CN113130896A - Positive electrode material for sodium ion battery and sodium ion battery comprising same - Google Patents
Positive electrode material for sodium ion battery and sodium ion battery comprising same Download PDFInfo
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- CN113130896A CN113130896A CN201911403664.1A CN201911403664A CN113130896A CN 113130896 A CN113130896 A CN 113130896A CN 201911403664 A CN201911403664 A CN 201911403664A CN 113130896 A CN113130896 A CN 113130896A
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- ion battery
- positive electrode
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 131
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 51
- 239000011734 sodium Substances 0.000 claims abstract description 75
- 239000000654 additive Substances 0.000 claims abstract description 40
- 229940091252 sodium supplement Drugs 0.000 claims abstract description 39
- 230000000996 additive effect Effects 0.000 claims abstract description 37
- 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 25
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 25
- 239000006258 conductive agent Substances 0.000 claims abstract description 20
- 239000011230 binding agent Substances 0.000 claims abstract description 14
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000007600 charging Methods 0.000 claims abstract description 10
- 239000013543 active substance Substances 0.000 claims abstract description 7
- 150000003388 sodium compounds Chemical class 0.000 claims abstract description 4
- -1 transition metal sodium salt Chemical class 0.000 claims description 20
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000002002 slurry Substances 0.000 claims description 14
- 229910020657 Na3V2(PO4)3 Inorganic materials 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 239000003792 electrolyte Substances 0.000 claims description 8
- 229960003351 prussian blue Drugs 0.000 claims description 8
- 239000013225 prussian blue Substances 0.000 claims description 8
- 159000000000 sodium salts Chemical class 0.000 claims description 8
- 229910052723 transition metal Inorganic materials 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000007773 negative electrode material Substances 0.000 claims description 6
- 230000001502 supplementing effect Effects 0.000 claims description 6
- 229910003321 CoFe Inorganic materials 0.000 claims description 5
- 229910004565 Na2Fe2(SO4)3 Inorganic materials 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical group [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910014485 Na0.44MnO2 Inorganic materials 0.000 claims description 4
- 229910021312 NaFePO4 Inorganic materials 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- 229910021385 hard carbon Inorganic materials 0.000 claims description 4
- PWKNBLFSJAVFAB-UHFFFAOYSA-N 1-fluoro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1F PWKNBLFSJAVFAB-UHFFFAOYSA-N 0.000 claims description 3
- 229910019441 NaTi2(PO4)3 Inorganic materials 0.000 claims description 3
- 229910010253 TiO7 Inorganic materials 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 238000004804 winding Methods 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- GPLIMIJPIZGPIF-UHFFFAOYSA-N 2-hydroxy-1,4-benzoquinone Chemical compound OC1=CC(=O)C=CC1=O GPLIMIJPIZGPIF-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 239000010450 olivine Substances 0.000 claims description 2
- 229910052609 olivine Inorganic materials 0.000 claims description 2
- 229910021384 soft carbon Inorganic materials 0.000 claims description 2
- 239000002562 thickening agent Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000000354 decomposition reaction Methods 0.000 abstract description 6
- 230000002427 irreversible effect Effects 0.000 abstract description 3
- 229910052782 aluminium Inorganic materials 0.000 description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 17
- 239000011888 foil Substances 0.000 description 15
- 239000007789 gas Substances 0.000 description 15
- 239000000203 mixture Substances 0.000 description 12
- 238000005096 rolling process Methods 0.000 description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000002033 PVDF binder Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 7
- 238000003825 pressing Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000005303 weighing Methods 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 238000007493 shaping process Methods 0.000 description 5
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 4
- 229910021543 Nickel dioxide Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 229910004639 Na2NiO2 Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- FISGLHSNQHXMGY-UHFFFAOYSA-N sodium;aminoazanide Chemical class [Na+].[NH-]N FISGLHSNQHXMGY-UHFFFAOYSA-N 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- PWEBUXCTKOWPCW-UHFFFAOYSA-N squaric acid Chemical compound OC1=C(O)C(=O)C1=O PWEBUXCTKOWPCW-UHFFFAOYSA-N 0.000 description 2
