CN116031403B - Preparation method and application of high-crystallinity Prussian blue analogue positive electrode material - Google Patents
Preparation method and application of high-crystallinity Prussian blue analogue positive electrode material Download PDFInfo
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- CN116031403B CN116031403B CN202211585773.1A CN202211585773A CN116031403B CN 116031403 B CN116031403 B CN 116031403B CN 202211585773 A CN202211585773 A CN 202211585773A CN 116031403 B CN116031403 B CN 116031403B
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- sodium
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- release capsule
- prussian blue
- crystallinity
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- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical class [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 17
- 239000002775 capsule Substances 0.000 claims abstract description 59
- GTSHREYGKSITGK-UHFFFAOYSA-N sodium ferrocyanide Chemical compound [Na+].[Na+].[Na+].[Na+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] GTSHREYGKSITGK-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000264 sodium ferrocyanide Substances 0.000 claims abstract description 19
- 235000012247 sodium ferrocyanide Nutrition 0.000 claims abstract description 19
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 18
- DCXPBOFGQPCWJY-UHFFFAOYSA-N trisodium;iron(3+);hexacyanide Chemical compound [Na+].[Na+].[Na+].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCXPBOFGQPCWJY-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000003839 salts Chemical class 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000010406 cathode material Substances 0.000 claims abstract description 9
- 239000010405 anode material Substances 0.000 claims abstract description 6
- 238000001291 vacuum drying Methods 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 27
- 229910001415 sodium ion Inorganic materials 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000008139 complexing agent Substances 0.000 claims description 10
- 239000004094 surface-active agent Substances 0.000 claims description 10
- 239000001509 sodium citrate Substances 0.000 claims description 7
- 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 7
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 229910001416 lithium ion Inorganic materials 0.000 claims description 6
- 239000012528 membrane Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000013268 sustained release Methods 0.000 claims description 6
- 239000012730 sustained-release form Substances 0.000 claims description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 5
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 5
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 claims description 4
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 4
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 4
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 4
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims description 4
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims description 4
- 239000001856 Ethyl cellulose Substances 0.000 claims description 3
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 3
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- 229920001249 ethyl cellulose Polymers 0.000 claims description 3
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 3
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 3
- 230000003204 osmotic effect Effects 0.000 claims description 3
- 229920000193 polymethacrylate Polymers 0.000 claims description 3
- -1 polyoxyethylene Polymers 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 claims description 2
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- 229920001479 Hydroxyethyl methyl cellulose Polymers 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 229920002385 Sodium hyaluronate Polymers 0.000 claims description 2
- 235000013871 bee wax Nutrition 0.000 claims description 2
- 239000012166 beeswax Substances 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 claims description 2
- 229960001484 edetic acid Drugs 0.000 claims description 2
- 230000003628 erosive effect Effects 0.000 claims description 2
- 229940075507 glyceryl monostearate Drugs 0.000 claims description 2
- 229920000609 methyl cellulose Polymers 0.000 claims description 2
- 239000001923 methylcellulose Substances 0.000 claims description 2
- 235000010981 methylcellulose Nutrition 0.000 claims description 2
- 239000001788 mono and diglycerides of fatty acids Substances 0.000 claims description 2
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 claims description 2
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 2
- ZPIRTVJRHUMMOI-UHFFFAOYSA-N octoxybenzene Chemical compound CCCCCCCCOC1=CC=CC=C1 ZPIRTVJRHUMMOI-UHFFFAOYSA-N 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 claims description 2
- 239000000176 sodium gluconate Substances 0.000 claims description 2
- 235000012207 sodium gluconate Nutrition 0.000 claims description 2
- 229940005574 sodium gluconate Drugs 0.000 claims description 2
- 229940010747 sodium hyaluronate Drugs 0.000 claims description 2
- 239000001433 sodium tartrate Substances 0.000 claims description 2
- 229960002167 sodium tartrate Drugs 0.000 claims description 2
- 235000011004 sodium tartrates Nutrition 0.000 claims description 2
- YWIVKILSMZOHHF-QJZPQSOGSA-N sodium;(2s,3s,4s,5r,6r)-6-[(2s,3r,4r,5s,6r)-3-acetamido-2-[(2s,3s,4r,5r,6r)-6-[(2r,3r,4r,5s,6r)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2- Chemical compound [Na+].CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 YWIVKILSMZOHHF-QJZPQSOGSA-N 0.000 claims description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000012983 electrochemical energy storage Methods 0.000 abstract description 3
- 239000003792 electrolyte Substances 0.000 description 11
- 229960003351 prussian blue Drugs 0.000 description 7
- 239000013225 prussian blue Substances 0.000 description 7
- 238000007789 sealing Methods 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 239000011734 sodium Substances 0.000 description 5
