CN108807991B - Doped cyano material, preparation method and application thereof, and sodium ion battery - Google Patents
Doped cyano material, preparation method and application thereof, and sodium ion battery Download PDFInfo
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- CN108807991B CN108807991B CN201811048022.XA CN201811048022A CN108807991B CN 108807991 B CN108807991 B CN 108807991B CN 201811048022 A CN201811048022 A CN 201811048022A CN 108807991 B CN108807991 B CN 108807991B
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- 239000000463 material Substances 0.000 title claims abstract description 170
- 125000004093 cyano group Chemical group *C#N 0.000 title claims abstract description 154
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 53
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000011734 sodium Substances 0.000 claims abstract description 21
- 239000011258 core-shell material Substances 0.000 claims abstract description 16
- 239000013078 crystal Substances 0.000 claims abstract description 9
- 239000007774 positive electrode material Substances 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 7
- 150000002500 ions Chemical class 0.000 claims description 33
- 239000011572 manganese Substances 0.000 claims description 29
- 235000002639 sodium chloride Nutrition 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 21
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 20
- 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 description 19
- 239000000264 sodium ferrocyanide Substances 0.000 claims description 19
- 235000012247 sodium ferrocyanide Nutrition 0.000 claims description 19
- 230000032683 aging Effects 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 229910002651 NO3 Inorganic materials 0.000 claims description 14
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 14
- 229910001437 manganese ion Inorganic materials 0.000 claims description 14
- 159000000000 sodium salts Chemical class 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 12
- 238000000975 co-precipitation Methods 0.000 claims description 12
- 238000003860 storage Methods 0.000 claims description 12
- 238000011282 treatment Methods 0.000 claims description 12
- 150000002696 manganese Chemical class 0.000 claims description 10
- 239000011780 sodium chloride Substances 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 6
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000011565 manganese chloride Substances 0.000 claims description 6
- 235000002867 manganese chloride Nutrition 0.000 claims description 6
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 229940071125 manganese acetate Drugs 0.000 claims description 4
- 229940099607 manganese chloride Drugs 0.000 claims description 4
- 229940099596 manganese sulfate Drugs 0.000 claims description 4
- 239000011702 manganese sulphate Substances 0.000 claims description 4
- 235000007079 manganese sulphate Nutrition 0.000 claims description 4
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 4
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-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
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- 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 3
- 235000011083 sodium citrates Nutrition 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- 235000010344 sodium nitrate 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
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- BZDIAFGKSAYYFC-UHFFFAOYSA-N manganese;hydrate Chemical compound O.[Mn] BZDIAFGKSAYYFC-UHFFFAOYSA-N 0.000 claims description 2
- 238000004146 energy storage Methods 0.000 abstract description 8
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 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 8
- 229910052708 sodium Inorganic materials 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 7
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 6
- 230000001351 cycling effect Effects 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- -1 ferricyanide ions Chemical class 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001429 cobalt ion Inorganic materials 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 150000004677 hydrates Chemical class 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- GFORUURFPDRRRJ-UHFFFAOYSA-N [Na].[Mn] Chemical compound [Na].[Mn] GFORUURFPDRRRJ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 229940097267 cobaltous chloride Drugs 0.000 description 1
- 229940045032 cobaltous nitrate Drugs 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229960003351 prussian blue Drugs 0.000 description 1
- 239000013225 prussian blue Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—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
-
- 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
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the technical field of novel energy storage batteries, and relates to a doped typeCyano material, preparation method and application and sodium ion battery. The chemical formula of the doped cyano material is NaxMn1‑y‑ zM1yM2z[Fe(CN)6]In the formula, 0<x≤2，0<y≤0.2，0<z is less than or equal to 0.2; m1 and M2 are doping elements; the cyano material has a crystal structure of rhombohedral phase; and exhibits a core-shell structure. The doped cyano material with the core-shell structure is applied to the positive electrode material of the sodium ion battery, and has high capacity, excellent rate capability and excellent cycle performance.
Description
Technical Field
The invention belongs to the technical field of novel energy storage batteries, and particularly relates to a doped cyano material, a preparation method and application thereof, and a sodium ion battery.
Background
With the continuous development of clean energy sources such as solar energy, wind energy, ocean energy and the like, the demand for high-efficiency energy storage batteries is increasing day by day. In addition, large-scale battery energy storage can play a role in 'peak clipping and valley filling' on electric power, and the service efficiency of the electric power is improved. Lead acid batteries, although low in price, have a low energy density, short life, and a pollution problem. Although the lithium ion battery has a mature technology and a high energy density, the cost is high. In recent years, with the development of smart phones, new energy vehicles and the like, the demand of lithium ion batteries is higher and higher, lithium resources face the problem of resource shortage, the global storage capacity is very limited and is not distributed uniformly, the price of raw materials rises rapidly, the requirement of large-scale energy storage cannot be met, and the rapid development of low-cost and high-performance energy storage devices in China is restricted.
In contrast, sodium resources are abundant in the earth, low in cost, and sodium has very similar physicochemical properties to lithium, and sodium ion batteries are receiving increasing attention in recent years as energy storage technologies that potentially replace lithium ion batteries. The sodium ion battery has the characteristics of abundant resources, good safety performance, low cost and suitability for large-scale energy storage application. However, in comparison with lithium ion batteries, the choice of anode materials is very limited, taking into account voltage, capacity and cost factors.