- 229910020084 (NixCoyMnz)O2 Inorganic materials 0.000 description 1
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021225 NaCoO2 Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [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
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Images
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
- H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/44—Methods for charging or discharging
- H01M10/446—Initial charging measures
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a positive electrode material for a sodium ion battery and the sodium ion battery comprising the positive electrode material, wherein the positive electrode material comprises a positive active substance, a binder, a conductive agent and a sodium supplement additive, and compared with the prior art, the positive electrode material has the following advantages: the sodium supplement additive added in the invention is a sodium compound, the potential of the anode cannot be changed, the sodium supplement additive can be decomposed during formation and charging, gas generated after decomposition can be removed during formation, and the generated sodium is transferred from the anode to the cathode during charging and forms an SEI film on the cathode, so that the sodium required for forming the SEI film is filled, the consumption of sodium ions of the anode can be reduced, the irreversible capacity of the sodium ion battery is reduced, the first coulomb efficiency of the sodium ion battery is improved, and the cycle performance of the sodium ion battery is improved. The method for compensating sodium ions by the sodium ion battery is safe, practical and convenient to operate.
Description
Technical Field
The invention belongs to the field of energy storage devices, and particularly relates to a positive electrode material for a sodium ion battery and the sodium ion battery comprising the positive electrode material.
Background
The sodium ion battery is a reliable choice for solving the problem of large-scale energy storage, has a working principle similar to that of a lithium ion battery, and realizes the chargeable and dischargeable performance of the battery by utilizing the continuous embedding/separation of sodium ions between a positive electrode and a negative electrode. Compared with the lithium ion battery, the sodium ion battery has the characteristics of rich sodium storage capacity, low price and the like; meanwhile, as the conductivity of the sodium salt in the electrolyte with the same concentration is about 20 percent higher than that of the lithium salt electrolyte, the electrolyte with low concentration can be used; in addition, sodium ions are difficult to form alloy with aluminum under low electrode potential, the negative electrode can adopt aluminum foil as a current collector, and the like, so that the cost is greatly reduced compared with a lithium ion battery due to the advantages, and the sodium ion battery has wide application prospect in large-scale energy storage.
Sodium ion batteries and lithium ion batteries appear to be only intercalating ions, but the requirements for the electrode materials are quite different. Due to the difference of the radius of the embedded ions, many electrode materials widely used in lithium ion batteries, such as graphite, cannot be well utilized in sodium ion batteries, and the use of other cathode materials causes the problem of active sodium ion loss during the first charge and discharge. Therefore, compared with the field of lithium ion batteries, the field of sodium ion batteries has a plurality of technical problems to be overcome, and the technical maturity of the sodium ion batteries is seriously lagged behind that of the lithium ion batteries.
The carbon-based material is considered as the sodium ion battery cathode material with the most development potential due to the advantages of abundant resources, environmental friendliness, low price and the like, wherein hard carbon, carbon black, carbon fiber, graphene and the like are successively reported. However, as analyzed above, the carbon-based material has a problem of loss of active sodium ions during the first charge and discharge, which also results in a problem that the first charge and discharge coulombic efficiency is extremely low, making it difficult to meet the current commercial application requirements.
Similar to carbon-based anode materials, Na2Fe2(SO4)3、Na2TiO7、NaTiOPO4、NaTi2(PO4)3Sodium ion battery cathode materials such as disodium terephthalate and 2, 5-hydroxy-1, 4-benzoquinone disodium have the problem of low first charge-discharge coulombic efficiency in different degrees. The low first charge-discharge coulombic efficiency has great influence on the battery, mainly reflected in the aspect of reducing the energy density of the battery, so that the research on finding a technology for improving the first charge-discharge coulombic efficiency of the sodium ion battery becomes a hotspot.
