CN116683017A - High-energy-density sodium-free negative electrode sodium battery - Google Patents
High-energy-density sodium-free negative electrode sodium battery Download PDFInfo
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- CN116683017A CN116683017A CN202310905001.XA CN202310905001A CN116683017A CN 116683017 A CN116683017 A CN 116683017A CN 202310905001 A CN202310905001 A CN 202310905001A CN 116683017 A CN116683017 A CN 116683017A
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- sodium
- aluminum foil
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- negative electrode
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- 239000011734 sodium Substances 0.000 title claims abstract description 96
- 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 title claims abstract description 72
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 72
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 53
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 51
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000011888 foil Substances 0.000 claims abstract description 50
- 239000003792 electrolyte Substances 0.000 claims abstract description 38
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002131 composite material Substances 0.000 claims abstract description 21
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims abstract description 15
- 230000001502 supplementing effect Effects 0.000 claims abstract description 12
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 239000006184 cosolvent Substances 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 43
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 239000007789 gas Substances 0.000 claims description 30
- 239000002904 solvent Substances 0.000 claims description 25
- 238000000231 atomic layer deposition Methods 0.000 claims description 22
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 15
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- 238000005229 chemical vapour deposition Methods 0.000 claims description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 230000001681 protective effect Effects 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
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- 239000000463 material Substances 0.000 claims description 9
- 239000000376 reactant Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
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- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 8
- 229910021389 graphene Inorganic materials 0.000 claims description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
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- 230000001105 regulatory effect Effects 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 230000001276 controlling effect Effects 0.000 claims description 6
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- 239000007787 solid Substances 0.000 claims description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 4
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 4
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- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 4
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 4
- 239000001509 sodium citrate Substances 0.000 claims description 4
- 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 claims description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 4
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- 238000010438 heat treatment Methods 0.000 claims description 3
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 3
- 229940039790 sodium oxalate Drugs 0.000 claims description 3
- UNUVOQUVNRHMOA-UHFFFAOYSA-L sodium squarate Chemical compound [Na+].[Na+].[O-]C1=C([O-])C(=O)C1=O UNUVOQUVNRHMOA-UHFFFAOYSA-L 0.000 claims description 3
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 2
- 229910020808 NaBF Inorganic materials 0.000 claims description 2
- 229910021201 NaFSI Inorganic materials 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- YLHQFGOOMKJFLP-LTFXOGOQSA-N Rotundic acid Natural products C1C[C@H](O)[C@@](C)(CO)[C@@H]2CC[C@@]3(C)[C@]4(C)CC[C@@]5(C(O)=O)CC[C@@H](C)[C@](O)(C)[C@H]5C4=CC[C@@H]3[C@]21C YLHQFGOOMKJFLP-LTFXOGOQSA-N 0.000 claims description 2
- QTONSPKDOKVNBJ-UHFFFAOYSA-N acetic acid;n'-(2-aminoethyl)ethane-1,2-diamine Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.NCCNCCN QTONSPKDOKVNBJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000006230 acetylene black Substances 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 229920002301 cellulose acetate Polymers 0.000 claims description 2
- 238000005234 chemical deposition Methods 0.000 claims description 2
- 239000006255 coating slurry Substances 0.000 claims description 2
- 239000011267 electrode slurry Substances 0.000 claims description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 229920003063 hydroxymethyl cellulose Polymers 0.000 claims description 2
- 229940031574 hydroxymethyl cellulose Drugs 0.000 claims description 2
- YLHQFGOOMKJFLP-UHFFFAOYSA-N ilexolic acid A Natural products C1CC(O)C(C)(CO)C2CCC3(C)C4(C)CCC5(C(O)=O)CCC(C)C(O)(C)C5C4=CCC3C21C YLHQFGOOMKJFLP-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- 239000013225 prussian blue Substances 0.000 claims description 2
- 229960003351 prussian blue Drugs 0.000 claims description 2
- 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 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 2
- 238000013461 design Methods 0.000 abstract description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 abstract description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 30
- 229910001415 sodium ion Inorganic materials 0.000 description 11
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- RQMIWLMVTCKXAQ-UHFFFAOYSA-N [AlH3].[C] Chemical compound [AlH3].[C] RQMIWLMVTCKXAQ-UHFFFAOYSA-N 0.000 description 4
- 230000002687 intercalation Effects 0.000 description 4
- 238000009830 intercalation Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 230000006399 behavior Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
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- 229910021385 hard carbon Inorganic materials 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 229920000447 polyanionic polymer Polymers 0.000 description 2
- 229940091252 sodium supplement Drugs 0.000 description 2
- 238000010345 tape casting Methods 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- ZMVMBTZRIMAUPN-UHFFFAOYSA-H [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZMVMBTZRIMAUPN-UHFFFAOYSA-H 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
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- 239000012300 argon atmosphere Substances 0.000 description 1
- 238000000277 atomic layer chemical vapour deposition Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000003177 cardiotonic effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
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- 239000000203 mixture Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to a sodium-free negative electrode sodium battery with high energy density, which comprises a sodium-free composite negative electrode, electrolyte, a diaphragm, a positive electrode and a sodium supplementing agent; sodium salt in the electrolyte is solute, diethylene glycol dimethyl ether (DEGDME) and tetraethylene glycol dimethyl ether (TEGDME) are used as cosolvent; the sodium-free composite negative electrode is obtained by covering a carbon material layer on an aluminum foil current collector, wherein the thickness of the carbon material layer is 5-10 mu m. The design thought of the sodium-free negative electrode battery with high energy density is based on the regulation and control of an electrolyte formula, and the current collector modified by the carbon material layer is used as a sodium-free negative electrode, so that a soft package battery with the power of more than 350 watt hours/kg is constructed, the high energy density chargeable and dischargeable sodium battery exceeding the lithium iron phosphate battery is realized, and the sodium-electric system without the negative electrode has very wide commercial prospect.