- 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 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- 229940099596 manganese sulfate Drugs 0.000 description 4
- 239000011702 manganese sulphate Substances 0.000 description 4
- 235000007079 manganese sulphate Nutrition 0.000 description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 4
- 229920001485 poly(butyl acrylate) polymer Polymers 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 238000000840 electrochemical analysis Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 230000036632 reaction speed Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 229960001763 zinc sulfate Drugs 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
A preparation method of a high-crystallinity Prussian blue analog cathode material belongs to the field of electrochemical energy storage, and the specific scheme comprises the following steps: step one, preparing a slow-release capsule, wherein the slow-release capsule contains a component A, and the component A comprises transition metal element salt, sodium ferrocyanide or sodium ferricyanide; preparing a solution B, wherein when the component A in the slow-release capsule is transition metal element salt, the solution B comprises sodium ferrocyanide or sodium ferricyanide; when the component A in the slow release capsule is sodium ferrocyanide or sodium ferricyanide, the solution B comprises transition metal element salt; step three, immersing the slow-release capsule prepared in the step one into the solution B in the step two for reaction, and vacuum drying the centrifuged product to obtain the Prussian blue analog anode material with high crystallinity; the Prussian blue analog positive electrode material with high crystallinity can improve the cycle performance, the multiplying power performance and the safety of the secondary battery.
Description
Technical Field
The invention belongs to the field of electrochemical energy storage, relates to a preparation method of a secondary battery anode material, and in particular relates to a preparation method and application of a high-crystallinity Prussian blue analogue anode material.
Background
The electrochemical energy storage technology has the advantages of high energy conversion efficiency, good safety, low maintenance cost, environmental friendliness and the like, and is considered as one of the most promising energy storage technologies. Currently, lithium Ion Batteries (LIBs) have been widely used in the fields of mobile electronic devices, electric vehicles, and the like due to their advantages of high energy density, long cycle life, no memory effect, and the like. However, lithium is low in the crust and is unevenly distributed worldwide, and thus LIBs are limited by resource reserves, which makes it difficult to support both electric vehicles and the development of large-scale energy storage.
In recent years, sodium Ion Batteries (SIBs) have a similar working principle to the LIBs, and sodium resources are abundant, widely distributed and low in cost, so that the requirements of large-scale energy storage can be met, and the sodium ion batteries are focused on in scientific research and industry. Prussian blue compounds are materials derived based on Prussian blue (Prussianblue) structures, and are commonly called Prussian blue analogues (Prussianblueanalogues, namely PBAs), and the chemical composition of the PBA can be expressed as A xTM[Fe(CN)6]y□1-y·nH2 O (x is more than 0 and less than or equal to 2; 0 < y.ltoreq.1), wherein A represents an alkali metal ion Li +、Na+ or K + or the like; t M represents a transition metal ion such as Fe, mn, co, ni, cu or Ti; and ∈s represents a null. In such a cubic lattice, transition metal ions coordinate to nitrogen atoms and Fe 2+ ions are adjacent to octahedra formed by carbon atoms, forming a 3D rigid framework with open ion channels and a broad interstitial space. Prussian blue analogues are considered ideal cationic (Li +、Na+、K+ or Zn 2+) positive electrode materials due to their unique open framework structure. Since there is only one electron redox centre in the lattice, these PBA materials can carry at least one cation per molecular unit, thus providing a fairly low ion insertion capacity of 40-70mAhg -1, with poor cycling performance, mainly due to the large number of defects in the material, leading to increased coordination of water. Prussian white belongs to one of Prussian blue analogues, and has the advantages of higher theoretical capacity, large gap, adjustable structure and chemical components, good frame stability and the like when used as a positive electrode material, and has very excellent electrochemical performance. Meanwhile, the material has the advantages of low cost, no toxicity, no harm, simple material preparation, low energy consumption and the like, and is a positive electrode material with very good commercial application prospect in sodium ion battery research. However, due to the restriction of the extremely fast reaction rate in the material coprecipitation preparation process, the obtained Prussian white material contains a large amount of Fe (CN) 6 vacancies, so that the crystallinity of the material is reduced. The existence of Fe (CN) 6 vacancies can damage the structural integrity, reduce the cycling stability of the material, simultaneously prevent electrons from conducting along the material frame, reduce the electron conductivity, and then influence the rapid diffusion of sodium ions, so that the rate performance is poor; in addition, the existence of vacancies can lead to the introduction of more crystal water in the crystal lattice of the material, influence sodium ions to enter the crystal lattice, and reduce the sodium intercalation content. In the process of charging the battery, the crystal water enters the electrolyte through Na (OH 2)+ units) along with the removal of sodium ions, and is slowly decomposed and has adverse effects on the stability of the electrolyte. and for interstitial water, the interstitial sites in the PBA material are occupied, so that migration of sodium ions is blocked during charge and discharge to influence sodium ion migration kinetics.