Some Prussian blue-based positive electrode materials contain larger vacancies in the structure, so that the deintercalation of sodium ions with larger sizes is facilitated, and high capacity is realized. However, the compound has the defects of poor conductivity, unstable structure and low tap density, more conductive agent needs to be added when the battery is manufactured, the energy density of the battery is reduced, and the processability of the material is poor. Therefore, it is necessary to optimize the structure and composition thereof to improve electrochemical performance; namely, the development of sodium ion cathode materials with excellent electrochemical properties is required to meet the demands of the market.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a doped cyano material, wherein the cyano material is doped with elements M1 and M2, so that the structural stability and the electrical conductivity of the cyano material can be improved, the cycling stability and the rate capability of the material can be improved, and the specific capacity of the material can also be improved.
The invention also aims to provide a preparation method of the doped cyano material, which is simple and convenient to operate and easy to implement, and the prepared material has high specific capacity, stable structure, high conductivity and excellent cycle performance and rate capability.
The invention also aims to provide an application of the doped cyano material in a sodium ion battery; a sodium ion battery; and an electronic device, an electric tool, an electric vehicle, or a power storage system including the sodium ion battery. The doped cyano material provided by the invention is applied to a sodium ion battery electrode, and can obviously improve the electrochemical performance of the sodium ion battery, particularly the specific capacity, the cycle performance and the rate capability.
In order to achieve the purpose, the invention adopts the technical scheme that:
according to one aspect of the invention, the invention provides a doped cyano material, wherein the cyano material has a chemical formula of NaxMn1-y-zM1yM2z[Fe(CN)6]In the formula, 0<x≤2，0<y≤0.2，0<z is less than or equal to 0.2; m1 and M2 are doping elements; the cyano material has a crystal structure of rhombohedral phase.
As a further preferable technical scheme, the doping element M1 is a non-electrochemically active metal element; the doping element M2 is an electrochemical active metal element;
and/or doping elements M1 and M2 on the Mn side of the cyano-group material;
preferably, the doping element M1 comprises at least one of nickel, copper, zinc or magnesium;
preferably, the doping element M2 comprises iron and/or cobalt.
As a further preferable technical scheme, the cyano material is of a core-shell structure, the core is a cyano material doped with M1, and the shell is a cyano material doped with M2;
preferably, the weight percentage content of the inner core is 5-25%, preferably 10-20%;
preferably, the weight percentage content of the shell is 75-95%, preferably 80-90%;
preferably, the molar ratio of the doping element M1 ion to the Mn ion is 1/20-1/4, preferably 1/20-1/10;
preferably, the molar ratio of the doping element M2 ion to the Mn ion is 1/20-1/4, preferably 1/20-1/10.
As a further preferable technical scheme, the source compound of the doping element M1 is one or more of chloride, sulfate, nitrate, acetate or hydrate of the doping element M1;
and/or the source compound of the doping element M2 is one or more of chloride, sulfate, nitrate, acetate or hydrate of the doping element M2;
preferably, the doped cyano material is a nano-scale doped cyano material, and the particle size is 400-600 nm.
According to another aspect of the present invention, the present invention provides a preparation method of the above doped cyano material, comprising the following steps:
(a) mixing sodium ferrocyanide, sodium salt and water to obtain a solution A;
(b) mixing soluble divalent manganese salt, soluble salt containing M1 and water to obtain solution B1;
mixing soluble divalent manganese salt, soluble salt containing M2 and water to obtain solution B2;
(c) and sequentially adding the solution B1 and the solution B2 into the solution A, and carrying out coprecipitation reaction to obtain the doped cyano material.
As a further preferred technical scheme, in the step (a), the sodium salt is selected from one or more of sodium chloride, sodium sulfate, sodium nitrate, sodium acetate and sodium citrate;
and/or, in the step (b), the soluble divalent manganese salt is selected from one or more of manganese chloride, manganese sulfate, manganese nitrate, manganese acetate or hydrate thereof;
and/or, in the step (b), the soluble salt containing M1 is selected from one or more of chloride, sulfate, nitrate, acetate or hydrate thereof;
and/or, in the step (b), the soluble salt containing M2 is selected from one or more of chloride, sulfate, nitrate, acetate or hydrate thereof;
preferably, the concentration of the sodium ferrocyanide in the solution A is 0.05-0.5 mol/L, and preferably 0.1-0.3 mol/L;
preferably, in the solution a, the molar ratio of sodium ions in the sodium salt to sodium ferrocyanide is 50-110: 1, preferably 70-90: 1;
preferably, in the solution B1, the concentration of the divalent manganese ions is 0.1-1 mol/L, and preferably 0.2-0.6 mol/L;
preferably, in the solution B1, the molar ratio of the M1 ions to the divalent manganese ions is 1/20-1/4, preferably 1/20-1/10;
preferably, in the solution B2, the concentration of the divalent manganese ions is 0.1-1 mol/L, and preferably 0.2-0.6 mol/L;
preferably, in the solution B2, the molar ratio of the M2 ions to the divalent manganese ions is 1/20-1/4, and preferably 1/20-1/10.
As a further preferable technical scheme, in the step (c), the coprecipitation reaction is carried out under a normal-pressure open system, the temperature is 40-90 ℃, and 70-90 ℃ is preferable;
preferably, the method also comprises the steps of aging treatment and post-treatment after the coprecipitation reaction is finished;
preferably, the temperature of the aging treatment is 40-90 ℃, and preferably 70-90 ℃;
preferably, the aging treatment time is 1-10 h, preferably 2-9 h;
preferably, the post-treatment comprises cooling, washing and drying treatments.
According to another aspect of the invention, the invention also provides an application of the doped cyano material in a sodium ion battery.
According to another aspect of the invention, the invention also provides a sodium-ion battery, which comprises the doped cyano material as a positive electrode material of the sodium-ion battery.
