CN116314590A - Sodium ion battery and preparation method thereof - Google Patents
Sodium ion battery and preparation method thereof Download PDFInfo
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- CN116314590A CN116314590A CN202310338155.5A CN202310338155A CN116314590A CN 116314590 A CN116314590 A CN 116314590A CN 202310338155 A CN202310338155 A CN 202310338155A CN 116314590 A CN116314590 A CN 116314590A
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- negative electrode
- sodium
- positive
- active material
- ion battery
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 66
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 56
- 239000002245 particle Substances 0.000 claims abstract description 43
- 239000007774 positive electrode material Substances 0.000 claims abstract description 39
- 238000005056 compaction Methods 0.000 claims abstract description 32
- 239000007773 negative electrode material Substances 0.000 claims abstract description 30
- 238000003756 stirring Methods 0.000 claims description 55
- 239000011248 coating agent Substances 0.000 claims description 47
- 238000000576 coating method Methods 0.000 claims description 47
- 239000011268 mixed slurry Substances 0.000 claims description 44
- 239000006258 conductive agent Substances 0.000 claims description 42
- 238000002156 mixing Methods 0.000 claims description 39
- 239000011230 binding agent Substances 0.000 claims description 36
- 239000011267 electrode slurry Substances 0.000 claims description 36
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 28
- 239000003792 electrolyte Substances 0.000 claims description 24
- -1 cyclic ester Chemical class 0.000 claims description 23
- 239000003292 glue Substances 0.000 claims description 22
- 239000003960 organic solvent Substances 0.000 claims description 19
- 238000005524 ceramic coating Methods 0.000 claims description 18
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 18
- 239000013538 functional additive Substances 0.000 claims description 17
- 239000011734 sodium Substances 0.000 claims description 14
- 229910052708 sodium Inorganic materials 0.000 claims description 14
- 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 13
- 229910021385 hard carbon Inorganic materials 0.000 claims description 13
- 239000002041 carbon nanotube Substances 0.000 claims description 12
- 230000035699 permeability Effects 0.000 claims description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 11
- 239000006229 carbon black Substances 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 235000006408 oxalic acid Nutrition 0.000 claims description 11
- 239000003755 preservative agent Substances 0.000 claims description 11
- 230000002335 preservative effect Effects 0.000 claims description 11
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 10
- SJHAYVFVKRXMKG-UHFFFAOYSA-N 4-methyl-1,3,2-dioxathiolane 2-oxide Chemical compound CC1COS(=O)O1 SJHAYVFVKRXMKG-UHFFFAOYSA-N 0.000 claims description 10
- 239000006183 anode active material Substances 0.000 claims description 10
- 159000000000 sodium salts Chemical class 0.000 claims description 10
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 9
- 235000010290 biphenyl Nutrition 0.000 claims description 9
- 239000004305 biphenyl Substances 0.000 claims description 9
- 239000004917 carbon fiber Substances 0.000 claims description 9
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 9
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 8
- 238000005096 rolling process Methods 0.000 claims description 8
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 229910021392 nanocarbon Inorganic materials 0.000 claims description 7
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 239000006230 acetylene black Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- 229920000447 polyanionic polymer Polymers 0.000 claims description 6
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 6
- IGARGHRYKHJQSM-UHFFFAOYSA-N cyclohexylbenzene Chemical compound C1CCCCC1C1=CC=CC=C1 IGARGHRYKHJQSM-UHFFFAOYSA-N 0.000 claims description 5
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052723 transition metal Inorganic materials 0.000 claims description 5
- 150000003624 transition metals Chemical class 0.000 claims description 5
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 4
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 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 4
- 239000004005 microsphere Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229960003351 prussian blue Drugs 0.000 claims description 4
- 239000013225 prussian blue Substances 0.000 claims description 4
- 235000010344 sodium nitrate Nutrition 0.000 claims description 4
- 239000004317 sodium nitrate Substances 0.000 claims description 4
- 229910021384 soft carbon Inorganic materials 0.000 claims description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- XXYVTWLMBUGXOK-UHFFFAOYSA-N [Na].FS(=N)F Chemical compound [Na].FS(=N)F XXYVTWLMBUGXOK-UHFFFAOYSA-N 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 229910021382 natural graphite Inorganic materials 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 235000002639 sodium chloride Nutrition 0.000 claims description 3
- 239000011775 sodium fluoride Substances 0.000 claims description 3
- 235000013024 sodium fluoride Nutrition 0.000 claims description 3
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 3
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 3
- 239000001488 sodium phosphate Substances 0.000 claims description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 3
- 235000011008 sodium phosphates Nutrition 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 7
- 238000009792 diffusion process Methods 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 4
- 238000003466 welding Methods 0.000 description 24
- 238000005520 cutting process Methods 0.000 description 16
- 239000004698 Polyethylene Substances 0.000 description 11
- 230000014759 maintenance of location Effects 0.000 description 11
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 8
- 229910000831 Steel Inorganic materials 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 239000002131 composite material Substances 0.000 description 8
- 230000006835 compression Effects 0.000 description 8
- 238000007906 compression Methods 0.000 description 8
- 238000011068 loading method Methods 0.000 description 8
- 238000007789 sealing Methods 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 239000010959 steel Substances 0.000 description 8
- 238000004804 winding Methods 0.000 description 8
- 239000006256 anode slurry Substances 0.000 description 7
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 6
- 229920002239 polyacrylonitrile Polymers 0.000 description 6
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 5
- 239000004642 Polyimide Substances 0.000 description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 description 5
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 5
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 5
- 229920001721 polyimide Polymers 0.000 description 5
- 229920003048 styrene butadiene rubber Polymers 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000000306 component Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 239000000661 sodium alginate Substances 0.000 description 2
- 235000010413 sodium alginate Nutrition 0.000 description 2
- 229940005550 sodium alginate Drugs 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- OKBPCTLSPGDQBO-UHFFFAOYSA-L disodium;dichloride Chemical compound [Na+].[Na+].[Cl-].[Cl-] OKBPCTLSPGDQBO-UHFFFAOYSA-L 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
- H01M4/139—Processes of manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the technical field of sodium ion batteries, and particularly relates to a sodium ion battery and a preparation method thereof. The utility model provides a sodium ion battery is through gram capacity, median particle diameter, single face compaction density and the compaction density with positive and negative electrode active material layer, the gram capacity and the scale factor control between the face density of positive and negative electrode active material layer are in certain limit, form balanced relation between each parameter, and this application adopts high porosity diaphragm, can effectively reduce the battery internal resistance for sodium ion can follow the embedding in a flexible way and deviate from, and evenly distributed is on the negative plate, in addition adopts the positive and negative electrode main material of small-diameter, can effectively shorten diffusion distance, reduce the volume variation in the circulation process, and then improve the low temperature cycle performance and the multiplying power performance of battery.
Description
Technical Field
The invention belongs to the technical field of sodium ion batteries, and particularly relates to a sodium ion battery and a preparation method thereof.
