations, large-scale energy storage and the like. Compared with a lithium ion battery, the sodium ion battery has the advantages that the crust reserve of sodium resources is rich (2.75%), is more than 400 times of lithium (0.0065%), and is uniform in global distribution and simple in extraction. In addition, the internal resistance of the sodium ion battery is higher than that of the lithium ion battery, the instantaneous heating value is less under the condition of short circuit, the temperature rise is lower, the thermal runaway temperature is higher than that of the lithium ion battery, and the safety is higher; the working temperature range of the sodium ion battery is wider (-40 ℃ to 80 ℃), and the sodium ion battery is suitable for extremely cold and hot scenes; the fast charge capability of the sodium ion battery is excellent, and the charge time only needs about 10 minutes; the sodium ion battery can adopt aluminum foils as positive and negative current collectors, and the current collector has lower cost. Therefore, the development of the technology of the sodium ion battery with high efficiency and low cost is of great significance.
The positive electrode material is used as a key component of the sodium ion battery, and influences the cost, energy density, cycle life and the like of the sodium ion battery. The positive electrode material affects the energy density and power density of the sodium ion battery by affecting the capacity of containing sodium ions and the smoothness of a transmission channel, and meanwhile, the stability and impurity components of the positive electrode material affect the service life of the battery. Currently, the main current sodium ion positive electrode materials comprise three main types of oxides, polyanion compounds and Prussian blue analogues. Compared with the prior art, the oxide positive electrode material has the advantages of simple structure, higher energy density and moderate cycle performance; the polyanion type positive electrode material has stable structure, lower energy density and best cycle performance; the Prussian blue analogues have adjustable working voltage, good multiplying power performance and improved cycle performance. Sodium iron sulfate (chemical formula Na 2+x Fe 2-y (SO 4 ) 3 X=0 to 0.7 and y=0 to 0.35) is a polyanion type positive electrode material applied to sodium ion batteries, has the advantages of rich crust of raw materials, low cost, high working voltage and good long cycle performance, and is reported in 2014 that the material shows the highest Fe in the existing positive electrode materials due to strong induction effect of sulfate radical 3+ /Fe 2+ Oxidation-reduction potential, thereby compensating short plates with insufficient energy density to a certain extent, and the theoretical energy density reaches 540Wh/kg. Non-stoichiometric ferric sodium sulfate has been reported to expand the scope of the search for this system. The three-dimensional skeleton structure of the sodium ferric sulfate can be kept stable in the sodium ion migration process, so that the circulating performance is good. One of the key problems with sodium iron sulfate is its sensitivity to air. Due to the interaction with moisture and oxygen in the air, sodium iron sulfate can generate surface residual alkali, and part of ferrous ions are oxidized, so that pulping and coating difficulties are increased, and specific capacity and cycle performance are deteriorated. Aiming at the problem, the related technology improves the oxidation resistance of the material by preparing the nitrogen-doped graphene coated ferric sodium sulfate positive electrode, and detects Fe after one month of exposure in the air 3+ (14%) was significantly lower than the uncoated material (29%). There are also reports of reduced graphene oxide coated sodium iron sulfate positive electrodes, but no material is provided to the environmentStability. However, in the existing researches, most of the graphene materials are needed, and the cost is high; and the flow is complex. And most of the obtained materials still contain ferric iron, which is unfavorable for the exertion of electrochemical performance.
Therefore, the method solves the problems of sensitivity to air humidity and oxidizing atmosphere and the like of the prior ferric sodium sulfate positive electrode material.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems existing in the prior art. Therefore, the invention provides the ferric sodium sulfate positive electrode material, and the amphipathic molecules with moderate hydrophilic-hydrophobic balance (HLB) are introduced in the preparation process, so that the surface of the prepared ferric sodium sulfate particles is uniformly coated with a layer of amphipathic molecules, wherein the hydrophilic ends of the amphipathic molecules point to the ferric sodium sulfate, and the hydrophobic ends point to the outer side, thereby isolating the contact between the ferric sodium sulfate particles and air and protecting the ferric sodium sulfate. The sodium ferric sulfate anode material provided by the invention can be placed in the air for a long time, and the electrochemical performance of the sodium ferric sulfate anode material is not obviously degraded after being placed for 12 months.
The second aspect of the invention provides a preparation method of the sodium iron sulfate positive electrode material.
The third aspect of the invention provides an application of the positive electrode material in sodium ion battery preparation.
A fourth aspect of the invention provides the use of a sodium ion battery in the field of secondary batteries.
