CN115832199A - Positive pole piece for sodium ion battery and sodium ion battery - Google Patents
Positive pole piece for sodium ion battery and sodium ion battery Download PDFInfo
- Publication number
- CN115832199A CN115832199A CN202211534197.8A CN202211534197A CN115832199A CN 115832199 A CN115832199 A CN 115832199A CN 202211534197 A CN202211534197 A CN 202211534197A CN 115832199 A CN115832199 A CN 115832199A
- Authority
- CN
- China
- Prior art keywords
- sodium
- positive electrode
- mof
- electrode sheet
- sodium ion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 84
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 238000000576 coating method Methods 0.000 claims abstract description 92
- 239000011248 coating agent Substances 0.000 claims abstract description 83
- 239000002808 molecular sieve Substances 0.000 claims abstract description 50
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000011734 sodium Substances 0.000 claims description 70
- -1 halide anion Chemical class 0.000 claims description 49
- 239000003792 electrolyte Substances 0.000 claims description 47
- 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 description 46
- 229910052708 sodium Inorganic materials 0.000 claims description 46
- 239000012621 metal-organic framework Substances 0.000 claims description 33
- 239000007774 positive electrode material Substances 0.000 claims description 31
- 150000001875 compounds Chemical class 0.000 claims description 28
- 239000010410 layer Substances 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 17
- 229910052720 vanadium Inorganic materials 0.000 claims description 17
- 159000000000 sodium salts Chemical class 0.000 claims description 14
- 229910052684 Cerium Inorganic materials 0.000 claims description 13
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 13
- 229910052748 manganese Inorganic materials 0.000 claims description 13
- 229910052723 transition metal Inorganic materials 0.000 claims description 13
- 150000003624 transition metals Chemical class 0.000 claims description 13
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims description 12
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 11
- 239000011575 calcium Substances 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- VCCATSJUUVERFU-UHFFFAOYSA-N sodium bis(fluorosulfonyl)azanide Chemical compound FS(=O)(=O)N([Na])S(F)(=O)=O VCCATSJUUVERFU-UHFFFAOYSA-N 0.000 claims description 9
- YLKTWKVVQDCJFL-UHFFFAOYSA-N sodium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Na+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F YLKTWKVVQDCJFL-UHFFFAOYSA-N 0.000 claims description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052791 calcium Inorganic materials 0.000 claims description 8
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 8
- 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 claims description 8
- 229910001428 transition metal ion Inorganic materials 0.000 claims description 8
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 8
- 239000003575 carbonaceous material Substances 0.000 claims description 7
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 claims description 6
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 5
- 239000011247 coating layer Substances 0.000 claims description 5
- 239000004210 ether based solvent Substances 0.000 claims description 5
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 4
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 4
- 229910020808 NaBF Inorganic materials 0.000 claims description 4
- 229910020892 NaBOB Inorganic materials 0.000 claims description 4
- 229910021201 NaFSI Inorganic materials 0.000 claims description 4
- 150000003983 crown ethers Chemical class 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 239000013082 iron-based metal-organic framework Substances 0.000 claims description 4
- 229920000447 polyanionic polymer Polymers 0.000 claims description 4
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 4
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 4
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 claims description 4
- XGPOMXSYOKFBHS-UHFFFAOYSA-M sodium;trifluoromethanesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C(F)(F)F XGPOMXSYOKFBHS-UHFFFAOYSA-M 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- 125000000129 anionic group Chemical group 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052680 mordenite Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 230000007704 transition Effects 0.000 claims 1
- 210000001787 dendrite Anatomy 0.000 description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 15
- 239000006258 conductive agent Substances 0.000 description 15
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- 239000003960 organic solvent Substances 0.000 description 13
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- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000654 additive Substances 0.000 description 9
- 210000004027 cell Anatomy 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
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- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 7
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
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- 239000008151 electrolyte solution Substances 0.000 description 4
- 239000005038 ethylene vinyl acetate Substances 0.000 description 4
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 3
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Secondary Cells (AREA)
Abstract
The present application relates to a positive electrode sheet for a sodium ion battery, the sheet comprising a functional coating, wherein the functional coating comprises one or more coatings selected from a molecular sieve coating or a MOF coating. The application also relates to a sodium ion secondary battery comprising the positive pole piece and an electric device comprising the sodium ion secondary battery.
Description
Technical Field
The present application relates to a positive electrode sheet for a sodium ion battery comprising a functional coating selected from one or more of a molecular sieve coating or a MOF coating. The application also relates to a sodium ion secondary battery containing the positive electrode plate and an electric device containing the secondary battery.
Background
Lithium ion batteries have been widely used in pure electric vehicles, hybrid electric vehicles, and smart phonesThe energy grid and the like. However, as the price of lithium ore continues to rise, the power battery industry is constantly searching for other ways to reduce costs, one of the most important ways being to develop sodium ion batteries. A sodium ion battery is a secondary battery that mainly operates by the intercalation and deintercalation of sodium ions between a positive electrode and a negative electrode. During charging and discharging, na + Embedding and extracting back and forth between two electrodes: during charging, na + De-intercalation from the positive electrode, intercalation into the negative electrode through the electrolyte; the opposite is true during discharge. The working principle of the lithium ion battery is similar to that of the lithium ion battery.
Sodium is chemically more reactive and more reactive with water than lithium, and therefore sodium ion batteries require more water removal. In addition, sodium ion batteries have poor oxidation resistance at high voltages and tend to form sodium dendrites. The positive pole piece is soaked in an organic solvent, so that a solvation structure is easily generated, and the coulomb efficiency is reduced. Therefore, there is a need in the art to develop a positive electrode sheet for a sodium ion battery, which can improve oxidation resistance at high voltage, inhibit the formation of sodium dendrites, and improve cycle performance of the sodium ion battery.
Disclosure of Invention
The present invention has been made in view of the above problems, and an object of the present invention is to provide a positive electrode sheet for a sodium ion battery, which can improve oxidation resistance at a high voltage at which the sodium ion battery operates, and effectively suppress growth of sodium dendrites, thereby solving the technical problems of a reduction in cycle efficiency and an increase in safety risk of the sodium ion battery due to the growth of sodium dendrites in the related art.
In order to achieve the above object, a first aspect of the present application provides a positive electrode sheet for a sodium ion battery, the sheet comprising a functional coating, wherein the functional coating comprises one or more coatings selected from a molecular sieve coating or an MOF coating.