Description
Technical Field
The invention belongs to the technical field of battery energy storage, in particular to the field of rechargeable sodium secondary batteries, and particularly relates to a sodium-free negative electrode sodium battery with high energy density.
Background
With the continuous development of the energy industry, lithium batteries are increasingly competing. However, the distribution of global lithium resource storage is limited and is closely related to geographic location; sodium ion batteries are a common type of battery. Unlike lithium resources, which are limited by distribution, sodium resources have the advantages of low cost, abundant resources, and the like, so that the sodium battery is expected to be applied to various large-scale energy storage systems. However, sodium ion batteries also have certain limitations in use, and the limited energy density is one of the drawbacks that limit their use. There are still significant disadvantages in some high energy demand applications. In order to compete with, or even replace, conventional lithium ion batteries in terms of energy density, it is necessary to consider the choice and balance of positive and negative electrodes.
The energy density of current sodium ion batteries (full cells based on intercalation) is generally low, limited by the larger atomic size and species of sodium, in order to compensate for the energy density differences with commercial lithium ion batteries. One solution is to replace the intercalation electrode in a sodium-ion battery with a metallic sodium negative electrode. However, even under relatively dry air, the stability of sodium metal is still poor, sodium metal is difficult to process into thin sodium cathodes, and excessive sodium metal cathodes with uncontrollable thickness are used in most of the work reported at present, which greatly affects energy density and mass production. Therefore, the sodium-free negative electrode is a solution idea, and the negative electrode is replaced by a current collector such as aluminum foil, copper foil and the like which do not contain metal sodium. Thus, sodium ions are deintercalated from the positive electrode during the first charge, depositing sodium on the surface of the current collector. Since the active sodium ions come from the positive electrode material completely, no sodium treatment problem exists before packaging, which facilitates the manufacturing process and greatly improves the battery energy density. However, in the current sodium-free negative electrode battery, the total number of sodium ions which are not subjected to sodium supplementing activity is very limited, so that the problems of low deposition and stripping efficiency, rapid capacity decay, large volume change, easiness in SEI formation cracking and the like are faced.
Disclosure of Invention
The invention realizes the negative-pole-free rechargeable sodium battery with ultra-high energy density (350 watt hours/kilogram). Comprises a sodium-free composite negative electrode, an organic ether electrolyte, a diaphragm, a positive electrode and a sodium supplementing agent. In order to achieve the above purpose, the present invention adopts the following technical scheme:
in order to achieve the above purpose, the present invention adopts the following technical scheme:
a high energy density sodium-free negative electrode sodium battery comprises a sodium-free composite negative electrode, an electrolyte, a diaphragm, a positive electrode and a sodium supplementing agent; the sodium salt in the electrolyte is solute, diethylene glycol dimethyl ether (DEGDME) and tetraethylene glycol dimethyl ether (TEGDME) are used as cosolvent, and the sodium-free composite negative electrode is obtained by covering a carbon material layer on an aluminum foil current collector, wherein the thickness of the carbon material layer is 5-10 mu m.
Fig. 1 is a schematic diagram of a full cell of the present invention with a sodium-free negative electrode, a positive electrode having a high specific energy layered oxide, an electrolyte solvent schematic diagram, and a negative electrode being a composite current collector.
