CN117174873A - Preparation method of positive electrode material, positive electrode plate, sodium ion battery and power utilization device - Google Patents
Preparation method of positive electrode material, positive electrode plate, sodium ion battery and power utilization device Download PDFInfo
- Publication number
- CN117174873A CN117174873A CN202311278288.4A CN202311278288A CN117174873A CN 117174873 A CN117174873 A CN 117174873A CN 202311278288 A CN202311278288 A CN 202311278288A CN 117174873 A CN117174873 A CN 117174873A
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- CN
- China
- Prior art keywords
- positive electrode
- sodium
- sulfate
- electrode material
- ferrous
- Prior art date
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 137
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 46
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000011734 sodium Substances 0.000 claims abstract description 126
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 114
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 112
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 111
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 107
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 91
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 91
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 91
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 90
- 239000002131 composite material Substances 0.000 claims abstract description 54
- 239000002994 raw material Substances 0.000 claims abstract description 51
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 47
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 46
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 46
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 38
- 238000000227 grinding Methods 0.000 claims abstract description 33
- 238000010438 heat treatment Methods 0.000 claims abstract description 24
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 23
- 239000010405 anode material Substances 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 238000001354 calcination Methods 0.000 claims abstract description 13
- 230000001603 reducing effect Effects 0.000 claims abstract description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 50
- 239000002245 particle Substances 0.000 claims description 30
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 20
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 20
- 239000000126 substance Substances 0.000 claims description 18
- 229910052742 iron Inorganic materials 0.000 claims description 15
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 12
- 239000010406 cathode material Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000002041 carbon nanotube Substances 0.000 claims description 9
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 9
- 235000002639 sodium chloride Nutrition 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- 229910021389 graphene Inorganic materials 0.000 claims description 5
- 239000002134 carbon nanofiber Substances 0.000 claims description 4
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- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- XBDUTCVQJHJTQZ-UHFFFAOYSA-L iron(2+) sulfate monohydrate Chemical compound O.[Fe+2].[O-]S([O-])(=O)=O XBDUTCVQJHJTQZ-UHFFFAOYSA-L 0.000 claims description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- 230000014759 maintenance of location Effects 0.000 abstract description 16
- 239000012298 atmosphere Substances 0.000 abstract description 12
- 239000010410 layer Substances 0.000 description 37
- 230000000052 comparative effect Effects 0.000 description 34
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- 239000003960 organic solvent Substances 0.000 description 9
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
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- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
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- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical class [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
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- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- VVNXEADCOVSAER-UHFFFAOYSA-N lithium sodium Chemical group [Li].[Na] VVNXEADCOVSAER-UHFFFAOYSA-N 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 229910000686 lithium vanadium oxide Inorganic materials 0.000 description 1
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 description 1
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- ZRZFJYHYRSRUQV-UHFFFAOYSA-N phosphoric acid trimethylsilane Chemical compound C[SiH](C)C.C[SiH](C)C.C[SiH](C)C.OP(O)(O)=O ZRZFJYHYRSRUQV-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 229960000380 propiolactone Drugs 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 239000002733 tin-carbon composite material Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
Classifications
-
- 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The application provides a preparation method of a positive electrode material, the positive electrode material, a positive electrode plate, a sodium ion battery and an electric device. The preparation method of the positive electrode material comprises the following steps: adding a raw material containing a sodium source, sulfate, ferrous salt and a carbon source into a closed container filled with reducing gas and having a heating function, and grinding and calcining the raw material under the heating condition to obtain a ferrous sodium sulfate and carbon composite anode material; wherein the reaction temperature T of the calcination treatment is kept to be 300 ℃ to 400 ℃. The method provided by the application prepares the positive electrode material compounded by sodium ferrous sulfate and carbon in a reducing atmosphere, so that the preparation process is simplified, the preparation speed of the positive electrode material is increased, and the preparation time is shortened; the purity of the positive electrode material compounded by the ferrous sodium sulfate and the carbon is improved, so that the performances of the positive electrode plate containing the positive electrode material, such as the first-cycle discharge gram capacity, the first-cycle charge and discharge efficiency, the circulation 1000-cycle capacity retention rate, the doubling performance and the like, are improved in the sodium ion battery.
Description
Technical Field
The application relates to the technical field of preparation of positive electrode materials, in particular to a preparation method of a positive electrode material, a positive electrode plate, a sodium ion battery and an electric device.
Background
The traditional lead-acid battery and nickel-cadmium battery have lower energy efficiency and serious pollution, the lithium ion battery in the sodium ion battery has high cost and the safety is to be improved, and the market demand of new energy automobiles is increased rapidly, so that the market demand is difficult to meet. The sodium ion battery has the advantages of high safety, low cost, environmental friendliness and the like, is favored by researchers, and promotes the wide research and application of the sodium ion battery. The positive electrode material in the sodium ion battery is an important component and plays a vital role.
Typical positive electrode materials for sodium ion batteries include layered transition metal oxides, prussian blue analogues, and polyanion positive electrode materials. The framework structure of the polyanion material such as the sodium ferrous sulfate positive electrode material is stable, and meanwhile, the induced effect of the polyanion positive electrode material can further improve the working voltage of the material. However, when the polyanion material such as the sodium ferrous sulfate anode material is prepared, the preparation process is complex, the preparation time is long and the like.
Therefore, finding a better method for preparing the positive electrode material such as the sodium ferrous sulfate positive electrode material is of great significance to the field.
Disclosure of Invention
The application provides a preparation method of a positive electrode material, the positive electrode material, a positive electrode plate, a sodium ion battery and an electric device, which simplify the preparation process, accelerate the preparation speed of the positive electrode material and shorten the preparation time.
In a first aspect, the present application provides a method for preparing a positive electrode material, including:
adding a raw material containing a sodium source, sulfate, ferrous salt and a carbon source into a closed container filled with reducing gas and having a heating function, and grinding and calcining the raw material under the heating condition to obtain a ferrous sodium sulfate and carbon composite anode material;
wherein the reaction temperature T of the calcination treatment is kept to be 300 ℃ to 400 ℃.
According to the application, the preparation process is simplified by grinding and heating calcination in the closed container, meanwhile, the raw materials are added into the closed container for grinding, the raw materials are impacted in the process, the raw materials are equivalent to a certain impact force at the inner wall of the container, the closed container is also heated, and when the raw materials are in contact with the inner wall of the container, the raw materials exchange heat with the inner wall of the container, so that the heat transfer effect on the raw materials is improved, and the preparation time is saved.
The method of the application can prepare the positive electrode material compounded by sodium ferrous sulfate and carbon in a reducing atmosphere, can avoid ferrous salt from being oxidized to generate ferric iron in the preparation process, can reduce trace impurity ferric iron contained in ferrous salt into ferrous iron, and can grind the ferrous iron to disperse raw materials, thereby ensuring that the reducing gas is more fully contacted with the raw materials, ensuring the reduction reaction to be more sufficient, being beneficial to improving the purity of the positive electrode material compounded by sodium ferrous sulfate and carbon and improving the mass percentage content of ferrous iron.
The application prevents the leakage of the reducing gas by being carried out in the closed container, thereby improving the safety of the preparation process. And the contact times of raw materials and the outside are reduced, the material is prevented from being subjected to hygroscopic oxidation, the purity of the anode material is further improved, and the mass percentage of ferrous iron in the anode material is improved.
The ferrous sodium sulfate and carbon composite positive electrode material prepared by the method is used for a positive electrode plate, and as the content of ferrous element in the positive electrode material is higher, the content of ferric element impurities is lower, the specific surface area of the positive electrode material is proper, the particle size is more uniform, and the performances of improved first-cycle discharge gram capacity, first-time charge and discharge efficiency, 1000-cycle circulation capacity retention rate, ploidy and the like are obtained in a sodium ion battery containing the positive electrode material.