According to the sodium iron sulfate positive electrode material, the positive electrode material comprises sodium iron sulfate and amphiphilic molecules for modifying the sodium iron sulfate, wherein the hydrophilic ends of the amphiphilic molecules face to the sodium iron sulfate, and the hydrophobic ends of the amphiphilic molecules face away from the sodium iron sulfate; the HLB of the amphipathic molecule is 10-16.
The sodium iron sulfate positive electrode material provided by the embodiment of the invention has at least the following beneficial effects:
in the preparation process of the sodium iron sulfate positive electrode material, the surface of sodium iron sulfate particles is surrounded by amphiphilic molecules by selecting the amphiphilic molecules with moderate hydrophilic-hydrophobic balance (HLB). The hydrophilic end of the amphipathic molecule points to the sodium iron sulfate, and the hydrophobic end points to the outside, so that contact between sodium iron sulfate particles and air is isolated, the stability of sodium iron sulfate in the air is effectively improved, and the sodium iron sulfate anode material can be stably placed in an air environment for 12 months without obvious attenuation of electrochemical performance.
According to some preferred embodiments of the invention, the amphipathic molecule has an HLB of 13 to 15.
According to some embodiments of the present invention, the amphiphilic molecule comprises polyoxypropylene (5 PO) wool alcohol ether, polyoxyethylene (5 EO) sorbitan monooleate, polyoxyethylene cetyl ether, polyoxyethylene (20 EO) sorbitan tristearate, polyoxyethylene lauryl ether, polyoxyethylene (20 EO) sorbitan trioleate, polyoxyethylene oxypropylene oleate, polyoxyethylene lanolin derivative, polyoxyethylene alcohol, polyoxyethylene polyoxyethylene monooleate, polyoxyethylene monopalmitate, polyoxyethylene monostearate, polyoxyethylene (10 EO) oleyl alcohol ether, polyoxyethylene monolaurate, polyoxyethylene alkylphenol, polyoxyethylene (10 EO) acetylated lanolin derivative, polyoxyethylene sorbitol lanolin derivative, polyoxyethylene alkylaryl ether polyoxyethylene monooleate, polyoxyethylene monopalmitate, polyoxyethylene monostearate, polyoxyethylene (10 EO) oleyl alcohol ether, polyoxyethylene monolaurate polyoxyethylene alkylphenol, polyoxyethylene (10 EO) acetylated lanolin derivative, polyoxyethylene sorbitol lanolin derivative, polyoxyethylene alkylaryl ether, at least one of polyoxyethylene oxypropylene stearate and polyoxyethylene monostearate.
According to some embodiments of the invention, the amphipathic molecule further comprises a mixed fatty acid polyoxyethylene ester and a polyoxyethylene resinate.
According to some preferred embodiments of the present invention, the amphiphilic molecule comprises at least one of polyoxyethylene (10 EO) acetylated lanolin derivative, polyoxyethylene sorbitol lanolin derivative, polyoxyethylene alkylaryl ether, polyoxyethylene monolaurate, polyoxyethylene lauryl ether, polyoxyethylene castor oil, polyoxyethylene vegetable oil, polyoxyethylene (4 EO) sorbitan monolaurate, cholesterol ether, lanolin ether, polyoxyethylene sorbitan monolaurate, polyoxyethylene (20 EO) sorbitan monostearate, polyoxyethylene (20 EO) oleyl ether, polyoxyethylene (20 EO) methyl glucoside sesquioleate, polyoxyethylene (16 EO) lanolin ether, polyoxyethylene (20 EO) sorbitan monooleate, and polyoxyethylene monostearate.
According to a second aspect of the present invention, a method for preparing the positive electrode material includes:
mixing and heating the preparation raw materials of the sodium iron sulfate, the amphiphilic molecules, the nonpolar organic solvent and the polar solvent, and removing impurities;
the mixed heating comprises a first heating and a second heating which are sequentially carried out;
the temperature of the first heating is 50-100 ℃; the time of the first heating is 1-12 h;
the temperature of the second heating is 120-250 ℃; the time of the second heating is 1-12 h.
The preparation method of the positive electrode material provided by the embodiment of the invention has at least the following beneficial effects:
1. the first low-temperature heating and heat preservation can promote the uniformity of the system, thereby providing favorable conditions for the second heating high-temperature coating, improving the air stability of the anode material and promoting the formation of the sodium iron sulfate anode material by the second heating and heat preservation.
2. The effective combination of the polar solvent and the nonpolar solvent can promote the amphiphilic molecules to form a protective layer with uniform hydrophilic ends facing the sodium iron sulfate and hydrophobic ends facing away from the sodium iron sulfate on the surface of the sodium iron sulfate sample.