Disclosure of Invention
The invention aims to provide a preparation method of a high-crystallinity Prussian blue analog cathode material, which adopts a capsule slow-release technology to reduce the reaction speed, inhibit vacancies and crystal water generated in the reaction process, improve the crystallinity of the Prussian blue analog and obtain the high-quality Prussian blue analog cathode material. The Prussian blue analog positive electrode material is applied to a secondary battery system, can improve the cycle performance and the multiplying power performance of the secondary battery, can reduce the influence of crystal water on electrolyte and cation migration, and improves the safety of the battery.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
The preparation method of the high-crystallinity Prussian blue analog cathode material comprises the following steps:
Step one, preparing a slow-release capsule, wherein the slow-release capsule contains a component A, and the component A comprises transition metal element salt, sodium ferrocyanide or sodium ferricyanide;
Preparing a solution B, wherein when the component A in the slow-release capsule is transition metal element salt, the solution B comprises sodium ferrocyanide or sodium ferricyanide; when the component A in the slow release capsule is sodium ferrocyanide or sodium ferricyanide, the solution B comprises transition metal element salt; when Prussian white materials are prepared, a transition metal element salt is selected to react with sodium ferrocyanide; when preparing Prussian blue materials, a transition metal salt is selected to react with sodium ferricyanide.
And thirdly, immersing the slow-release capsule prepared in the first step into the solution B in the second step for reaction, and drying the centrifuged product in vacuum to obtain the Prussian blue analog anode material with high crystallinity.
As a preferable scheme, when the component A in the slow release capsule is transition metal element salt, the slow release capsule also comprises complexing agent, and the solution B also comprises surfactant; when the component A in the slow release capsule is sodium ferrocyanide or sodium ferricyanide, the slow release capsule also comprises a surfactant, and the solution B also comprises a complexing agent.
As a preferred embodiment, the solution B further comprises a surfactant and a complexing agent.
The core of the preparation method is to control the contact amount of the transition metal element salt and sodium ferrocyanide/sodium ferricyanide, reduce the reaction speed and inhibit the vacancy and the crystallization water generated in the reaction process.
Further, in the first step, the sustained-release capsule comprises one or a combination of a plurality of skeleton type sustained-release capsules, membrane control type sustained-release capsules and osmotic pump type sustained-release capsules.
Further, the skeleton type slow release capsule comprises one or a combination of a plurality of hydrophilic gel skeleton slow release capsules, insoluble skeleton slow release capsules and corrosion type skeleton slow release capsules; the skeleton material of the hydrophilic gel skeleton slow-release capsule comprises one or a combination of a plurality of hydroxypropyl methyl cellulose, methyl cellulose and hydroxyethyl cellulose; the framework material of the insoluble framework sustained-release capsule comprises one or the combination of two of ethyl cellulose and polymethacrylate; the matrix material of the erosion matrix slow-release capsule comprises beeswax, stearyl alcohol and glyceryl monostearate.
The coating material of the membrane-controlled slow-release capsule and the material of the semipermeable membrane of the osmotic pump type slow-release capsule are made of framework materials of hydrophilic gel framework slow-release capsules or framework materials of insoluble framework slow-release capsules.