According to another aspect of the present invention, the present invention also provides an electronic device, an electric tool, an electric vehicle, or an electric power storage system including the sodium ion battery described above.
Compared with the prior art, the invention has the beneficial effects that:
1. the cyano material is doped with two heterogeneous elements, so that the cyano material has comprehensive high capacity, long cycle life and excellent rate capability.
2. The preparation method has the advantages of simple process, low cost, short period, low energy consumption, suitability for industrial production and the like.
3. The doped cyano material is applied to the sodium ion battery electrode, so that the electrochemical performance of the sodium ion battery, particularly the specific capacity, the cycle performance and the rate capability can be obviously improved; and the defects of limited lithium resource reserve and high cost of the existing lithium ion battery and the problems of limited anode material and non-ideal electrochemical performance of the existing sodium ion battery are further solved. An electronic device, an electric tool, an electric vehicle or a power storage system including the sodium ion battery has at least the same advantages as the sodium ion battery.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a schematic structural diagram of a doped cyano material prepared in example 1 of the present invention;
FIG. 2 is an X-ray diffraction pattern (XRD pattern) of the doped cyano material prepared in example 1 of the present invention;
fig. 3 is a charge-discharge curve diagram of a sodium ion battery assembled by using the doped cyano material prepared in example 1 of the present invention as a positive electrode material.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to embodiments and examples, but those skilled in the art will understand that the following embodiments and examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. Those who do not specify the conditions are performed according to the conventional conditions or the conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
In a first aspect, there is provided in at least one embodiment a doped cyano material, the cyano material having the formula NaxMn1-y-zM1yM2z[Fe(CN)6]In the formula, 0<x≤2，0<y≤0.2，0<z is less than or equal to 0.2; m1 and M2 are doping elements; the cyano material has a crystal structure of rhombohedral phase.
The doped cyano material consists of doped sodium manganese ferrocyanide with a nano structure, is applied to a sodium ion battery as a positive electrode material, and has high capacity, excellent cycle performance and rate capability. In addition, the electrochemical performance of the cyano material with the rhombohedral phase lattice structure is superior to that of the cubic phase material, especially in the aspect of capacity. Therefore, the battery can be better applied to the field of sodium-ion batteries.
Preferably, the doped cyano material is a nano-scale doped cyano material, and the particle size is 400-600 nm. The nano structure is beneficial to the de-intercalation of sodium, thereby improving the rate capability; however, the particle size should not be too large or too small, the too small size is easily corroded by the electrolyte, which is not favorable for improving the cycle performance, and the volume energy density of the battery can be reduced, while the too large particle is not favorable for the diffusion of sodium ions. Typically, but not limitatively, the particle size of the material may be, for example, 400nm, 420nm, 450nm, 480nm, 500nm, 520nm, 550nm, 580nm or 600 nm.
In a preferred embodiment, the cyano material is a core-shell structure, the inner core is a cyano material doped with M1, and the outer shell is a cyano material doped with M2.
In a preferred embodiment, the doping element M1 is a non-electrochemically active metal element; the doping element M2 is an electrochemical active metal element;
and/or doping elements M1 and M2 are doped on the Mn side of the cyano-group material.
The cyano material particles obtained by the invention have a core-shell structure, the core of the particles is a cyano material doped with electrochemically inactive (non-electrochemically active) M1, and the shell of the particles is a cyano material doped with electrochemically active M2. By electrochemically active is meant that the capacity is provided by chemical valence change during charging and discharging, e.g. Co2+(divalent cobalt ion) oxidizable to Co upon charging3+(trivalent cobalt ions) which can be reversibly reduced to Co upon discharge2+Thereby providing capacity; but not electrochemically active elements such as Cu2+(divalent copper ions) cannot provide capacity by valence change.
Preferably, the doping element M1 of the core is an electrochemically inactive element, typically but not limited to, for example, nickel, copper, zinc, magnesiumAnd the structural stability and the electrical conductivity of the cyano-group material can be improved by doping the elements, so that the cycling stability and the rate capability of the material are improved, but the capacity of the material is reduced by excessive doping, so that the doping amount needs to be controlled within a reasonable range. Preferably, the elements M1 ion and Mn ion (Mn) are doped2+) The molar ratio of (a) is 1/20-1/4, and more preferably 1/20-1/10; typically, but not limited to, the molar ratio of the doping element M1 ion to the Mn ion may be, for example, 1/20, 1/18, 1/16, 1/15, 1/14, 1/12, 1/10, 1/8, 1/6, 1/5, or 1/4. Except for the doping amount of M1, the inner core is NaxMn1-yM1y[Fe(CN)6]The content of the active ingredients also needs to be reasonably controlled; preferably, the inner core NaxMn1-yM1y[Fe(CN)6]Is 5 to 25 percent, and further preferably, the inner core NaxMn1-yM1y[Fe(CN)6]The weight percentage of the component (A) is 10-20%; typically, but not by way of limitation, the weight percent content of the inner core may be, for example, 5%, 6%, 8%, 10%, 12%, 14%, 15%, 16%, 18%, 20%, 22%, 24%, or 25%. Too much core content will reduce the capacity of the product and too little core content will reduce the cycling stability and rate capability of the material, and therefore, it is desirable to control the core content within the above reasonable range.
