CN113860330A - Preparation method of Prussian blue secondary battery cathode material with low-defect crystal structure - Google Patents
Preparation method of Prussian blue secondary battery cathode material with low-defect crystal structure Download PDFInfo
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- 229960003351 prussian blue Drugs 0.000 title claims abstract description 114
- 239000013225 prussian blue Substances 0.000 title claims abstract description 114
- 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 title claims abstract description 113
- 239000010406 cathode material Substances 0.000 title claims abstract description 57
- 239000013078 crystal Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 21
- 239000007774 positive electrode material Substances 0.000 claims abstract description 19
- 239000002608 ionic liquid Substances 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000012265 solid product Substances 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 12
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 238000004140 cleaning Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000011259 mixed solution Substances 0.000 claims description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 17
- 239000011734 sodium Substances 0.000 claims description 14
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 8
- 239000000264 sodium ferrocyanide Substances 0.000 claims description 7
- GTSHREYGKSITGK-UHFFFAOYSA-N sodium ferrocyanide Chemical group [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 7
- 235000012247 sodium ferrocyanide Nutrition 0.000 claims description 7
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 5
- 230000002431 foraging effect Effects 0.000 claims description 3
- JIWPXWWZICHKEO-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;dihydrogen phosphate Chemical compound OP(O)([O-])=O.CCCC[N+]=1C=CN(C)C=1 JIWPXWWZICHKEO-UHFFFAOYSA-M 0.000 claims description 2
- 230000032683 aging Effects 0.000 abstract description 9
- 238000004146 energy storage Methods 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
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- 239000010405 anode material Substances 0.000 description 31
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- 230000014759 maintenance of location Effects 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 238000009616 inductively coupled plasma Methods 0.000 description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
- 238000011056 performance test Methods 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
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- 230000008014 freezing Effects 0.000 description 5
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- 229910001416 lithium ion Inorganic materials 0.000 description 5
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- 238000001878 scanning electron micrograph Methods 0.000 description 5
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
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- 238000010277 constant-current charging Methods 0.000 description 2
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- 229910021389 graphene Inorganic materials 0.000 description 2
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- 230000005012 migration Effects 0.000 description 2
- 239000011268 mixed slurry Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- ZRGWIXMPMASFPS-UHFFFAOYSA-N 1-butyl-3-methyl-1,2-dihydroimidazol-1-ium;dihydrogen phosphate Chemical compound OP(O)([O-])=O.CCCC[NH+]1CN(C)C=C1 ZRGWIXMPMASFPS-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
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- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- UETZVSHORCDDTH-UHFFFAOYSA-N iron(2+);hexacyanide Chemical compound [Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] UETZVSHORCDDTH-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C3/00—Cyanogen; Compounds thereof
- C01C3/08—Simple or complex cyanides of metals
- C01C3/12—Simple or complex iron cyanides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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
Abstract
The invention relates to a preparation method of a Prussian blue secondary battery cathode material with a low-defect crystal structure, belonging to the technical field of secondary battery cathode material preparation. Adding the ionic liquid, the Prussian blue precursor and hydrochloric acid into water, uniformly mixing, reacting at 70-90 ℃ for 15-30 h, aging at 5-40 ℃ for 24-72 h, performing solid-liquid separation, cleaning and drying collected solid products to obtain the Prussian blue cathode material with the low-defect crystal structure. The method has the advantages of simple and easily-obtained raw materials, simple operation of technological process, good experimental reproducibility and easy realization of industrial production, and the prepared Prussian blue positive electrode material shows good cycle performance and rate capability when being used as the positive electrode material of an organic sodium ion battery and the positive electrode material of a water system zinc ion battery, thereby providing bright prospect for applying a low-cost and high-safety secondary battery to the field of large-scale energy storage.
Description
Technical Field
The invention relates to a preparation method of a Prussian blue material with a low-defect crystal structure for a secondary battery anode material, belonging to the technical field of preparation of secondary battery anode materials.