The invention controls the thickness of a thinner carbon material layer, aims to furthest weaken the volume and mass ratio of the cathode to the whole battery, and simultaneously uses a uniform carbon layer modified current collector to induce Na metal nucleation, deposition and stripping behaviors, prevent the generation of dead sodium and the rapid capacity attenuation caused by unnecessary active Na loss, thereby obtaining the sodium-free cathode full battery with high energy density and stable circulation.
The invention adopts the current collector modified by the coating to replace the traditional negative electrode with hard carbon/soft carbon and the like which can be embedded/extracted. Conventionally, during charging of sodium ion batteries, ions move from the positive electrode material to the negative electrode material, resulting in Na removal (or removal of other ions) from the positive electrode material. During discharge, ions then move from the negative electrode material back to the positive electrode material, resulting in intercalation ions (or other intercalation of ions) of the positive electrode material. To achieve this, the N/P ratio in sodium ion batteries is typically matched in the range of 1.05 to 1.1:1. Wherein the N/P ratio generally refers to the capacitance ratio of the negative electrode (N) and the positive electrode (P). This ratio has an important influence on the performance of the battery, in particular, the cycle performance and safety. The formula is as follows: N/P ratio = negative theoretical capacitance (mAh/g)/positive theoretical capacitance (mAh/g). Therefore, the volume of the negative electrode is up to 20% -35%. In the present invention, however, all the active materials of the battery are derived from the positive electrode material and the sodium supplement agent, and the negative electrode does not have conventional negative electrodes such as hard carbon/soft carbon which can be inserted/extracted. In order to realize the high reversible circulation of negative electrode sodium deposition and sodium stripping, the loss of active Na in the circulation process and the formation of dead sodium are reduced, so that the invention adopts an ether solvent with good deposition and stripping efficiency as an electrolyte solvent, and the invention modifies the current collector of the negative electrode, so that the ether electrolyte can be better infiltrated, and the dendritic-free deposition of sodium metal on the negative electrode side is realized.
Further, in the electrolyte, sodium salt is solute, and the sodium salt is selected from NaPF 6 、NaBF 4 、NaClO 4 At least one of NaFSI, naFSI; the concentration of sodium salt in the electrolyte is 0.1M-1.8M, preferably 0.8-1.2M, such as 1M,1.1M; diethylene glycol dimethyl ether (deggme) and tetraethylene glycol dimethyl ether (teggme) are used as cosolvent, and the volume ratio of deggme to teggme is 4:1 to 9:1. the compound solvent of DEGDME and TEGDME is used as the electrolyte solvent, so that the oxidation stability is obviously improved. The electrolyte possesses an average deposition/stripping coulombic efficiency for the aluminum current collector of over 99.7% based on the characteristics of the ether solvent. The invention adopts chain+chain cosolvent mixture, and aims at researching interaction among long-chain ethers and regulating solvation structure. As shown in FIG. 1, compared with DEGDME, TEGDME has longer molecular chain length, lower LUMO energy level, stronger oxidation stability, larger dielectric constant and larger binding force of Na ions, and can increase the overall oxidation stability of the electrolyte.
The invention optimizes the formula of the ether electrolyte, so that the ether electrolyte has ultrahigh Na deposition/stripping efficiency and high-voltage stability, can avoid unnecessary active Na loss in the charge and discharge process to realize long cycle life of the sodium-free cathode full battery, and can be matched with the high-voltage and high-capacity O3 type transition metal layered oxide positive electrode. The choice of the positive electrode material directly determines, among other things, the energy density of the battery. High capacitance, high conductivity materials can provide higher energy densities, however the resistance of the electrolyte to high voltage charge and discharge processes is fundamental.
According to the invention, the compatibility of the electrolyte and the anode interface is improved by modifying the carbon material layer of the anode current collector. The modification process can be achieved by forming a carbon material coating on the surface of the current collector, the thickness of the carbon material being controlled to be 5-10 μm. The process of covering the surface of the current collector with the carbon material layer can be performed by a tape casting method through a bar coater, and can also be generated through physical evaporation, atomic layer deposition, chemical vapor deposition and other methods. The method for modifying the current collector by the carbon material layer with specific thickness can obviously improve the energy density of the whole battery and reduce the volume and the quality of the whole battery.
In the coating process by a tape casting method, the sodium-free composite negative electrode is obtained by coating slurry formed by mixing carbon material powder, a conductive agent, a binder and a solvent on an aluminum foil current collector and drying; the carbon material powder is at least one selected from soft carbon powder, carbon fiber, carbon nanotube, graphite and graphene; the binder is at least one selected from polyacrylic acid (PAA), sodium carboxymethylcellulose (CMC), styrene Butadiene Rubber (SBR), polytetrafluoroethylene (PTFE) and polyvinyl alcohol (PVA); the conductive agent is at least one selected from acetylene black, conductive graphite, graphene and Super P; the solvent is one or more selected from water, N-methyl pyrrolidone and ethanol.