Through setting up the functional coating who selects from specific coating material, the positive pole piece of this application can change the solvation structure composition of sodium salt, reduces desolvation ability, and the oxidation resistance of electrolyte in the sodium battery is promoted to a wide margin to the formation of suppression sodium dendrite.
In any embodiment, the functional coating has a thickness of 0.3 to 20 μm, alternatively 0.5 to 15 μm, and further alternatively 1 to 8 μm. The thickness of the functional coating has a substantial effect on the formation of sodium dendrites and the cycling performance of the sodium ion battery. If the functional coating is too thick, the energy density of the battery is reduced; if the functional coating is too thin, the solvating structure cannot be effectively changed, resulting in a limited effect of improving oxidation resistance.
In any embodiment, the molecular sieve in the molecular sieve coating is selected from one or more of 3A (potassium a type), 4A (sodium a type), 5A (calcium a type), 10Z (calcium Z type), 13Z (sodium Z type), Y (sodium Y type), sodium mordenite type molecular sieves. In further embodiments, the MOF in the MOF coating is selected from one or more of Fe-MOF, ni-MOF, co-MOF, mn-MOF, cu-MOF. The coulombic efficiency and cycle performance of the sodium ion battery can be further adjusted by selecting different coating materials.
In any embodiment, the positive electrode active material is selected from one or more of a layered transition metal oxide, a polyanionic compound, and a prussian blue analog. In some embodiments, the layered transition metal oxide is Na x MO 2 Wherein M is one or more of Ti, V, mn, co, ni, fe, cr and Cu, and x is more than 0 and less than or equal to 1. In some embodiments, the polyanionic compound is a compound having sodium ions, transition metal ions, and tetrahedral (YO) type 4 ) n- A class of compounds of anionic units, wherein the transition metal is at least one of Mn, fe, ni, co, cr, cu, ti, zn, V, zr and Ce, Y is at least one of P, S and Si, n represents (YO) 4 ) n- The valence of (a); or the polyanionic compound is a compound having a sodium ion, a transition metal ion, a tetrahedral (YO) form 4 ) n- Anion unit and halide anion, wherein the transition metal is at least one of Mn, fe, ni, co, cr, cu, ti, zn, V, zr and Ce, Y is at least one of P, S and Si, and n represents (YO) 4 ) n- Halogen is at least one of F, cl and Br; or the polyanion compound is a compound having a sodium ion,Tetrahedral type (YO) 4 ) n- Anion cell, polyhedral cell (ZO) y ) m+ And optionally a halogen anion, Y is at least one of P, S and Si, n represents (YO 4) n- Z represents at least one transition metal selected from Mn, fe, ni, co, cr, cu, ti, zn, V, zr and Ce, and m represents (ZOy) m+ Halogen is at least one of F, cl and Br. In some embodiments, the prussian blue analog is a compound having sodium ions, transition metal ions, and cyanide ions (CN) - ) The compound of (1), wherein the transition metal is at least one of Mn, fe, ni, co, cr, cu, ti, zn, V, zr and Ce. In some embodiments, the positive active material is selected from NaNi 1/3 Fe 1/3 Mn 1/3 O 2 、Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 、NaFePO 4 、Na 3 V 2 (PO 4 ) 3 And NaMnFe (CN) 6 。
In any embodiment, the functional coating layer covers the positive electrode active material layer.
In any embodiment, the functional coating is present in an amount of 1 to 5 weight percent, alternatively 1.5 to 2.5 weight percent, based on the total weight of the positive active material layer and the functional coating in the positive electrode sheet.
The second aspect of the present application provides a sodium ion secondary battery, comprising a positive electrode plate, a negative electrode plate, an isolation film and an electrolyte, wherein the positive electrode plate is the positive electrode plate according to the first aspect of the present application.
In any embodiment, the electrolyte is an electrolyte formed by dissolving a sodium salt electrolyte in a solvent. In some embodiments, the solvent is an ether-based solvent, optionally selected from one or more of ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, diethylene glycol diethyl ether, 1, 3-dioxolane, tetrahydrofuran, methyltetrahydrofuran, diphenyl ether, crown ethers. The sodium salt electrolyte is selected from sodium hexafluorophosphate (NaPF) 6 ) Sodium difluorooxalato (NaDFOB),Sodium tetrafluoroborate (NaBF) 4 ) Sodium bisoxalato (NaBOB), sodium perchlorate, sodium hexafluoroarsenate, sodium bis (fluorosulfonyl) imide (NaFSI), sodium trifluoromethanesulfonate, sodium bis (trifluoromethanesulfonyl) imide (NaTFSI). In some embodiments, the negative electrode is selected from sodium metal negative electrodes, carbon material negative electrodes, and other non-carbon material negative electrodes.
In any embodiment, the molar concentration of the sodium salt electrolyte is from 0.5mol/L to 8mol/L, alternatively from 1mol/L to 4mol/L.
A third aspect of the present application provides an electric device including the sodium ion secondary battery according to the second aspect of the present application.
Drawings
In order to more clearly illustrate the technical solution of the present application, the drawings required to be used in the embodiments of the present application will be briefly described below. It is obvious that the drawings described below are only some embodiments of the application, and that for a person skilled in the art, other drawings can be obtained from the drawings without inventive effort.
Fig. 1 is a schematic view of a sodium ion secondary battery according to an embodiment of the present application.
Fig. 2 is an exploded view of the sodium ion secondary battery according to the embodiment of the present application shown in fig. 1.
Fig. 3 is a schematic diagram of a battery pack according to an embodiment of the present application.
Fig. 4 is an exploded view of the battery pack in one embodiment of the present application shown in fig. 3.
Fig. 5 is a schematic diagram of an apparatus in which a battery pack is used as a power source in one embodiment of the present application.
Description of the reference numerals
1 Battery pack
2 upper box body
3 lower box body
4 cell module
5 sodium ion secondary battery
51 casing
52 electrode assembly
53 cover plate
Detailed Description
For the sake of brevity, some numerical ranges are specifically disclosed herein. However, any lower limit may be combined with any upper limit to form ranges not explicitly recited; and any lower limit may be combined with any other lower limit to form a range not explicitly recited, and any upper limit may be combined with any other upper limit to form a range not explicitly recited. Furthermore, each separately disclosed point or individual value may itself, as a lower or upper limit, be combined with any other point or individual value or with other lower or upper limits to form ranges not explicitly recited.
Sodium ion batteries have significant cost advantages over lithium ion batteries and are currently in a rapidly growing state. However, sodium is more chemically active than lithium and tends to form solvated structures with organic solvents in the electrolyte at high operating voltages, making it more susceptible to oxidation. Sodium dendrites continue to grow due to the trace but continuous oxidative decomposition of the positive active material, resulting in a decrease in the cycle performance of the battery and even a safety risk.