Further, the complexing agent comprises one or more of citric acid, sodium citrate, nitrilotriacetic acid, ethylenediamine tetraacetic acid, sodium tartrate, sodium hyaluronate and sodium gluconate; the surfactant comprises one or a combination of a plurality of sodium dodecyl benzene sulfonate, cetyltrimethylammonium bromide, P123, triethylene glycol, polyethylene glycol octyl phenyl ether and polyoxyethylene.
Further, the molar ratio of the sodium ferrocyanide to the sodium ferricyanide to the transition metal element salt is 1:2-2:1; the mol ratio of the transition metal element salt to the complexing agent is 1:1-1:4; the mass ratio of the sodium ferrocyanide to the sodium ferricyanide to the surfactant is 2:1-2:5.
Further, in the second step, the solvent of the solution B is deionized water.
In the third step, the reaction temperature is 70-90 ℃, the stirring reaction is carried out for 6-15h, and the aging time is 5-15h.
The high-crystallinity Prussian blue analog positive electrode material prepared by the preparation method is applied to sodium ion batteries, lithium ion batteries or zinc ion batteries.
Compared with the prior art, the invention has the beneficial effects that:
1. The Prussian blue analog cathode material prepared by the invention is nucleated, dispersed and uniformly deposited by a slow-release technology, so that the formed material has stable structure and high crystallinity, and the particle size and the crystallinity of the material can be controlled by controlling the type of capsules and the reaction condition in the preparation process, so that the particle size distribution condition can be well controlled, and the dispersibility and the crystallinity of the material are further improved.
(2) Compared with the prior art, the Prussian blue analog cathode material prepared by the invention has the advantages of more uniform dispersion, higher crystallinity, controllable dispersion granularity and reaction speed, and is beneficial to industrial production.
(3) The Prussian blue analog positive electrode material prepared by the method is used as a positive electrode material of a sodium ion battery/a lithium ion battery/a zinc ion battery, and can obviously improve the cycle performance, the multiplying power performance and the safety of the battery.
Drawings
FIG. 1 is a scanning electron microscope image of Prussian white synthesized in example 1;
FIG. 2 is an XRD pattern of Prussian white synthesized in example 1;
Fig. 3 is a white scanning electron microscope of prussian synthesized in example 4;
Fig. 4 is a drawing of a prussian blue scanning electron microscope synthesized in example 6;
FIG. 5 is a graph of sodium ion battery charge and discharge;
fig. 6 is a graph of cycling performance of a zinc ion cell.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings and examples, and it is apparent that the described examples are only some, but not all, of the examples of the invention, and all other examples obtained by those skilled in the art without making any inventive effort are within the scope of the present invention.
Example 1
A preparation method of a Prussian Bai Zheng pole material with high crystallinity comprises the following steps:
(1) Uniformly mixing 0.5g of manganese sulfate, 1g of sodium citrate and 0.5g of hydroxypropyl methylcellulose, and filling into an empty capsule to obtain a slow-release capsule;
(2) 1.5g of sodium ferrocyanide and 2g of cetyltrimethylammonium bromide CTAB are added into 50mL of water to prepare solution B;
(3) Immersing the slow-release capsule into the solution B, magnetically stirring, and performing coprecipitation reaction for 12 hours at 80 ℃ with the stirring speed of 30r/min; stopping stirring, aging for 5 hours,
(4) And finally, sequentially filtering and washing by deionized water and ethanol, and vacuum drying to obtain the Prussian Bai Zheng pole material with high dispersibility and high crystallinity. The scanning electron microscope diagram of Prussian white synthesized in this example is shown in fig. 1, and the XRD diagram is shown in fig. 2.
Example 2
The difference from example 1 is that in step (1), 0.3g of manganese sulfate, 0.2g of zinc sulfate, 1g of sodium citrate and 0.5g of ethyl cellulose are uniformly mixed and added into empty capsules, and the rest of the steps are the same as in example 1.
Example 3
The difference from example 1 is that 2g of sodium ferrocyanide and 2g of sodium dodecylbenzenesulfonate were added to 50mL of water in step (2) to prepare solution B, and the rest of the steps were the same as in example 1.