According to some embodiments of the invention, the first heating is at a temperature of 70-90 ℃; the time of the first heating is 1-3 h.
According to some embodiments of the invention, the second heating is at a temperature of 170-190 ℃; the second heating time is 3-5 h.
According to some embodiments of the invention, the first heating is at a temperature of 80 ℃; the time of the first heating is 2h.
According to some embodiments of the invention, the second heating is at a temperature of 180 ℃; the time of the second heating is 4h.
According to some embodiments of the invention, the step of removing impurities comprises cooling, solid-liquid separation, washing and drying to obtain the target product.
According to some embodiments of the invention, a method for preparing the positive electrode material includes:
s1: mixing the preparation raw materials of the sodium iron sulfate, the amphiphilic molecules, the nonpolar organic solvent and the polar solvent to obtain a mixed solution;
s2: placing the mixed solution in the step S1 in a stainless steel reaction kettle with a polytetrafluoroethylene lining, and heating;
s3: and (3) heating, cooling to normal temperature, and carrying out suction filtration (solid-liquid separation), absolute alcohol washing and natural airing to obtain a target product.
The preparation method provided by the invention has the advantages of simple preparation steps, low energy consumption, good product uniformity and high yield.
According to some embodiments of the invention, the polar solvent comprises at least one of water, formamide, acetone, trifluoroacetic acid, ethanol, chloroform, diethyl ether, acetic acid, acetonitrile, isopropanol, methanol, dimethyl sulfoxide, acetonitrile, N-dimethylformamide, hexamethylphosphoramide, pyridine, tetramethyl ethylenediamine, triethylamine, N-butanol, dioxane, tetrahydrofuran, and methyl formate.
According to some embodiments of the invention, the non-polar solvent comprises at least one of benzene, carbon tetrachloride, hexane, isooctane, methylene chloride, cyclohexane, petroleum ether, and pentane.
According to some embodiments of the invention, the preparation raw materials of the sodium iron sulfate comprise sodium sulfate and ferrous sulfate hydrate.
According to some embodiments of the invention, the ferrous sulfate hydrate includes at least one of ferrous sulfate monohydrate, ferrous sulfate pentahydrate, and ferrous sulfate heptahydrate.
According to some embodiments of the invention, the ratio of the polar solvent, the non-polar solvent, the amphiphilic molecule, the sodium sulfate and the ferrous sulfate hydrate is 1-20:1-20:10-500:5-6.75:10-13.5, wherein the polar solvent and the non-polar solvent are calculated in volume liters, the amphiphilic molecule is calculated in mass grams, and the sodium sulfate and the ferrous sulfate hydrate are calculated in mass moles of the substance.
According to some preferred embodiments of the present invention, the ratio of the polar solvent, the non-polar solvent, the amphiphilic molecule, the sodium sulfate and the ferrous sulfate hydrate is 10-20:10-20:100-500:5-6.75:10-13.5, wherein the polar solvent and the non-polar solvent are calculated in volume liters, the amphiphilic molecule is calculated in mass grams, and the sodium sulfate and the ferrous sulfate hydrate are calculated in mass moles.
According to some preferred embodiments of the invention, the ratio of the polar solvent, the non-polar solvent, the amphiphilic molecule, the sodium sulfate and the ferrous sulfate hydrate is 10:10:100:6:12, wherein polar solvent and non-polar solvent are calculated in volume liters, amphiphilic molecule are calculated in mass grams, sodium sulfate and ferrous sulfate hydrate are calculated in mass moles of substance.
Use of a positive electrode material according to an embodiment of the third aspect of the invention in a sodium ion battery.
According to some embodiments of the invention, the method for preparing a sodium ion battery comprises:
a1: mixing a sodium ferric sulfate anode material, a conductive agent and a binder in a mass ratio of 8:1:1, fully grinding, and then adding a proper amount of N-methylpyrrolidone to form uniform slurry; coating the slurry on the surface of an aluminum foil by using a scraper, drying in vacuum, cutting into wafers with the diameter of 10mm, compacting, and reserving as a positive electrode plate for standby.
A2: the sodium metal is pressed into slices in a glove box protected by inert gas, cut into wafers with the diameter of 12mm and reserved as the negative electrode of the battery for standby.
A3: commercial glass fiber films were cut into 16mm diameter disks and left as a separator for use.
A4: in an inert gas-protected glove box, the prepared battery positive electrode, the prepared separator and the prepared battery negative electrode are sequentially and tightly stacked, and commercial electrolyte (1.0M NaClO 4 in EC: pc=1:1 vol%) to completely wet the separator, and then the above-mentioned stacked portion was sealed into a button cell case to complete the cell assembly.