According to an embodiment of one aspect of the application, the preparation method satisfies at least one of the following conditions:
the sodium source comprises one or more of sodium sulfate, sodium nitrate, sodium chloride and sodium hydroxide;
the sulfate comprises one or more of sodium sulfate and ferrous sulfate;
the ferrous salt comprises one or more of ferrous sulfate, ferrous sulfate heptahydrate and ferrous sulfate monohydrate;
the carbon source comprises one or more of graphite, carbon nano tubes, carbon nano fibers, graphene and carbon black;
the sodium source and the sulfate are the same substance;
the ferrous salt and the sulfate are the same substance.
According to an embodiment of one aspect of the application, the method fulfils at least one of the following conditions:
in the raw materials, the molar ratio of sulfate groups to sodium elements is 1: (0.28 to 2.5);
in the raw materials, the molar ratio of iron element to sodium element is 1: (0.8-1.8);
in the raw materials, the mass content of the carbon source is 1% -6%, and optionally 4% -5%.
According to an embodiment of one aspect of the application, the gram capacity of the sodium ferrous sulfate and carbon composite cathode material is above 98 mAh/g.
According to an embodiment of one aspect of the present application, a method of preparing comprises: mixing grinding medium with the raw materials in a mass ratio of 1: (0.02-20) and mixing the components.
According to an embodiment of one aspect of the application, the method fulfils at least one of the following conditions:
the sealed container takes the rotation speed of 350-700r/min as the grinding time of 4-10 h;
the grinding medium comprises one or more of zirconia ceramic particles, silicon carbide particles and alumina particles;
the grinding medium is a sphere, and the diameter of the grinding medium is 0.5 cm-2 cm.
In a second aspect, the present application provides a positive electrode material comprising the sodium ferrous sulfate and carbon composite positive electrode material produced by the production method of the first aspect.
According to an embodiment of one aspect of the present application, the mass percentage content n of the ferric iron element in all the iron elements in the positive electrode material satisfies: n is less than 1%.
According to an embodiment of an aspect of the present application, the average particle diameter Dv50 of the positive electrode material of the ferrous sodium sulfate and carbon composite is 0.2-0.5 μm.
According to an embodiment of one aspect of the application, the specific surface area of the positive electrode material of the ferrous sodium sulfate and carbon composite is 12-17m 2 /g。
According to an embodiment of one aspect of the present application, a positive electrode material of sodium ferrous sulfate and carbon composite includes:
sodium ferrous sulfate positive electrode material particles with a chemical general formula of Na m Fe n SO 4 Wherein 0.22.ltoreq.m < 2,0.28.ltoreq.n < 2, optionally m+2n=2; and
carbon at least partially coats the sodium ferrous sulfate positive electrode material particles.
In a third aspect, the application provides a positive electrode plate, which comprises a positive electrode current collector and a positive electrode film layer positioned on at least one side of the positive electrode current collector, wherein the positive electrode film layer comprises a positive electrode material prepared by the method in the first aspect and compounded by sodium ferrous sulfate and carbon or a positive electrode material prepared by the method in the second aspect and compounded by sodium ferrous sulfate and carbon.
In a fourth aspect, the present application provides a sodium ion battery comprising the positive electrode sheet of the third aspect.
In a fifth aspect, the present application provides an electrical device comprising the sodium ion battery of the fourth aspect.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the application and together with the description, serve to explain the principles of the application.
FIG. 1 shows a microscopic image of a positive electrode material of the composite of sodium ferrous sulfate and carbon of example 1 of the present application;
Fig. 2 shows the first charge and discharge curves of the positive electrode material of the sodium ferrous sulfate and carbon composite of example 1 of the present application in a sodium ion battery.
Specific embodiments of the present application have been shown by way of the above drawings and will be described in more detail below. The drawings and the written description are not intended to limit the scope of the inventive concepts in any way, but rather to illustrate the inventive concepts to those skilled in the art by reference to the specific embodiments.
Detailed Description
Each example or embodiment in this specification is described in a progressive manner, each example focusing on differences from other examples.
In the description of the present specification, reference to the terms "one embodiment," "some embodiments," "illustrative embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the application. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In the description of the present application, the meaning of "plurality" means at least two, for example, two, three, etc., unless specifically defined otherwise. The meaning of "plurality" or "several" means at least two, for example, two, three, etc., unless specifically defined otherwise.
Polyanionic compounds are the generic names of compounds containing tetrahedral or octahedral anionic structural units (XOm) n- (x= P, S, as, W, etc.). The compound mainly comprises NaMPO 4 (M is a transition metal), naMPO 4 F and sodium fast ion conductor (NaSICON). These structural units are linked into a three-dimensional network structure by strong covalent bonds and form higher coordination voids occupied by other metal ions, so that the polyanion-type compound cathode material has a different crystal phase structure from that of the metal oxide cathode material and various outstanding properties such as higher voltage and stability determined by the structure.
Sodium ferrous sulfate is a typical polyanion type positive electrode material, has higher working voltage, can reach 3.8V generally, can provide excellent energy density, and is worth popularizing and applying.
The iron element in the ferrous sulfate sodium positive electrode material is generally in a +2 valence state. In polyanionic compounds such as sodium ferrous sulfate, the transition metal, iron, accepts electrons during charging and combines with sodium ions to form the compound. During charging, the valence state of the iron element is changed from a lower oxidation state to a high oxidation state so as to attract and intercalate more sodium ions. During the discharge process, the iron element is reduced back to a lower oxidation state, releasing sodium ions embedded in the positive electrode material.
To sum up, the related art may consider: the existence of a small amount of ferric sodium sulfate (ferric iron) in the ferrous sodium sulfate positive electrode material is a normal phenomenon, and the relative performance of the sodium ion battery is not influenced by the positive electrode material in the positive electrode plate.
In addition, polyanion compounds such as sodium ferrous sulfate positive electrode materials have poor conductivity and ion conducting effect.
In view of the above problems, in the related art, sodium ferrous sulfate positive electrode materials are often modified to overcome the above problems. The conductivity of the modified material can be improved after being purely doped and modified, but other unavoidable problems exist in the sodium ferrous sulfate anode material. In the research, it is found that the positive electrode material obtained by simple blending is used for preparing the positive electrode plate, and the expected effect cannot be achieved on the improvement of the high-rate and other quick charge performances of the sodium ion battery, so that the preparation method of the sodium ferrous sulfate positive electrode material cannot be simply improved.
The preparation process of the ferrous sodium sulfate positive electrode material comprises a dry process and a wet process.
In the dry process, the preparation method of the sodium iron sulfate comprises the following steps: a1, carrying out vacuum drying on ferrous sulfate heptahydrate to obtain anhydrous ferrous sulfate, wherein the vacuum drying is carried out in a vacuum oven, and the temperature of the vacuum drying is 100-300 ℃; a2, adding sodium sulfate and ferrous sulfate into a zirconia ball milling tank according to a certain proportion, adding zirconia balls, and charging nitrogen for protection, and performing ball milling treatment to obtain a precursor; the ball-milling treatment has a ball-material ratio of (50:1) - (1:20), the ball-milling rotation rate is 200-1000r/min, the revolution rate is 100-500r/min, and the ball-milling time is 0.1-24h; and a3, transferring the ball-milled precursor into a box-type furnace, performing heat treatment under the protection of nitrogen, and then crushing the heat-treated product into powder to obtain sodium iron sulfate, wherein the heat treatment temperature is 300-400 ℃ and the time is 0.1-24h. The method is a dry ball milling process, the whole preparation process takes longer time, the materials need to be continuously transferred, and the materials are easy to wet and oxidize during the process, so that gram capacity, cycle performance and charge and discharge performance of the materials are affected.
Based on the problems, the application provides a preparation method of a positive electrode material, the positive electrode material, a positive electrode plate, a sodium ion battery and an electric device, and aims to accelerate the speed of preparing the positive electrode material and shorten the preparation time, and provides a sodium ferrous sulfate positive electrode material with higher first-turn discharge gram capacity and high charge-discharge efficiency when being used for the sodium ion battery.