The main sodium supplementing methods at present mainly include a sodium powder spraying method, an organic sodium solution spraying method, a positive electrode additive sodium supplementing method and the like. However, the sodium powder method and the organic sodium solution method both use metallic sodium directly, which results in very strict requirements on environment, difficulty in large-scale production and safety problems. Therefore, the development of simple and efficient sodium supplementing technology is of great significance.
Disclosure of Invention
In order to overcome the defects and defects of the prior art, the invention aims to provide a positive electrode material for a sodium-ion battery and the sodium-ion battery comprising the same. Through a large number of experimental researches, the inventor of the application finds that the sodium supplement additive for the positive electrode has higher gram capacity and lower first effect, so that a large number of sodium ions are separated in the normal charging process and are used for supplementing the sodium ions consumed by the SEI film formed by the negative electrode, and a large number of sodium ions cannot be accepted due to the lower first effect in the discharging process, so that the capacity of the battery is improved.
In order to achieve the above object, the present invention provides a positive electrode material for a sodium ion battery, the positive electrode material including a positive electrode active material, a binder, a conductive agent, and a sodium supplement additive;
the sodium supplement additive is one or the combination of transition metal sodium salt, sodium azide, squaric acid sodium salt, hydrazide sodium salt and prussian blue sodium salt.
In the invention, the sodium supplement additive can decompose and release sodium ions during formation charging, and the sodium supplement additive can be converted into a solid substance (such as a positive electrode active substance) or a gas.
Illustratively, the sodium supplement additive is a transition metal sodium salt NamMO2Wherein M is not less than 1.5 and not more than 2.05, M is selected from one or more of Mn, Co and Ni, and contains transition metal sodium salt NamMO2The transition metal sodium salt Na is formed and charged by the positive electrode material for the sodium ion batterymMO2Will decompose and release sodium ions and convert into NaMO which can be used as anode active material2. For example, the transition metal sodium salt is selected from Nam(NixCoyMnz)O2Wherein x is more than or equal to 1 and more than or equal to 0, y is more than or equal to 1 and more than or equal to 0, z is more than or equal to 1 and x + y + z is 1; for example, the transition metal sodium salt is selected from Na2MO2E.g. selected from Na2NiO2、Na2CoO2Or Na2MnO2。
Illustratively, when the sodium supplement additive is sodium azide, the sodium azide is NaN3Which decomposes and releases sodium ions while converting to nitrogen.
Illustratively, when the sodium supplement additive is a sodium salt of a squaric acid, the sodium salt of the squaric acid is Na2C3O3、Na2C4O4、Na2C5O5、Na2C6O6One or a combination thereof, which decomposes and releases sodium ions while converting to CO2。
Illustratively, when the sodium supplement additive is a sodium hydrazide salt, the sodium hydrazide salt is Na2(CONHNH2)2Which decomposes and releases sodium ions while being converted into a gas and a sodium salt that can serve as a positive electrode active material.
Illustratively, when the sodium supplement additive is Prussian blue sodium salt, the Prussian blue sodium salt is selected from NapM1Fe(CN)6Wherein p is a number between 1 and 2, M1At least one selected from the group consisting of Mn, Fe, Co, Ni and Zn, which decomposes and releases sodium ions while being converted into NaM that can be used as a positive electrode active material1Fe(CN)6,M1At least one selected from Mn, Fe, Co, Ni and Zn. Illustratively, the Prussian blue sodium salt is selected from Na1.72MnFe(CN)6、Na1.4MnFe(CN)6、Na1.92Fe[Fe(CN)6]、NaCo[Fe(CN)6]·H2O、Na2CoFe(CN)6One or a combination thereof.
According to the invention, the sodium supplement additive accounts for 0.1-20 wt%, preferably 0.2-15 wt%, such as 0.5-10 wt%, such as 0.1 wt%, 0.5 wt%, 0.8 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 15 wt% or 20 wt% of the total mass of the positive electrode material.