The inventor of the invention researches and discovers that by arranging the functional coating on the positive plate for the sodium-ion battery, the composition of a sodium salt solvation structure can be changed due to the pores and size effects of the functional coating, the desolvation energy is reduced, trace but continuous oxidative decomposition is inhibited, and the oxidation resistance of the electrolyte in the sodium-ion battery is greatly improved. In addition, the high reversibility of the anode of the sodium-ion battery is well protected.
Specifically, the present application provides in a first aspect a positive electrode sheet for a sodium-ion battery, the sheet comprising a functional coating, wherein the functional coating comprises one or more coatings selected from a molecular sieve coating or a MOF coating.
Without being bound to any particular theory, the inventors believe that by providing a functional coating selected from specific coating materials, the applied functional coating has a large number of voids of different sizes, thereby creating a certain size effect. Under the influence of this effect, the solvation structure of sodium ions formed in the organic solvent in the electrolyte is changed, the desolvation energy is reduced, and the micro-scale but continuous oxidative decomposition is inhibited. The inhibition of oxidative decomposition greatly improves the oxidation resistance of the electrolyte in the sodium battery, thereby inhibiting the formation of sodium dendrites.
In some embodiments, the functional coating has a thickness of 0.3 to 20 μm, alternatively 0.5 to 15 μm, further alternatively 1 to 8 μm. The functional coating may be coated on the positive active material layer of the positive electrode sheet by various suitable coating methods, such as spraying, knife coating, roll coating, or dip coating. The thickness of the functional coating has a substantial effect on the formation of sodium dendrites and the cycling performance of the sodium ion battery. The functional coating is too thick, and the energy density of the battery is reduced; the functional coating is too thin to effectively change the solvation structure, resulting in a limited effect of improving oxidation resistance.
In some embodiments, the molecular sieve in the molecular sieve coating is selected from one or more of 3A (potassium a type), 4A (sodium a type), 5A (calcium a type), 10Z (calcium Z type), 13Z (sodium Z type), Y (sodium Y type), sodium mordenite type molecular sieves. The conventional molecular sieve is a synthetic hydrated aluminosilicate (zeolite) or natural zeolite with molecular sieving effect, and has a chemical formula of (M' 2 M)O·Al 2 O 3 ·xSiO 2 ·yH 2 O, M', M are respectively monovalent and divalent cations such as K + 、Na + 、Ca 2+ And Ba 2+ And the like. It has many pore canals with uniform pore diameter and regularly arranged holes, and the molecular sieves with different pore diameters separate the molecules with different sizes and shapes. According to SiO 2 And Al 2 O 3 The molecular ratio of (A) is different, and molecular sieves with different pore diameters can be obtained. Generally, molecular sieves having different crystal structures can be classified into types, such as 3A type, 4A type, and 5A type. 4A type is A type molecular sieve with pore diameter
Containing Na + The A-type molecular sieve of (A) is denoted as Na-A; if Na therein + Quilt K + Displacement, pore diameter of about
Namely 3A type molecular sieve; for example, more than 1/3 of Na in Na-A + Quilt Ca 2+ Displacement of pore diameter of about
Namely 5A type molecular sieve.
Molecular sieves with other elements have also been synthesized in the prior art. For example, molecular sieves can be classified by framework element composition into aluminosilicate-based molecular sieves, aluminophosphate-based molecular sieves, and framework heteroatom molecular sieves. In addition, molecular sieves with pore sizes less than 2nm, 2-50nm and greater than 50nm, which are classified by pore size, are referred to as microporous, mesoporous and macroporous molecular sieves, respectively. The molecular sieve is characterized in that the molecular sieve contains metal ions with lower electrovalence and larger ionic radius and water in a chemical compound state, water molecules are continuously lost after heating, but the crystal skeleton structure is unchanged, a plurality of cavities with the same size are formed, the cavities are connected with a plurality of micropores with the same diameter, the diameters of the micropores are uniform, molecules with the diameter smaller than that of a pore channel can be adsorbed into the inner part of the cavities, molecules with the diameter larger than that of the pore channel are excluded, and molecules with different shapes and diameters, molecules with different polarity degrees, molecules with different boiling points or molecules with different saturation degrees can be separated, namely the molecular sieve has the function of sieving the molecules, so the molecular sieve is called as the molecular sieve. The above mentioned molecular sieves are all commercially available.
In further embodiments, the MOFs in the MOF coating are selected from one or more of Fe-MOF, ni-MOF, co-MOF, mn-MOF, cu-MOF. MOFs are called Metal Organic Framework (Metal Organic Framework) and refer to a class of coordination polymers having a three-dimensional pore structure, typically with Metal ions as the attachment points, and Organic ligand supports constituting spatial 3D extensions. The organic ligand-metal composite material comprises nodes and connecting bridges, wherein a framework structure is formed by combining organic ligands (connecting bridges) with different connecting numbers and metal ion nodes. Such a frame structure may be rigid or flexible and have an extremely large inner surface. MOFs can be prepared by self-assembly of metal salts with organic ligands, with diverse and controllable structures. The metal ion can be selected from ions of metals such as Al, fe, co, ni, cu, mn, zn, ti, etc., and the organic coordination can be selected from terephthalic acid, terphthalic acid, trimesic acid, 2, 5-dihydroxyterephthalic acid, porphyrin, folic acid, cyclodextrin and its derivatives, etc.
In some embodiments, the functional coating can be selected from one or more of the molecular sieve coatings or MOF coatings described above, such as a single molecular sieve or MOF-forming coating, two or more molecular sieves or two or more MOF-forming coatings, and a coating of one or more molecular sieves mixed with one or more MOFs. The functional coating can be formed by dispersing a powder of the molecular sieve and/or the MOF in an organic solvent to form a uniform slurry, optionally adding a suitable binder, and then coating the slurry on the surface of the positive electrode sheet to form a functional coating with a predetermined thickness. In some embodiments, the functional coating can have a porosity of 30 to 80%, alternatively 50 to 75%, based on the total volume of the functional coating. When the positive electrode plate is immersed in the electrolyte, the organic solvent in the electrolyte enters the pores of the functional coating and forms a solvated structure with sodium ions at the interface between the functional coating and the positive electrode active material layer. Due to the size effect of the functional coating, the composition of the formed solvated structures can be effectively changed, and the desolvation energy can be reduced, so that the micro-scale but continuous oxidative decomposition of the functional coating can be inhibited.