Further, in the casting method coating process, the mass ratio of the carbon material powder to the conductive agent to the binder is 7-9:1-2:1-2, such as 8:1:1. The mass-volume ratio of the total mass of the carbon material powder, the conductive agent and the binder to the solvent is 1g:2-4mL, and diluting the slurry. The coating process requires extrusion coating on aluminum foil using a bar coater to achieve the effect of ultra-thin coating. Further, the thickness of the coating is 5-10 μm. Although the ether-based electrolyte can stabilize the deposition/exfoliation process of metallic sodium, the selection and surface modification of the current collector also plays an important role in the nucleation and deposition behavior of the initial sodium. The invention controls the thickness of the coating to be 5-10 mu m, can solve the problem of electrolyte infiltration and induces initial sodium metal nucleation. In particular, when the carbon fiber and the carbon nanotube are used as the carbon material and the conductive agent, the carbon material and the binder are used according to the following ratio of 7-9: and (3) pulping according to the mass ratio of 1 to prepare the slurry.
Preferably, the carbon material layer preparation process is realized by deposition methods such as Chemical Vapor Deposition (CVD) and Atomic Layer Deposition (ALD). In the CVD method, an aluminum foil is placed in a specific reaction chamber, and then a gas containing a carbon source (e.g., methane or ethylene) is reacted with the surface of the aluminum foil by adjusting atmosphere control, temperature, and gas flow rate to form a carbon material coating. In the ALD method, an aluminum foil is also placed in a specific reaction chamber, and then a carbon source and a reactant gas, such as formaldehyde, formic acid, etc., are introduced as a carbon source gas, and ammonia, water vapor, etc., as a reactant gas by way of alternate feeding, to produce a carbon material coating.
In a preferred embodiment of the present invention, the carbon material layer is coated on the aluminum foil by chemical deposition (CVD), comprising the steps of:
a1. placing an aluminum foil in a CVD reaction chamber to ensure clean surfaces of the aluminum foil;
b1. establishing protective atmosphere control in the reaction chamber, wherein typical protective atmosphere control comprises nitrogen or argon environment;
c1. heating the reaction chamber and controlling the temperature to 700-900 ℃;
d1. introducing a gas containing a carbon source (such as at least one of methane, ethane, propane, ethylene and acetylene) into the reaction chamber, and enabling the carbon source gas to chemically react with the surface of the aluminum foil in a protective atmosphere;
e1. the reaction temperature is controlled between 700 ℃ and 900 ℃, and the gas flow rate is controlled between 0.1 and 0.5m 3 /h; this ensures adequate mixing and circulation of the gases within the reaction chamber, providing good reaction conditions. To ensure uniform distribution of the carbon material;
f1. and regulating the deposition time to form a carbon material layer of 5-10 mu m on the surface of the aluminum foil.
In another preferred embodiment of the present invention, the carbon material layer is coated on the aluminum foil by Atomic Layer Deposition (ALD), comprising the steps of:
a2. placing an aluminum foil in an ALD reaction chamber to ensure clean surfaces of the aluminum foil;
b2. protective atmosphere control in an ALD reaction chamber, typical protective atmosphere control including nitrogen or argon environments;
c2. introducing a carbon source and reactant gases such as formaldehyde, formic acid and the like as carbon source gases by adopting an alternate feeding mode; ammonia gas and water vapor are used as reactant gas;
d2. by controlling the temperature and gas flow of the reaction chamber, the uniform deposition of each layer of carbon material is ensured, the reaction temperature is usually 250-400 ℃, and the gas flow rate is controlled to be 1-3m 3 /h；
e2. The carbon material is formed into a carbon material layer of 5-10 mu m on the surface of the aluminum foil through proper ALD cycle times.
The carbon material coating obtained by the above-described CVD or ALD deposition method may be composed of a Porous carbon material, such as Porous carbon (Porous carbon) or Graphene (Graphene), which has a high specific surface area and excellent electrochemical properties, and may provide more excellent functions and characteristics to the battery.