According to some embodiments of the invention, the conductive agent comprises: at least one of conductive carbon black, ketjen black, super P, conductive carbon spheres, conductive graphite, carbon nanotubes, carbon fibers and graphene.
According to some embodiments of the invention, the adhesive comprises: at least one of vinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, carboxymethyl cellulose, SBR rubber and polyolefin.
After the ferric sodium sulfate positive electrode material prepared in the invention is assembled into a battery, the hydrophobic end of the amphiphilic molecule can be well connected with the positive electrode and the organic solvent in the electrolyte, so that the wettability between the positive electrode and the electrolyte is increased, and an effective path is provided for rapid conduction of sodium ions. Compared with other methods, the method provided by the invention has the advantages of simple scheme flow and low energy consumption; the prepared ferric sodium sulfate anode has good air stability and good multiplying power performance.
Use of a sodium-ion battery according to an embodiment of the fourth aspect of the present invention in the field of secondary batteries.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
The foregoing and/or additional aspects and advantages of the invention will become apparent and may be better understood from the following description of embodiments taken in conjunction with the accompanying drawings in which:
FIG. 1 is a schematic structural diagram of a sodium iron sulfate positive electrode material according to example 1 of the present invention;
FIG. 2 is an XRD pattern of the sodium iron sulfate positive electrode material prepared in example 1 (fresh sample), the sodium iron sulfate positive electrode material prepared in example 1 after 12 months in air (sample after 12 months of standing), and standard ferrous sulfate;
fig. 3 is an SEM image of the sodium iron sulfate positive electrode material prepared in example 1 (fresh sample), and the sodium iron sulfate positive electrode material prepared in example 1 after being left in air for 12 months (sample after being left for 12 months);
fig. 4 is a graph of the cycle capacity of the battery prepared starting from (fresh sample) and (sample after 12 months of rest) of example 1;
fig. 5 is charge and discharge curves of 500 th and 900 th turns of the battery prepared using the sample of example 1 after 12 months of rest as a raw material.
Detailed Description
Embodiments of the present invention are described in detail below, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to like or similar elements or elements having like or similar functions throughout. The embodiments described below by referring to the drawings are illustrative only and are not to be construed as limiting the invention.
Example 1
The embodiment discloses a sodium ferric sulfate positive electrode material and a preparation method thereof, and the specific steps are as follows:
s1: mixing 10 liters of distilled water, 10 liters of benzene, 100 grams of polyoxyethylene castor oil, 6 moles of sodium sulfate and 12 moles of ferrous sulfate heptahydrate to obtain a mixed solution;
s2: placing the mixed solution in a stainless steel reaction kettle with a 40-liter polytetrafluoroethylene lining, heating to 80 ℃, preserving heat for 2 hours, then heating to 180 ℃, and preserving heat for 4 hours;
s3: cooling to normal temperature, filtering (solid-liquid separation), washing with absolute alcohol, and naturally airing to obtain the target product.
Figure 2 is an XRD pattern of the fresh sample obtained in example 1, the sample after 12 months of rest in air, and standard ferrous sulfate. As can be seen from the figure, the diffraction spectrum of the sample obtained in example 1 matches well with the standard diffraction spectrum, and the XRD of the sample after 12 months of standing in air still matches well with the standard diffraction spectrum.
Fig. 3 is an SEM image of the sample obtained in example 1 after 12 months of standing in air. From the graph, the sample is still good in appearance after being placed, and the problems of deformation, surface roughening, tiny particle precipitation and the like of particles are not found;
fig. 4 is a graph of the cycle capacity of the battery prepared from the materials of example 1 (fresh sample) and (sample after 12 months of rest). As seen from the figure, both show good cycle stability, and the long cycle performance of the sample after being placed is basically maintained at the original level;
fig. 5 is a charge-discharge curve of 500 th and 900 th turns of the battery prepared by using the sample of example 1 after 12 months of standing as a raw material; as can be seen from the figure, the electrochemical reversibility and stability of the sample after resting are good.
Examples 2 to 8 were modified from example 1 only in the type of the nonpolar solvent, and the specific experimental conditions are shown in table 1.
Examples 9 to 10 were compared with example 1, and the specific experimental conditions are shown in Table 1, except that the volume of the nonpolar solvent was changed.
Examples 11 to 18 were modified in the type of polar solvent as compared with example 1, and specific experimental conditions are shown in table 1.
Examples 19 to 20 were compared with example 1, and the specific experimental conditions are shown in table 1, except that the volume of the polar solvent was changed.