Preferably, the doping element M2 of the shell is an electrochemically active element, typically but not limited to, iron, cobalt, and the like, and by doping such an element, on one hand, the high capacity of the cyano material can be maintained, and on the other hand, the structural stability and the electrical conductivity of the cyano material can be further improved by doping a heterogeneous element, so that the cycling stability and the rate capability of the material can be improved, but too much doping can reduce the operating voltage of the material (Co) and excessive doping can reduce the operating voltage of the material2+/Co3+And Fe2+/Fe3+The operating voltage of the oxidation/reduction pair is lower than Mn2+/Mn3+) And excessive doping of cobalt increases the material preparation cost, so the doping amount needs to be controlled within a reasonable range. Preferably, the elements M2 ion and Mn ion (Mn) are doped2+) The molar ratio of (A) is 1/20 to 1/4, and more preferably 1/20 to 1/10; typically, but not limited to, the molar ratio of the doping element M2 ion to the Mn ion may be, for example, 1/20, 1/18, 1/16, 1/15, 1/14, 1/12, 1/10, 1/8, 1/6, 1/5, or 1/4. Except for the doping amount of M2, the shell NaxMn1-zM2z[Fe(CN)6]The content of the active ingredients also needs to be reasonably controlled; preferably, the shell NaxMn1-zM2z[Fe(CN)6]Is 75 to 95 weight percent, and further preferably, the shell NaxMn1-zM2z[Fe(CN)6]The weight percentage of the component (A) is 80-90%; typically, but not by way of limitation, the weight percent content of the shell may be, for example, 75%, 76%, 78%, 80%, 82%, 84%, 85%, 86%, 88%, 90%, 92%, 94%, or 95%. Too much shell content will reduce the rate capability and cycle stability of the product, and too little shell content will reduce the capacity of the material, and therefore, it is necessary to control the shell content within the above reasonable range.
Through the optimization, the capacity, the working voltage, the rate capability and the cycle life can be optimized and balanced.
In a preferred embodiment, the source compound of the doping element M1 includes, but is not limited to, one or more of chloride, sulfate, nitrate, acetate or hydrate thereof of the doping element M1;
and/or the source compound of the doping element M2 comprises one or more of chloride, sulfate, nitrate, acetate or hydrate of the doping element M2.
In the present invention, the source and type of the source compound of the doping element M1 and the source compound of the doping element M2 are not particularly limited, and various materials known to those skilled in the art may be used; if it is commercially available, it can be prepared by itself by a method known to those skilled in the art.
In a second aspect, in at least one embodiment, there is provided a method for preparing the above-mentioned doped cyano material, comprising the steps of:
(a) mixing sodium ferrocyanide, sodium salt and water to obtain a solution A;
(b) mixing soluble divalent manganese salt, soluble salt containing M1 and water to obtain solution B1;
mixing soluble divalent manganese salt, soluble salt containing M2 and water to obtain solution B2;
(c) and sequentially adding the solution B1 and the solution B2 into the solution A, and carrying out coprecipitation reaction to obtain the doped cyano material.
The preparation method of the invention can not only improve the structural stability and the electrical conductivity of the cyano material, thereby having remarkable promoting effect on improving the cycling stability and the rate capability of the material, but also improving the specific capacity of the material; meanwhile, the process flow is relatively simple, the implementation is easy, the adopted equipment is simple, the cost is low, the production time is short, the environmental pollution is less, the production efficiency is high, the energy consumption is low, and the industrial production is easy to realize.
In a preferred embodiment, the method comprises:
step (a): dissolving sodium ferrocyanide and sodium salt in deionized water, and fully stirring to obtain a solution A;
preferably, the sodium salt includes, but is not limited to, one or more of sodium chloride, sodium sulfate, sodium nitrate, sodium acetate, and sodium citrate; sodium chloride is more preferable.
Tests show that in the sodium salt, high sodium salt concentration is beneficial to forming rhombohedral phase cyano compounds, and rhombohedral phase cyano compounds have high sodium content, so that the capacity of the product can be improved. Preferably, the molar ratio of sodium ions in the sodium salt to sodium ferrocyanide is 50-110: 1, and more preferably the molar ratio is 70-90: 1; typically, but not limitatively, the molar ratio may be, for example, 50: 1. 55: 1. 60: 1. 65: 1. 70: 1. 75: 1. 80: 1. 85: 1. 90: 1. 95: 1. 100, and (2) a step of: 1. 105: 1 or 110: 1.
preferably, the concentration of the sodium ferrocyanide in the solution A is 0.05-0.5 mol/L, and preferably 0.1-0.3 mol/L; typically, but not by way of limitation, the concentration of sodium ferrocyanide can be, for example, 0.05mol/L, 0.1mol/L, 0.15mol/L, 0.2mol/L, 0.25mol/L, 0.3mol/L, 0.35mol/L, 0.4mol/L, 0.45mol/L, or 0.5 mol/L.
Step (b 1): dissolving soluble divalent manganese salt and soluble salt containing M1 in deionized water, and fully stirring to obtain solution B1;
preferably, the soluble manganous salt includes, but is not limited to, one or more of manganese chloride, manganese sulfate, manganese nitrate, manganese acetate or hydrates thereof;
preferably, the soluble salt containing M1 includes, but is not limited to, one or more of chloride, sulfate, nitrate, acetate or hydrate thereof.
In the solution B1, divalent manganese ion (Mn)2+) The concentration of (b) is 0.1-1 mol/L, preferably 0.2-0.6 mol/L; typically, but not by way of limitation, Mn2+The concentration of (B) may be, for example, 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L, 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L or 1 mol/L. Proper amount of Mn2+The amount is favorable for promoting the integrity of the crystallization of the cyano material, but the excessive Mn2+Will affect the incorporation of the element M1 and will increase the cost of manufacture.