Preparation method of ferrous sodium sulfate and carbon composite positive electrode material
In a first aspect, the application provides a preparation method of a positive electrode material compounded by sodium ferrous sulfate and carbon, which comprises the following steps:
adding a raw material containing a sodium source, sulfate, ferrous salt and a carbon source into a closed container filled with reducing gas and having a heating function, and grinding and calcining the raw material under the heating condition to obtain a ferrous sodium sulfate and carbon composite anode material;
wherein the reaction temperature T of the calcination treatment is kept to be 300 ℃ to 400 ℃.
According to an embodiment of the present application, the reducing atmosphere means that a gas atmosphere having reducing properties is provided in a chemical or industrial process, which helps to reduce a substance that can undergo an oxidation-reduction reaction or to maintain the substance in a reduced state. The reducing atmosphere comprises one or more of hydrogen atmosphere and carbon monoxide atmosphere.
Grinding raw materials under heated conditions according to embodiments of the present application can be understood as: it is necessary to ensure that heating and grinding are performed simultaneously for a period of time.
According to the embodiment of the application, the preparation of the ferrous sodium sulfate and carbon composite anode material is carried out in a reducing atmosphere, ferric iron can be prevented from being generated by oxidation of ferrous salt in the preparation process, trace impurity ferric iron contained in ferrous salt can be reduced into ferrous iron, and the proportion of ferrous iron in all iron elements in the ferrous sodium sulfate and carbon composite anode material is improved, so that the performances of the positive electrode plate containing the ferrous sodium sulfate and carbon composite anode material, such as the discharge gram capacity, the first charge-discharge efficiency, the 1000-cycle capacity retention rate, the doubling performance and the like, in a sodium ion battery are improved.
In the preparation process, the reaction rate of sodium source, sulfate and ferrous salt in the raw materials is relatively slow, and the raw materials can be given a certain impact force by grinding under the heating condition, so that the reaction speed is favorably increased, and the reaction time is shortened.
According to the embodiment of the application, the grinding and calcining treatment is carried out in the closed container, so that on one hand, the contact times of raw materials and the outside are reduced, the moisture absorption and the oxidation of the materials are prevented, the oxidation of ferrous elements into ferric iron is avoided, and the purity of the product is improved; on the other hand, the reaction is carried out in a closed container filled with a reducing atmosphere, which is advantageous in accelerating the reaction rate.
According to the embodiment of the application, the temperature of the calcination treatment can be measured by detecting the temperature of the inner wall of the closed container, and can be 300-400 ℃ or 350-380 ℃. Controlling the temperature range of the closed container can have important influence on the performance and structure of the sodium ferrous sulfate anode material. Different temperature conditions can affect aspects such as morphology, crystallinity and the like of the crystal. The high crystallinity facilitates the diffusion and ion transport of active sodium ions in subsequent electrochemical cycles, thereby improving the performance of the sodium ion battery.
The grinding in the application is beneficial to improving the reaction speed and fully mixing the raw materials participating in the reaction.
The heating mode in the application comprises at least one of electric heating, flame heating and microwave heating.
In some alternative embodiments, the method of preparation satisfies at least one of the following conditions:
the sodium source comprises one or more of sodium sulfate, sodium nitrate, sodium chloride and sodium hydroxide;
the sulfate comprises one or more of sodium sulfate and ferrous sulfate;
the ferrous salt comprises one or more of ferrous sulfate, ferrous sulfate heptahydrate and ferrous sulfate monohydrate;
the carbon source comprises one or more of graphite, carbon nano tube, carbon nano fiber, graphene and carbon black;
the sodium source and the sulfate are the same substance;
ferrous salt and sulfate are the same substance.
In some embodiments, ferrous sulfate, sodium sulfate, and a carbon source are mixed to obtain a raw material.
In some alternative embodiments, the molar ratio of sulfate groups to sodium elements in the starting material is 1: (0.28-2.5).
According to the embodiment of the application, the control of the molar ratio of the sulfate group to the sodium element in the above range is beneficial to preparing the ferrous sodium sulfate positive electrode material containing the sulfate group and the sodium element in a proper ratio on the basis of saving raw materials. The molar ratio of the ferrous sodium sulfate positive electrode material is in the range so that the ferrous sodium sulfate positive electrode material has higher sodium ion content.
In addition, the molar ratio of the sulfate group to the sodium element is controlled within the range, so that the proportion of the ferrous sodium sulfate and carbon composite positive electrode material in a reaction product is improved, the purity of the ferrous sodium sulfate and carbon composite positive electrode material is improved, and the discharge gram capacity of a positive electrode plate containing the ferrous sodium sulfate and carbon composite positive electrode material in a sodium ion battery is improved.
In some alternative embodiments, the molar ratio of elemental iron to elemental sodium in the starting material is 1: (0.8-1.8).
According to the embodiment of the application, the molar ratio of the iron element to the sodium element is controlled within the range, so that the ferrous sodium sulfate anode material containing the iron element and the sodium element with a proper proportion can be prepared on the basis of saving raw materials. The iron element can replace part of the sodium element and form a stable crystal structure with the sulfate group. In the charge and discharge process of the battery, the molar ratio of the iron element to the sodium element in the positive electrode material is in the range, the iron element can participate in oxidation-reduction reaction, effective charge compensation is provided for de-intercalation of sodium ions, and the stability of a crystal structure is still maintained, so that the sodium ferrous sulfate positive electrode material has good electrochemical performance, such as higher capacity retention rate, improved charge-discharge voltage platform and the like.
In some alternative embodiments, the carbon source is present in the raw material in an amount of 1% to 6%, optionally 4% to 5% by mass.
According to the embodiment of the application, the mass content of the carbon source in the raw material is controlled within the range, so that on one hand, the conductivity of the ferrous sodium sulfate positive electrode material can be improved, and the dynamic performance including the quick charge performance in the sodium ion battery can be improved; on the other hand, the carbon with the content can reduce the contact area of the ferrous sodium sulfate anode material and electrolyte in the sodium ion battery, reduce the occurrence of side reaction, reduce the gas yield of the battery and improve the storage performance of the battery; the circulation capacity retention rate of the positive electrode plate containing the ferrous sodium sulfate positive electrode material in a sodium ion battery is improved. The structural stability of the positive electrode material is also improved.
In addition, the mass content of the carbon source in the raw material can effectively solve the problem that the sodium ferrous sulfate positive electrode material is easy to crush under pressure, and improve the stability of the sodium ferrous sulfate positive electrode material.
In some alternative embodiments, the gram capacity of the sodium ferrous sulfate and carbon composite cathode material is up to 98mAh/g or more.
In some alternative embodiments, the method of making comprises: grinding medium and raw materials are mixed according to the mass ratio of 1: (0.02-20) and mixing the components.
According to the embodiment of the application, the mass ratio of the grinding medium to the raw material is controlled in the reaction, so that the raw material can be sufficiently ground, the reaction degree is promoted to be improved on the basis of accelerating the reaction rate, and the purity of the sodium ferrous sulfate positive electrode material is improved.
In some alternative embodiments, the closed vessel is subjected to grinding at a rotational speed of 350-700r/min for a period of 4-10 hours.
According to the embodiment of the application, the rotation speed of the closed container and the grinding time are controlled within the ranges, and the prepared raw materials are given some impact force within a certain time, so that the reaction rate is favorably accelerated, the reaction is more complete, and the sodium ferrous sulfate anode material with higher purity is obtained.
In some alternative embodiments, the grinding media comprises one or more of zirconia ceramic particles, silicon carbide particles, and alumina particles.
The zirconia ceramic particles may also be abbreviated as zirconium beads. The grinding medium has the property of high temperature resistance, does not participate in the reaction, and can grind substances mixed with the grinding medium to refine the particle size.