Further, in the sodium-free negative electrode sodium battery with high energy density, the separator material is selected from one or more than two of polyethylene, polypropylene, cellulose acetate and hydroxymethyl cellulose. The positive electrode is not particularly limited, and a positive electrode of a sodium ion battery conventional in the art can be obtained by diluting a solid of a positive electrode active material, a conductive agent, a binder and a sodium supplementing material according to a mass ratio of 8-10:1-2:1-2:1-2 with a solvent to obtain a slurry, uniformly coating the obtained slurry on an aluminum foil current collector, and drying the aluminum foil current collector; further, when preparing the positive electrode slurry, the slurry is diluted and mixed uniformly according to the dosage of 800-1000 mu L of solvent in the total proportion of 1g of positive electrode material, conductive agent, adhesive and sodium supplementing material. In order to achieve high energy density, the higher the positive electrode amount, the better the positive electrode material slurry is disposed. But requires the incorporation of a sodium-free negative electrode.
Further, the positive electrode active material is selected from transition metal layered oxide positive electrode, polyanion positive electrode material and Prussian blue typeOne or more of the positive electrode materials; the conductive agent is at least one selected from carbon black, conductive graphite and graphene; the binder is at least one selected from polyacrylic acid (PAA), sodium carboxymethylcellulose (CMC), styrene Butadiene Rubber (SBR), polytetrafluoroethylene (PTFE) and polyvinyl alcohol (PVA); the solvent is one or more of water, N-methyl pyrrolidone and ethanol; the sodium supplementing material is selected from sodium oxalate (Na) 2 C 2 O 4 ) Sodium squarate (Na) 2 C 4 O 4 ) Sodium phosphide (Na) 3 P)、Na 2 C 3 O 5 Rotundic acid disodium salt (Na) 2 C 6 O 6 ) One or more of commercial Sodium Citrate (SC), ethylenediamine tetraacetic acid disodium salt (EDTA-4 Na) and diethylenetriamine pentaacetic acid salt (DTPA-5 Na).
Compared with the prior art, the organic ether electrolyte provided by the invention has higher oxidation stability and average coulombic efficiency, and can simultaneously consider a high specific energy positive electrode, a sodium supplementing agent decomposed under high pressure and a sodium-free negative electrode. And the energy density calculated based on combination has competitive potential, and the electrolyte has simple components and wide application prospect.
Drawings
Fig. 1 is a schematic diagram of a full cell of the sodium-free negative electrode of the present invention.
FIG. 2 is a system theoretical energy density calculation.
Fig. 3 is a graph showing contact angle comparison before and after modification of the negative electrode.
Fig. 4 is a charge-discharge curve of the battery of example 1 at a 1C rate.
Fig. 5 is a charge-discharge curve of the battery of example 4 at a 1C rate.
Fig. 6 is an SEM photograph of the composite current collector obtained in example 1.
Detailed Description
The non-metal ion doped battery cathode material according to the present invention will be further described with reference to specific examples and drawings, but it should be understood that the scope of the present invention is not limited to the following examples.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
Example 1
1) Adding tetraethyleneglycol dimethyl ether (TEGDME) and diethylene glycol dimethyl ether (DEGDME) as mixed ether solvents according to the volume ratio of 1:9 in an argon atmosphere glove box; naPF is put into 6 Adding mixed ether solvent to prepare electrolyte with the concentration of 1M, and fully stirring and mixing the electrolyte by magnetic stirring until the electrolyte is stable and clear to obtain the electrolyte;
2) Mixing soft carbon powder, super P conductive additive and PAA binder according to the mass ratio of 8:1:1 to obtain solid powder, and diluting the solid powder with water as a solvent to obtain uniformly dispersed slurry, wherein the mass volume ratio of the solid powder to the water is 1g:2mL of the prepared slurry was extrusion coated on aluminum foil using a bar coater, dried in a forced air oven at 60℃for two hours, and dried overnight at 80℃under vacuum to give a composite current collector, characterized by SEM electron microscopy, having a thickness of 10. Mu.m, as shown in FIG. 6.
3) P2 type positive electrode Na 2/3 Ni 1/3 Mn 1/3 Ti 1/3 O 2 Active substance, ketjen black conductive agent additive, PVDF binder and Na 2 C 2 O 4 Sodium supplement 8:1:1:2, and NMP is used as solvent to dilute the slurry into uniform dispersion. The prepared slurry was extrusion coated on aluminum foil with a 250 μm doctor blade, dried in a 60 ℃ air-blast oven for two hours, and dried under vacuum at 80 ℃ overnight to obtain a composite positive electrode sheet.
4) And assembling the button cell, namely sequentially assembling the positive electrode shell, the composite positive electrode plate, the Whatman diaphragm, the negative electrode composite current collector and the negative electrode shell, injecting electrolyte and completely sealing, and testing the electrochemical performance.