Examples 21 to 40 were modified in the types of amphiphilic molecules as compared with example 1, and specific experimental conditions are shown in Table 1.
Examples 41 to 45 were modified only in terms of the mass of the amphipathic molecules as compared with example 1, and the specific experimental conditions are shown in Table 1.
Examples 46 to 48 were modified in the amount of sodium sulfate material as compared with example 1, and the specific experimental conditions are shown in Table 1.
Examples 49 to 50 were modified in the type of ferrous sulfate hydrate as compared with example 1, and specific experimental conditions are shown in table 1.
Examples 51 to 53 were modified in terms of the amount of ferrous sulfate heptahydrate material as compared with example 1, and the specific experimental conditions are shown in table 1.
Examples 54 to 55 were modified only by T1 as compared with example 1, and the specific experimental conditions are shown in Table 1.
Examples 56 to 57 were modified from example 1 only by t1, and the specific experimental conditions are shown in Table 1.
Examples 58 to 59 were modified only by T2 as compared with example 1, and the specific experimental conditions are shown in Table 1.
Examples 60 to 61 were modified by t2 alone compared with example 1, and the specific experimental conditions are shown in Table 1.
Examples 62 to 65 were compared with example 1, in which a mixed polar solvent, a mixed nonpolar solvent, a mixed amphipathic molecule and a mixed ferrous sulfate hydrate were used.
Examples 66 to 67 were modified in combination with examples 1 by T1, T1, T2 and T2, and the specific experimental conditions are shown in Table 1.
Table 1 experimental conditions for examples 2 to 67
Comparative example 1
This comparative example discloses a sodium iron sulfate positive electrode material and a method for preparing the same, and this comparative example is different from example 1 in that the polyoxyethylated castor oil in example 1 is not included, and other conditions are the same as in example 1.
Comparative example 2
This comparative example discloses a sodium iron sulfate positive electrode material and a method for preparing the same, and the comparative example is different from example 1 in that distilled water in example 1 is not included, and other conditions are the same as in example 1.
Comparative example 3
This comparative example discloses a sodium iron sulfate positive electrode material and a method for preparing the same, and the comparative example is different from example 1 in that benzene in example 1 is not included, and other conditions are the same as in example 1.
Comparative example 4
This comparative example discloses a sodium iron sulfate positive electrode material and a preparation method thereof, and the comparative example is different from example 1 in that the temperature is directly raised to 180 ℃ without performing a 2-hour heat preservation operation at 80 ℃ under the same other conditions as in example 1.
Comparative example 5
The comparative example discloses a sodium iron sulfate positive electrode material and a preparation method thereof, and the comparative example is different from example 1 in that the temperature is kept for 2 hours at 80 ℃ and is not raised to 180 ℃ any more, and other conditions are the same as example 1.
Comparative example 6
This comparative example discloses a sodium iron sulfate positive electrode material and a method for preparing the same, and the comparative example is different from example 1 in that tetraethyleneglycol oleic acid having an HLB of less than 10 (HLB value of 7.7) is introduced into an amphipathic molecule, and other conditions are the same as example 1.
Comparative example 7
This comparative example discloses a sodium iron sulfate positive electrode material and a method for preparing the same, and the comparative example is different from example 1 in that potassium oleate having an HLB of more than 16 (HLB value of 20) is introduced into an amphipathic molecule, and other conditions are the same as example 1.
Test example 1
Test example 1 is a sodium ion battery prepared from the sodium ferric sulfate positive electrode materials of comparative examples 1 to 7 and examples 1 to 67, and the preparation method comprises the following steps:
a1: preparing a positive electrode: the positive electrode active materials of examples 1 to 67 and comparative examples 1 to 7, conductive carbon (SuperP) and a binder (polyvinylidene fluoride) are mixed according to the mass ratio of 7.5:1.5:1, and a proper amount of nitrogen methyl pyrrolidone is added after the mixture is sufficiently ground to form uniform slurry; coating the slurry on the surface of an aluminum foil by using a scraper, drying in vacuum, cutting into wafers with the diameter of 10mm, compacting, and reserving as a positive electrode plate for standby.
A2: preparing a negative electrode: the sodium metal is pressed into slices in a glove box protected by inert gas, cut into wafers with the diameter of 12mm and reserved as the negative electrode of the battery for standby.
A3: preparing a diaphragm: commercial glass fiber films were cut into 16mm diameter disks and left as a separator for use.