In some embodiments, the positive electrode active material is selected from one or more of a layered transition metal oxide, a polyanionic compound, and a prussian blue analog.
In the layered transition metal oxide, the transition metal may be at least one of Mn, fe, ni, co, cr, cu, ti, zn, V, zr, and Ce. The layered transition metal oxide is, for example, na x MO 2 Wherein M is one or more of Ti, V, mn, co, ni, fe, cr and Cu, and x is more than 0 and less than or equal to 1.
The polyanionic compound may have sodium ion, transition metal ion, and tetrahedral type (YO) 4 ) n- A class of compounds of anionic units. The transition metal can be at least one of Mn, fe, ni, co, cr, cu, ti, zn, V, zr and Ce; y may be P, S and Si is at least one of; n represents (YO) 4 ) n- The valence of (c).
The polyanionic compound may also have a sodium ion, transition metal ion, tetrahedral (YO) 4 ) n- Anionic units and halogen anions. The transition metal can be at least one of Mn, fe, ni, co, cr, cu, ti, zn, V, zr and Ce; y may be at least one of P, S and Si, and n represents (YO) 4 ) n- The valence of (a); the halogen may be at least one of F, cl and Br.
The polyanionic compound may also have a tetrahedral (YO) form with sodium ions 4 ) n- Anion unit, polyhedral unit (ZO) y ) m+ And optionally a halide anion. Y may be at least one of P, S and Si, and n represents (YO 4) n- The valence of (a); z represents a transition metal, and may be at least one of Mn, fe, ni, co, cr, cu, ti, zn, V, zr and Ce, and m represents (ZOy) m+ The valence of (a); the halogen may be at least one of F, cl and Br.
In some embodiments, the polyanionic compound is, for example, naffepo 4 、Na 3 V 2 (PO 4 ) 3 、NaM’PO 4 F (M' is one or more of V, fe, mn and Ni) and Na 3 (VO y ) 2 (PO 4 ) 2 F 3-2y (0. Ltoreq. Y. Ltoreq.1).
In some embodiments, the prussian blue analog can be a compound having sodium ions, transition metal ions, and cyanide ions (CN) - ) A class of compounds of (1). The transition metal may be at least one of Mn, fe, ni, co, cr, cu, ti, zn, V, zr and Ce. Prussian blue analogues are for example Na a Me b Me’ c (CN) 6 Wherein Me and Me' are respectively and independently at least one of Ni, cu, fe, mn, co and Zn, a is more than 0 and less than or equal to 2, b is more than 0 and less than 1, and c is more than 0 and less than 1.
In some embodiments, a particular positive electrode active material is, for example, naNi 1/3 Fe 1/3 Mn 1/3 O 2 、Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 、NaFePO 4 、Na 3 V 2 (PO 4 ) 3 、NaMnFe(CN) 6 But is not particularly limited, and thus a positive active material conventionally used for a sodium ion battery may be selected.
In the preparation of the positive electrode sheet, the positive active material may be dispersed in an organic solvent (e.g., N-methylpyrrolidone (NMP)) with a binder, a conductive agent, etc. to prepare a uniform slurry, which is coated on a positive current collector, followed by drying at high temperature. The dried pole piece can be rolled and cut into a predetermined shape. As described above, a slurry in which a molecular sieve and/or MOF is dispersed in an organic solvent may be coated on a pole piece to form a functional coating of a predetermined thickness, and dried at high temperature so that the functional coating is coated on the surface of the pole piece in the form of a film. The selection of the binder is not particularly limited, and may be one or more of Styrene Butadiene Rubber (SBR), aqueous acrylic resin, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), ethylene-vinyl acetate copolymer (EVA), polyacrylic acid (PAA), carboxymethyl cellulose (CMC), polyvinyl alcohol (PVA), and polyvinyl butyral (PVB), as an example. The kind of the conductive agent is not particularly limited, and those skilled in the art can select the conductive agent according to actual needs. As an example, the conductive agent for the positive electrode material may be selected from one or more of superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers. In some embodiments, the positive electrode active material, the conductive agent, and the binder are included in the positive electrode sheet slurry in a weight ratio of 70 to 90:5-15:5-15, optionally 75-85:8-12:8-12. In some embodiments, the functional coating is present in an amount of 1 to 5 wt%, optionally 1.5 to 2.5 wt%, based on the total weight of the positive active material layer and the functional coating in the positive electrode sheet.
The second aspect of the present application provides a sodium ion secondary battery, comprising a positive electrode plate, a negative electrode plate, an isolation film and an electrolyte, wherein the positive electrode plate is the positive electrode plate according to the first aspect of the present application.
In some embodiments, the electrolyte is an electrolyte formed by dissolving a sodium salt electrolyte in a solvent. In some embodiments, the solvent is an ether-based solvent, optionally selected from one or more of ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, diethylene glycol diethyl ether, 1, 3-dioxolane, tetrahydrofuran, methyltetrahydrofuran, diphenyl ether, crown ethers. In a further embodiment, the solvent is selected from the group consisting of ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, diethylene glycol diethyl ether, in particular diethylene glycol dimethyl ether or diethylene glycol diethyl ether. In some embodiments, the organic solvent is not a carbonate-based solvent.
In some embodiments, the sodium salt electrolyte is selected from sodium hexafluorophosphate (NaPF) 6 ) Sodium difluorooxalato (NaDFOB), sodium tetrafluoroborate (NaBF) 4 ) Sodium bisoxalato (NaBOB), sodium perchlorate, sodium hexafluoroarsenate, sodium bis (fluorosulfonyl) imide (NaFSI), sodium trifluoromethanesulfonate, sodium bis (trifluoromethanesulfonyl) imide (NaTFSI). In further embodiments, the sodium salt electrolyte is selected from sodium hexafluorophosphate, sodium bis (fluorosulfonyl) imide, and sodium bis (trifluoromethanesulfonyl) imide, and in particular is sodium hexafluorophosphate.
In some embodiments, the molar concentration of the sodium salt electrolyte is from 0.5mol/L to 8mol/L, alternatively from 1mol/L to 4mol/L.
In some embodiments, the negative electrode is selected from sodium metal negative electrodes, carbon material negative electrodes, and other non-carbon material negative electrodes. The sodium metal negative electrode includes a non-negative solution. There is no particular limitation on the selection of the negative electrode, and a negative electrode material conventionally used in sodium ion batteries may be selected.
A third aspect of the present application provides an electric device including the sodium ion secondary battery according to the second aspect of the present application.