In some alternative embodiments, the grinding media is spheres and the grinding media has a diameter of 0.5 to 2cm. In some embodiments, the grinding media is zirconium beads, optionally 1cm in diameter.
In some alternative embodiments, the calcination treatment of the raw materials is followed by a pulverization step of pulverizing the sodium ferrous sulfate and carbon-compounded cathode material to produce sodium ferrous sulfate cathode material particles.
In some alternative embodiments, after calcining the raw materials, comprising: and in an inert atmosphere, crushing the sodium ferrous sulfate and carbon composite anode material to prepare sodium ferrous sulfate anode material particles. In some alternative embodiments, the inert atmosphere comprises one or more of a nitrogen atmosphere, an argon atmosphere, and a helium atmosphere.
Positive electrode material
In a second aspect, the present application provides a positive electrode material comprising the sodium ferrous sulfate and carbon composite positive electrode material produced by the production method of the first aspect.
In some alternative embodiments, the mass percentage n of ferric iron in all iron elements in the positive electrode material satisfies: n is less than 1%.
According to the embodiment of the application, the content of ferric iron in all iron elements in the positive electrode material compounded by ferrous sodium sulfate and carbon is in the range, so that the content of ferric iron and other impurities in the material is reduced, and the gram capacity, the first charge and discharge efficiency and the circulating capacity retention rate of the material in a sodium ion battery are improved. In some alternative embodiments, the particle size of the sodium ferrous sulfate positive electrode material particles is 0.05 to 0.5 μm.
In some alternative embodiments, the average particle size Dv50 of the positive electrode material of sodium ferrous sulfate and carbon composite is 0.2-0.5 μm.
The volume average particle diameter Dv50 is a particle diameter corresponding to a cumulative volume distribution percentage of the material of 50% and can be measured by a device and a method known in the art. For example, reference may be made to GB/T19077-2016 particle size distribution laser diffraction, conveniently using a laser particle size analyzer, such as Mastersizer 2000E, of Markov instruments, UK.
In some alternative embodiments, the specific surface area of the positive electrode material of the ferrous sodium sulfate and carbon composite is 12-17m 2 And/g. Optionally, the specific surface area of the positive electrode material compounded by the ferrous sodium sulfate and the carbon is 13-15m 2 /g。
In some alternative embodiments, the positive electrode material of sodium ferrous sulfate and carbon composite includes:
sodium ferrous sulfate positive electrode material particles with a chemical general formula of Na m Fe n SO 4 Wherein 0.22.ltoreq.m < 2,0.28.ltoreq.n < 2, optionally m+2n=2; and
carbon at least partially coats the sodium ferrous sulfate positive electrode material particles.
In some of the above embodiments, the chemical formulas of sodium ferrous sulfate positive electrode materials commonly used in the art are listed, and it is understood that sodium ferrous sulfate positive electrode materials include, but are not limited to, the above materials, and the relative ratios of m, n, and sulfate in the above chemical formulas are understood to be the molar ratios thereof in the above chemical formulas. Other known sodium ferrous sulfate positive electrode materials can be selected by those skilled in the art according to actual needs. As an example, the sodium ferrous sulfate positive electrode material is Na 1.5 Fe(SO 4 ) 1.75 。
According to the embodiment of the application, the molecular compound of which the chemical general formula of the ferrous sodium sulfate positive electrode material particles can be expressed, and the number of sodium elements can be 0.22-2, so that the specific capacity of the ferrous sodium sulfate positive electrode material can be improved, and the energy density of a sodium ion battery can be improved.
In summary, the raw materials such as sodium source, sulfate, ferrous salt and carbon source can be added into a closed container for ball milling, and the raw materials are impacted by a grinding medium in the process and are subjected to certain pressure, and the closed container is heated at the moment, so that the reaction comprises solid solution reaction, and the reaction is performed under the conditions of high pressure and high heat, thereby improving the reaction rate and ensuring that the reaction is more sufficient.
Positive electrode plate
In a third aspect, the application provides a positive electrode plate, which comprises a positive electrode current collector and a positive electrode film layer positioned on at least one side of the positive electrode current collector, wherein the positive electrode film layer comprises a positive electrode material prepared by the method in the first aspect and compounded by sodium ferrous sulfate and carbon or a positive electrode material prepared by the method in the second aspect and compounded by sodium ferrous sulfate and carbon.
The application does not limit the positive current collector, and a metal foil, a porous metal plate or a composite current collector can be used. The composite current collector may include a polymeric material base layer and a metal layer formed on at least one surface of the polymeric material base material. The composite current collector may be formed by forming a metal material (copper, copper alloy, nickel alloy, titanium alloy, silver alloy, etc.) on a polymer material substrate (such as a substrate of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.). As one example, the current collector is one of aluminum foil, carbon coated aluminum foil.
In some embodiments, the positive electrode current collector has two surfaces opposite to each other in the thickness direction thereof, and the positive electrode film layer may be disposed on one surface of the current collector or may be disposed on both surfaces of the positive electrode current collector at the same time. For example, the positive electrode current collector has two surfaces opposing in the thickness direction thereof, and the positive electrode film layer is provided on either one or both of the two opposing surfaces of the current collector.
In some embodiments, the positive electrode film layer may partially or completely cover the surface of the positive electrode current collector, and the second positive electrode film layer may partially or completely cover the surface of the first positive electrode film layer. For example, the positive electrode film layer completely covers either of the opposite surfaces of the current collector.
In some embodiments, the positive electrode film layer includes a conductive agent and a binder.
In some embodiments, the positive electrode sheet satisfies at least one of the following conditions:
1) The conductive agent comprises one or more of conductive carbon black (SP), acetylene black, graphite, graphene, carbon Nano Tube (CNT) and carbon nano fiber;
2) The binder comprises one or more of polyvinylidene fluoride (PVDF), modified polyvinylidene fluoride, polyvinylidene chloride, modified polyvinylidene chloride, polyvinylidene fluoride copolymer, polyvinylidene chloride copolymer, polymethyl methacrylate and styrene butadiene rubber.
In some of the above embodiments, a few conductive agents and binders are specifically listed, but it should be understood that the present application is not limited to these, and may include, but not limited to, these, and those skilled in the art may select conductive agents or binders known in the art according to actual needs.
The components and the mass percentages thereof in the positive electrode film layer are not limited in the application, and can be adjusted by a person skilled in the art according to the known components and the mass percentages thereof in the positive electrode film layer.
For example, in some embodiments, the positive electrode film layer satisfies at least one of the following conditions:
1) The mass percentage of the sodium ferrous sulfate and carbon composite anode material in the anode film layer is 70-99.8%;
2) The mass percentage of the conductive agent in the positive electrode film layer is 0.1-10%;
3) The mass percentage of the binder in the positive electrode film layer is 0.1-10%.
The application also provides a method for manufacturing the positive plate, which can comprise the following steps:
s10: adding a positive electrode material, a conductive agent and a binder into a solvent to obtain positive electrode slurry;
s20: and coating the positive electrode slurry on a positive electrode current collector, and drying to obtain a positive electrode plate.
The solvent may include Dimethylformamide (DMF), diethylformamide, dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), methanol, ethanol, 1-propanol, 2-propanol (isopropanol), 1-butanol (N-butanol), 2-methyl-1-propanol (isobutanol), 2-butanol (sec-butanol), 1-methyl-2-propanol (tert-butanol), pentanol, hexanol, heptanol or octanol; diols such as one or more of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1, 3-propanediol, 1, 3-butanediol, 1, 5-pentanediol, hexanediol, glycerol, trimethylolpropane, pentaerythritol, sorbitol, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, tetraethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, acetone, methyl ethyl ketone, methyl propyl ketone, cyclopentanone, ethyl acetate, gamma-butyrolactone, and epsilon-propiolactone. These solvents may be used alone or in combination of two or more. As one example, the first solvent and the second solvent may be N-methylpyrrolidone (NMP).