A4: assembling a battery: in an inert gas-protected glove box, the prepared battery positive electrode, the prepared separator and the prepared battery negative electrode are sequentially and tightly stacked, and commercial electrolyte (1.0M NaClO 4 in EC: pc=1:1 vol%) to completely wet the separator, and then the above-mentioned stacked portion was sealed into a button cell case to complete the cell assembly.
Performance test: sodium ion batteries prepared from the sodium ferric sulfate positive electrode materials of comparative examples 1 to 7 and examples 1 to 67 were tested. The constant-current charge and discharge test adopts a BTSDA test system of Shenzhen Xinwei electronic Co Ltd, the environment is a constant temperature and humidity room (25 ℃ and 35%), and the test voltage range is 2.0-4.5V. The first ten rounds of magnification were taken at 0.1C, and the eleventh round of starting magnification was changed to 1C (1c=120 mAh/g). The test results are shown in table 2; wherein the median voltage refers to the median voltage of the 100 th turn, the capacity retention refers to the capacity retention of the 1000 th turn relative to the 11 th turn, and the test results are shown in table 2.
Table 2: electrochemical test results for sodium ion batteries
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As can be seen from table 2:
compared with the sodium ion battery prepared by preparing the ferric sodium sulfate positive electrode material in the embodiment 1, the influence rules of different preparation conditions on the product performance are summarized as follows:
as can be seen from the sodium ion batteries prepared from the sodium iron sulfate positive electrode materials of examples 2 to 8 and example 1, the types of nonpolar solvents have little influence on the electrochemical performance and air stability of the batteries;
as can be seen from the preparation of the sodium ion batteries from the sodium ferric sulfate positive electrode materials in examples 9 and 10 and example 1, when the volume ratio of the nonpolar solvent is too small, the specific capacities of the positive electrode material and the positive electrode material after 12 months of storage are reduced, and the specific capacity reduction is more serious after storage, which indicates that too small volume of the nonpolar solvent is unfavorable for the generation of the positive electrode material and is unfavorable for the stability of the positive electrode material in air; when the volume ratio of the nonpolar solvent reaches a certain value, the electrochemical performance and the air stability of the cathode material are not greatly influenced.
As is clear from the sodium ion batteries prepared from the sodium iron sulfate positive electrode materials of examples 11 to 18 and example 1, the kind of the polar solvent has little influence on the electrochemical properties and air stability of the product.
As can be seen from the preparation of the sodium ion batteries from the sodium ferric sulfate positive electrode materials in examples 19 and 20 and example 1, when the volume ratio of the polar solvent is too small, the specific capacities of the positive electrode material and the positive electrode material after 12 months of storage are reduced, and the specific capacity reduction is more serious after storage, which indicates that the too small volume of the polar solvent is unfavorable for the air stability of the positive electrode material; after the volume ratio reaches a certain value, the electrochemical performance and the air stability are not greatly influenced.
As can be seen from the sodium ion batteries prepared from the sodium iron sulfate positive electrode materials of examples 21 to 40 and example 1, the amphiphilic molecules with different HLB values have little influence on the electrochemical performance of the positive electrode material, but have a significant influence on the air stability of the positive electrode material. When the amphipathic molecules with HLB values between 13 and 15 (corresponding to examples 21 to 29) are adopted, the initial specific capacity, the median voltage and the capacity retention rate of the positive electrode material are higher after the positive electrode material is placed for 12 hours, which indicates that the air stability of the sample is better.
From the sodium ion batteries prepared from the sodium iron sulfate positive electrode materials of examples 41 to 45 and example 1, it is known that the amount of the amphiphilic molecules used affects the air stability of the product. When the amount of the amphipathic molecules used was too small (examples 41 and 42), the electrochemical performance of the positive electrode material became poor after 12 months of storage, indicating that the air stability of the positive electrode material was insufficient; when the amount of the amphipathic molecules is sufficient (examples 1 and 43 to 45), the sample has good air stability; preferably 100/6 g of amphiphilic molecule is used per mole of sodium sulphate.
As is clear from the sodium ion batteries prepared from the sodium iron sulfate positive electrode materials of examples 46 to 53 and example 1, the amounts of sodium sulfate substances, ferrous sulfate hydrate, and ferrous sulfate hydrate substances have little influence on the electrochemical properties and air stability of the products.
As can be seen from the preparation of the sodium ion batteries from the sodium iron sulfate positive electrode materials of examples 54 to 57 and example 1, the electrochemical performance and air stability of the samples were poor when the heating temperature and the heat preservation time were insufficient in the first stage; the heating temperature in the first stage is preferably 80℃and the holding time is preferably 2 hours.