According to the invention, the positive active substance accounts for 80-99.5 wt% of the total mass of the positive material; the binder accounts for 0.1-5 wt% of the total mass of the positive electrode material; the conductive agent accounts for 0.1-5.0 wt% of the total mass of the positive electrode material.
According to the present invention, the positive active material is selected from positive electrode materials having sodium ion battery activity, including but not limited to the following: NaFePO4、Na3V2(PO4)3、Na2Fe2(SO4)3、Na3Ni2SbO6、Na0.44MnO2。
According to the invention, the NaFePO4、Na3V2(PO4)3、Na2Fe2(SO4)3The crystal phase structure of (A) is olivine type, the Na is3Ni2SbO6The structure of (A) is a layered structure, the Na0.44MnO2The structure of (2) is a tunnel structure.
According to the present invention, the binder and the conductive agent are a binder and a conductive agent for a positive electrode, which are conventional in the art.
The invention also provides a preparation method of the positive electrode material for the sodium-ion battery, which comprises the following steps:
and mixing the positive active substance, the binder, the conductive agent and the sodium supplement additive with the solvent to prepare positive slurry, namely preparing the positive material for the sodium-ion battery.
The invention also provides a positive electrode which comprises a positive electrode current collector and the positive electrode material for the sodium-ion battery, wherein the positive electrode material is arranged on one side or two side surfaces of the positive electrode current collector.
According to the invention, the positive current collector is an aluminum foil.
The invention also provides a sodium ion battery which comprises the positive electrode.
According to the invention, the sodium-ion battery further comprises a negative electrode, a separator and an electrolyte.
According to the present invention, the negative electrode includes a negative electrode current collector and a negative electrode material for a sodium ion battery disposed on one or both side surfaces of the negative electrode current collector, the negative electrode material for a sodium ion battery includes a negative electrode active material selected from graphite, soft carbon, hard carbon, Na, a conductive agent, a binder and a thickener2Fe2(SO4)3、Na2TiO7、NaTiOPO4、NaTi2(PO4)3And one or a combination of disodium terephthalate and disodium 2, 5-hydroxy-1, 4-benzoquinone.
The invention also provides a preparation method of the sodium-ion battery, which comprises the following steps:
(1) preparing a positive electrode for a sodium ion battery and a negative electrode for the sodium ion battery;
(2) winding the positive electrode for the sodium ion battery and the negative electrode for the sodium ion battery obtained in the step (1) with a diaphragm to prepare a sodium ion battery cell;
(3) and (3) filling the sodium ion battery core into a battery shell, injecting electrolyte, and removing generated gas along with the air bag belt after formation to prepare the sodium ion battery.
The invention also provides a sodium ion battery sodium supplementing method, which comprises the following steps:
a) preparing a sodium ion battery, wherein a positive pole piece of the sodium ion battery comprises a positive pole material for the sodium ion battery, and the positive pole material for the sodium ion battery comprises a sodium supplement additive;
b) in the formation stage of the battery, the first charging voltage range is controlled to be 1.5V-4.1V, so that the sodium supplement additive reacts and releases sodium ions to participate in forming an SEI film;
c) the voltage range of the battery for cyclic charge and discharge is controlled, so that the sodium ion battery enters a normal charge and discharge use state, and the sodium compound after the reaction of the sodium supplement additive exists in the battery.