Example 2
A sodium negative electrode sodium battery was produced in the same manner as in example 1, except that: sodium oxalate (Na) 2 C 2 O 4 ) Sodium squarate (Na) 2 C 4 O 4 ). The other steps are the same as in example 1.
Example 3
A sodium negative electrode sodium battery was produced in the same manner as in example 1, except that: the transition metal layered oxide P2 anode is changed into a vanadium sodium phosphate polyanion anode.
Example 4
A sodium negative electrode sodium battery was produced in the same manner as in example 1, except that: changing the transition metal layered oxide P2 positive electrode into a transition metal layered oxide O3 positive electrode (NaLi) 1/9 Ni 2/9 Fe 2/9 Mn 4/9 B 1/50 O 2 )。
Example 5
A sodium negative electrode sodium battery was produced in the same manner as in example 1, except that: in the mixed ether solution, the volume ratio of TEGDME to DEGDME is 1:9.
example 6
A sodium negative electrode sodium battery was produced in the same manner as in example 1, except that: in the mixed ether solution, the volume ratio of TEGDME to DEGDME is 1:3.
example 7
A sodium negative electrode sodium battery was produced in the same manner as in example 1, except that: in the mixed ether solution, the volume ratio of TEGDME to DEGDME is 1:14.
example 8
A sodium negative electrode sodium battery was produced in the same manner as in example 1, except that: in the step 2, the coating amount of the slurry is regulated and controlled to obtain the carbon-aluminum composite current collector, wherein the carbon-aluminum composite current collector is characterized by an SEM (scanning electron microscope) and has the thickness of 5 mu m.
Example 9
Step 3) and step 4) are the same as in example 1, except that in the sodium-free composite anode, the process of covering the aluminum foil current collector with the carbon material layer is deposited by CVD as follows:
a1. aluminum foil was placed in a CVD reactor chamber sized to diameter: 10 cm; length: a cylindrical structure of 20 cm and ensures clean surface of aluminum foil in the reaction chamber;
b1. establishing a nitrogen atmosphere in the reaction chamber to avoid the influence of oxygen;
c1. heating the reaction chamber and controlling the temperature to 700 ℃;
d1. introducing methane into the reaction chamber to enable carbon source gas to chemically react with the surface of the aluminum foil in protective atmosphere;
e1. maintaining the temperature at 700 deg.C and methane flow rate at 0.3m 3 And/h, which ensures adequate mixing and circulation of the gases in the reaction chamber, providing good reaction conditions to ensure uniform distribution of the carbon material;
f1. and regulating the deposition time to form a 10 mu m carbon material layer on the surface of the aluminum foil by the carbon material.
Example 10
Step 3) and step 4) are the same as in example 1, except that in the sodium-free composite anode, the process of covering the aluminum foil current collector with the carbon material layer is deposited using BLD as follows:
a2. aluminum foil was placed in an ALD reaction chamber sized to diameter: 10 cm; length: a cylindrical structure of 30 cm and ensures clean surfaces of aluminum foils in the reaction chamber; ensuring clean surface of the aluminum foil;
b2. argon is flushed into the ALD reaction chamber, and an argon protective atmosphere is established;
c2. introducing formaldehyde as a carbon source and ammonia as a reactant gas in an alternate feeding mode;
d2. by controlling the temperature of the reaction chamber to 300 ℃ and the formaldehyde flow rate to 1m 3 /h, ammonia flow rate 1m 3 And/h, ensuring uniform deposition of each layer of carbon material;
e2. and (3) regulating the ALD cycle times to enable the carbon material to form a 10 mu m carbon material layer on the surface of the aluminum foil.
Comparative example 1
A sodium negative electrode sodium battery was produced in the same manner as in example 1, except that: in the step 2, the coating amount of the slurry is regulated to obtain the carbon-aluminum composite current collector, and the carbon-aluminum composite current collector is characterized by an SEM (scanning electron microscope) and has the thickness of about 20 mu m.
Comparative example 2
A sodium negative electrode sodium battery was produced in the same manner as in example 1, except that: the electrolyte solvent was a single DEGDME.
Comparative example 3
A sodium negative electrode sodium battery was produced in the same manner as in example 1, except that: the electrolyte solvent was a single TEGDME.
Comparative example 4
A sodium negative electrode sodium battery was produced in the same manner as in example 1, except that: aluminum foil is directly used as a current collector without modification of the negative electrode.
Application exampleTesting of electrochemical Properties
Electrochemical performance test: the assembled batteries in the examples and comparative examples were tested. Charge and discharge cycles were performed at a current density of 1C. The electrochemical properties of the rechargeable and dischargeable non-negative sodium batteries of the examples and comparative examples of the present invention were tested and the results are shown in table 1.