Preferably, in the solution B1, M1 ions and Mn2+The molar ratio of (A) is 1/20-1/4, preferably 1/20-1/10.
Step (b 2): dissolving soluble divalent manganese salt and soluble salt containing M2 in deionized water, and fully stirring to obtain solution B2;
preferably, the soluble manganous salt includes, but is not limited to, one or more of manganese chloride, manganese sulfate, manganese nitrate, manganese acetate or hydrates thereof;
preferably, the soluble salt containing M2 includes, but is not limited to, one or more of chloride, sulfate, nitrate, acetate or hydrate thereof.
In the solution B2, divalent manganese ion (Mn)2+) The concentration of (b) is 0.1-1 mol/L, preferably 0.2-0.6 mol/L; typically, but not by way of limitation, Mn2+The concentration of (B) may be, for example, 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L, 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L or 1 mol/L. Proper amount of Mn2+The amount is favorable for promoting the integrity of the crystallization of the cyano material, but the excessive Mn2+Will affect the incorporation of the element M2 and will increase the cost of manufacture.
Preferably, in the solution B2, M2 ions and Mn2+The molar ratio of (A) is 1/20-1/4, preferably 1/20-1/10.
Step (c): sequentially dropwise adding the solution B1 and the solution B2 obtained in the step (B1) and the step (B2) into the solution A obtained in the step (a), and carrying out coprecipitation reaction to obtain the doped cyano material with the core-shell structure;
preferably, the ratio of the total volume of the solution B1 and the solution B2 to the volume of the solution A is 0.75-1.25: 1, preferably 0.8-1.2: 1; typically, but not limitatively, the volume ratio may be, for example, 0.75: 1. 0.8: 1. 0.85: 1. 0.9: 1. 0.95: 1. 1.0: 1. 1.05: 1. 1.1: 1. 1.2: 1 or 1.25: 1.
preferably, the volume ratio of the solution B2 to the solution B1 is 2-20: 1, preferably 4 to 18: 1; typically, but not limitatively, the volume ratio may be, for example, 2: 1. 4: 1. 5: 1. 6: 1. 8: 1. 10: 1. 12: 1. 14: 1. 15: 1. 16: 1. 18: 1 or 20: 1.
the coprecipitation reaction is carried out in a normal-pressure open system, preferably, the temperature of the coprecipitation reaction is 40-90 ℃, preferably 70-90 ℃, and further preferably 80-90 ℃. The coprecipitation reaction temperature is too low, the cyano material is not completely crystallized, and the sodium content is low; in addition, low reaction temperature will reduce the solubility of the raw materials, thereby reducing the preparation efficiency; the reaction temperature is too high, and water as a reaction medium is evaporated too fast, so that the formation of a product is influenced.
Preferably, the product after the coprecipitation reaction is further subjected to aging treatment and post-treatment. The aging process can further improve the crystal integrity of the product, and the aging time is 1-10 hours, preferably 2-9 hours; the ageing temperature is the same as the reaction temperature, and the ageing is carried out in an open system.
Preferably, the post-treatment comprises cooling, washing or drying treatment, wherein the vacuum drying temperature is 100-120 ℃, preferably 105-115 ℃, and the drying time is 12-36 hours, preferably 14-28 hours, under the drying condition, the adsorbed water, the zeolite water and the crystal water can be effectively removed, so that the capacity is higher, but the excessively high drying temperature can cause the destruction of the cyano material structure, thereby reducing the capacity.
It should be understood that the contents not described in detail in the description of the above-mentioned doped cyano material and the preparation method are common parameters that can be easily conceived by those skilled in the art, and thus, the detailed description thereof may be omitted.
In a third aspect, there is provided in at least one embodiment the use of one of the above-described doped cyano materials in a sodium ion battery.
In a fourth aspect, there is provided in at least one embodiment a sodium ion battery comprising the doped cyano material described above as a positive electrode material of the sodium ion battery.
The doped cyano material provided by the invention can be used as a positive electrode material to be applied to a sodium ion battery.
It should be understood that the core of the sodium ion battery is to include the doped cyano material of the present invention, and the components and structure of the positive electrode of the sodium ion battery can refer to the prior art except for adopting the doped cyano material as an active material; the cathode, electrolyte, diaphragm and sodium ion battery structure and the preparation method thereof can all refer to the conventional technology.
The doped cyano material prepared by the invention has the advantages of high specific capacity, stable structure, high conductivity, good cycling stability, excellent rate performance and excellent electrochemical performance; the positive electrode material is applied to the sodium ion battery, so that the capacity, the cycle frequency and the rate capability of the battery can be improved, and the service life of the battery is prolonged.
In a fifth aspect, there is provided in at least one embodiment an electronic device, a power tool, an electric vehicle, or a power storage system comprising the sodium-ion battery. An electronic device, an electric tool, an electric vehicle, or a power storage system including the sodium ion battery of the present invention has at least the same advantages as the sodium ion battery described above.
Among them, the electronic device may be an electronic device that performs various functions (e.g., playing music) using a sodium ion battery as a power source for operation. The power tool may be a power tool that uses a sodium ion battery as a driving power source to move a moving part (e.g., a drill bit). The electric vehicle may be an electric vehicle that runs on a sodium ion battery as a drive power source, and may be an automobile (including a hybrid vehicle) equipped with other drive sources in addition to the sodium ion battery. The power storage system may be a power storage system that uses a sodium ion battery as a power storage source. For example, in a home electric power storage system, electric power is stored in a sodium ion battery serving as an electric power storage source, and the electric power stored in the sodium ion battery is consumed as needed to enable use of various devices such as home electronic products.