Background
New energy automobiles are receiving increasing attention due to the rapid growth of clean energy demand. As a core component, a power battery is one of the keys for the development of new energy automobiles. Along with the development of the problems of price rising, limited resource reserves and the like of the lithium ion battery, the sodium ion battery with wide resource distribution gradually enters the field of vision of people. Sodium batteries are an important branch in energy technology, compared with lithium batteries, sodium reserves are far higher than lithium, and materials used by sodium batteries can be low-cost and easily-obtained, so that the sodium batteries have the inherent advantage of price. In addition, the lithium battery is easy to generate dendrites and the like, so that potential safety hazards of short circuit spontaneous combustion are caused, and the sodium battery is not easy to generate dendrites, so that the safety is far higher than that of the lithium battery, and therefore, the sodium ion battery is one of the most development potential technologies.
However, compared with a lithium ion battery, the sodium ion battery still has the problems of low energy density and insufficient cycle life, and meanwhile, the high-rate and ultralow-temperature discharge performance of the sodium ion battery is an important advantage of the sodium ion battery compared with the lithium ion battery, so that the improvement of the long cycle life and the high-rate performance of the sodium ion battery is a key problem in the current sodium ion battery industry research.
At present, the research in the sodium battery industry focuses on how to improve the film forming quality of the negative electrode SEI film so as to improve the performance of the battery, but the research on the influence of the intrinsic characteristics (such as microstructure composition/particle size/specific surface area and the like) of the negative electrode material on the performance of the battery is less.
Disclosure of Invention
The invention aims at: the sodium ion battery has obviously enhanced low-temperature cycle performance and rate capability when the value of the parameter scale factor of the positive and negative plates of the sodium ion battery is controlled within a certain range.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
according to one aspect of the application, the application provides a sodium ion battery, which comprises a positive electrode plate, a negative electrode plate, a diaphragm and electrolyte, wherein the positive electrode plate comprises a negative electrode current collector and a positive electrode active material layer coated on the negative electrode current collector, and the negative electrode plate comprises a negative electrode current collector and a negative electrode active material layer coated on the negative electrode current collector;
wherein the gram capacity C of the positive electrode active material layer Positive direction (mAh/g), median particle diameter D Positive direction (μm), single-sided compaction density M Positive direction (g/m 2 ) Density of compaction P Positive direction (g/cm 3 ) The following relation is satisfied:
gram Capacity C of the negative electrode active material layer Negative pole (mAh/g), median particle diameter D Negative pole (μm), single-sided compaction density M Negative pole (g/m 2 ) Density of compaction P Negative pole (g/cm 3 ) The following relation is satisfied:
preferably, the C Positive direction The C is Negative pole Said M Positive direction And said M Negative pole The following relation is satisfied:
preferably, the C Positive direction The value range of (C) is 130-C Positive direction 180 or less, the D Positive direction The value range of (2) is 3-D Positive direction 15 or less, the M Positive direction The value range of (2) is 150-M Positive direction 210 or less, the P Positive direction The value range of (2) is 2.9-P Positive direction ≤3.3。
Preferably, the method comprises the steps of,the C is Negative pole The value range of (C) is 320-C Negative pole < 400, said D Negative pole The value range of (2) is not less than 5D Negative pole 16 or less, the M Negative pole The value range of (2) is 70-M Negative pole Less than or equal to 100, the P Negative pole The value range of (2) is 0.9-P Negative pole ≤1.1。
Preferably, the diaphragm is a ceramic diaphragm, the porosity of the diaphragm is 40-50%, the air permeability is 120-210s/100ml, the thickness is 9-20 mu m, and the puncture strength is more than or equal to 5N.
Preferably, the electrolyte comprises an organic solvent, sodium salt and a functional additive;
the organic solvent is one or more of diethyl carbonate, dimethyl carbonate, ethylene carbonate, ethyl carbonate, propylene carbonate, fluorine-containing, sulfur-containing or unsaturated bond-containing chain or cyclic ester;
the sodium salt is one or more of sodium perchlorate, sodium difluorosulfimide, sodium hexafluorophosphate, sodium chloride, sodium fluoride, sodium sulfate, sodium carbonate, sodium phosphate, sodium nitrate, sodium tetrafluoroborate, sodium difluorooxalato borate and sodium bisoxalato borate;
the functional additive is one or more of biphenyl, phenyl cyclohexane, vinylene carbonate, fluoroethylene carbonate and propylene sulfite.
Preferably, the positive electrode active material layer includes a positive electrode active material, a conductive agent, and a binder; the anode active material layer includes an anode active material, a conductive agent, and a binder;
the positive electrode active material is at least one of layered transition metal oxide, polyanion compound, prussian blue and Prussian white and organic positive electrode material;
the negative electrode active material is at least one of hard carbon, soft carbon, carbon fiber, graphitized carbon microsphere, artificial graphite and natural graphite;
the conductive agent is one or more of carbon black, superP, carbon nano tube, acetylene black, keqin black, conductive graphite and nano carbon fiber;
the binder may include one or more of polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, polyacrylonitrile, polyimide, polyacrylic acid, polyacrylonitrile, polymethyl methacrylate, such as polypropylene, polyethylene, styrene-butadiene rubber, carboxymethyl cellulose, sodium alginate, etc.
Preferably, the median particle diameter of the layered transition metal is 5-13 mu m, and the gram capacity is more than or equal to 170mAh/g. Preferably, the median particle diameter of the hard carbon is 5-9 mu m, and the gram capacity is more than or equal to 350mAh/g.
According to another aspect of the present application, there is provided a method for preparing a sodium ion battery, comprising the steps of:
1) Preparation of positive electrode:
s1, mixing a positive electrode active material, a conductive agent and a binder (94-98): stirring the mixture in the weight ratio of (1-3), and adding 0.1-1 part of oxalic acid to mix to prepare anode mixed slurry;
s2, preparing a binder into a glue solution with the solid content of 4-6%, and mixing the positive electrode mixed slurry and the glue solution according to the weight ratio (96-98): (1-3) stirring uniformly, adding 0.1-1 parts by weight of a conductive agent, adding N-methyl pyrrolidone step by step, stirring uniformly to obtain positive electrode slurry with the viscosity of 4800-5200Pa.s, coating the positive electrode slurry on a positive electrode current collector, and drying and rolling to obtain a positive electrode plate;
2) Preparation of the negative electrode:
s1, mixing a negative electrode active material, a binder and a conductive agent (92-96): (1-4): mixing the components (1-4) in a weight ratio to prepare negative electrode mixed slurry;
s2, adding deionized water into the negative electrode mixed slurry step by step, uniformly stirring, sequentially adding 1-4 parts of binder and 0.1-0.5 part of preservative, uniformly stirring to obtain negative electrode slurry with the viscosity of 2800-3200Pa.s, coating the negative electrode slurry on a negative electrode current collector, and drying and rolling to obtain a negative electrode sheet;
3) Preparation of the separator: coating a ceramic coating with a thickness of 3-5 mu m on the PE base film;
4) Preparation of electrolyte: organic solvent, sodium salt and functional additive are mixed according to the proportion of (75-85): mixing the components (3-8) in a weight ratio;
5) And preparing the negative plate, the positive plate, the diaphragm and the electrolyte into a sodium ion battery.