The invention has the beneficial effects that:
the invention provides a positive electrode material for a sodium ion battery and the sodium ion battery comprising the positive electrode material, wherein the positive electrode material comprises a positive active substance, a binder, a conductive agent and a sodium supplement additive, and compared with the prior art, the positive electrode material has the following advantages:
the sodium supplement additive added in the invention is a sodium compound, the potential of the anode cannot be changed, the sodium supplement additive can be decomposed during formation and charging, gas generated after decomposition can be removed during formation, and the generated sodium is transferred from the anode to the cathode during charging and forms an SEI film on the cathode, so that the sodium required for forming the SEI film is filled, the consumption of sodium ions of the anode can be reduced, the irreversible capacity of the sodium ion battery is reduced, the first coulomb efficiency of the sodium ion battery is improved, and the cycle performance of the sodium ion battery is improved. The method for compensating sodium ions by the sodium ion battery is safe, practical and convenient to operate.
Drawings
Fig. 1 is a charge cycle curve of the sodium ion batteries of example 1 and comparative example 1 of the present invention.
Detailed Description
The preparation method of the present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
Example 1
A preparation method of a sodium-ion battery comprises the following steps:
(1) adding Na as sodium supplement additive in sequence2NiO2And a positive electrode active material Na3V2(PO4)3The conductive agent Super P and the adhesive PVDF are mixed according to the weight ratio of 3: 93: 2: 2 weighing 100g of the mixture, mixing the weighed mixture in 40g of NMP solvent, stirring the mixture in vacuum to obtain uniform slurry, then uniformly coating the slurry on an aluminum foil current collector, baking the aluminum foil current collector in a 10m oven at 100 ℃ in a rolling way (the rolling belt is 2m/min), baking the aluminum foil current collector in vacuum at 85 ℃ for 20 hours, then cold pressing and slitting the aluminum foil current collector to obtain Na containing a sodium supplement additive2NiO2The positive electrode sheet of (1);
(2) and (2) mixing the positive plate obtained in the step (1) with a mixture of hard carbon: conductive agent Super P: CMC: SBR 95: 2: 1.5: 1.5 winding the obtained negative plate and the sodium ion battery diaphragm into a sodium ion battery cell after vacuum stirring, coating, cold pressing and slitting;
(3) sodium ion battery core is filled into an aluminum plastic film battery package and injected with sodium hexafluorophosphate (NaPF) containing 1mol/L6) Ethyl Carbonate (EC): methyl ethyl carbonate (EMC): diethyl carbonate (DEC) ═ 1: 1: 1 (volume ratio), an electrolyte containing 2 wt% Vinylene Carbonate (VC) and 3 wt% 1, 3-Propane Sultone (PS); in the formation stage, the material is charged to 3.4V with 0.1C, then charged to 4.2V with 0.2C constant current, and then charged to 0.05C with 4.2V constant voltage cutoff current, at this time, Na2NiO2Decomposed to release Na ions and partially converted to NaNiO as positive active material2And release a small amount of gas. Removing gas by pumpingAnd obtaining the sodium ion battery with the positive electrode supplemented with sodium.
Example 2
A preparation method of a sodium-ion battery comprises the following steps:
(1) adding sodium supplement additive Prussian blue Na according to sequence2CoFe(CN)6And a positive electrode active material Na3V2(PO4)3The conductive agent Super P and the adhesive PVDF are mixed according to the weight ratio of 3: 93: 2: 2 weighing 100g of the mixture, mixing the weighed mixture in 40g of NMP solvent, stirring to obtain uniform slurry, uniformly coating the slurry on an aluminum foil current collector, baking the aluminum foil current collector in a 10m oven at 100 ℃ in a rolling way (the rolling belt is 2m/min), baking the aluminum foil current collector in a vacuum way at 85 ℃ for 20 hours, then cold pressing and slitting the aluminum foil current collector to obtain the Na containing sodium supplement additive2CoFe(CN)6The positive electrode sheet of (1);
(2) the same as example 1;
(3) the difference from example 1 is that in the formation stage, Na2CoFe(CN)6Decomposition occurs to release Na ions while partially converting into NaCoFe (CN) as a positive electrode active material6And release a small amount of gas. And removing gas through the step of air extraction, and shaping to obtain the sodium ion battery with the positive electrode supplemented with sodium.