Background
The traditional fossil energy has the problem of limited resources and causes pollution to the environment in use, so that the use of clean renewable energy becomes a trend. However, renewable energy sources such as wind energy and solar energy have different stability and continuity problems, and an energy storage device is required to store the energy generated by the renewable energy sources and effectively utilize the energy. The lithium ion battery has the advantages of high capacity, high voltage, long service life and the like, but because the lithium storage capacity on the earth is limited, the lithium storage capacity is not uniform, the exploitation difficulty is high, the price of raw materials of the lithium ion battery is high, and the price fluctuation is large, the development of a new secondary battery for realizing large-scale energy storage is very necessary. The sodium element is positioned below the lithium element in the I main group in the chemical element periodic table, and the sodium element and the lithium element have similar properties, so that the sodium-ion battery is also similar to a lithium-ion battery and can also be used as an energy storage carrier. From the aspect of resource reserves, the sodium ion battery has obvious advantages that the mass abundance of sodium element in the earth crust is 2.64%, the mass abundance of lithium element is only 0.006%, and a large amount of sodium also exists in the ocean, so that the production cost of the sodium ion battery is far lower than that of the lithium ion battery, and because of the characteristics, the sodium ion battery is considered as the best choice for replacing the lithium ion battery in the aspect of large-scale energy storage. Meanwhile, the aqueous battery is not only low in cost but also relatively environmentally friendly as compared to the organic system battery. More importantly, the safety is extremely high, the fuel can not be burnt even if the fuel is punctured, and the fuel has a very bright application prospect in the future energy storage field.
Prussian Blue (PB) is a hexacyanoferrate, has an open framework structure, rich redox active sites and strong structural stability, is one of few matrix materials capable of accommodating larger alkaline cations (such as Na and Zn ions) due to large ion channels and lattice gaps, and can easily perform reversible ion intercalation and deintercalation reactions. Because of the excellence in such structural characteristics, PB is widely used in new low-cost positive electrode materials for organic sodium ion batteries and aqueous zinc ion batteries. But defects and crystal water in the prussian blue crystal structure seriously impair electrochemical properties such as capacity, cycle stability, rate capability and the like of PB. The PB Materials prepared in the early studies of S.H.Yu et al, both reversible specific capacity and cycling stability were unsatisfactory (Yu S H, Shokohimemehr M, Hyeon T, et al, Iron Hexacynanoperrate Nanoparticles as refractory Materials for Lithium and Sodium Rechargeable Batteries [ J ]. Journal of ECS Electrochem Letters,2013,2(4): A39-A41). Z.f. Ma et al, the graphene oxide-Prussian blue composite material prepared by using the heat treatment method reduces the crystal water content in PB and obtains PB with good cycle stability, but the graphene oxide used in this method is expensive in cost and complicated in preparation process, and cannot be applied to the commercial demand of mass production (Yang D, Xu J, Ma Z F, prassian blue with a chemically associated water as a superior catalyst for the solvent-ion bases [ J ]. Journal of Chemical Communications,2015,51(38):8181 and 8184).
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of a Prussian blue anode material with a low-defect crystal structure, which is mainly characterized in that a specific type of ionic liquid with a specific concentration is added to increase the solution viscosity of a reaction system, induce the migration of water, increase the stability of the crystal structure and promote the generation of a dominant crystal face, and the defect of the crystal structure of the Prussian blue anode material is reduced under the combined action of hydrochloric acid, so that the electrochemical performance of the anode material can be improved; the Prussian blue anode material prepared by the method can be matched with aqueous electrolyte to construct an aqueous zinc ion battery, and can also be matched with organic electrolyte to construct an organic sodium ion battery, so that the cycle performance of the battery is enhanced, and the cost of the battery is further reduced.
The purpose of the invention is realized by the following technical scheme.