The invention has the beneficial effects that: the gram capacity, the median particle diameter, the single-sided compaction density and the compaction density of the positive and negative electrode active material layers are controlled within a certain range, and the gram capacity and the proportion factor between the surface density of the positive and negative electrode active material layers form a balance relation between the parameters.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a graph showing the capacity retention rate of the batteries prepared in examples 1 to 3 after 1000 weeks of cycling at a charge/discharge rate of 4C/10C.
Fig. 2 to 3 are graphs showing capacity retention rate data of the battery prepared in example 1 at various discharge currents.
Fig. 4 to 5 are graphs showing capacity retention rate data when the battery prepared in example 1 was discharged at different temperatures.
Detailed Description
In order to make the technical solution and advantages of the present invention more apparent, the technical solution of the present invention will be clearly and completely described in conjunction with specific embodiments, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
According to one aspect of the application, the application provides a sodium ion battery, which comprises a positive electrode plate, a negative electrode plate, a diaphragm and electrolyte, wherein the positive electrode plate comprises a negative electrode current collector and a positive electrode active material layer coated on the negative electrode current collector, and the negative electrode plate comprises a negative electrode current collector and a negative electrode active material layer coated on the negative electrode current collector;
wherein the gram capacity C of the positive electrode active material layer Positive direction (mAh/g), median particle diameter D Positive direction (μm), single-sided compaction density M Positive direction (g/m 2 ) Density of compaction P Positive direction (g/cm 3 ) The following relation is satisfied:
gram Capacity C of the negative electrode active material layer Negative pole (mAh/g), median particle diameter D Negative pole (μm), single-sided compaction density M Negative pole (g/m 2 ) Density of compaction P Negative pole (g/cm 3 ) The following relation is satisfied:
the gram capacity, median particle diameter, single-sided compacted density and scaling factor between the compacted densities of the positive and negative electrode active material layers represented by the formulas (1) and (2) all affect the exertion of electrochemical performance of the sodium ion battery. For example, the single-sided compacted density and median particle size of the positive and negative electrode active materials reflect the compacted density of the positive and negative electrode active materials, and proper compacted density can increase the discharge capacity of the electrode, reduce polarization, and prolong the life of the battery, while the exertion of gram capacity of the positive and negative electrode materials can affect the capacity, cycle performance, and the like of the battery. The regulation and control of any of the above parameters can affect the battery performance, and the influence of each parameter on the battery performance is staggered and difficult to quantify, and the influence of each factor needs to be balanced to regulate and control the overall performance of the battery. The ratio factor among the factors in the positive electrode active material layer in the formula (1) has comprehensive influence on the cycle performance, sodium precipitation condition and the like of the battery, and the value of the formula (1) is controlled to be between 0.7 and 10; similarly, the value of the formula (2) is controlled between 10 and 80, so that the negative electrode plate can be fully wetted by electrolyte even if the negative electrode plate has higher compaction density, and the normal-temperature cycle retention rate of the battery is improved.
Preferably, the C Positive direction The C is Negative pole Said M Positive direction And said M Negative pole The following relation is satisfied:
the ratio between the gram capacity and the area density of the positive and negative electrode active material layers in the formula (3) affects the cycle performance of the battery, when the ratio of the formula (3) is too small, the positive electrode cannot be fully utilized, and the gram capacity is affected, and when the ratio of the formula (3) is too large, the battery is irreversibly lost, so that the battery capacity is relatively low, the battery energy density is also reduced, therefore, it is very important to control the ratio of the formula (3) in a proper range, and the ratio is controlled between 1.05 and 1.2, so that the cycle performance of the battery can be obviously provided.
Preferably, the C Positive direction The value range of (C) is 130-C Positive direction 180 or less, the D Positive direction The value range of (2) is 3-D Positive direction 15 or less, the M Positive direction The value range of (2) is 150-M Positive direction 210 or less, the P Positive direction The value range of (2) is 2.9-P Positive direction Less than or equal to 3.3; for example C Positive direction May be 130, 140, 150, 160, 170, 180, D Positive direction Can be 3, 4.5, 6.5, 7.5, 8.5, 9.5, 12, 13.5, 15, M Positive direction May be 150, 160, 170, 190, 200, 210, P Positive direction May be 2.9, 3.0, 3.2, 3.3.
Preferably, the C Negative pole The value range of (C) is 320-C Negative pole < 400, said D Negative pole The value range of (2) is not less than 5D Negative pole 16 or less, the M Negative pole The value range of (2) is 70-M Negative pole Less than or equal to 100, the P Negative pole The value range of (2) is 0.9-P Negative pole Less than or equal to 1.1; for example C Negative pole May be 320, 350, 360, 370, 380, D Negative pole Can be 5, 7, 9,11、13、15、16，M Negative pole May be 70, 75, 85, 95, 100, P Negative pole May be 0.9, 1.0, 1.1.
Preferably, the diaphragm is a ceramic diaphragm, the porosity of the diaphragm is 40-50%, the air permeability is 120-210s/100ml, the thickness is 9-20 mu m, and the puncture strength is more than or equal to 5N; for example, the porosity can be 40%, 42%, 44%, 46%, 48%, 50%, the air permeability can be 120s/100ml, 140s/100ml, 160s/100ml, 180s/100ml, 190s/100ml, 210s/100ml, the thickness can be 9 mu m, 10 mu m, 12 mu m, 15 mu m, 16 mu m, 18 mu m, 19 mu m, 20 mu m, the puncture strength can be 5N, 6N, 8N, 10N, and the high porosity diaphragm can effectively reduce the internal resistance of the battery and realize rapid embedding and extraction of sodium ions.
Preferably, the electrolyte comprises an organic solvent, sodium salt and a functional additive;
the organic solvent is one or more of diethyl carbonate, dimethyl carbonate, ethylene carbonate, ethyl carbonate, propylene carbonate, fluorine-containing, sulfur-containing or unsaturated bond-containing chain or cyclic ester, for example, propylene carbonate is added as a main organic solvent, and the organic solvent is compatible with the hard carbon of the cathode active material with small particle size, so that the diffusion distance can be effectively shortened, the volume change in the circulating process can be reduced, and the low-temperature performance can be remarkably improved;
the sodium salt is one or more of sodium perchlorate, sodium difluorosulfimide, sodium hexafluorophosphate, sodium chloride, sodium fluoride, sodium sulfate, sodium carbonate, sodium phosphate, sodium nitrate, sodium tetrafluoroborate, sodium difluorooxalato borate and sodium bisoxalato borate;
the functional additive is one or more of biphenyl, phenyl cyclohexane, vinylene carbonate, fluoroethylene carbonate and propylene sulfite.