Example 3
A preparation method of a sodium-ion battery comprises the following steps:
(1) in dry air (moisture content below 1% humidity) and avoid contact with copper, rubber, polyvinyl chloride products, direct contact with skin and respiratory tract. Sodium azide NaN as sodium supplement additive is added in sequence3And a positive electrode active material Na3V2(PO4)3The conductive agent Super P and the adhesive PVDF are mixed according to the weight ratio of 3: 93: 2: 2 weighing 100g of the mixture, mixing the mixture in 40g of solvent NMP, stirring to obtain uniform slurry, then uniformly coating the slurry on an aluminum foil current collector, carrying out rolling baking in a 10m oven at 100 ℃ (rolling belt is 2m/min), carrying out vacuum baking at 85 ℃ for 20h, then carrying out cold pressing and slitting to obtain the NaN containing sodium azide3The positive electrode sheet of (1);
(2) the same as example 1;
(3) the difference from example 1 is that in the formation stage,NaN3The decomposition occurs to release Na ions, and part of N is generated and released2(ii) a And removing gas through the step of air extraction, and shaping to obtain the sodium ion battery with the positive electrode supplemented with sodium.
Example 4
A preparation method of a sodium-ion battery comprises the following steps:
(1) sodium citrate Na as sodium supplement additive is added in sequence2C4O4And a positive electrode active material Na3V2(PO4)3The conductive agent Super P and the adhesive PVDF are mixed according to the weight ratio of 3: 93: 2: 2 weighing 100g of Na, mixing the Na with 40g of NMP solvent, stirring to obtain uniform slurry, uniformly coating the slurry on an aluminum foil current collector, baking in a 10m oven at 100 ℃ in a rolling way (the rolling belt is 2m/min), baking in vacuum at 85 ℃ for 20 hours, then cold pressing and cutting to obtain the Na-containing solution2C4O4The positive electrode sheet of (1);
(2) the same as example 1;
(3) the difference from example 1 is that in the formation stage, Na2C4O4The decomposition occurs to release Na ions, and partial CO is generated and released2(ii) a And removing gas through the step of air extraction, and shaping to obtain the sodium ion battery with the positive electrode supplemented with sodium.
Example 5
A preparation method of a sodium-ion battery comprises the following steps:
(1) adding sodium supplement additive hydrazide sodium salt Na according to the sequence2(CONHNH2)2And a positive electrode active material Na3V2(PO4)3The conductive agent Super P (conductive carbon, SP) and the binder PVDF are mixed according to the weight ratio of 3: 93: 2: 2 weighing 100g of Na, mixing the Na with 40g of NMP solvent, stirring to obtain uniform slurry, uniformly coating the slurry on an aluminum foil current collector, baking in a 10m oven at 100 ℃ in a rolling way (the rolling belt is 2m/min), baking in vacuum at 85 ℃ for 20 hours, then cold pressing and cutting to obtain the Na-containing solution2(CONHNH2)2The positive electrode sheet of (1);
(2) the same as example 1;
(3) the difference from example 1 is thatStage (Na)2(CONHNH2)2The decomposition is carried out to release Na ions, and Co and CO are generated and released2、CH4、H2、C2H4、NH3And (4) removing the gas by the step of air exhaust after the gas is equalized into the gas, and shaping to obtain the sodium ion battery with the positive electrode supplemented with sodium.