The composition and structure of the sodium ion battery are explained in detail below.
Generally, a sodium ion battery includes a positive electrode tab, a negative electrode tab, a separator, and an electrolyte. In the process of charging and discharging the battery, active sodium ions are inserted and removed back and forth between the positive pole piece and the negative pole piece. The isolating film is arranged between the positive pole piece and the negative pole piece and plays a role in isolation. The electrolyte plays a role in conducting ions between the positive pole piece and the negative pole piece.
[ electrolyte ]
The sodium ion secondary battery according to the present application contains an electrolytic solution. The electrolyte plays a role in conducting ions between the positive pole piece and the negative pole piece. The electrolyte includes an electrolyte salt and a solvent.
In the present application, the electrolyte salt may be a common electrolyte salt in a sodium ion battery, such as a sodium salt. As an example, the electrolyte salt may be selected from sodium hexafluorophosphate (NaPF) 6 ) Sodium difluorooxalato (NaDFOB), sodium tetrafluoroborate (NaBF) 4 ) Sodium bisoxalato (NaBOB), sodium perchlorate, sodium hexafluoroarsenate, sodium bis (fluorosulfonyl) imide (NaFSI), sodium trifluoromethanesulfonate, sodium bis (trifluoromethanesulfonyl) imide (NaTFSI).
The kind of the solvent can be selected according to actual requirements. In some embodiments, the solvent is a non-aqueous solvent. In some embodiments, the solvent is an ether-based solvent, optionally selected from one or more of ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, diethylene glycol diethyl ether, 1, 3-dioxolane, tetrahydrofuran, methyltetrahydrofuran, diphenyl ether, crown ethers. In a further embodiment, the solvent is selected from the group consisting of ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, diethylene glycol diethyl ether, in particular diethylene glycol dimethyl ether or diethylene glycol diethyl ether. In some embodiments, the organic solvent is not a carbonate-based solvent.
In some embodiments, other additives may also optionally be included in the electrolyte. For example, the additive can comprise a negative electrode film forming additive, can also comprise a positive electrode film forming additive, and can also comprise an additive capable of improving certain performances of the battery, such as an additive capable of improving the overcharge performance of the battery, an additive capable of improving the high-temperature performance of the battery, an additive capable of improving the low-temperature performance of the battery, and the like. As an example, the additive is at least one selected from the group consisting of a sulfate compound having an unsaturated bond, a sulfite compound, a sultone compound, a disulfonic acid compound, a nitrile compound, an aromatic compound, an isocyanate compound, a phosphazene compound, a cyclic acid anhydride compound, a phosphite compound, a phosphate compound, a borate compound, and a carboxylate compound.
[ Positive electrode sheet ]
The positive pole piece comprises a positive pole current collector and a positive pole active material layer arranged on at least one surface of the positive pole current collector, wherein the positive pole active material layer comprises a positive pole active material and a conductive agent.
As an example, the positive electrode current collector has two surfaces opposite in its own thickness direction, and the positive electrode active material layer is disposed on either or both of the two surfaces opposite to the positive electrode current collector.
The positive electrode current collector can adopt a metal foil or a composite current collector. For example, as the metal foil, aluminum foil may be used. The composite current collector may include a polymer material base layer and a metal layer formed on at least one surface of the polymer material base layer. The composite current collector may be formed by forming a metal material (e.g., aluminum alloy, nickel alloy, titanium alloy, silver alloy, etc.) on a polymer base material (e.g., a base material of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
The positive electrode active material layer disposed on the surface of the positive electrode current collector includes a positive electrode active material. The positive electrode active material used in the present application may have any conventional positive electrode active material used in a secondary battery. In some embodiments, the positive electrode active material may be selected from one or more of a layered transition metal oxide, a polyanion compound, and a prussian blue analog. Specific materials are for example NaNi 1/3 Fe 1/3 Mn 1/3 O 2 、Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 、NaFePO 4 、Na 3 V 2 (PO 4 ) 3 、NaMnFe(CN) 6 . These materials are commercially available. The surface of the positive electrode active material may be coated with carbon.
The positive electrode active material layer optionally includes a conductive agent. However, the kind of the conductive agent is not particularly limited, and those skilled in the art can select the conductive agent according to actual needs. As an example, the conductive agent for the positive electrode material may be selected from one or more of superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
The positive electrode active material layer may further optionally include a binder. As an example, the binder may be one or more of Styrene Butadiene Rubber (SBR), aqueous acrylic resin, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), ethylene-vinyl acetate copolymer (EVA), polyacrylic acid (PAA), carboxymethyl cellulose (CMC), polyvinyl alcohol (PVA), and polyvinyl butyral (PVB).
The positive electrode sheet can be prepared according to methods known in the art. As an example, the carbon-coated cathode active material, the conductive agent, and the binder may be dispersed in a solvent, such as N-methylpyrrolidone (NMP), to form a uniform cathode slurry; and coating the positive electrode slurry on a positive electrode current collector, and drying, cold pressing and the like to obtain the positive electrode piece.
In some embodiments, a slurry of molecular sieves and/or MOFs can be coated onto the pole piece to form a functional coating of a predetermined thickness and dried at an elevated temperature such that the functional coating is applied as a film to the surface of the pole piece. In some embodiments, a functional coating having a thickness of 0.3 to 20 μm can be formed by dispersing a powder of molecular sieve and/or MOF in a solvent to form a uniform slurry, optionally adding a suitable binder, and then coating the slurry on the surface of the positive electrode sheet. The choice of solvent and binder can be the same as described above for the preparation of the positive electrode sheet.
[ negative electrode sheet ]
The negative pole piece includes negative current collector and sets up the negative material layer on negative current collector at least one surface, and the negative material layer includes negative active material.
As an example, the negative electrode current collector has two surfaces opposite in its own thickness direction, and the negative electrode material layer is disposed on either or both of the two surfaces opposite to the negative electrode current collector.
In the electrode assembly of the present application, the negative current collector may employ a metal foil or a composite current collector. For example, as the metal foil, copper foil can be used. The composite current collector may include a polymer base layer and a metal layer formed on at least one surface of the polymer base material. The composite current collector may be formed by forming a metal material (e.g., copper alloy, nickel alloy, titanium alloy, silver alloy, etc.) on a polymer material base material (e.g., a base material of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
In the electrode assembly of the present application, the negative electrode material layer typically contains a negative electrode active material, and optionally a binder, an optional conductive agent, and other optional auxiliaries, and is typically formed by coating and drying a negative electrode slurry. The negative electrode slurry coating is generally formed by dispersing a negative electrode active material and optionally a conductive agent and a binder, etc. in a solvent and uniformly stirring. The solvent may be N-methylpyrrolidone (NMP) or deionized water.