Preferably, the positive electrode active material layer includes a positive electrode active material, a conductive agent, and a binder; the anode active material layer includes an anode active material, a conductive agent, and a binder;
the positive electrode active material is at least one of layered transition metal oxide, polyanion compound, prussian blue and Prussian white and organic positive electrode material;
the negative electrode active material is at least one of hard carbon, soft carbon, carbon fiber, graphitized carbon microsphere, artificial graphite and natural graphite;
the conductive agent is at least one or more of carbon black, superP, carbon nano tube, acetylene black, ketjen black, conductive graphite and nano carbon fiber, for example, the carbon nano tube and the carbon black are combined to form a continuous conductive network in the electrode active material, and the pole piece has higher toughness after being added, can improve the peeling caused by the volume change of the material in the charging and discharging process, and prolongs the cycle life; the penetration capability of the electrolyte in the electrode material can be greatly improved.
Preferably, the median particle diameter of the layered transition metal is 5-13 mu m, and the gram capacity is more than or equal to 170mAh/g. Preferably, the median particle diameter of the hard carbon is 5-9 mu m, and the gram capacity is more than or equal to 350mAh/g; for example, the median particle diameter of the layered transition metal can be 5 mu m, 6 mu m, 9 mu m, 11 mu m and 13 mu m, the gram capacity can be 170mAh/g, 180mAh/g and 200mAh/g, and the layered transition metal with small particle diameter is adopted, so that the contact area with electrolyte is larger, and meanwhile, the diffusion path of sodium ions is shortened, thereby being beneficial to the intercalation and deintercalation of sodium ions in the material under high current density; the median particle diameter of the hard carbon can be 5 mu m, 6 mu m, 8 mu m and 9 mu m, the gram capacity can be 350mAh/g, 380mAh/g and 400mAh/g, and the diffusion distance can be effectively shortened and the volume change in the circulating process can be reduced by adopting the hard carbon with small particle diameter, so that the low-temperature performance can be obviously improved.
According to another aspect of the present application, there is provided a method for preparing a sodium ion battery, comprising the steps of:
1) Preparation of positive electrode:
s1, mixing a positive electrode active material, a conductive agent and a binder (94-98): stirring the mixture in the weight ratio of (1-3), and adding 0.1-1 part of oxalic acid to mix to prepare anode mixed slurry;
s2, preparing a binder into a glue solution with the solid content of 4-6%, and mixing the positive electrode mixed slurry and the glue solution according to the weight ratio (96-98): (1-3) stirring uniformly, adding 0.1-1 parts by weight of a conductive agent, adding N-methyl pyrrolidone step by step, stirring uniformly to obtain positive electrode slurry with the viscosity of 4800-5200Pa.s, coating the positive electrode slurry on a positive electrode current collector, and drying and rolling to obtain a positive electrode plate;
2) Preparation of the negative electrode:
s1, mixing a negative electrode active material, a binder and a conductive agent (92-96): (1-4): mixing the components (1-4) in a weight ratio to prepare negative electrode mixed slurry;
s2, adding deionized water into the negative electrode mixed slurry step by step, uniformly stirring, sequentially adding 1-4 parts of binder and 0.1-0.5 part of preservative, uniformly stirring to obtain negative electrode slurry with the viscosity of 2800-3200Pa.s, coating the negative electrode slurry on a negative electrode current collector, and drying and rolling to obtain a negative electrode sheet;
3) Preparation of the separator: coating a ceramic coating of 3-5 μm, for example, 3 μm, 4 μm, 5 μm, on the PE base film;
4) Preparation of electrolyte: organic solvent, sodium salt and functional additive are mixed according to the proportion of (75-85): mixing the components (3-8) in a weight ratio;
5) And preparing the negative plate, the positive plate, the diaphragm and the electrolyte into a sodium ion battery.
The present application is further described below in connection with specific examples.
Example 1
The embodiment provides a sodium ion battery and a preparation method thereof, and the specific steps are as follows:
1) Preparation of positive electrode:
s1, stirring a layered oxide of an anode active material with a D50 particle size of 5 mu m and a gram capacity of 170mAh/g and carbon black of a conductive agent in a weight ratio of 96:1.8, and adding 0.3 part of oxalic acid for mixing to prepare anode mixed slurry;
s2, preparing adhesive polyvinylidene fluoride into glue solution with the solid content of 5.75%, and mixing the anode mixed slurry and the glue solution according to the weight ratio of 98:1.4 stirring uniformly, adding 0.4 weight part of conductive agent carbon nano tube slurry, adding N-methyl pyrrolidone step by step, stirring uniformly to obtain positive electrode slurry with the viscosity of 4800-5200Pa.s, coating the positive electrode slurry on a positive electrode current collector, wherein the coating weight is 18mg/cm 2 And is rolled after being dried, and the compaction density is 3.2g/cm 3 Cutting into pole pieces with the width of 57.5mm after rolling,welding aluminum tabs with the width of 0.1mm to 4mm to obtain a positive plate;
2) Preparation of the negative electrode:
s1, mixing hard carbon with a D50 particle size of 7 mu m and a gram capacity of 350mAh/g of negative electrode active material, binder carboxymethyl cellulose and conductive agent carbon black in a weight ratio of 94.1:1.5:1.4 to prepare negative electrode mixed slurry;
s2, adding deionized water into the negative electrode mixed slurry step by step, uniformly stirring, sequentially adding 2.7 parts of binder styrene-butadiene rubber and 0.3 part of preservative SFC, uniformly stirring to obtain negative electrode slurry with the viscosity of 2800-3200Pa.s, coating the negative electrode slurry on a negative electrode current collector, wherein the coating weight is 8.9mg/cm 2 And is rolled after being dried, and the compaction density is 0.98g/cm 3 . Cutting the cathode sheet into a 59mm wide pole piece after the spoke pressure is finished, and welding an aluminum-nickel composite tab with the width of 0.1mm x 4mm at the head and the tail of the pole piece to obtain a cathode sheet;
3) Preparation of the separator: coating a ceramic coating with the width of 61mm, the air permeability of 200s/100ml and the puncture strength of 5N on a PE base film;
4) Preparation of electrolyte: mixing organic solvents of propylene carbonate, methyl ethyl carbonate, ethylene carbonate, sodium hexafluorophosphate, functional additives of fluoroethylene carbonate, biphenyl and propylene sulfite according to the weight ratio of 26:38:16:16:0.5:1.5:3;
5) And winding the positive plate, the negative plate and the diaphragm into a cylindrical sodium ion battery, and loading into a circular shell, wherein a negative lug is welded with the steel shell at the bottom, a positive lug is welded with a cap at the top through laser welding, and the cylindrical sodium ion battery is formed after compression and sealing.
Example 2
Unlike example 1, the median particle diameter of the positive electrode active material layered oxide was 9 μm.
The remainder is the same as embodiment 1 and will not be described here again.
Example 3
Unlike example 1, the median particle diameter of the positive electrode active material layered oxide was 13 μm.
The remainder is the same as embodiment 1 and will not be described here again.