Example 4
The difference from example 1 is that in step (1), 0.3g of manganese sulfate, 0.2g of zirconium chloride and 1g of sodium citrate are placed in a semipermeable membrane made of hydroxyethyl cellulose to prepare a membrane-controlled slow-release capsule, and the rest steps are the same as in example 1, and a scanning electron microscope diagram of Prussian white synthesized in this example is shown in fig. 3.
Example 5
The difference from example 1 is that in step (1), 0.3g of manganese sulfate, 0.2g of zinc sulfate and 1g of sodium citrate are placed in a coating made of polymethacrylate to prepare a film-controlled slow release capsule, and the rest steps are the same as in example 1.
Example 6
A preparation method of a Prussian blue positive electrode material with high crystallinity is different from that of the embodiment 1 in that in the step (1), 0.5g of ferric sulfate, 1g of sodium citrate and 0.5g of hydroxypropyl methylcellulose are uniformly mixed and filled into empty capsules to obtain slow-release capsules; in the step (2), 2.2g of sodium ferricyanide and 2g of cetyltrimethylammonium bromide CTAB are added into 50mL of water to prepare a solution B; the rest steps are the same as those of the embodiment 1, and a scanning electron microscope diagram of Prussian blue synthesized by the embodiment is shown in fig. 4.
Preparation method of battery anode material
In order to explore the electrochemical properties of different positive electrode materials, the synthetic materials are coated on the current collector to prepare the working electrode, and the specific process can be divided into the following steps:
(1) Mixing: the prepared Prussian white/Prussian blue cathode material, conductive carbon black (SupperP) and polyvinylidene fluoride (PVDF) were mixed in a ratio of 7:2:1, and adding a proper amount of N-methyl pyrrolidone (NMP) solvent dropwise to obtain slurry with proper viscosity, and stirring for 12h. PVDF is dissolved in N-methyl pyrrolidone (NMP) in advance to prepare a binder, and the mass fraction of the binder is 5wt%.
(2) Coating: the preparation method comprises the steps of taking a pretreated carbon paper/stainless steel mesh as a current collector of a zinc ion battery, taking a pretreated aluminum foil or a carbon-coated aluminum foil as a current collector of a lithium/sodium ion battery, firstly cutting the current collector into wafers with the diameter of 10mm, and then uniformly coating the mixed slurry on the surface of the current collector. The active loading is about 1-2mgcm -2.
(3) And (3) drying: and (5) placing the coated pole piece into a vacuum drying oven at 60 ℃ for vacuum drying for 12 hours, and sealing and preserving so as to facilitate the subsequent assembly test of the button cell.
Example 7
Application of Prussian Bai Zheng electrode material prepared in example 1 in sodium ion battery.
Electrochemical tests were performed using CR2032 type battery cases assembled on button cells. It was necessary to die cut a 200 μm thick metallic sodium foil into 14mm diameter discs, die cut a Waterman glass fiber septum into 16mm, and pre-formulate an EC of 1MNaPF 6: : DEC: DMC (1:1:1) electrolyte is ready for use. The assembly steps are as follows: firstly, putting the prepared positive pole piece into a positive pole shell, dripping a certain volume of electrolyte, then sequentially stacking a Waterman glass fiber diaphragm, a sodium sheet negative electrode, a gasket, an elastic sheet and a negative pole shell, and finally sealing by a small hydraulic sealing machine. The assembled battery typically requires 10 hours of rest to ensure that the pole pieces are sufficiently wetted by the electrolyte. The charge and discharge curves of the battery are shown in fig. 5.
Example 8
Application of Prussian Bai Zheng electrode material prepared in example 1 in lithium ion batteries. Electrochemical tests were performed using CR2032 type battery cases assembled on button cells. It was necessary to die cut a 200 μm thick metallic lithium foil into 14mm diameter discs, die cut PP separator into 16mm and pre-formulate EC of 1MLiPF 6: : DEC: DMC (1:1:1) electrolyte is ready for use. The assembly steps are as follows: firstly, placing the prepared positive pole piece into a positive pole shell, dripping a certain volume of electrolyte, then stacking a PP diaphragm, a lithium piece negative electrode, a gasket, an elastic piece and a negative pole shell in sequence, and finally sealing by a small hydraulic sealing machine. The assembled battery typically requires 10 hours of rest to ensure that the pole pieces are sufficiently wetted by the electrolyte.