The specific kind of the negative electrode active material is not limited, and active materials known in the art and capable of being used for a negative electrode of a sodium ion secondary battery may be used, and those skilled in the art may select them according to actual needs. As an example, the negative electrode active material may be selected from a sodium metal negative electrode, a carbon material negative electrode, and other non-carbon material negative electrodes.
As an example, the conductive agent may be selected from one or more of superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
As an example, the binder may be selected from one or more of 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).
Other optional adjuvants are, for example, thickeners such as sodium carboxymethylcellulose (CMC-Na), etc.
[ isolation film ]
The electrode assembly using the electrolyte solution further includes a separator. The isolating film is arranged between the positive pole piece and the negative pole piece and plays a role in isolation. The type of the separator is not particularly limited, and any known separator having a porous structure and good chemical and mechanical stability may be used. In some embodiments, the material of the isolation film may be selected from one or more of glass fiber, non-woven fabric, polyethylene, polypropylene and polyvinylidene fluoride. The separator may be a single-layer film or a multilayer composite film, and is not particularly limited. When the separator is a multilayer composite film, the materials of the respective layers may be the same or different, and are not particularly limited.
In some embodiments, the positive electrode tab, the negative electrode tab, and the separator may be manufactured into an electrode assembly through a winding process or a lamination process.
In some embodiments, the secondary battery may include an exterior package. The exterior package may be used to enclose the electrode assembly and the electrolyte.
In some embodiments, the outer package of the secondary battery may be a hard case, such as a hard plastic case, an aluminum case, a steel case, or the like. The outer package of the secondary battery may also be a pouch, such as a pouch-type pouch. The material of the soft bag may be plastic, and examples of the plastic include polypropylene (PP), polybutylene terephthalate (PBT), polybutylene succinate (PBS), and the like.
The shape of the secondary battery is not particularly limited, and may be a cylindrical shape, a square shape, or any other shape. For example, fig. 1 shows a sodium ion secondary battery 5 having a square structure as an example.
In some embodiments, referring to fig. 2, the overwrap may include a housing 51 and a cover plate 53. The housing 51 may include a bottom plate and a side plate connected to the bottom plate, and the bottom plate and the side plate enclose to form an accommodating cavity. The housing 51 has an opening communicating with the accommodating chamber, and a cover plate 53 can be provided to cover the opening to close the accommodating chamber. The positive electrode tab, the negative electrode tab, and the separator may be formed into the electrode assembly 52 through a winding process or a lamination process. An electrode assembly 52 is enclosed within the receiving cavity. The electrolyte is impregnated into the electrode assembly 52. The number of electrode assemblies 52 included in the sodium ion secondary battery 5 may be one or more, and may be selected by those skilled in the art according to specific practical needs.
The secondary battery of the present application may include a battery cell form, a battery module form, or a battery pack form. In some embodiments, the battery cells may be assembled into a battery module. In some embodiments, the battery cells may be assembled into a battery pack. In some embodiments, the battery module may also be assembled into a battery pack. The number of sodium ion secondary batteries included in the battery module 4 may be one or more, and the specific number may be selected by those skilled in the art according to the application and capacity of the battery module 4. In the battery module 4, the plurality of sodium ion secondary batteries 5 may be arranged in series in the longitudinal direction of the battery module. Of course, the arrangement may be in any other manner. The plurality of sodium-ion secondary batteries 5 may be further fixed by a fastener. Alternatively, the battery module 4 may further include a case having an accommodation space in which the plurality of sodium ion secondary batteries 5 are accommodated.
In some embodiments, the sodium ion secondary batteries 5 or the battery modules 4 can be assembled into the battery pack 1, and the number of the sodium ion secondary batteries 5 or the battery modules 4 contained in the battery pack 1 can be selected by a person skilled in the art according to the application and the capacity of the battery pack 1.
Fig. 3 and 4 are a battery pack 1 as an example. Referring to fig. 3 and 4, a battery pack 1 may include a battery case and a plurality of battery cells disposed in the battery case. The battery box comprises an upper box body 2 and a lower box body 3, wherein the upper box body 2 can be covered on the lower box body 3, and an enclosed space for containing a battery monomer is formed.
In addition, this application still provides an electric installation, the device includes the sodium ion secondary battery that this application provided. The sodium ion secondary battery may be used as a power source of the device and also as an energy storage unit of the device. The device may be, but is not limited to, a mobile device (e.g., a cell phone, a laptop computer, etc.), an electric vehicle (e.g., a pure electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, an electric bicycle, an electric scooter, an electric golf cart, an electric truck, etc.), an electric train, a ship and satellite, an energy storage system, and the like. As the device, a battery pack may be selected according to its use requirements.
Fig. 5 is an apparatus as an example. The device is a pure electric vehicle, a hybrid electric vehicle, or a plug-in hybrid electric vehicle, etc. In order to meet the demand of the device for high power and high energy density of the sodium ion secondary battery, a battery pack or a battery module may be used.
Examples
Hereinafter, examples of the present application will be described. The following embodiments are described as illustrative only and are not to be construed as limiting the present application. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available. All experimental steps were carried out at atmospheric pressure, unless otherwise specified.
The raw materials used are as follows:
molecular formula K of 3A (potassium A type) molecular sieve n Na 12-n [(AlO 2 ) 12 (SiO 2 ) 12 ]·xH 2 O
Molecular formula of 4A (Na A type) molecular sieve Na 12 [(AlO 2 ) 12 (SiO 2 ) 12 ]·xH 2 O
Molecular formula of 5A (calcium A type) molecular sieve Ca n Na 12-2n [(AlO2) 12 (SiO 2 ) 12 ]·xH 2 O
The 3A (potassium A) molecular sieve, the 4A (sodium A) molecular sieve and the 5A (calcium A) molecular sieve are all purchased from Shanghai Aladdin Biotechnology Ltd;
Fe-MOF: MIL-100 (Fe), ligand trimesic acid, which is formed by self-assembly of iron ions and ligand trimesic acid;
Co-MOF is Co-MOF-74, the ligand is 2, 5-dihydroxy terephthalic acid,
Ni-MOF is Ni-MOF-74, a ligand is 2, 5-dihydroxyterephthalic acid,
Mn-MOF is Mn-MOF-74, the ligand is 2, 5-dihydroxyterephthalic acid, and the Mn-MOF, the ligand and the 2, 5-dihydroxyterephthalic acid are formed by self-assembly of corresponding metal ions.