Example 4
The sodium ion battery and the preparation method thereof provided by the embodiment are as follows:
1) Preparation of positive electrode:
s1, stirring a polyanion compound of a positive electrode active material with a D50 particle size of 6 mu m and a gram capacity of 160mAh/g and a conductive agent SuperP in a weight ratio of 94:2.1, and adding 0.2 part of oxalic acid for mixing to prepare positive electrode mixed slurry;
s2, preparing binder carboxymethyl cellulose into a glue solution with the solid content of 4.85%, uniformly stirring the anode mixed slurry and the glue solution according to the weight ratio of 96:2, adding 0.5 part by weight of conductive agent carbon black slurry, adding N-methyl pyrrolidone step by step, uniformly stirring to obtain anode slurry with the viscosity of 4800-5200Pa.s, coating the anode slurry on an anode current collector, and coating the anode current collector with the weight of 13mg/cm 2 And is rolled after being dried, and the compaction density is 2.9g/cm 3 Cutting the rolled sheet into a sheet with the width of 57.5mm, and welding an aluminum tab with the width of 0.1mm or 4mm to obtain a positive electrode sheet;
2) Preparation of the negative electrode:
s1, mixing hard carbon with the D50 particle size of 8 mu m and the gram capacity of 360mAh/g of negative electrode active material, binder carboxymethyl cellulose and conductive agent nano carbon nano tubes in a weight ratio of 93.5:1.6:1.2 to prepare negative electrode mixed slurry;
s2, adding deionized water into the negative electrode mixed slurry step by step, uniformly stirring, sequentially adding 1.8 parts of binder styrene-butadiene rubber and 0.30 part of preservative SFC, uniformly stirring to obtain negative electrode slurry with the viscosity of 2800-3200Pa.s, coating the negative electrode slurry on a negative electrode current collector, wherein the coating weight is 7mg/cm 2 And is rolled after being dried, and the compaction density is 0.9g/cm 3 . Cutting the cathode sheet into a 59mm wide pole piece after the spoke pressure is finished, and welding an aluminum-nickel composite tab with the width of 0.1mm x 4mm at the head and the tail of the pole piece to obtain a cathode sheet;
3) Preparation of the separator: coating a 4 mu m ceramic coating on the PE base film, wherein the width of the ceramic coating is 63mm, the air permeability is 200s/100ml, and the puncture strength is 6N;
4) Preparation of electrolyte: mixing organic solvents of propylene carbonate, methyl ethyl carbonate, ethylene carbonate, sodium hexafluorophosphate, functional additives of fluoroethylene carbonate, biphenyl and propylene sulfite according to the weight ratio of 23:41:15:16:0.3:1.4:5;
5) And winding the positive plate, the negative plate and the diaphragm into a cylindrical sodium ion battery, and loading into a circular shell, wherein a negative lug is welded with the steel shell at the bottom, a positive lug is welded with a cap at the top through laser welding, and the cylindrical sodium ion battery is formed after compression and sealing.
Example 5
The sodium ion battery and the preparation method thereof provided by the embodiment are as follows:
1) Preparation of positive electrode:
s1, stirring Prussian blue serving as a positive electrode active material with the D50 particle size of 8 mu m and the gram capacity of 150mAh/g and a conductive agent carbon nano tube in a weight ratio of 95:1, and adding 0.4 part of oxalic acid for mixing to prepare positive electrode mixed slurry;
s2, preparing adhesive polytetrafluoroethylene into glue solution with solid content of 5.5%, uniformly stirring the positive electrode mixed slurry and the glue solution according to a weight ratio of 94.5:1.3, adding 0.3 part by weight of conductive agent carbon black slurry, adding N-methyl pyrrolidone step by step, uniformly stirring to obtain positive electrode slurry with viscosity of 4800-5200Pa.s, coating the positive electrode slurry on a positive electrode current collector, wherein the coating weight is 8mg/cm 2 And is rolled after being dried, and the compaction density is 1.1g/cm 3 Cutting the rolled sheet into a sheet with the width of 57.5mm, and welding an aluminum tab with the width of 0.1mm or 4mm to obtain a positive electrode sheet;
2) Preparation of the negative electrode:
s1, mixing hard carbon with a D50 particle size of 8 mu m and a gram capacity of 370mAh/g of negative electrode active material, binder polyimide and conductive agent acetylene black in a weight ratio of 93:1.8:2.0 to prepare negative electrode mixed slurry;
s2, adding deionized water into the negative electrode mixed slurry step by step, uniformly stirring, sequentially adding 1.8 parts of adhesive polyvinyl alcohol and 0.35 part of preservative SFC, uniformly stirring to obtain negative electrode slurry with the viscosity of 2800-3200Pa.s, coating the negative electrode slurry on a negative electrode current collector, wherein the coating weight is 7mg/cm 2 And rolling after drying, compactingThe degree of the reaction is 0.9g/cm 3 . Cutting the cathode sheet into a 59mm wide pole piece after the spoke pressure is finished, and welding an aluminum-nickel composite tab with the width of 0.1mm x 4mm at the head and the tail of the pole piece to obtain a cathode sheet;
3) Preparation of the separator: coating a 4 mu m ceramic coating on the PE base film, wherein the width of the ceramic coating is 63mm, the air permeability is 200s/100ml, and the puncture strength is 6N;
4) Preparation of electrolyte: mixing organic solvents of propylene carbonate, methyl ethyl carbonate, ethylene carbonate, sodium hexafluorophosphate, functional additives of fluoroethylene carbonate, biphenyl and propylene sulfite according to the weight ratio of 24:36:20:18:0.6:2.3:4;
5) And winding the positive plate, the negative plate and the diaphragm into a cylindrical sodium ion battery, and loading into a circular shell, wherein a negative lug is welded with the steel shell at the bottom, a positive lug is welded with a cap at the top through laser welding, and the cylindrical sodium ion battery is formed after compression and sealing.
Example 6
The sodium ion battery and the preparation method thereof provided by the embodiment are as follows:
1) Preparation of positive electrode:
s1, stirring a polyanion compound of a positive electrode active material with a D50 particle size of 10 mu m and a gram capacity of 145mAh/g and acetylene black serving as a conductive agent in a weight ratio of 95:2, and adding 0.6 part of oxalic acid to mix to prepare positive electrode mixed slurry;
s2, preparing adhesive polyimide into glue solution with solid content of 4.85%, uniformly stirring the anode mixed slurry and the glue solution according to a weight ratio of 96.5:1.8, adding 0.6 part by weight of conductive agent carbon nanotube slurry, adding N-methylpyrrolidone in steps, uniformly stirring to obtain anode slurry with viscosity of 4800-5200Pa.s, coating the anode slurry on an anode current collector, and coating the anode slurry with weight of 16mg/cm 2 And is rolled after being dried, and the compaction density is 3.1g/cm 3 Cutting the rolled sheet into a sheet with the width of 57.5mm, and welding an aluminum tab with the width of 0.1mm or 4mm to obtain a positive electrode sheet;
2) Preparation of the negative electrode:
s1, mixing carbon fiber of a negative electrode active material with the D50 particle size of 6 mu m and the gram capacity of 350mAh/g, polyimide binder and carbon black of a conductive agent in a weight ratio of 92.8:2.5:2.5 to prepare negative electrode mixed slurry;
s2, adding deionized water into the negative electrode mixed slurry step by step, uniformly stirring, sequentially adding 1.8 parts of binder polyacrylonitrile and 0.4 part of preservative SFC, uniformly stirring to obtain negative electrode slurry with the viscosity of 2800-3200Pa.s, coating the negative electrode slurry on a negative electrode current collector, wherein the coating weight is 8mg/cm 2 And is rolled after being dried, and the compaction density is 1.0g/cm 3 . Cutting the cathode sheet into a 59mm wide pole piece after the spoke pressure is finished, and welding an aluminum-nickel composite tab with the width of 0.1mm x 4mm at the head and the tail of the pole piece to obtain a cathode sheet;
3) Preparation of the separator: coating a ceramic coating with the thickness of 3.5 mu m on the PE base film, wherein the width of the ceramic coating is 63mm, the air permeability is 200s/100ml, and the puncture strength is 6N;
4) Preparation of electrolyte: mixing organic solvents of propylene carbonate, methyl ethyl carbonate, ethylene carbonate, sodium hexafluorophosphate, functional additives of fluoroethylene carbonate, biphenyl and propylene sulfite according to the weight ratio of 25:39:16:19:0.5:1.9:5;
5) And winding the positive plate, the negative plate and the diaphragm into a cylindrical sodium ion battery, and loading into a circular shell, wherein a negative lug is welded with the steel shell at the bottom, a positive lug is welded with a cap at the top through laser welding, and the cylindrical sodium ion battery is formed after compression and sealing.