The present invention will be further described with reference to specific examples, comparative examples and the accompanying drawings.
Example 1
A doped cyano material, wherein the chemical formula of the cyano material is NaxMn1-y-zNiyFez[Fe(CN)6]In the formula, 0<x≤2，0<y≤0.2，0<z is less than or equal to 0.2; the cyano material has a crystal structure of rhombohedral phase.
The preparation method of the doped cyano material comprises the following steps:
dissolving sodium ferrocyanide and sodium chloride in deionized water, and uniformly stirring to obtain a solution A, wherein the concentration of ferricyanide ions in the solution is 0.1mol/L, and the molar weight of the sodium chloride is 80 times that of the sodium ferrocyanide;
dissolving manganous sulfate and nickel sulfate in deionized water to obtain Mn2+Solution B1 with a concentration of 0.2mol/L, in which Ni2+With Mn2+In a molar ratio of 1: 10;
dissolving manganous sulfate and ferrous sulfate in deionized water to obtain Mn2+Solution B2 at a concentration of 0.2mol/L, in which Fe2+With Mn2+In a molar ratio of 1: 10;
dropwise adding the solution B1 into the solution A to obtain a nickel-doped cyano material inner core, then dropwise adding the solution B2 into the solution A, growing an iron-doped cyano material outer shell on the basis of the nickel-doped cyano material inner core, and finally obtaining the doped cyano material with a core-shell structure, wherein the volume ratio of the total volume of the solution B1 to the solution B2 to the volume of the solution A is 1: 1, the volume ratio of the solution B2 to the solution B1 is 4: 1. and during dripping, keeping the temperature of the solution at 85 ℃, aging for 5 hours after dripping is finished, and cooling, washing and drying to obtain the doped cyano material with the core-shell structure.
Fig. 1 is a schematic structural diagram of a doped cyano material prepared in embodiment 1 of the present invention, and as shown in fig. 1, the doped cyano material of the present invention has a core-shell structure, wherein a weight ratio of a core to a shell is 1: 4.
FIG. 2 is an X-ray diffraction pattern of a doped cyano material prepared in example 1 of the present invention; as shown in FIG. 2, XRD detection shows that the product has rhombohedral phase structure.
The doped cyano material prepared in the embodiment is used as a positive electrode, metal sodium is used as a negative electrode, glass fiber is used as a diaphragm, and NaClO4The Ethylene Carbonate (EC)/diethyl carbonate (DEC) solution is used as an electrolyte to assemble a battery, a charge-discharge test is carried out (the potential range is 2-4V, 1C corresponds to 150mA/g), the specific capacity is 145mAh/g at 0.1C (see figure 3), and the capacity retention rate is 90% after 100 times of charge-discharge at 1C.
Comparative example 1
A cyano material, which differs from example 1 in that the cyano material is not doped with the elements M1 and M2.
The preparation process of the cyano material of this comparative example is similar to that of example 1, except that neither solution B1 nor solution B2 has ions of doping elements, i.e. is not doped, and the other conditions are the same.
The specific capacity of the product obtained in the comparative example 1 at 0.1C is 138mAh/g, and the specific capacity retention rate is 78% after 1C charging and discharging at 100 times.
Comparative example 2
A doped cyano material, which is different from the embodiment 1 in that the cyano material is not doped with the element M2.
The preparation process of the cyano material of this comparative example is similar to that of example 1, except that the solution B1 contains the dopant ion Ni2+While the solution B2 does not contain doping ion Fe2+I.e. the product shell is not subjected to Fe2+Doping, and other conditions are the same.
The specific capacity of the product obtained in the comparative example 2 at 0.1C is 137mAh/g, and the specific capacity retention rate is 77% after 1C charging and discharging at 100 times.
Comparative example 3
A doped cyano material, which is different from the embodiment 1 in that the cyano material is not doped with the element M1.
The preparation process of the cyano material of this comparative example is similar to that of example 1, except that solution B1 does not contain Ni as a dopant ion2+The solution B2 contains doping ions Fe2+I.e. the product core is not subjected to Ni2+Doping, and other conditions are the same.
The specific capacity of the product obtained in the comparative example 3 at 0.1C is 139mAh/g, and the specific capacity retention rate of 1C charging and discharging at 100 times is 76%.
Comparative example 4
Different from the embodiment 1, the doped cyano material has the doping elements M1 of Fe and M2 of Ni, namely M1 and M2 are exchanged.
The preparation process of the cyano material of this comparative example is similar to that of example 1, except that the doping ions in solution B1 and solution B2 are exchanged, i.e. Fe is applied to the core in the product2+Doping, shell portion Ni2+Doping, and other conditions are the same.
The specific capacity of the product obtained in the comparative example 4 at 0.1C is 132mAh/g, and the specific capacity retention rate of the product after 1C charging and discharging at 100 times is 72%.
Example 2
A doped cyano material, wherein the chemical formula of the cyano material is NaxMn1-y-zCuyCoz[Fe(CN)6]In the formula, 0<x≤2，0<y≤0.2，0<z is less than or equal to 0.2; the cyano material has a crystal structure of rhombohedral phase.