All MOF materials were purchased from a college laboratory in cooperation with a company.
Example 1
[ PREPARATION OF POSITIVE ELECTRODE PIECE ]
Fully dissolving 10wt% of polyvinylidene fluoride binder into N-methyl pyrrolidone, and adding 10wt% of carbon black conductive agent and 80wt% of positive active material Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 And preparing uniformly dispersed slurry. The slurry was uniformly coated on the surface of the aluminum foil, and then transferred to a vacuum drying oven to be completely dried. And rolling the obtained pole piece. The coating amount of the positive active material on the obtained pole piece is 0.3g/1540.25mm 2 。
Fully dissolving 20wt% of polyvinylidene fluoride binder in N-methyl pyrrolidone, and adding 80wt% to 3A molecular sieve powder to prepare uniformly dispersed slurry. And uniformly coating the slurry on the surface of the pole piece, and then transferring the pole piece to a vacuum drying oven for complete drying. And punching the obtained pole piece to obtain the positive pole piece. The coating amount of the 3A molecular sieve on the obtained polar plate is 0.006g/1540.25mm 2 。
[ PREPARATION OF NEGATIVE ELECTRODE PIECE ]
Adding 4wt% of carbon nanotube material and 1.6wt% of polymer binder sodium carboxymethyl cellulose into water, stirring to form uniform slurry, coating the slurry on the surface of copper foil, transferring the copper foil to a vacuum drying oven, completely drying, and then punching to obtain the negative pole piece.
[ preparation of electrolyte ]
In an argon atmosphere glove box (H) 2 O<0.1ppm，O 2 <0.1 ppm), sodium salt sodium hexafluorophosphate NaPF 6 Dissolved in organic solvent diethylThe mixture was stirred uniformly in glycol dimethyl ether to obtain an electrolyte solution having a sodium salt concentration of 1mol/L, i.e., the electrolyte solution of example 1.
[ isolating film ]
Polypropylene film was used as the separator.
Examples 2 to 7 and 15 to 19
The other steps of examples 2-7 and 15-19 were the same as example 1, except that the functional coating was different.
Examples 8 to 14 and 20
The other steps of examples 8 to 14 and 20 were the same as example 1 except for the difference in the electrolyte.
Comparative examples 1 to 2
Comparative examples 1-2 are the same as example 1 except that the positive electrode of comparative example 1 does not include a functional coating, and the functional coating on the positive electrode of comparative example 2 is a sodium carboxymethyl cellulose (CMC-Na) coating.
[ preparation of sodium ion Battery ]
And (3) stacking the positive pole piece, the isolating membrane and the negative pole piece in the embodiment 1 in sequence to enable the isolating membrane to be positioned between the positive pole piece and the negative pole piece to play an isolating role, and adding the electrolyte to assemble a laminated battery, namely the sodium ion secondary battery in the embodiment 1.
The sodium ion battery products of examples 2 to 20 and comparative examples 1 to 2 were also prepared according to the above procedure.
[ Battery Performance test ]
1. Electrochemical window
The electrolyte needs to be stable over the operating voltage range of the cell, and the range of voltages over which the electrolyte is electrochemically stable is often referred to as the electrochemical window.
Electrochemical window testing the cyclic voltammogram was tested primarily. And controlling the potential of the research electrode to scan from Ei (initial potential) to a potential negative direction at a speed V, changing the scanning direction after time t, retracing to the initial potential at the same speed, then reversing the potential again, and repeatedly scanning, wherein the area without the oxidation-reduction peak is the electrochemical window obtained by detection.
2. Coulombic efficiency
Taking example 1 as an example, the prepared sodium ion secondary battery is charged to 4.2V at 25 ℃ with a constant current of 1/3C, and then charged with a constant voltage of 4.2V until the current is reduced to 0.05C, so as to obtain a first charge capacity (Cc 1); and discharging to 2.5V at a constant current of 1/3C to obtain a first discharge capacity (Cd 1), and calculating the coulomb efficiency of the sodium-ion battery according to the following formula.
Sodium ion battery coulombic efficiency = first discharge capacity (Cd 1)/first charge capacity (Cc 1)
The test procedure of the comparative example and other examples was the same as above.
3. Capacity retention rate
Taking the example 1 as an example, the sodium ion battery is charged to 4.2V at 45 ℃ by a constant current of 1C, then charged to 0.05C by a constant voltage of 4.2V, and then discharged to 2.5V by a constant current of 1C, so as to obtain a first-turn discharge capacity (Cd 1); and repeating the charge and discharge to the nth circle to obtain the discharge capacity of the sodium-ion battery after n circles of circulation, recording the discharge capacity as Cdn, and calculating the capacity retention rate of the sodium-ion battery according to the following formula:
capacity retention = discharge capacity after n cycles (Cdn)/first cycle discharge capacity (Cd 1).
The test procedure of the comparative example and other examples was the same as above.
4. Sodium dendrite
The sodium ion battery after 200 cycles of the above cycle was placed in an argon atmosphere glove box (H) 2 O<0.1ppm，O 2 <0.1 ppm), and visually observing the surface appearance of the negative pole piece to determine whether sodium dendrite is generated. The negative pole piece has no white point, the negative pole piece is judged to have no sodium dendrite condition, the negative pole piece has sporadic white points, the negative pole piece is judged to have slight sodium dendrite condition, and the negative pole piece has dense rough and rough white points, and the negative pole piece is judged to have serious sodium dendrite condition.
The sodium ion batteries prepared in examples 1 to 20 and comparative examples 1 to 2 were subjected to the performance test as described above, and the test results are summarized in table 1 below.
TABLE 1
The test results of table 1 show that the positive electrode sheet of the present invention can significantly improve the coulombic efficiency and cycle performance of a sodium ion secondary battery comprising the same by including a functional coating layer of a certain thickness, while no significant sodium dendrite formation is observed, or sodium dendrite formation is only slight. In contrast, in comparative example 1, in the case where the functional coating was not applied, severe sodium dendrite precipitation was observed, and the coulombic efficiency and capacity retention rate of the battery were also significantly reduced. In addition, when the functional coating is other types of coatings, such as the CMC-Na coating used in comparative example 2, a reduction in coulombic efficiency and capacity retention, as well as severe sodium dendrite precipitation, is also observed.
The thickness of the functional coating on the positive pole piece also has a substantial effect on the performance of the pole piece. As shown in example 19, when the thickness of the functional coating on the positive electrode sheet was as low as 0.2 μm, the effect of suppressing sodium dendrites was slightly insufficient, and slight precipitation of sodium dendrites on the surface of the negative electrode sheet was observed, and the coulombic efficiency and the capacity retention rate of the battery were also reduced.