The specific types and contents of the positive electrode material, the conductive agent and the binder of the composite of the sodium ferrous sulfate and the carbon can be selected according to the above embodiments, and will not be described herein.
Further, the areal density of the first positive electrode film layer is adjusted by controlling the amount of addition of the first positive electrode slurry coated on the current collector.
If necessary, after the positive electrode film layer is formed by the above method, a rolling process may be further performed. In this case, in consideration of physical properties of the finally prepared composite positive electrode sheet, such as thickness and compacted density of the positive electrode film layer in the positive electrode sheet, drying and rolling may be performed under appropriate conditions, without particular limitation.
The composite positive electrode sheet in the application does not exclude other additional functional layers besides the positive electrode film layer. For example, in certain embodiments, the positive electrode sheet of the present application further comprises a conductive coating (e.g., composed of a conductive agent and a binder) disposed on the surface of the current collector sandwiched between the current collector and the first positive electrode film layer. In certain embodiments, the positive electrode sheet of the present application further comprises a conductive coating disposed on the surface of the first positive electrode film layer sandwiched between the positive electrode film layer and the current collector.
Sodium ion battery
In a fourth aspect, the present application provides a sodium ion battery comprising the positive electrode sheet of the third aspect.
According to the application, the positive electrode plate of any embodiment of the first aspect is included in the sodium ion battery, so that the sodium ion battery has the beneficial effects of the first aspect.
In some alternative embodiments, the sodium ion battery includes a negative electrode sheet, a separator, and an electrolyte. The materials, construction and methods of making the negative electrode tabs used in the sodium ion batteries of the present application may include any technique known in the art.
The negative electrode tab includes a current collector and a negative electrode active material layer disposed on at least one surface of the current collector and including a negative electrode active material. As an example, the current collector has two surfaces opposing in the thickness direction thereof, and the anode active material layer is provided on either one or both of the two opposing surfaces of the current collector. The current collector is not limited by the present application, and the current collector provided according to the first aspect is selected. As one example, the current collector is copper foil.
The specific kind of the anode active material is not particularly limited, and may be selected according to the need. For example, the anode active material may use one or more of a carbonaceous material, a metal compound that can be alloyed with lithium, a metal oxide that can be doped and undoped with lithium, and a composite including a metal compound and a carbonaceous material. As an example, the carbonaceous material may include one or more of artificial graphite, natural graphite, graphitized carbon fiber, and amorphous carbon; the metal compound which can be alloyed with lithium may include one or more of silicon (Si), aluminum (Al), tin (Sn), lead (Pb), zinc (Zn), bismuth (Bi), indium (In), magnesium (Mg), gallium (Ga), cadmium (Cd), si alloy, sn alloy, or Al alloy; the metal oxide, which may be doped and undoped with lithium, may include SiOv (0 <v<2)、SnO 2 One or more of vanadium oxide and lithium vanadium oxide; the composite comprising the metal compound and the carbonaceous material may comprise a Si-C composite and/or a Sn-C composite. These negative electrode active materials may be used alone or in combination of two or more.
In some embodiments, the anode active material layer further optionally includes a binder. The binder may be at least one selected from Styrene Butadiene Rubber (SBR), polyacrylic acid (PAA), sodium Polyacrylate (PAAs), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium Alginate (SA), polymethacrylic acid (PMAA), and carboxymethyl chitosan (CMCS).
In some embodiments, the anode active material layer may further optionally include a conductive agent. The conductive agent may include at least one of conductive carbon black, acetylene black, discrete carbon nanotubes, carbon fibers, ketjen black, and graphene.
In some embodiments, the anode active material layer may also optionally include other adjuvants, such as thickening agents (e.g., sodium carboxymethyl cellulose (CMC-Na)), and the like.
However, the present application is not limited to the above materials, and other known materials that can be used as a negative electrode active material, a conductive agent, a binder, and a thickener may be used as the negative electrode tab of the present application.
The negative electrode sheet of the present application may be prepared according to a conventional method in the art. For example, the negative electrode active material, the conductive agent, the binder and the thickener are dispersed in a solvent, wherein the solvent can be N-methyl pyrrolidone (NMP) or deionized water to form uniform negative electrode slurry, the negative electrode slurry is coated on a negative electrode current collector, and the negative electrode active material layer is obtained after drying and cold pressing, so as to obtain the negative electrode plate.
The negative electrode tab in the present application does not exclude other additional functional layers than the negative electrode active material layer. For example, in certain embodiments, the negative electrode tab of the present application further comprises a conductive primer layer (e.g., composed of a conductive agent and a binder) interposed between the current collector and the negative electrode active material layer, disposed on the surface of the current collector. The isolating film is arranged between the positive pole piece and the negative pole piece, and mainly plays a role in preventing the positive pole piece and the negative pole piece from being short-circuited, and meanwhile, active ions can pass through the isolating film. The type of the separator is not particularly limited, and any known porous separator having good chemical stability and mechanical stability can be used.
In some embodiments, the material of the isolating film may be one or more selected from glass fiber, non-woven fabric, polyethylene, polypropylene and polyvinylidene fluoride, but is not limited to these. Optionally, the material of the isolation film may include polyethylene and/or polypropylene. The separator may be a single-layer film or a multilayer composite film. When the isolating film is a multi-layer composite film, the materials of all layers are the same or different. In some embodiments, a ceramic coating, a metal oxide coating may also be provided on the barrier film. The electrolyte plays a role in conducting active ions between the positive pole piece and the negative pole piece. The electrolyte that can be used in the sodium-ion battery of the present application can be an electrolyte known in the art.
In some embodiments, the electrolyte may include an organic solvent, an electrolyte salt, and optional additives, and the types of the organic solvent, the electrolyte salt, and the additives are not particularly limited and may be selected according to the needs.
In some embodiments, the sodium ion battery is a lithium-sodium mixed ion battery, and the electrolyte salt may include a lithium salt and/or a sodium salt. As an example, the lithium salt includes, but is not limited to LiPF 6 Lithium hexafluorophosphate, liBF 6 Lithium tetrafluoroborate, liClO 4 (lithium perchlorate), liFeSI (lithium bis-fluorosulfonyl imide), liTFSI (lithium bis-trifluoromethanesulfonyl imide), liTFS (lithium trifluoromethanesulfonate), liDFOB (lithium difluorooxalato borate), liBOB (lithium bisoxalato borate), liPO 2 F 2 At least one of (lithium difluorophosphate), liDFOP (lithium difluorodioxalate phosphate) and LiTFOP (lithium tetrafluorooxalate phosphate), and sodium salt selected from NaPF 6 、NaClO 4 、NaBCl 4 、NaSO 3 CF 3 Na (CH) 3 )C 6 H 4 SO 3 At least one of them.
In some embodiments, the organic solvent includes, by way of example, but is not limited to at least one of Ethylene Carbonate (EC), propylene Carbonate (PC), ethylmethyl carbonate (EMC), diethyl carbonate (DEC), dimethyl carbonate (DMC), dipropyl carbonate (DPC), methylpropyl carbonate (MPC), ethylpropyl carbonate (EPC), butylene Carbonate (BC), fluoroethylene carbonate (FEC), methyl Formate (MF), methyl Acetate (MA), ethyl Acetate (EA), propyl Acetate (PA), methyl Propionate (MP), ethyl Propionate (EP), propyl Propionate (PP), methyl Butyrate (MB), ethyl Butyrate (EB), 1, 4-butyrolactone (GBL), sulfolane (SF), dimethylsulfone (MSM), methylsulfone (EMS), and diethylsulfone (ESE). The organic solvents may be used singly or in combination of two or more. Alternatively, two or more of the above organic solvents are used simultaneously.