Example 6
A preparation method of a sodium-ion battery comprises the following steps:
(1) adding Na as sodium supplement additive in sequence2NiO2、Na2CoO2Positive electrode active material Na3V2(PO4)3The conductive agent Super P and the adhesive PVDF are mixed according to the weight ratio of 1.5: 1.5: 93: 2: 2 weighing 100g of the mixture, mixing the weighed 100g of the mixture in 40g of solvent NMP, stirring the mixture in vacuum to obtain uniform slurry, then uniformly coating the slurry on an aluminum foil current collector, carrying out rolling baking on the aluminum foil current collector in a 10m baking oven at 100 ℃ (a rolling belt is 2m/min), carrying out vacuum baking at 85 ℃ for 20 hours, then carrying out cold pressing and slitting to obtain the Na containing the mixed sodium supplement additive2NiO2And Na2CoO2The positive electrode sheet of (1);
(2) the same as example 1;
(3) the difference from example 1 is that in the formation stage, Na2NiO2And Na2CoO2Decomposed to release Na ions and partially converted to NaNiO as positive active material2And NaCoO2And release a small amount of gas. And removing gas through the step of air extraction, and shaping to obtain the sodium ion battery with the positive electrode supplemented with sodium.
Comparative example 1
Compared with example 1, the difference is only that: positive electrode active material Na3V2(PO4)3The conductive agent Super P (conductive carbon, SP) and the binder PVDF are mixed according to the weight ratio of 96: 2: 2 weigh 100g of the mixture in 40g of solvent NMP, and then prepare a positive plate and a cell and test method the same as example 1.
Test example 1
The sodium ion batteries of examples 1 to 6 and comparative example 1 were each subjected to a capacity test, and a primary charge efficiency test and a cycle performance test.
The method for testing the first charging efficiency comprises the following steps: first, the charge is carried out from the open-circuit voltage to 4.1V by 0.1C current, then the constant-voltage charge cutoff current is 0.01C under 4.1V, and finally the discharge is carried out from 0.2C to 3.0V, and the discharge capacity is divided by the charge capacity, thus obtaining the first charge efficiency. The test results are shown in table 1.
The method for testing the cycle performance comprises the following steps: charging to 4.1V at 0.5C, constant-voltage charging to 0.02C at 4.1V, and discharging to 3.0V at 0.5C, and comparing the discharge capacity as the cyclic discharge capacity. The highest discharge capacity in the first three times among the cyclic discharge capacities was taken as 100%. The test results are shown in table 1.
Table 1 first charge efficiency and cycle performance test results of sodium ion batteries of examples 1 to 6 and comparative example 1
As can be seen from the test results of table 1: after the sodium is supplemented to the positive plate of the sodium-ion battery, when the content of the sodium supplement additive is only 3%, the first efficiency of the sodium-ion battery is obviously improved, the irreversible capacity of the sodium-ion battery is obviously reduced, the capacity retention rate of the sodium-ion battery after 100 cycles is higher than that of the sodium supplement additive, and the capacity and the service life of the sodium-ion battery are effectively improved. This is because the sodium supplied to the positive electrode can effectively replace the sodium originally released from the positive electrode, and becomes a component of the SEI film at the negative electrode, thereby achieving the first improvement in efficiency. In addition, the consumption of sodium released from the positive electrode is reduced, so that the lithium ion battery has good protection effect on the structural stability of the positive electrode, and the cycle performance of the sodium ion battery can be effectively improved. The preparation method of the sodium ion battery is simple, easy to operate, good in repeatability, low in cost, small in environmental pollution and suitable for industrial production.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A positive electrode material for a sodium ion battery, wherein the positive electrode material comprises a positive electrode active substance, a binder, a conductive agent and a sodium supplement additive;
the sodium supplement additive is one or the combination of transition metal sodium salt, sodium azide, squaric acid sodium salt, hydrazide sodium salt and prussian blue sodium salt.
2. The positive electrode material for sodium-ion batteries according to claim 1, wherein the transition metal sodium salt is NamMO2Wherein M is more than or equal to 1.5 and less than or equal to 2.05, and M is selected from one or more of Mn, Co and Ni;
preferably, the squaric acid sodium salt is Na2C3O3、Na2C4O4、Na2C5O5、Na2C6O6One or a combination thereof;
preferably, the sodium salt of hydrazide is Na2(CONHNH2)2;
Preferably, the Prussian blue sodium salt is selected from NapM1Fe(CN)6Wherein p is a number between 1 and 2, M1At least one selected from the group consisting of Mn, Fe, Co, Ni and Zn;
preferably, the Prussian blue sodium salt is selected from Na1.72MnFe(CN)6、Na1.4MnFe(CN)6、Na1.92Fe[Fe(CN)6]、NaCo[Fe(CN)6]·H2O、Na2CoFe(CN)6One or a combination thereof.