TABLE 1
As can be seen from the energy density comparison chart of fig. 2, by adopting the organic linear ether solvent to couple the electrolyte and the design and application of the non-negative electrode rechargeable sodium battery, the energy density exceeds 300 watt-hours/kg, is hopeful to reach 400 watt-hours/kg, exceeds the energy density of a full battery matched with lithium iron phosphate and graphite, and brings new hope in application. As can be seen from fig. 3, the contact angle of the original aluminum foil substrate is approximately 30 degrees, which can be considered to be difficult to wet. And above the current collector after coating modification, the contact angle of the electrolyte is less than 5 degrees, which can be considered to be fully spread.
From the test results of the half cells of each example in the half cells of table 1, it can be seen that: and for a full battery with the linear ether coupling solvent and the modified negative current collector being matched, the initial capacity is high, and the cycle retention rate is good. Fig. 4 and 5 represent charge and discharge curves of the batteries of example 1 and example 4, respectively, at a 1C rate.
In summary, the invention provides a design model of a high-energy-density chargeable and dischargeable sodium battery, which is simple and feasible and has low cost. The matching of the high-voltage high-capacity anode and the sodium-free cathode is realized through the ether electrolyte formula with relatively low concentration and high voltage. The carbon layer on the aluminum foil is modified to form an ideal current collector to achieve flat, dendrite-free island deposition. A needle of cardiotonic is injected for the development of the non-negative electrode battery, and the non-negative electrode sodium-electricity system has very broad commercial prospect.
Claims (10)
1. A high energy density sodium-free negative electrode sodium battery comprises a sodium-free composite negative electrode, an electrolyte, a diaphragm, a positive electrode and a sodium supplementing agent; the electrolyte is characterized in that sodium salt in the electrolyte is solute, and diethylene glycol dimethyl ether (DEGDME) and tetraethylene glycol dimethyl ether (TEGDME) are used as cosolvent; the sodium-free composite negative electrode is obtained by covering a carbon material layer on an aluminum foil current collector, wherein the thickness of the carbon material layer is 5-10 mu m.
2. The sodium battery of claim 1, wherein in the electrolyte, sodium salt is a solute, and wherein the sodium salt is selected from the group consisting of NaPF 6 、NaBF 4 、NaClO 4 At least one of NaFSI, naFSI; the concentration of sodium salt in the electrolyte is 0.1M-1.8M, preferably 0.8-1.2M.
3. The sodium battery of claim 1, wherein the volume ratio of deggme to teggme in the electrolyte is 4:1 to 9:1.
4. the sodium battery of claim 1, wherein the carbon material layer is applied to the aluminum foil current collector by a process comprising casting, physical evaporation, atomic layer deposition, chemical vapor deposition.
5. The sodium battery according to claim 4, wherein in the coating process by a casting method, the sodium-free composite negative electrode is obtained by coating slurry formed by mixing carbon material powder, a conductive agent, a binder and a solvent on an aluminum foil current collector and drying; the carbon material powder is at least one selected from soft carbon powder, carbon fiber, carbon nanotube, graphite and graphene; the binder is at least one selected from polyacrylic acid (PAA), sodium carboxymethylcellulose (CMC), styrene Butadiene Rubber (SBR), polytetrafluoroethylene (PTFE) and polyvinyl alcohol (PVA); the conductive agent is at least one selected from acetylene black, conductive graphite, graphene and Super P; the solvent is selected from one or more of water, N-methyl pyrrolidone and ethanol;
further, in the casting method coating process, the mass ratio of the carbon material powder to the conductive agent to the binder is 7-9:1-2:1-2; the mass-volume ratio of the total mass of the carbon material powder, the conductive agent and the binder to the solvent is 1g:2-4mL, and diluting the slurry.
6. The sodium battery of claim 4, wherein the carbon material layer preparation process is achieved by Chemical Vapor Deposition (CVD) or Atomic Layer Deposition (ALD);
further, in the CVD method, an aluminum foil is placed in a specific reaction chamber, and then a gas containing a carbon source (e.g., methane or ethylene) is reacted with the surface of the aluminum foil by adjusting atmosphere control, temperature, and gas flow rate to form a carbon material coating;
in the ALD method, an aluminum foil is placed in a specific reaction chamber, and then a carbon source and a reactant gas, such as formaldehyde, formic acid, etc., are introduced as the carbon source gas, and ammonia, water vapor, etc., as the reactant gas by way of alternate feeding, to generate a carbon material coating.