In some embodiments, the additives may include negative film-forming additives, positive film-forming additives, and may also include additives that improve certain properties of the battery, such as additives that improve the overcharge performance of the battery, additives that improve the high or low temperature performance of the battery, and the like.
As an example, the additive includes, but is not limited to, at least one of fluoroethylene carbonate (FEC), vinylene Carbonate (VC), vinyl Ethylene Carbonate (VEC), vinyl sulfate (DTD), propylene sulfate, ethylene Sulfite (ES), 1, 3-Propane Sultone (PS), 1, 3-Propane Sultone (PST), sulfonate cyclic quaternary ammonium salt, succinic anhydride, succinonitrile (SN), adiponitrile (AND), tris (trimethylsilane) phosphate (TMSP), tris (trimethylsilane) borate (TMSB).
The electrolyte may be prepared according to a conventional method in the art. For example, the organic solvent, electrolyte salt, and optional additives may be uniformly mixed to obtain the electrolyte. The order of addition of the materials is not particularly limited, and for example, electrolyte salt and optional additives are added into an organic solvent and mixed uniformly to obtain an electrolyte; or adding electrolyte salt into the organic solvent, and then adding optional additives into the organic solvent to be uniformly mixed to obtain the electrolyte.
Power utilization device
In a fifth aspect, the present application provides an electrical device comprising the sodium ion battery of the fourth aspect.
According to the present application, since the electricity using device includes the sodium ion battery of any one of the embodiments of the fourth aspect, the electricity using device has the advantageous effect.
The power consumption device of the present application is not particularly limited, and may be any electronic apparatus known in the art. In some embodiments, the electronic device may include, but is not limited to, a notebook computer, a pen-input computer, a mobile computer, an electronic book player, a portable telephone, a portable facsimile machine, a portable copier, a portable printer, a headset, a video recorder, a liquid crystal television, a portable cleaner, a portable CD-player, a mini-compact disc, a transceiver, an electronic notepad, a calculator, a memory card, a portable audio recorder, a radio, a backup power source, a motor, an automobile, a motorcycle, a power assisted bicycle, a lighting fixture, a toy, a game machine, a clock, an electric tool, a flash light, a camera, a household large battery, a lithium ion capacitor, and the like.
Hereinafter, embodiments of the present application are described. The following examples are illustrative only and are not to be construed as limiting the application. The examples are not to be construed as limiting the specific techniques or conditions described in the literature in this field or as per the specifications of the product. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
The embodiment provides a preparation method of a sodium ferrous sulfate positive electrode material, which comprises the following steps:
the first step: weighing 38.00kg of FeSO 4 24.14kg of Na 2 SO 4 3.27kg of single-walled Carbon Nanotubes (CNT); wherein Na is 2 SO 4 And FeSO 4 The molar ratio of the sodium element to the iron element is 1.36:1, and the mass ratio of the carbon-based material in the raw materials of the raw materials is 5%;
and a second step of: adding the raw materials into a closed container, simultaneously adding zirconium beads (the ball-to-material ratio is 1:15) with the same mass, wherein the diameter of each zirconium bead is 1cm, and simultaneously introducing hydrogen gas to tightly close the closed container;
and a third step of: and (3) ball milling is carried out on zirconium beads in the closed container at the speed of 500rpm, the cavity of the closed container is heated, the temperature in the ball milling cavity is 350 ℃ in an electric heating mode, and after ball milling and sintering are carried out for 5 hours, ball milling and heating are stopped.
Fourth step: and (5) when the temperature of the closed container is reduced to room temperature, taking out the material, and crushing in a nitrogen atmosphere to obtain the ferrous sodium sulfate anode material.
Example 2
The embodiment of the present application is different from embodiment 1 in that: raw material Na 2 SO 4 And FeSO 4 The molar ratio of the sodium element to the iron element is 1.5:1.
Example 3
The embodiment of the present application is different from embodiment 1 in that: raw material Na 2 SO 4 And FeSO 4 The molar ratio of the sodium element to the iron element is 1.8:1.
Examples 4 to 5
The embodiment of the present application is different from embodiment 1 in that: crushing is carried out in nitrogen atmosphere to obtain ferrous sodium sulfate positive electrode materials, and the specific surface areas of the materials are different as shown in table 2.
Example 6
This embodiment differs from embodiment 1 in that: 5.232kg of single-walled Carbon Nanotubes (CNT) was added, and the mass content of the carbon source in the raw material was 8%.
Comparative example 1
This comparative example differs from example 1 in that: nitrogen was used instead of hydrogen in a closed environment. The comparative example provides a preparation method of a sodium ferrous sulfate positive electrode material, which comprises the following steps:
the first step: weighing 38.00kg of FeSO 4 24.14kg of Na 2 SO 4 3.27kg of single-walled Carbon Nanotubes (CNT); wherein Na is 2 SO 4 And FeSO 4 The molar ratio of the sodium element to the iron element is 1.36:1, and the carbon-based material accounts for 5%wt;
and a second step of: adding the raw materials into a closed container, adding zirconium beads with the same mass, wherein the diameter of each zirconium bead is 1cm, and introducing nitrogen gas to tightly close the closed container;
and a third step of: and (3) rotating the sealed container at 500rpm for ball milling, heating the ball milling cavity, performing ball milling sintering for 5 hours at the temperature of 350 ℃ in the ball milling cavity by using an electric heating mode, stopping ball milling and heating, and taking out the material after the temperature is reduced to the room temperature.
Fourth step: crushing the material in nitrogen atmosphere, and obtaining the anode material compounded by sodium ferrous sulfate and carbon after crushing.
Comparative example 2
This comparative example differs from example 1 in that:
and a third step of: and (3) ball milling is carried out on the closed container at a speed of 500rpm, ball milling is stopped after ball milling is carried out for 5 hours, then the ball milling cavity is heated, the temperature in the ball milling cavity is 350 ℃, and after heating and sintering are carried out for 5 hours, the ball milling and heating are stopped.
Comparative example 3
This comparative example differs from example 6 in that: this comparative example differs from example 1 in that: nitrogen was used instead of hydrogen in a closed environment.
Test part
1) Ferric iron content detection
The ferric iron content of the positive electrode materials compounded by sodium ferrous sulfate and carbon prepared in the examples and the comparative examples is detected according to GB/T33828-2017, and the content results of all iron elements in the positive electrode materials compounded by sodium ferrous sulfate and carbon of the ferric iron are shown in table 1.
TABLE 1
Table 1 shows that when the positive electrode materials of the composite of sodium ferrous sulfate and carbon are prepared in examples 1-6, the reaction time is 5H, and the content of all iron elements in the prepared positive electrode materials of the composite of sodium ferrous sulfate and carbon is less than or equal to 0.66%.
Example 1 in comparison with comparative examples 1 and 1, comparative example 1 uses nitrogen instead of the hydrogen of the example in a closed environment, comparative example 2 is not heated and ground at the same time, and the content of all iron elements in the positive electrode material of the composite of sodium ferrous sulfate and carbon in comparative example 1 is 3.28%, so that the content of the iron elements in the prepared positive electrode material of the composite of sodium ferrous sulfate and carbon is higher.
Example 1 compared with comparative example 2, comparative example 2 has no stage of simultaneous heating and grinding, and adopts a mode of heating first and then ball milling, so that the reaction time of the prepared positive electrode material of the composite of sodium ferrous sulfate and carbon is 10H, and the preparation time is longer. The procedure in comparative example 2 was ball milling followed by 5 hours, with a total reaction time of 10 hours, and longer preparation time compared to the example, indicating that simultaneous heating and ball milling accelerates the rate of preparation of the positive electrode material, shortening the preparation time.
And the content of all iron elements in the positive electrode material of the composite of sodium ferrous sulfate and carbon is 1.26% for the ferric iron element in comparative example 2, and the ferric iron content in comparative example 2 is slightly higher than that in example 1, probably due to insufficient solid solution reaction.