Example 9
Application of Prussian blue cathode material prepared in example 6 in zinc ion battery. Electrochemical tests were performed using CR2032 type battery cases assembled on button cells. Firstly, punching a metal zinc foil with the thickness of 200 mu m into a circular sheet with the diameter of 14mm, punching a Waterman glass fiber diaphragm into 16mm, and preparing ZnSO 4 or Zn (CF 3SO3)2 electrolyte with proper concentration in advance for standby use, wherein the assembling step is that firstly, the prepared positive pole piece is put into a positive pole shell, a certain volume of electrolyte is dripped into the positive pole shell, then, the glass fiber diaphragm, a zinc sheet negative pole, a gasket, a spring sheet and a negative pole shell are sequentially stacked, and finally, a small hydraulic sealing machine is used for sealing.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (6)
1. The preparation method of the high-crystallinity Prussian blue analog cathode material is characterized by comprising the following steps of:
Step one, preparing a slow-release capsule, wherein the slow-release capsule contains a component A, and the component A comprises transition metal element salt, sodium ferrocyanide or sodium ferricyanide;
preparing a solution B, wherein when the component A in the slow-release capsule is transition metal element salt, the solution B comprises sodium ferrocyanide or sodium ferricyanide; when the component A in the slow release capsule is sodium ferrocyanide or sodium ferricyanide, the solution B comprises transition metal element salt, and the solvent of the solution B is deionized water;
Immersing the slow-release capsule prepared in the first step into the solution B in the second step for reaction, wherein the reaction temperature is 70-90 ℃, stirring and reacting for 6-15h, the aging time is 5-15h, and vacuum drying the centrifuged product to obtain the Prussian blue analog anode material with high crystallinity;
in the second step, the solution B also comprises a surfactant and a complexing agent;
Or alternatively
When the component A in the slow release capsule is transition metal element salt, the slow release capsule also comprises a complexing agent, and the solution B also comprises a surfactant;
when the component A in the slow release capsule is sodium ferrocyanide or sodium ferricyanide, the slow release capsule also comprises a surfactant, and the solution B also comprises a complexing agent.
2. The method for preparing the high-crystallinity Prussian blue analog positive electrode material according to claim 1, wherein the method is characterized by comprising the following steps: in the first step, the slow release capsule comprises one or a combination of a plurality of skeleton type slow release capsules, membrane control type slow release capsules and osmotic pump type slow release capsules.
3. The method for preparing the high-crystallinity Prussian blue analog positive electrode material according to claim 2, wherein the method is characterized by comprising the following steps: the skeleton type slow release capsule comprises one or a combination of a plurality of hydrophilic gel skeleton slow release capsules, insoluble skeleton slow release capsules and corrosion type skeleton slow release capsules; the skeleton material of the hydrophilic gel skeleton slow-release capsule comprises one or a combination of a plurality of hydroxypropyl methyl cellulose, methyl cellulose and hydroxyethyl cellulose; the framework material of the insoluble framework sustained-release capsule comprises one or the combination of two of ethyl cellulose and polymethacrylate; the matrix material of the erosion matrix slow-release capsule comprises beeswax, stearyl alcohol and glyceryl monostearate.
4. The method for preparing the high-crystallinity Prussian blue analog positive electrode material according to claim 1, wherein the method is characterized by comprising the following steps: the complexing agent comprises one or more of citric acid, sodium citrate, nitrilotriacetic acid, ethylenediamine tetraacetic acid, sodium tartrate, sodium hyaluronate and sodium gluconate; the surfactant comprises one or a combination of a plurality of sodium dodecyl benzene sulfonate, cetyltrimethylammonium bromide, P123, triethylene glycol, polyethylene glycol octyl phenyl ether and polyoxyethylene.
5. The method for preparing the high-crystallinity Prussian blue analog positive electrode material according to claim 1, wherein the method is characterized by comprising the following steps: the molar ratio of sodium ferrocyanide to sodium ferricyanide to transition metal element salt is 1:2-2:1; the mol ratio of the transition metal element salt to the complexing agent is 1:1-1:4; the mass ratio of the sodium ferrocyanide to the sodium ferricyanide to the surfactant is 2:1-2:5.
6. Use of a high crystallinity prussian blue analogue positive electrode material prepared by the preparation method of any one of claims 1-5 in sodium ion batteries, lithium ion batteries or zinc ion batteries.
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