7. The sodium battery of claim 6, wherein the carbon material layer is coated on the aluminum foil by chemical deposition (CVD), comprising the steps of:
a1. placing an aluminum foil in a CVD reaction chamber to ensure clean surfaces of the aluminum foil;
b1. establishing protective atmosphere control in the reaction chamber, wherein typical protective atmosphere control comprises nitrogen or argon environment;
c1. heating the reaction chamber and controlling the temperature to 700-900 ℃;
d1. introducing a gas containing a carbon source (such as at least one of methane, ethane, propane, ethylene and acetylene) into the reaction chamber, and enabling the carbon source gas to chemically react with the surface of the aluminum foil in a protective atmosphere;
e1. the reaction temperature is controlled between 700 ℃ and 900 ℃; the gas flow rate is controlled to be 0.1-0.5m 3 /h；
f1. And regulating the deposition time to form a carbon material layer of 5-10 mu m on the surface of the aluminum foil.
8. The sodium battery of claim 6, wherein the carbon material layer is coated on the aluminum foil by Atomic Layer Deposition (ALD), comprising the steps of:
a2. placing an aluminum foil in an ALD reaction chamber to ensure clean surfaces of the aluminum foil;
b2. protective atmosphere control in an ALD reaction chamber, typical protective atmosphere control including nitrogen or argon environments;
c2. introducing a carbon source and reactant gases such as formaldehyde, formic acid and the like as carbon source gases by adopting an alternate feeding mode; ammonia gas and water vapor are used as reactant gas;
d2. by controlling the temperature and gas flow of the reaction chamber, the uniform deposition of each layer of carbon material is ensured, the reaction temperature is usually 250-400 ℃, and the gas flow rate is controlled to be 1-3m 3 /h；
e2. And (3) regulating the ALD cycle times to enable the carbon material to form a carbon material layer with the thickness of 5-10 mu m on the surface of the aluminum foil.
9. The sodium battery according to claim 1, wherein the separator material is selected from one or a combination of two or more of polyethylene, polypropylene, cellulose acetate, and hydroxymethyl cellulose; the positive electrode is prepared by diluting solid of a positive electrode active material, a conductive agent, a binder and a sodium supplementing material in a mass ratio of 8-10:1-2:1-2:1-2 with a solvent to obtain slurry, uniformly coating the obtained slurry on an aluminum foil current collector, and drying; further, when preparing the positive electrode slurry, the slurry is diluted and mixed uniformly according to the dosage of 800-1000 mu L of solvent in the total proportion of 1g of positive electrode material, conductive agent, adhesive and sodium supplementing material.
10. The sodium battery according to claim 9, wherein the positive electrode active material is selected from one or more of a transition metal layered oxide positive electrode, a polyanionic positive electrode material, and a prussian blue type positive electrode material; the conductive agent is at least one selected from carbon black, conductive graphite and graphene; the binder is at least one selected from polyacrylic acid (PAA), sodium carboxymethylcellulose (CMC), styrene Butadiene Rubber (SBR), polytetrafluoroethylene (PTFE) and polyvinyl alcohol (PVA); the solvent is one or more of water, N-methyl pyrrolidone and ethanol; the sodium supplementing material is selected from sodium oxalate (Na) 2 C 2 O 4 ) Sodium squarate (Na) 2 C 4 O 4 ) Sodium phosphide (Na) 3 P)、Na 2 C 3 O 5 Rotundic acid disodium salt (Na) 2 C 6 O 6 ) One or more of commercial Sodium Citrate (SC), ethylenediamine tetraacetic acid disodium salt (EDTA-4 Na) and diethylenetriamine pentaacetic acid salt (DTPA-5 Na).
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117832514A (en) * | 2024-03-06 | 2024-04-05 | 中国科学技术大学 | Carbon-coated aluminum foil current collector and application thereof |
| CN118073635A (en) * | 2024-04-17 | 2024-05-24 | 宁波兴航能源科技有限公司 | Sodium ion battery based on olivine-structure ferric phosphate and application thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117832514A (en) * | 2024-03-06 | 2024-04-05 | 中国科学技术大学 | Carbon-coated aluminum foil current collector and application thereof |
| CN117832514B (en) * | 2024-03-06 | 2024-06-07 | 中国科学技术大学 | Carbon-coated aluminum foil current collector and application thereof |
| CN118073635A (en) * | 2024-04-17 | 2024-05-24 | 宁波兴航能源科技有限公司 | Sodium ion battery based on olivine-structure ferric phosphate and application thereof |
| CN118073635B (en) * | 2024-04-17 | 2024-07-23 | 宁波兴航能源科技有限公司 | Sodium ion battery based on olivine-structure ferric phosphate and application thereof |
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