A preparation method of a Prussian blue cathode material with a low-defect crystal structure comprises the following steps,
adding the ionic liquid, the Prussian blue precursor and hydrochloric acid into water, and uniformly mixing to obtain a mixed solution; the mixed solution is transferred to 70-90 ℃ to react for 15-30 h, then is placed at 5-40 ℃ to be aged for 24-72 h, then is subjected to solid-liquid separation, and the collected solid product is cleaned and dried to obtain the Prussian blue cathode material with the low-defect crystal structure.
In the mixed solution, the concentration of the ionic liquid is 1-3 g/L, the mass ratio of the Prussian blue precursor to the ionic liquid is 4-12: 1, and the concentration of hydrochloric acid is 0.05-0.2 mol/L.
The prussian blue precursor is an iron-based cyanide, preferably an iron-based sodium-containing cyanide, and more preferably sodium ferrocyanide.
The ionic liquid is 1-butyl-3-methylimidazolium oxide or 1-butyl-3-methylimidazolium dihydrogen phosphate.
Further, completely dissolving the ionic liquid in water, adding and dissolving a Prussian blue precursor, and finally adding hydrochloric acid and uniformly mixing to obtain a mixed solution.
The invention discloses a positive electrode material of an organic sodium-ion battery, which is a Prussian blue positive electrode material with a low-defect crystal structure prepared by the method.
The invention discloses a cathode material of a water system zinc ion battery, which is a Prussian blue cathode material with a low-defect crystal structure prepared by the method.
Has the advantages that:
(1) the invention provides a novel Prussian blue anode material synthesis method, which is characterized in that an iron-based cyanide Prussian blue precursor, ionic liquid with specific species and concentration and hydrochloric acid with specific concentration are selected for carrying out thermal reaction, and the temperature and time of the heating reaction are strictly regulated and controlled, so that the Prussian blue anode material with a low-defect crystal structure is obtained, the raw materials are simple and easy to obtain, the preparation process is simple to operate, the experimental reproducibility is good, and the industrial production is easy to realize.
(2) The ionic liquid used in the preparation method plays roles in increasing the solution viscosity, inducing water migration, increasing the stability of the crystal structure and promoting the generation of a dominant crystal face in the preparation process, and the defect of the crystal structure of the Prussian blue cathode material is reduced under the combined action of the ionic liquid and hydrochloric acid; and the loss of the ionic liquid is small, the recycling of the mother liquid can be realized, and the effects of saving materials and reducing cost are achieved.
(3) The Prussian blue positive electrode material prepared by the method has high specific capacity, high coulombic efficiency and high capacity retention rate, shows good cycle performance and rate capability when being used as a positive electrode material of an organic sodium ion battery and a positive electrode material of a water-system zinc ion battery, and provides bright prospect for applying a low-cost and high-safety secondary battery to the field of large-scale energy storage.
Drawings
Fig. 1 is an X-ray diffraction (XRD) pattern of the prussian blue cathode material prepared in example 1.
Fig. 2 is a Scanning Electron Microscope (SEM) image of the prussian blue cathode material prepared in example 1.
Fig. 3 is a cycle life chart of an organic CR2032 coin sodium ion battery assembled using the prussian blue positive electrode material prepared in example 1.
Fig. 4 is a charge/discharge graph of the organic CR2032 coin sodium ion battery assembled using the prussian blue positive electrode material prepared in example 1 at cycle 1, 5, 10 and 50.
Fig. 5 is a rate performance graph of an organic CR2032 coin sodium ion battery assembled using the prussian blue positive electrode material prepared in example 1.
Fig. 6 is a cycle life diagram of an aqueous CR2032 coin zinc-ion battery assembled using the prussian blue positive electrode material prepared in example 1.
Detailed Description
The present invention is further illustrated by the following detailed description, wherein the processes are conventional unless otherwise specified, and the starting materials are commercially available from a public perspective unless otherwise specified.