As can be seen from the preparation of the sodium ion batteries from the sodium iron sulfate positive electrode materials of examples 58 to 61 and example 1, the electrochemical performance and air stability of the samples were poor when the heating temperature and the heat preservation time were insufficient in the second stage; the second stage heating temperature is preferably 180℃and the incubation time is 4 hours.
As can be seen from the sodium ion batteries prepared from the sodium iron sulfate positive electrode materials of examples 62 to 65 and example 1, the addition of the mixed polar solvent, the mixed nonpolar solvent, the mixed amphiphilic molecule and the mixed ferrous sulfate hydrate has little influence on the electrochemical performance and the air stability of the product.
As can be seen from the sodium ion batteries prepared from the sodium iron sulfate positive electrode materials of examples 66 to 67 and example 1, the time of the first heating stage cannot be too short, the heating temperature of the second stage cannot be too low, otherwise the electrochemical performance and air stability of the sample will be poor.
Examples 2 to 67 compared with comparative examples 1 to 7, the following conclusions were drawn:
the comparison of examples 2-67 with comparative example 1 shows that when no amphiphilic molecule is used, the electrochemical performance of the initial sample is equivalent, but the electrochemical performance of the sample after 12 months of standing is obviously degraded, which indicates that the amphiphilic molecule plays a good role in protecting the air stability of the sample.
The comparison results of examples 2 to 67 and comparative examples 2 to 3 show that when no polar solvent or nonpolar solvent is added, the electrochemical performance of the initial battery is equivalent, but the electrochemical performance of the sample after 12 months of standing is remarkably deteriorated, and the capacity retention rate of comparative examples 2 to 3 is slightly better than that of comparative example 1; it is speculated that the possible reason is that the effective combination of polar and nonpolar solvents can promote the amphiphilic molecules to form a uniform protective layer with the hydrophilic ends of the amphiphilic molecules facing toward the sodium iron sulfate and the hydrophobic ends of the amphiphilic molecules facing away from the sodium iron sulfate on the surface of the sodium iron sulfate sample.
The comparison of examples 2-67 with comparative example 4 shows that the low temperature heating and heat preservation in the first stage can improve the air stability of the sample; it is speculated that the reason is that the low temperature heating and incubation of the first stage can promote uniformity of the system, thereby providing favorable conditions for high temperature coating.
Comparison of examples 2-67 with comparative example 5 shows that the high temperature heating and incubation of the second stage has a great effect on the electrochemical properties of the initial sample. The reason is that the second stage is a stage of generating a sodium iron sulfate sample, and the cathode material used in comparative example 5 was not subjected to high-temperature heating and heat preservation, so that a sodium iron sulfate cathode could not be formed, and the specific capacity obtained by the test was mostly derived from physical adsorption.
The comparison results of examples 2-67 and comparative examples 6 and 7 show that when the HLB value of the amphipathic molecules adopted is outside 10-16, the electrochemical performance of the initial sample is equivalent, but the electrochemical performance of the sample after 12 months of standing is obviously declined, which indicates that the HLB value of the amphipathic molecules has a certain influence on the protection effect; presumably, the reason is that amphipathic molecules having too high or too low an HLB value are difficult to form an effective protective layer on the sodium iron sulfate positive electrode.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of one of ordinary skill in the art without departing from the spirit of the present invention.
Claims (10)
1. The positive electrode material of the sodium iron sulfate is characterized by comprising sodium iron sulfate and an amphiphilic molecule for modifying the sodium iron sulfate, wherein the hydrophilic end of the amphiphilic molecule faces towards the sodium iron sulfate, and the hydrophobic end of the amphiphilic molecule faces away from the sodium iron sulfate; the HLB of the amphipathic molecule is 10-16,
the preparation method of the sodium iron sulfate positive electrode material comprises the following steps:
mixing and heating the preparation raw materials of the sodium iron sulfate, the amphiphilic molecules, the nonpolar solvent and the polar solvent, and removing impurities;
the mixed heating comprises a first heating and a second heating which are sequentially carried out;
the temperature of the first heating is 50-100 ℃; the time of the first heating is 1-12 h;
the temperature of the second heating is 120-250 ℃; the time of the second heating is 1-12 h.