In addition, the type of the functional coating, the electrolyte in the electrolyte and the selection of the organic solvent also have certain influence on the electrical properties of the sodium ion secondary battery. For example, ethyl methyl carbonate was selected as the organic solvent in example 20, which showed reduced coulombic efficiency and capacity retention compared to the ether-based solvent, and slight sodium dendrite precipitation was observed. In the embodiment of the invention, 3A (potassium A type) molecular sieve is selected as a material of a functional coating, naPF 6 Further improved effects are obtained as an electrolyte salt and/or diethylene glycol dimethyl ether as an organic solvent.
While the application has been described with reference to an embodiment, various modifications may be made and equivalents may be substituted for elements thereof without departing from the scope of the application. In particular, the technical features mentioned in the embodiments can be combined in any way as long as there is no structural conflict. The present application is not intended to be limited to the particular embodiments disclosed herein but is to cover all embodiments that may fall within the scope of the appended claims.
Claims (18)
1. A positive electrode sheet for a sodium ion battery, the sheet comprising a functional coating, wherein the functional coating comprises one or more coatings selected from a molecular sieve coating or a MOF coating.
2. The positive electrode sheet according to claim 1, wherein the functional coating has a thickness of 0.3-20 μ ι η, optionally 0.5-15 μ ι η, further optionally 1-8 μ ι η.
3. The positive electrode sheet according to claim 1 or 2, wherein the molecular sieve in the molecular sieve coating is selected from one or more of 3A (potassium A type), 4A (sodium A type), 5A (calcium A type), 10Z (calcium Z type), 13Z (sodium Z type), Y (sodium Y type), and sodium mordenite type molecular sieves.
4. The positive electrode sheet according to any one of claims 1 to 3, wherein the MOF in the MOF coating is selected from one or more of Fe-MOF, ni-MOF, co-MOF, mn-MOF, cu-MOF.
5. The positive electrode sheet according to any one of claims 1 to 4, comprising a positive electrode active material layer, wherein the positive electrode active material is selected from one or more of a layered transition metal oxide, a polyanion compound, and a Prussian blue analog.
6. The positive electrode sheet according to claim 5, wherein the layered transition metal oxide is Na x MO 2 Wherein M is one or more of Ti, V, mn, co, ni, fe, cr and Cu, and x is more than 0 and less than or equal to 1.
7. The positive electrode sheet according to claim 5, wherein the polyanionic compound is sodium ion-bearing, transition goldBelonging to the ion and tetrahedral type (YO) 4 ) n- A class of compounds of anionic units, wherein the transition metal is at least one of Mn, fe, ni, co, cr, cu, ti, zn, V, zr and Ce, Y is at least one of P, S and Si, n represents (YO) 4 ) n- The valence of (a); or
The polyanion compound is a compound having a sodium ion, a transition metal ion, a tetrahedral type (YO) 4 ) n- Anion unit and halide anion, wherein the transition metal is at least one of Mn, fe, ni, co, cr, cu, ti, zn, V, zr and Ce, Y is at least one of P, S and Si, and n represents (YO) 4 ) n- Halogen is at least one of F, cl and Br; or
The polyanionic compound is a compound having a sodium ion, tetrahedral (YO) 4 ) n- Anion unit, polyhedral unit (ZO) y ) m+ And optionally a halogen anion, Y is at least one of P, S and Si, n represents (YO 4) n- Z represents at least one transition metal selected from Mn, fe, ni, co, cr, cu, ti, zn, V, zr and Ce, and m represents (ZOy) m+ Halogen is at least one of F, cl and Br.
8. The positive electrode sheet of claim 5, wherein the Prussian blue analog is of sodium ion, transition metal ion and cyanide ion (CN) - ) The transition metal is at least one of Mn, fe, ni, co, cr, cu, ti, zn, V, zr and Ce.
9. The positive electrode sheet according to claim 5, wherein the positive active material is selected from NaNi 1/3 Fe 1/3 Mn 1/3 O 2 、Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 、NaFePO 4 、Na 3 V 2 (PO 4 ) 3 And NaMnFe (CN) 6 。
10. The positive electrode sheet according to any one of claims 5 to 9, wherein the functional coating layer is overlaid on the positive electrode active material layer.
11. The positive electrode sheet according to any one of claims 1 to 5, wherein the amount of the functional coating layer is 1 to 5 wt%, optionally 1.5 to 2.5 wt%, based on the total weight of the positive electrode active material layer and the functional coating layer in the positive electrode sheet.
12. A sodium ion secondary battery, comprising a positive electrode plate, a negative electrode plate, a separator and an electrolyte, wherein the positive electrode plate is the positive electrode plate of any one of claims 1 to 11.
13. The secondary battery according to claim 12, wherein the electrolyte is an electrolyte in which a sodium salt electrolyte is dissolved in a solvent.
14. The secondary battery according to claim 13, wherein the solvent is an ether-based solvent, optionally selected from one or more of ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 1, 3-dioxolane, tetrahydrofuran, methyltetrahydrofuran, diphenyl ether, crown ether.
15. The secondary battery of any one of claims 13 or 14 wherein the sodium salt electrolyte is selected from sodium hexafluorophosphate (NaPF) 6 ) Sodium difluorooxalato (NaDFOB), sodium tetrafluoroborate (NaBF) 4 ) Sodium bisoxalato (NaBOB), sodium perchlorate, sodium hexafluoroarsenate, sodium bis (fluorosulfonyl) imide (NaFSI), sodium trifluoromethanesulfonate, sodium bis (trifluoromethanesulfonyl) imide (NaTFSI).
16. The secondary battery of any of claims 13 to 15, wherein the molar concentration of the sodium salt electrolyte is from 0.5 to 8mol/L, optionally from 1 to 4mol/L.
17. The secondary battery according to any one of claims 12 to 16, wherein the anode comprises one or more selected from a sodium metal anode, a carbon material anode, and a silicon-containing material anode.
18. An electric device comprising the sodium ion secondary battery according to any one of claims 12 to 17.
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| CN202211534197.8A CN115832199B (en) | 2022-12-02 | 2022-12-02 | Positive electrode plate for sodium ion battery and sodium ion battery |
| PCT/CN2023/115855 WO2024113992A1 (en) | 2022-12-02 | 2023-08-30 | Positive electrode sheet for sodium-ion battery, and sodium-ion battery |
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