The preparation method of the doped cyano material comprises the following steps:
dissolving sodium ferrocyanide and sodium chloride in deionized water, and uniformly stirring to obtain a solution A, wherein the concentration of ferricyanide ions in the solution is 0.2mol/L, and the molar weight of the sodium chloride is 90 times that of the sodium ferrocyanide;
dissolving manganous chloride and copper chloride in deionized water to obtain Mn2+Solution B1 with a concentration of 0.4mol/L, in which Cu2+With Mn2+In a molar ratio of 1: 20;
dissolving manganous chloride and cobaltous chloride in deionized water to obtain Mn2+Solution B2 with a concentration of 0.4mol/L, wherein Co2+With Mn2+In a molar ratio of 1: 20;
firstly, dropwise adding the solution B1 into the solution A to obtain a copper-doped cyano material inner core, then dropwise adding the solution B2 into the solution A, growing a cobalt-doped cyano material outer shell on the basis of the copper-doped cyano material inner core, and finally obtaining the doped cyano material with a core-shell structure, wherein the volume ratio of the total volume of the solution B1 to the solution B2 to the volume of the solution A is 1: 1, the volume ratio of the solution B2 to the solution B1 is 6: 1. and during dripping, keeping the temperature of the solution at 80 ℃, aging for 5 hours after dripping is finished, and cooling, washing and drying to obtain the doped cyano material with the core-shell structure.
The doped cyano material is of a core-shell structure, wherein the weight ratio of a core to a shell is 1: 6. XRD detection shows that the product has rhombohedral phase structure.
The doped cyano material prepared in the embodiment is used as a positive electrode, metal sodium is used as a negative electrode, glass fiber is used as a diaphragm, and NaClO4The Ethylene Carbonate (EC)/diethyl carbonate (DEC) solution is used as an electrolyte to assemble a battery, and a charge-discharge test is carried out (the potential range is 2-4V, 1C corresponds to 150mA/g), the specific capacity is 142mAh/g at 0.1C, and the capacity retention rate is 91% after 100 times of charge-discharge at 1C.
Example 3
A doped cyano material, wherein the chemical formula of the cyano material is NaxMn1-y-zZnyCoz[Fe(CN)6]In the formula, 0<x≤2，0<y≤0.2，0<z is less than or equal to 0.2; the cyano material has a crystal structure of rhombohedral phase.
The preparation method of the doped cyano material comprises the following steps:
dissolving sodium ferrocyanide and sodium chloride in deionized water, and uniformly stirring to obtain a solution A, wherein the concentration of ferricyanide ions in the solution is 0.3mol/L, and the molar weight of the sodium chloride is 70 times that of the sodium ferrocyanide;
dissolving manganous nitrate and zinc nitrate in deionized water to obtain Mn2+Solution B1 with a concentration of 0.6mol/L, in which Zn2+With Mn2+In a molar ratio of 1: 15;
dissolving manganous nitrate and cobaltous nitrate in deionized water to obtain Mn2+Solution B2 with a concentration of 0.6mol/L, wherein Co2+With Mn2+In a molar ratio of 1: 15;
dropwise adding the solution B1 into the solution A to obtain a zinc-doped cyano material inner core, then dropwise adding the solution B2 into the solution A, growing a cobalt-doped cyano material outer shell on the basis of the zinc-doped cyano material inner core, and finally obtaining the doped cyano material with a core-shell structure, wherein the volume ratio of the total volume of the solution B1 to the solution B2 to the volume of the solution A is 1: 1, the volume ratio of the solution B2 to the solution B1 is 9: 1. and during dripping, keeping the temperature of the solution at 90 ℃, aging for 5 hours after dripping is finished, and cooling, washing and drying to obtain the doped cyano material with the core-shell structure.
The doped cyano material is of a core-shell structure, wherein the weight ratio of a core to a shell is 1: 9. XRD detection shows that the product has rhombohedral phase structure.
The doped cyano material prepared in the embodiment is used as a positive electrode, metal sodium is used as a negative electrode, glass fiber is used as a diaphragm, and NaClO4The Ethylene Carbonate (EC)/diethyl carbonate (DEC) solution is used as an electrolyte to assemble a battery, and a charge-discharge test is carried out (the potential range is 2-4V, 1C corresponds to 150mA/g), the specific capacity is 140mAh/g at 0.1C, and the capacity retention rate is 90% after 100 times of charge-discharge at 1C.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (35)
1. The doped cyano material is characterized in that the chemical formula of the cyano material is NaxMn1-y-zM1yM2z[Fe(CN)6]In the formula, 0<x≤2，0<y≤0.2，0<z is less than or equal to 0.2; m1 and M2 are doping elements; the cyano material has a crystal structure of rhombohedral phase;
the cyano-group material is of a core-shell structure, the inner core is the cyano-group material doped with M1, and the outer shell is the cyano-group material doped with M2;
the doping element M1 comprises at least one of nickel, copper, zinc or magnesium, and the doping element M2 comprises iron and/or cobalt;
the weight percentage of the inner core is 5-25%, and the weight percentage of the outer shell is 75-95%.
2. The doped cyano material of claim 1, wherein the doping element M1 is a non-electrochemically active metal element; the doping element M2 is an electrochemical active metal element;
and/or doping elements M1 and M2 are doped on the Mn side of the cyano-group material.
3. The doped cyano material of claim 1, wherein the weight percentage of the core is 10% to 20%.
4. The doped cyano material of claim 1, wherein the shell comprises 80 to 90 weight percent.
5. The doped cyano material of claim 1, wherein the molar ratio of the M1 ion to the Mn ion is 1/20-1/4.
6. The doped cyano material of claim 5, wherein the molar ratio of the M1 ion to the Mn ion is 1/20-1/10.
7. The doped cyano material of claim 1, wherein the molar ratio of the M2 ion to the Mn ion is 1/20-1/4.
8. The doped cyano material of claim 7, wherein the molar ratio of the M2 ion to the Mn ion is 1/20-1/10.
9. The doped cyano material according to any one of claims 1 to 8, wherein the source compound of the doping element M1 is one or more of chloride, sulfate, nitrate, acetate or hydrate of the doping element M1;
and/or the source compound of the doping element M2 is one or more of chloride, sulfate, nitrate, acetate or hydrate of the doping element M2.