Example 7
The sodium ion battery and the preparation method thereof provided by the embodiment are as follows:
1) Preparation of positive electrode:
s1, stirring Prussian white, which is an anode active material with a D50 particle size of 6 mu m and a gram capacity of 180mAh/g, and conductive graphite, which is a conductive agent, according to a weight ratio of 95:2.5, and adding 0.3 part of oxalic acid for mixing to prepare anode mixed slurry;
s2, preparing adhesive polyacrylic acid into glue solution with solid content of 4.65%, uniformly stirring the anode mixed slurry and the glue solution according to a weight ratio of 97:2, adding 0.6 part by weight of conductive agent Keqin black slurry, adding N-methyl pyrrolidone step by step, and uniformly stirring to obtain the adhesive with viscosity of 4800-5200Positive electrode slurry of Pa.s, and coated on a positive electrode current collector, wherein the coating weight is 16mg/cm 2 And is rolled after being dried, and the compaction density is 3.1g/cm 3 Cutting the rolled sheet into a sheet with the width of 57.5mm, and welding an aluminum tab with the width of 0.1mm or 4mm to obtain a positive electrode sheet;
2) Preparation of the negative electrode:
s1, mixing soft carbon with the D50 particle size of 9 mu m and the gram capacity of 360mAh/g of negative electrode active material, binder carboxymethyl cellulose and conductive agent nano carbon nano tubes in a weight ratio of 94.5:1.6:1.2 to prepare negative electrode mixed slurry;
s2, adding deionized water into the negative electrode mixed slurry step by step, uniformly stirring, sequentially adding 1.8 parts of binder styrene-butadiene rubber and 0.4 part of preservative SFC, uniformly stirring to obtain negative electrode slurry with the viscosity of 2800-3200Pa.s, coating the negative electrode slurry on a negative electrode current collector, wherein the coating weight is 8mg/cm 2 And is rolled after being dried, and the compaction density is 1.0g/cm 3 . Cutting the cathode sheet into a 59mm wide pole piece after the spoke pressure is finished, and welding an aluminum-nickel composite tab with the width of 0.1mm x 4mm at the head and the tail of the pole piece to obtain a cathode sheet;
3) Preparation of the separator: coating a 4.5 mu m ceramic coating on the PE base film, wherein the width of the ceramic coating is 63mm, the air permeability is 200s/100ml, and the puncture strength is 6N;
4) Preparation of electrolyte: mixing organic solvents of dimethyl carbonate, methyl ethyl carbonate, sodium salt of sodium bis-fluorosulfonyl imide, phenyl cyclohexane serving as a functional additive, biphenyl and propylene sulfite according to the weight ratio of 23:41:15:16:0.3:1.4:5;
5) And winding the positive plate, the negative plate and the diaphragm into a cylindrical sodium ion battery, and loading into a circular shell, wherein a negative lug is welded with the steel shell at the bottom, a positive lug is welded with a cap at the top through laser welding, and the cylindrical sodium ion battery is formed after compression and sealing.
Example 8
The sodium ion battery and the preparation method thereof provided by the embodiment are as follows:
1) Preparation of positive electrode:
s1, stirring Prussian white, which is an anode active material with the D50 particle size of 8 mu m and the gram capacity of 150mAh/g, and conductive graphite, which is a conductive agent, according to the weight ratio of 95:1, and adding 0.3 part of oxalic acid for mixing to prepare anode mixed slurry;
s2, preparing binder polyacrylonitrile into glue solution with solid content of 5.5%, uniformly stirring the positive electrode mixed slurry and the glue solution according to the weight ratio of 94.5:1.3, adding 0.3 part by weight of conductive graphite slurry of conductive agent, adding N-methyl pyrrolidone step by step, uniformly stirring to obtain positive electrode slurry with viscosity of 4800-5200Pa.s, coating the positive electrode slurry on a positive electrode current collector, wherein the coating weight is 8mg/cm 2 And is rolled after being dried, and the compaction density is 1.1g/cm 3 Cutting the rolled sheet into a sheet with the width of 57.5mm, and welding an aluminum tab with the width of 0.1mm or 4mm to obtain a positive electrode sheet;
2) Preparation of the negative electrode:
s1, mixing carbon fiber of a negative electrode active material with the D50 particle size of 8 mu m and the gram capacity of 330mAh/g, styrene-butadiene rubber as a binder and nano carbon fiber of a conductive agent according to the weight ratio of 93:1.8:2.0 to prepare negative electrode mixed slurry;
s2, adding deionized water into the negative electrode mixed slurry step by step, stirring uniformly, sequentially adding 1.8 parts of adhesive polyvinyl alcohol and 0.3 part of preservative SFC, stirring uniformly to obtain negative electrode slurry with the viscosity of 2800-3200Pa.s, coating on a negative electrode current collector, and coating with the weight of 8mg/cm 2 And is rolled after being dried, and the compaction density is 1.1g/cm 3 . Cutting the cathode sheet into a 59mm wide pole piece after the spoke pressure is finished, and welding an aluminum-nickel composite tab with the width of 0.1mm x 4mm at the head and the tail of the pole piece to obtain a cathode sheet;
3) Preparation of the separator: coating a ceramic coating with the width of 63mm, the air permeability of 200s/100ml and the puncture strength of 6N on a PE base film, wherein the ceramic coating is 3.2 mu m;
4) Preparation of electrolyte: mixing organic solvents of propylene carbonate, methyl ethyl carbonate, sodium salt sodium chloride, functional additives of fluoroethylene carbonate, biphenyl and propylene sulfite according to the weight ratio of 38:40:18:0.6:2.3:4;
5) And winding the positive plate, the negative plate and the diaphragm into a cylindrical sodium ion battery, and loading into a circular shell, wherein a negative lug is welded with the steel shell at the bottom, a positive lug is welded with a cap at the top through laser welding, and the cylindrical sodium ion battery is formed after compression and sealing.