Example 6 in comparison with comparative example 2, comparative example 3 uses nitrogen instead of the hydrogen of example 6 in a closed environment, comparative example 3 is not heated and ground at the same time, the content of all iron elements in the positive electrode material of the composite of sodium ferrous sulfate and carbon in comparative example 3 is 3.35%, so that the content of the iron elements in the prepared positive electrode material of the composite of sodium ferrous sulfate and carbon is higher.
Microscopic observation was made on the positive electrode material of the composite of sodium ferrous sulfate and carbon obtained in example 1, as shown in fig. 1, in which a portion of the agglomerated mass, which is the positive electrode material of sodium ferrous sulfate, was observed; the precursor wire with a certain length is doped carbon, and the material has a certain pore, which is favorable for infiltration of electrolyte.
2) Preparation of sodium ion batteries
Preparing a positive electrode plate: the sodium ferrous sulfate and carbon composite positive electrode materials prepared in the embodiment and the comparative example are respectively used for preparing a positive electrode plate, wherein the sodium ferrous sulfate and carbon composite positive electrode material, a conductive agent Super-p and a binder polyvinylidene fluoride are weighed according to the mass ratio of 90:5:5, the three materials are dispersed in an N-methyl pyrrolidone solvent, uniformly mixed and then coated on an aluminum foil, and the aluminum foil is dried for 12 hours under the vacuum condition of 120 ℃ to obtain the positive electrode plate, and the surface density of the obtained positive electrode plate is 9.5-11.5 g/cm 2 ；
Electrolyte solution: sodium perchlorate is used as a solute, and the concentration of the solute is 1mol/L. Ethylene carbonate and dimethyl carbonate with the volume ratio of 1:1 are used as solvents to prepare electrolyte;
negative pole piece: homogenizing 94wt% of anode active material hard carbon, 2wt% of SP, 2.8wt% of SBR and 1.2wt% of CMC under the condition of taking deionized water as a solvent, coating the slurry on a 6 mu m copper foil, baking at 85 ℃, rolling and die cutting, and compacting to obtain the anode active material with the density of 0.95g/cm 3 After the powder is brushed by die cuttingAnd baking the electrode plate at 100 ℃ for 12 hours to obtain the negative electrode plate.
Isolation film: coating 4 mu m Al on a polyethylene isolating film substrate with the thickness of 12 mu m 2 O 3 And (3) coating.
Preparation of a positive electrode material button cell: placing the positive electrode plate, the diaphragm, the sodium plate, the gasket and the elastic sheet in a CR2032 button cell in sequence, injecting 200 μl of electrolyte, and packaging to obtain the button cell for testing the charge-discharge gram capacity and the first charge-discharge efficiency of the positive electrode material.
And (3) preparing a sodium ferrous sulfate soft-package battery cell: and after the positive pole piece, the negative pole piece and the isolating film are assembled, packaging the assembled positive pole piece, the negative pole piece and the isolating film in an aluminum plastic film, and injecting electrolyte to obtain the soft-package sodium ion battery.
3) Determination of specific surface area of cathode Material
And 5g of the obtained positive electrode material powder is taken and placed into a sample tube, heated and degassed, and weighed after degassing, and placed on a test instrument. After the adsorption amount of the gas on the solid surface at different relative pressures is measured at a constant temperature and low temperature (-296.7 ℃), the adsorption amount of the sample monolayer is calculated based on the multilayer adsorption theory of Yu Bulang Noll-Eltt-Taylor (BET) and the formula thereof, so that the specific surface area of the positive electrode material is calculated.
4) Volume expansion rate test of battery
After the battery was fully charged to 4.2V at 1C, it was left to stand in an incubator at 80 ℃ for 10 days. And the initial volume of the battery and the volume after standing for 10 days are measured by a drainage method, so as to obtain the volume expansion rate of the battery.
Volume expansion (%) = (volume after 10 days of rest/initial volume-1) ×100% of the battery.
The specific surface area measurement and the high-temperature gas production test were performed on the cathode materials of the composite of sodium ferrous sulfate and carbon prepared in examples and comparative examples, and the results are shown in table 2.
TABLE 2
According to the detection results of table 2, when the content of ferric iron element is low in examples 1 to 6, the volume expansion of the sodium ferrous sulfate positive electrode material can be controlled to a certain extent by controlling the specific surface area of the sodium ferrous sulfate positive electrode material, and when the specific surface area is large, the volume expansion rate is large.
Compared with the comparison of the example 1 and the comparison example 1-2, the example 6 has lower content of ferric iron element and smaller volume expansion rate when the specific surface area is the same as that of the comparison example 3, and is beneficial to the storage and preservation of the positive electrode sheet containing the ferrous sulfate sodium positive electrode material in a battery.
3) First-round discharge gram capacity and first-time charge-discharge efficiency test:calculating according to the size and the surface density of the positive plate in the button cell to obtain the mass of sodium ferrous sulfate active substances contained in the positive plate in the button cell as m; the button cell was charged to 4.5V at a constant current with a current density of 0.1C, 1c=120 mA/g, the charge capacity C1 was recorded, then discharged to 2.0V at a constant current with a current density of 0.1C, the discharge capacity C2 was recorded, the first charge gram capacity was C1/m, and the first discharge gram capacity was C2/m.
First charge-discharge efficiency test = C2/C1%
4) Cycle capacity retention test：
And (3) charging the prepared sodium ion battery at a constant current and constant voltage of 1C under the environment of 22+/-5 ℃, wherein the charging cut-off voltage is 4.5V, the cut-off current is 0.05C, the battery is placed for 10min, the cut-off voltage is 2.0V under the constant current of 1C, the battery is placed for 10min, the battery is subjected to cyclic test according to the steps, and the capacity retention rate of the battery is tested after 1000 cycles.
5) Battery power factor
1. At room temperature, the battery cell is put to 2.0V at constant current of 0.5 ℃ for stopping, and is kept stand for 10min;
2. charging to 4.5V with constant current and constant voltage of 0.5C, cutting off the current to 0.05C, and standing for 10min;
3. discharging constant current of 0.5C to 2.0V, standing for 10min;
4. the battery cell is charged to 4.5V with 5C current and constant voltage, the current is cut off to 0.05C, and the battery cell is kept stand for 10min to obtain the 5C charging constant current and constant voltage ratio, the numerical value of the ratio can reflect the charging condition of the battery, and the larger the ratio is, the better the effect of quick charging and discharging is.
The sodium ion cell was tested as described in the test section above and the results are shown in table 3 and fig. 2.
TABLE 3 Table 3
According to Table 1, the initial charge/discharge g capacities of examples 1 to 6 were 107mAh/g, 102mAh/g, 98mAh/g, 105mAh/g, 106mAh/g, 104mAh/g, and the initial charge/discharge efficiencies of examples 1 to 6 were 99.8%, 99.6%, 99.7%, 99.8%, 99.2%, respectively, and the 1000-cycle capacity retention rates of examples 1 to 6 were 96.6%, 97.2%, 96.2%, 96.6%, 96.0%, respectively. The 5C rate charging constant current constant voltage ratios of examples 1-6 were 97.5%, 96.8%, 96.2%, 97.1%, 98.2%, 97.5%, respectively.
Example 6 has an increased carbon content compared to example 1, and has a lower capacity retention rate for 1000 cycles due to the higher carbon content in the cathode material, and the lower sodium ferrous sulfate content; the 5C rate charge constant current constant voltage ratio of example 6 is comparable to that of example 1, and the analysis may be that the carbon content of example 6 is increased, whereas the content of all iron elements in the positive electrode material of the ferric iron element in example 1, which is a composite of sodium ferrous sulfate and carbon, is lower.