3. The positive electrode material for a sodium-ion battery according to claim 1 or 2, wherein the sodium supplement additive accounts for 0.1-20 wt%, preferably 0.2-15 wt%, for example 0.5-10 wt% of the total mass of the positive electrode material.
4. The positive electrode material for sodium-ion batteries according to any one of claims 1 to 3, wherein the positive electrode active material accounts for 80 to 99.5 wt% of the total mass of the positive electrode material; the binder accounts for 0.1-5 wt% of the total mass of the positive electrode material; the conductive agent accounts for 0.1-5.0 wt% of the total mass of the positive electrode material;
preferably, the positive active material is selected from positive electrode materials having sodium ion battery activity such as: NaFePO4、Na3V2(PO4)3、Na2Fe2(SO4)3、Na3Ni2SbO6、Na0.44MnO2;
Preferably, the NaFePO4、Na3V2(PO4)3、Na2Fe2(SO4)3The crystal phase structure of (A) is olivine type, the Na is3Ni2SbO6The structure of (A) is a layered structure, the Na0.44MnO2The structure of (2) is a tunnel structure.
5. The method for producing a positive electrode material for a sodium-ion battery as defined in any one of claims 1 to 4, comprising the steps of:
and mixing the positive active substance, the binder, the conductive agent and the sodium supplement additive with the solvent to prepare positive slurry, namely preparing the positive material for the sodium-ion battery.
6. A positive electrode comprising a positive electrode current collector and the positive electrode material for sodium ion batteries according to any one of claims 1 to 4 provided on one or both side surfaces of the positive electrode current collector.
7. A sodium ion battery comprising the positive electrode of claim 6.
8. The sodium-ion battery of claim 7, wherein the sodium-ion battery further comprises a negative electrode, a separator, and an electrolyte;
preferably, the negative electrode comprises a negative electrode current collector and a negative electrode current collector arranged on the negative electrode current collectorA negative electrode material for sodium ion batteries on one or both surfaces, the negative electrode material for sodium ion batteries comprising a negative electrode active material selected from graphite, soft carbon, hard carbon, Na, a conductive agent, a binder and a thickener2Fe2(SO4)3、Na2TiO7、NaTiOPO4、NaTi2(PO4)3And one or a combination of disodium terephthalate and disodium 2, 5-hydroxy-1, 4-benzoquinone.
9. A preparation method of a sodium-ion battery comprises the following steps:
(1) preparing a positive electrode for a sodium ion battery and a negative electrode for the sodium ion battery;
(2) winding the positive electrode for the sodium ion battery and the negative electrode for the sodium ion battery obtained in the step (1) with a diaphragm to prepare a sodium ion battery cell;
(3) and (3) filling the sodium ion battery core into a battery shell, injecting electrolyte, and removing generated gas along with the air bag belt after formation to prepare the sodium ion battery.
10. A method for supplementing sodium for a sodium-ion battery comprises the following steps:
a) preparing a sodium ion battery, wherein a positive pole piece of the sodium ion battery comprises a positive pole material for the sodium ion battery, and the positive pole material for the sodium ion battery comprises a sodium supplement additive;
b) in the formation stage of the battery, the first charging voltage range is controlled to be 1.5V-4.1V, so that the sodium supplement additive reacts and releases sodium ions to participate in forming an SEI film;
c) the voltage range of the battery for cyclic charge and discharge is controlled, so that the sodium ion battery enters a normal charge and discharge use state, and the sodium compound after the reaction of the sodium supplement additive exists in the battery.
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