Example 9
The sodium ion battery and the preparation method thereof provided by the embodiment are as follows:
1) Preparation of positive electrode:
s1, stirring an organic positive electrode material of a positive electrode active material with a D50 particle size of 6 mu m and a gram capacity of 130mAh/g and a conductive agent carbon nano tube in a weight ratio of 95:2, and adding 4 parts of oxalic acid for mixing to obtain positive electrode mixed slurry;
s2, preparing adhesive polyimide into glue solution with solid content of 4.65%, uniformly stirring the anode mixed slurry and the glue solution according to a weight ratio of 97:1.8, adding 0.5 part by weight of conductive agent acetylene black slurry, adding N-methyl pyrrolidone in steps, uniformly stirring to obtain anode slurry with viscosity of 4800-5200Pa.s, coating the anode slurry on an anode current collector, wherein the coating weight is 18mg/cm 2 And is rolled after being dried, and the compaction density is 3.2g/cm 3 Cutting the rolled sheet into a sheet with the width of 57.5mm, and welding an aluminum tab with the width of 0.1mm or 4mm to obtain a positive electrode sheet;
2) Preparation of the negative electrode:
s1, mixing graphitized carbon microspheres with the D50 particle size of 7 mu m and the gram capacity of 350mAh/g of negative electrode active material with a binder polyacrylonitrile and a conductive agent carbon black in a weight ratio of 92.8:2.5:2.5 to prepare negative electrode mixed slurry;
s2, adding deionized water into the negative electrode mixed slurry step by step, uniformly stirring, sequentially adding 1.8 parts of binder polyacrylonitrile and 0.3 part of preservative SFC, uniformly stirring to obtain negative electrode slurry with the viscosity of 2800-3200Pa.s, coating the negative electrode slurry on a negative electrode current collector, wherein the coating weight is 9mg/cm 2 And is rolled after being dried, and the compaction density is 1.0g/cm 3 . Cutting the cathode sheet into a 59mm wide pole piece after the spoke pressure is finished, and welding an aluminum-nickel composite tab with the width of 0.1mm x 4mm at the head and the tail of the pole piece to obtain a cathode sheet;
3) Preparation of the separator: coating a 4.0 mu m ceramic coating on the PE base film, wherein the width of the ceramic coating is 63mm, the air permeability is 200s/100ml, and the puncture strength is 6N;
4) Preparation of electrolyte: mixing organic solvents of propylene carbonate, ethylene carbonate, sodium hexafluorophosphate, functional additives of fluoroethylene carbonate and propylene sulfite according to the weight ratio of 60:15:16:19:0.5:5;
5) And winding the positive plate, the negative plate and the diaphragm into a cylindrical sodium ion battery, and loading into a circular shell, wherein a negative lug is welded with the steel shell at the bottom, a positive lug is welded with a cap at the top through laser welding, and the cylindrical sodium ion battery is formed after compression and sealing.
Example 10
The sodium ion battery and the preparation method thereof provided by the embodiment are as follows:
1) Preparation of positive electrode:
s1, stirring a polyanion compound of a positive electrode active material with a D50 particle size of 7 mu m and a gram capacity of 160mAh/g and a conductive agent carbon nano tube in a weight ratio of 95:2.5, and adding 0.45 part of oxalic acid for mixing to prepare positive electrode mixed slurry;
s2, preparing a binder sodium alginate into a glue solution with the solid content of 4.85%, uniformly stirring the positive electrode mixed slurry and the glue solution according to the weight ratio of 97:2, adding 0.6 part by weight of conductive agent carbon black slurry, adding N-methyl pyrrolidone step by step, uniformly stirring to obtain a positive electrode slurry with the viscosity of 4800-5200Pa.s, coating the positive electrode slurry on a positive electrode current collector, and coating the positive electrode slurry with the weight of 16mg/cm 2 And is rolled after being dried, and the compaction density is 3.1g/cm 3 Cutting the rolled sheet into a sheet with the width of 57.5mm, and welding an aluminum tab with the width of 0.1mm or 4mm to obtain a positive electrode sheet;
2) Preparation of the negative electrode:
s1, mixing negative electrode active material artificial graphite with a D50 particle size of 8 mu m and a gram capacity of 350mAh/g, binder polytetrafluoroethylene and conductive agent nano carbon nano tubes in a weight ratio of 94.5:1.6:1.2 to prepare negative electrode mixed slurry;
s2, adding deionized water into the negative electrode mixed slurry step by step, uniformly stirring, sequentially adding 1.8 parts of binder polyvinylidene fluoride and 0.5 part of preservative SFC, and uniformly stirring to obtain the product with the viscosity of 2800-320Negative electrode slurry of 0Pa.s and coated on a negative electrode current collector, wherein the coating weight is 10mg/cm 2 And is rolled after being dried, and the compaction density is 1.1g/cm 3 . Cutting the cathode sheet into a 59mm wide pole piece after the spoke pressure is finished, and welding an aluminum-nickel composite tab with the width of 0.1mm x 4mm at the head and the tail of the pole piece to obtain a cathode sheet;
3) Preparation of the separator: coating a ceramic coating with the thickness of 3.5 mu m on the PE base film, wherein the width of the ceramic coating is 63mm, the air permeability is 200s/100ml, and the puncture strength is 6N;
4) Preparation of electrolyte: the organic solvent propylene carbonate, dimethyl carbonate, sodium nitrate, phenyl cyclohexane as a functional additive, vinylene carbonate and fluoroethylene carbonate are mixed according to the proportion of 53: mixing at a weight ratio of 23:15:0.3:1.4:5;
5) And winding the positive plate, the negative plate and the diaphragm into a cylindrical sodium ion battery, and loading into a circular shell, wherein a negative lug is welded with the steel shell at the bottom, a positive lug is welded with a cap at the top through laser welding, and the cylindrical sodium ion battery is formed after compression and sealing.
The electrochemical performance of the sodium ion batteries prepared in examples 1 to 3 were tested, and the test results are shown in fig. 1 to 5.
As can be seen from fig. 1, the capacity retention rates after 1000 weeks of the cycles of example 1, example 2 and example 3 are 92.51%, 79.67% and 69.98% respectively under the charge-discharge rate of 4C/10C, and the cycle performance of example 1 is more excellent, mainly because the positive electrode main material with smaller particle size and the high porosity diaphragm are adopted, and the internal resistance of the battery can be effectively reduced on the premise of satisfying the balance of heat shrinkage strength, so that rapid intercalation and deintercalation of sodium ions can be realized.