2. The ferric sodium sulfate positive electrode material according to claim 1, wherein the amphiphilic molecule comprises at least one of polyoxypropylene lanolate, polyoxyethylene sorbitan monooleate, polyoxyethylene cetyl ether, polyoxyethylene sorbitan tristearate, polyoxyethylene lauryl ether, polyoxyethylene sorbitan trioleate, polyoxyethylene oxypropylenoate, polyoxyethylene lanolin derivatives, polyoxyethylene monooleate, polyoxyethylene monopalmitate, polyoxyethylene monostearate, polyoxyethylene oleyl ether, polyoxyethylene monolaurate, polyoxyethylene alkylphenol, polyoxyethylene acetylated lanolin derivatives, polyoxyethylene sorbitol lanolate derivatives, polyoxyethylene alkylaryl ethers, polyoxyethylene monolaurate, polyoxyethylene lauryl ether, polyoxyethylene castor oil, polyoxyethylene vegetable oils, cholesterol ethers, lanolin ethers, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monostearate, polyoxyethylene oleyl ether, polyoxyethylene methyl glucoside sesquioleate, polyoxyethylene lanolate, polyoxyethylene sorbitol monooleate, polyoxyethylene monostearate, polyoxyethylene monooleate, polyoxyethylene ether, polyoxyethylene stearyl alcohol, polyoxyethylene oleyl alcohol, polyoxyethylene fatty alcohol, polyethylene glycol monopalmitate, polyoxyethylene cetyl monolaurate, polyoxyethylene propylene oxide monostearate, and polyoxyethylene propylene monostearate.
3. The sodium iron sulfate positive electrode material according to claim 1, wherein the temperature of the first heating is 70 to 90 ℃; the time of the first heating is 1-3 h.
4. The sodium iron sulfate positive electrode material according to claim 1, wherein the temperature of the second heating is 170-190 ℃; the second heating time is 3-5 h.
5. The ferric sodium sulfate positive electrode material according to claim 1, wherein the nonpolar solvent comprises at least one of benzene, carbon tetrachloride, hexane, isooctane, methylene chloride, cyclohexane, petroleum ether, and pentane.
6. The ferric sodium sulfate positive electrode material according to claim 1, wherein the polar solvent comprises at least one of water, formamide, acetone, trifluoroacetic acid, ethanol, chloroform, diethyl ether, acetic acid, acetonitrile, isopropanol, methanol, dimethyl sulfoxide, acetonitrile, N-dimethylformamide, hexamethylphosphoramide, pyridine, tetramethyl ethylenediamine, triethylamine, N-butanol, dioxane, tetrahydrofuran, and methyl formate.
7. The ferric sodium sulfate positive electrode material according to claim 1, wherein the preparation raw materials of the ferric sodium sulfate comprise sodium sulfate and ferrous sulfate hydrate.
8. The ferric sodium sulfate positive electrode material according to claim 7, wherein a ratio of the polar solvent, the nonpolar solvent, the amphipathic molecule, the sodium sulfate, and the ferrous sulfate hydrate is 1 to 20: 1-20: 10-500: 5 to 6.75:10 to 13.5, wherein the polar solvent and the nonpolar solvent are calculated in volume liter, the amphipathic molecules are calculated in mass gram, and sodium sulfate and ferrous sulfate hydrate are calculated in mass mole.
9. Use of a positive electrode material according to any one of claims 1 to 8 in the preparation of a sodium ion battery.
10. Use of a sodium-ion battery according to claim 9 in the field of secondary batteries.
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| CN110521036A (en) * | 2017-06-27 | 2019-11-29 | 日本电气硝子株式会社 | Sodium ion secondary battery positive active material |
| CN114050246A (en) * | 2021-11-16 | 2022-02-15 | 郑州大学 | Micron-sized porous sodium ferrous sulfate/carbon composite cathode material and sodium ion battery or sodium battery prepared from same |
| CN114792798A (en) * | 2022-04-25 | 2022-07-26 | 湖北万润新能源科技股份有限公司 | Sodium manganese silicate cathode material, preparation method thereof, cathode and battery |
| CN115050934A (en) * | 2022-05-31 | 2022-09-13 | 四川大学 | Hydrophobic oleophilic Na 2 Fe 2 （SO 4 ） 3 /C positive electrode material and preparation method thereof |
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| CN110521036A (en) * | 2017-06-27 | 2019-11-29 | 日本电气硝子株式会社 | Sodium ion secondary battery positive active material |
| CN114050246A (en) * | 2021-11-16 | 2022-02-15 | 郑州大学 | Micron-sized porous sodium ferrous sulfate/carbon composite cathode material and sodium ion battery or sodium battery prepared from same |
| CN114792798A (en) * | 2022-04-25 | 2022-07-26 | 湖北万润新能源科技股份有限公司 | Sodium manganese silicate cathode material, preparation method thereof, cathode and battery |
| CN115050934A (en) * | 2022-05-31 | 2022-09-13 | 四川大学 | Hydrophobic oleophilic Na 2 Fe 2 （SO 4 ） 3 /C positive electrode material and preparation method thereof |
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