10. The doped cyano material of claim 9, wherein the doped cyano material is a nano-scale doped cyano material, and the particle size is 400-600 nm.
11. The method for preparing the doped cyano material according to any one of claims 1 to 10, comprising the following steps:
(a) mixing sodium ferrocyanide, sodium salt and water to obtain a solution A;
(b) mixing soluble divalent manganese salt, soluble salt containing M1 and water to obtain solution B1;
mixing soluble divalent manganese salt, soluble salt containing M2 and water to obtain solution B2;
(c) and sequentially adding the solution B1 and the solution B2 into the solution A, and carrying out coprecipitation reaction to obtain the doped cyano material.
12. The method for preparing the doped cyano material according to claim 11, wherein in the step (a), the sodium salt is selected from one or more of sodium chloride, sodium sulfate, sodium nitrate, sodium acetate and sodium citrate;
and/or, in the step (b), the soluble divalent manganese salt is selected from one or more of manganese chloride, manganese sulfate, manganese nitrate, manganese acetate or hydrate thereof;
and/or, in the step (b), the soluble salt containing M1 is selected from one or more of chloride, sulfate, nitrate, acetate or hydrate thereof;
and/or, in the step (b), the soluble salt containing M2 is selected from one or more of chloride, sulfate, nitrate, acetate or hydrate thereof.
13. The method for preparing the doped cyano material according to claim 11, wherein the concentration of the sodium ferrocyanide in the solution A is 0.05-0.5 mol/L.
14. The method for preparing the doped cyano material according to claim 13, wherein the concentration of the sodium ferrocyanide in the solution A is 0.1-0.3 mol/L.
15. The preparation method of the doped cyano material according to claim 11, wherein in the solution a, the molar ratio of sodium ions in the sodium salt to sodium ferrocyanide is 50-110: 1.
16. the preparation method of the doped cyano material according to claim 15, wherein in the solution a, the molar ratio of sodium ions in the sodium salt to sodium ferrocyanide is 70-90: 1.
17. the method for preparing the doped cyano material according to claim 11, wherein the concentration of the divalent manganese ions in the solution B1 is 0.1-1 mol/L.
18. The preparation method of the doped cyano material as claimed in claim 17, wherein the concentration of the divalent manganese ions in the solution B1 is 0.2-0.6 mol/L.
19. The preparation method of the doped cyano material as claimed in claim 11, wherein the molar ratio of M1 ions to divalent manganese ions in the solution B1 is 1/20-1/4.
20. The method for preparing the doped cyano material of claim 19, wherein the molar ratio of M1 ions to divalent manganese ions in the solution B1 is 1/20-1/10.
21. The method for preparing the doped cyano material according to claim 11, wherein the concentration of the divalent manganese ions in the solution B2 is 0.1-1 mol/L.
22. The method for preparing the doped cyano material according to claim 21, wherein the concentration of the divalent manganese ions in the solution B2 is 0.2-0.6 mol/L.
23. The preparation method of the doped cyano material as claimed in claim 11, wherein the molar ratio of M2 ions to divalent manganese ions in the solution B2 is 1/20-1/4.
24. The method for preparing the doped cyano material of claim 23, wherein in the solution B2, the molar ratio of M2 ions to divalent manganese ions is 1/20-1/10.
25. The method for preparing the doped cyano material according to any one of claims 11 to 24, wherein in the step (c), the coprecipitation reaction is performed in an open system at normal pressure and at a temperature of 40 to 90 ℃.
26. The method for preparing the doped cyano material according to claim 25, wherein the temperature is 70-90 ℃.
27. The method for preparing a doped cyano material according to claim 25, further comprising aging and post-treating steps after the completion of the co-precipitation reaction.
28. The method for preparing a doped cyano material according to claim 27, wherein the temperature of the aging process is 40 to 90 ℃.
29. The method for preparing a doped cyano material according to claim 28, wherein the temperature of the aging process is 70 to 90 ℃.
30. The method for preparing a doped cyano material according to claim 27, wherein the aging time is 1 to 10 hours.
31. The method for preparing a doped cyano material according to claim 30, wherein the aging time is 2 to 9 hours.
32. The method for preparing the doped cyano material according to claim 27, wherein the post-treatment comprises cooling, washing and drying treatments.
33. Use of the doped cyano material of any one of claims 1 to 10 in a sodium ion battery.
34. A sodium ion battery comprising the doped cyano material according to any one of claims 1 to 10 as a positive electrode material of the sodium ion battery.
35. An electronic device, power tool, electric vehicle, or power storage system comprising the sodium-ion battery of claim 34.
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| CN109599530A (en) * | 2018-12-11 | 2019-04-09 | 银隆新能源股份有限公司 | A kind of cell positive pole piece preparation method and battery positive pole piece |
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| CN110311115B (en) * | 2019-07-04 | 2022-06-03 | 上海汉行科技有限公司 | Surface-modified cyano-frame material and preparation method and application thereof |
| CN111600011A (en) * | 2020-04-24 | 2020-08-28 | 国网浙江省电力有限公司电力科学研究院 | Doped prussian blue material and preparation method and application thereof |
| CN114551805B (en) * | 2022-02-25 | 2024-03-12 | 厦门市美耐威新能源科技有限公司 | Gradient graded Prussian blue sodium ion positive electrode material and preparation method thereof |
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