As can be seen from fig. 2 to 3, the batteries manufactured in example 1 exhibited excellent rate performance at discharge currents of 2C, 3C, 5C, and 10C, with capacity retention rates of 98.83%, 98.60%, 98.38%, and 93.15%, respectively; when the battery is at a discharge current of 1C, the capacity retention rate is 100.10%, the energy retention rate is 100.13%, and under the same voltage, a material with small particle size is selected, so that the multiplying power performance is better, because the specific surface area of the material with small particle size is larger, the contact area of the material and electrolyte is larger, meanwhile, the diffusion path of sodium ions is shortened, the insertion and extraction of sodium ions in the material under the condition of large current density are facilitated, more charge quantity can be stored by the battery, and more charge can be stored by the battery with larger capacity, so that more energy is released.
As can be seen from fig. 4 to 5, the batteries produced in example 1 were discharged at-30 ℃, -10 ℃, 0 ℃, 60 ℃, with capacity retention rates of 84.2%, 91.3%, 93.8%, 105.8%, respectively, and energy retention rates of 69.2%, 81.8%, 90.5%, 104.1%, respectively. It is explained that the battery capacity retention ratio remains in an optimal state even at-30 deg.c because the present application uses a small-particle-diameter anode active material hard carbon, which can effectively shorten the diffusion distance, reduce the volume change during the cycle, and thus can significantly improve the low-temperature performance.
Variations and modifications of the above embodiments will occur to those skilled in the art to which the invention pertains from the foregoing disclosure and teachings. Therefore, the present invention is not limited to the above-described embodiments, but is intended to be capable of modification, substitution or variation in light thereof, which will be apparent to those skilled in the art in light of the present teachings. In addition, although specific terms are used in the present specification, these terms are for convenience of description only and do not limit the present invention in any way.
Claims (10)
1. The sodium ion battery is characterized by comprising a positive electrode plate, a negative electrode plate, a diaphragm and electrolyte, wherein the positive electrode plate comprises a negative electrode current collector and a positive electrode active material layer coated on the negative electrode current collector, and the negative electrode plate comprises a negative electrode current collector and a negative electrode active material layer coated on the negative electrode current collector;
wherein the gram capacity C of the positive electrode active material layer Positive direction (mAh/g), median particle diameter D Positive direction (μm), single-sided compaction density M Positive direction (g/m 2 ) Density of compaction P Positive direction (g/cm 3 ) The following relation is satisfied:
gram Capacity C of the negative electrode active material layer Negative pole (mAh/g), median particle diameter D Negative pole (μm), single-sided compaction density M Negative pole (g/m 2 ) Density of compaction P Negative pole (g/cm 3 ) The following relation is satisfied:
2. the sodium ion battery of claim 1, wherein the C Positive direction The C is Negative pole Said M Positive direction And said M Negative pole The following relation is satisfied:
3. a sodium ion battery according to claim 1 or 2, wherein said C Positive direction The value range of (C) is 130-C Positive direction 180 or less, the D Positive direction The value range of (2) is 3-D Positive direction 15 or less, the M Positive direction The value range of (2) is 150-M Positive direction 210 or less, the P Positive direction The value range of (2) is 2.9-P Positive direction ≤3.3。
4. A sodium ion battery according to claim 1 or 2, wherein said C Negative pole The value range of (C) is 320-C Negative pole < 400, said D Negative pole The value range of (2) is not less than 5D Negative pole 16 or less, the M Negative pole The value range of (2) is 70-M Negative pole Less than or equal to 100, the P Negative pole The value range of (2) is 0.9-P Negative pole ≤1.1。
5. The sodium ion battery of claim 1, wherein the membrane is a ceramic membrane, the porosity of the membrane is 40-50%, the air permeability is 120-210s/100ml, the thickness is 9-20 μm, and the puncture strength is not less than 5N.
6. The sodium ion battery of claim 1, wherein the electrolyte comprises an organic solvent, a sodium salt, and a functional additive;
the organic solvent is one or more of diethyl carbonate, dimethyl carbonate, ethylene carbonate, ethyl carbonate, propylene carbonate, fluorine-containing, sulfur-containing or unsaturated bond-containing chain or cyclic ester;
the sodium salt is one or more of sodium perchlorate, sodium difluorosulfimide, sodium hexafluorophosphate, sodium chloride, sodium fluoride, sodium sulfate, sodium carbonate, sodium phosphate, sodium nitrate, sodium tetrafluoroborate, sodium difluorooxalato borate and sodium bisoxalato borate;
the functional additive is one or more of biphenyl, phenyl cyclohexane, vinylene carbonate, fluoroethylene carbonate and propylene sulfite.
7. The sodium ion battery of claim 1, wherein the positive electrode active material layer comprises a positive electrode active material, a conductive agent, and a binder; the anode active material layer includes an anode active material, a conductive agent, and a binder;
the positive electrode active material is at least one of layered transition metal oxide, polyanion compound, prussian blue and Prussian white and organic positive electrode material;
the negative electrode active material is at least one of hard carbon, soft carbon, carbon fiber, graphitized carbon microsphere, artificial graphite and natural graphite;
the conductive agent is one or more of carbon black, superP, carbon nano tube, acetylene black, keqin black, conductive graphite and nano carbon fiber.
8. The sodium ion battery of claim 7, wherein the layered transition metal has a median particle size of 5-13 μm and a gram capacity of greater than or equal to 170mAh/g.
9. The sodium ion battery of claim 7, wherein the hard carbon median particle size is 5-9 μm and gram capacity is greater than or equal to 350mAh/g.
10. A method of manufacturing a sodium ion battery according to any one of claims 1 to 9, comprising the steps of:
1) Preparation of positive electrode:
s1, mixing a positive electrode active material, a conductive agent and a binder (94-98): stirring the mixture in the weight ratio of (1-3), and adding 0.1-1 part of oxalic acid to mix to prepare anode mixed slurry;
s2, preparing a binder into a glue solution with the solid content of 4-6%, and mixing the positive electrode mixed slurry and the glue solution according to the weight ratio (96-98): (1-3) stirring uniformly, adding 0.1-1 parts by weight of a conductive agent, adding N-methyl pyrrolidone step by step, stirring uniformly to obtain positive electrode slurry with the viscosity of 4800-5200Pa.s, coating the positive electrode slurry on a positive electrode current collector, and drying and rolling to obtain a positive electrode plate;
2) Preparation of the negative electrode:
s1, mixing a negative electrode active material, a binder and a conductive agent (92-96): (1-4): mixing the components (1-4) in a weight ratio to prepare negative electrode mixed slurry;
s2, adding deionized water into the negative electrode mixed slurry step by step, uniformly stirring, sequentially adding 1-4 parts of binder and 0.1-0.5 part of preservative, uniformly stirring to obtain negative electrode slurry with the viscosity of 2800-3200Pa.s, coating the negative electrode slurry on a negative electrode current collector, and drying and rolling to obtain a negative electrode sheet;
3) Preparation of the separator: coating a ceramic coating with a thickness of 3-5 mu m on the PE base film;
4) Preparation of electrolyte: organic solvent, sodium salt and functional additive are mixed according to the proportion of (75-85): mixing the components (3-8) in a weight ratio;
5) And preparing the negative plate, the positive plate, the diaphragm and the electrolyte into a sodium ion battery.
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