Compared with the example, the positive electrode material compounded by sodium ferrous sulfate and carbon in comparative example 1 has higher content of trivalent iron element, the first-cycle discharge gram capacity of comparative example 1 is 93mAh/g at most, the first-cycle charge-discharge efficiency is 97.4%, the capacity retention rate of 1000 cycles is 94.2%, and the three parameters are respectively lower than those in examples 1-3, so that when the content of trivalent iron element in the positive electrode material compounded by sodium ferrous sulfate and carbon is higher, the positive electrode material is used as the positive electrode material, and the first-cycle discharge gram capacity, the first-cycle charge-discharge efficiency and the capacity retention rate of 1000 cycles are influenced to a certain extent. Therefore, the content of ferric iron element in the positive electrode material compounded by ferrous sodium sulfate and carbon is reduced, and the performances of the first-cycle discharge gram capacity, the first-cycle charge and discharge efficiency, the 1000-cycle capacity retention rate, the doubling performance and the like of the sodium ion battery are improved.
Compared with the embodiment 1, the reaction time is longer in the process of preparing the anode material compounded by the sodium ferrous sulfate and the carbon, the content of ferric element is slightly higher than that of the embodiment 1, the first-cycle discharge gram capacity of the embodiment 2 is at most 102mAh/g, the first-time charge-discharge efficiency is 98.8%, the capacity retention rate of 1000 cycles is 96.4%, and the three parameters are respectively lower than that of the embodiment 1, so that the reaction time in the process of preparing the anode material compounded by the sodium ferrous sulfate and the carbon is controlled, the production efficiency can be improved, the content of the ferric element can be improved to a certain extent, and the performances such as the first-cycle discharge gram capacity, the first-time charge-discharge efficiency, the capacity retention rate of 1000 cycles and the ploidy of the sodium ion battery are improved.
The 5C rate charging constant current constant voltage ratios of examples 1 to 5 are 97.5%, 96.8%, 96.2%, 97.1%, 98.2%, respectively, the 5C rate charging constant current constant voltage ratios of comparative examples 1 to 2 are 94.1% and 95.6%, respectively, and the 5C rate charging constant current constant voltage ratios of examples 1 to 5 are compared with those of comparative examples 1 to 2, and the examples are superior to those of comparative examples 1 to 2, because the ferrous iron content of the positive electrode material of the sodium ferrous sulfate and carbon composite in the examples is higher than that of the positive electrode material prepared in the comparative examples, and the specific surface area of the examples is superior to or equivalent to that of the comparative examples, thereby improving the charge and discharge performance of the examples.
Example 6 compared with comparative example 3, the ferrous iron content of the positive electrode material of the ferrous sodium sulfate and carbon composite is higher than that of comparative example 3, and the first-cycle discharge gram capacity, the first-cycle charge-discharge efficiency and the 1000-cycle capacity retention charge-discharge performance of the examples are superior to those of the comparative example.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present application, and not for limiting the same; although the application has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the application.
Claims (10)
1. A method for preparing a positive electrode material, comprising:
adding a raw material containing a sodium source, sulfate, ferrous salt and a carbon source into a closed container filled with reducing gas and having a heating function, and grinding and calcining the raw material under the heating condition to obtain a ferrous sodium sulfate and carbon composite anode material;
wherein the reaction temperature T of the calcination treatment is kept to be 300 ℃ to 400 ℃.
2. The preparation method according to claim 1, wherein the preparation method satisfies at least one of the following conditions:
the sodium source comprises one or more of sodium sulfate, sodium nitrate, sodium chloride and sodium hydroxide;
the sulfate comprises one or more of sodium sulfate and ferrous sulfate;
the ferrous salt comprises one or more of ferrous sulfate, ferrous sulfate heptahydrate and ferrous sulfate monohydrate;
the carbon source comprises one or more of graphite, carbon nano tubes, carbon nano fibers, graphene and carbon black;
the sodium source and the sulfate are the same substance;
the ferrous salt and the sulfate are the same substance.
3. The method of preparation according to claim 1, wherein the method satisfies at least one of the following conditions:
in the raw materials, the molar ratio of sulfate groups to sodium elements is 1: (0.28 to 2.5);
in the raw materials, the molar ratio of iron element to sodium element is 1: (0.8-1.8);
in the raw materials, the mass content of the carbon source is 1% -6%, and optionally 4% -5%.
4. The method according to claim 1, wherein the gram capacity of the sodium ferrous sulfate and carbon composite cathode material is not less than 98mAh/g.
5. The method according to claim 1 or 4, wherein the preparation method comprises: mixing grinding medium with the raw materials in a mass ratio of 1: (0.02-20) and mixing the components.
6. The method of claim 5, wherein the method of preparation satisfies at least one of the following conditions:
the sealed container takes the rotation speed of 350-700r/min as the grinding time of 4-10 h;
the grinding medium comprises one or more of zirconia ceramic particles, silicon carbide particles and alumina particles;
the grinding medium is a sphere, and the diameter of the grinding medium is 0.5 cm-2 cm.
7. A positive electrode material characterized by comprising the sodium ferrous sulfate and carbon composite positive electrode material produced by the production method according to any one of claims 1 to 6;
optionally, the mass percentage content n of ferric iron in all iron elements in the positive electrode material is as follows: n is less than 1%;
optionally, the average particle diameter Dv50 of the positive electrode material compounded by the ferrous sodium sulfate and the carbon is 0.2-0.5 mu m;
optionally, the specific surface area of the positive electrode material compounded by the ferrous sodium sulfate and the carbon is 12m 2 /g-17m 2 /g；
Optionally, the positive electrode material of the ferrous sodium sulfate and carbon composite comprises:
sodium ferrous sulfate positive electrode material particles with a chemical general formula of Na m Fe n SO 4 Wherein 0.22.ltoreq.m < 2,0.28.ltoreq.n < 2, optionally m+2n=2, and
and carbon at least partially coating the ferrous sodium sulfate positive electrode material particles.
8. A positive electrode sheet, characterized in that the positive electrode sheet comprises a positive electrode current collector and a positive electrode film layer positioned on at least one side of the positive electrode current collector, the positive electrode film layer comprising the positive electrode material prepared by the preparation method of any one of claims 1 to 6 or the positive electrode material of claim 7.
9. A sodium ion battery comprising the positive electrode sheet of claim 8.
10. An electrical device comprising the sodium ion battery of claim 9.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117438570A (en) * | 2023-12-21 | 2024-01-23 | 江苏中兴派能电池有限公司 | Sodium ferric sulfate composite positive electrode material, preparation method thereof, positive electrode and battery |
| CN117776269A (en) * | 2023-12-19 | 2024-03-29 | 无锡钠科能源科技有限公司 | Sodium ferrous sulfate positive electrode material and preparation method and application thereof |
| CN117855457A (en) * | 2024-03-07 | 2024-04-09 | 江苏众钠能源科技有限公司 | Positive electrode active material, preparation method and application thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117776269A (en) * | 2023-12-19 | 2024-03-29 | 无锡钠科能源科技有限公司 | Sodium ferrous sulfate positive electrode material and preparation method and application thereof |
| CN117776269B (en) * | 2023-12-19 | 2024-10-22 | 无锡钠科能源科技有限公司 | Sodium ferrous sulfate positive electrode material and preparation method and application thereof |
| CN117438570A (en) * | 2023-12-21 | 2024-01-23 | 江苏中兴派能电池有限公司 | Sodium ferric sulfate composite positive electrode material, preparation method thereof, positive electrode and battery |
| CN117438570B (en) * | 2023-12-21 | 2024-03-12 | 江苏中兴派能电池有限公司 | Sodium ferric sulfate composite positive electrode material, preparation method thereof, positive electrode and battery |
| CN117855457A (en) * | 2024-03-07 | 2024-04-09 | 江苏众钠能源科技有限公司 | Positive electrode active material, preparation method and application thereof |
| CN117855457B (en) * | 2024-03-07 | 2024-06-04 | 江苏众钠能源科技有限公司 | Positive electrode active material, preparation method and application thereof |
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