In the following examples:
XRD test: phase analysis was performed on the prussian blue positive electrode material prepared in the examples using Rigaku-D/max-2550pc type X-ray powder diffractometer from hitachi, japan, using Cu-k as a radiation source, a wavelength of 1.5406, a Ni filter, a tube flow of 40mA, a tube pressure of 40KV, a scanning range of 10 ° to 90 °, a scanning speed of 8 °/min, and a step size of 0.02 °; phase identification and crystal structure information were analyzed by the JADE6.0 software;
and (4) SEM test: observing the micro-morphology of the Prussian blue cathode material prepared in the example by adopting a scanning electron microscopy tester of model S-4800 produced by HITACHI company with the acceleration voltage of 20 KV;
assembling an organic CR2032 button sodium-ion battery: mixing the Prussian blue positive electrode material prepared in the embodiment, acetylene black and polyvinylidene fluoride (PVDF) according to the mass ratio of 7:2:1, coating the uniformly mixed slurry on an aluminum foil, drying and shearing into a wafer as a positive electrode; the metal sodium sheet is used as a negative electrode, and Whatman glass fiber (GF/D) is used as a diaphragm; organic electrolyteFrom NaClO4EC (ethylene carbonate), DEC (diethyl carbonate) and FEC (fluoroethylene carbonate), NaClO4The concentration is 1.0mol/L, the volume ratio of EC to DEC is 1:1, and the mass fraction of FEC in the electrolyte is 5%; assembling a sodium ion battery in an argon glove box;
assembling a water system CR2032 type button zinc ion battery: mixing the Prussian blue positive electrode material prepared in the embodiment, acetylene black and polyvinylidene fluoride (PVDF) according to the mass ratio of 7:2:1, coating the uniformly mixed slurry on a titanium foil, drying and cutting into a wafer to be used as a positive electrode; the metal zinc sheet is used as a negative electrode, and Whatman glass fiber (GF/D) is used as a diaphragm; the aqueous electrolyte is ZnCl with the concentration of 31mol/L2An aqueous solution; then assembling the zinc ion battery in an indoor environment;
and (3) electrochemical performance testing: and testing the assembled sodium ion battery or zinc ion battery by adopting a Land battery tester produced by Jinnuo electronics Limited company in Wuhan, wherein the testing voltage is 2.0-4.2V.
Example 1
Adding 0.5g of 1-butyl-3-methyl imidazolium oxide into 200mL of deionized water, stirring for 20min, adding 2.42g of sodium ferrocyanide, stirring for 20min, adding 1.92g of a 37 wt% hydrochloric acid aqueous solution, and stirring for 3min to obtain a light green mixed solution; putting the light green mixed solution into a glass reaction kettle, putting the glass reaction kettle into a drying oven, reacting at 80 ℃ for 24 hours, then putting the glass reaction kettle at 25 ℃ for aging for 24 hours, then sequentially using deionized water and ethanol to centrifugally clean the mixture obtained after aging, collecting mother liquor for recycling, putting the solid product obtained after cleaning into a freezer at-15 ℃ for freezing for 12 hours until all residual liquid is frozen and frozen, and then putting the frozen solid product into a freezer dryer at-50 ℃ for drying for 48 hours to obtain the Prussian blue cathode material with the low-defect crystal structure.
The prussian blue cathode material prepared in this example was characterized, and the results are as follows:
the XRD spectrum obtained by the test in figure 1 is in accordance with the standard card JCPDS52-1907, which shows that the prepared product is a pure-phase cubic Prussian blue cathode material; the sharp peak shape shows that the prepared Prussian blue cathode material has high crystallinity.
As can be seen from the SEM image of fig. 2, the prussian blue positive electrode material prepared was cubic in shape and had a smooth surface.
The prepared Prussian blue anode material is tested by an inductively coupled plasma emission spectrometer (ICP), the number of defects in each molecule of the Prussian blue anode material is 0.07, the Prussian blue anode material belongs to a low-defect crystal structure, and the test results are shown in Table 1 in detail.
TABLE 1
| Example 1 | Na％wt | Fe％wt | C％wt | N％wt | Number of defects per molecule |
| Prussian blue cathode material | 13.36 | 32.14 | 16.75 | 19.54 | 0.07 |
The prepared Prussian blue cathode material is assembled into an organic system CR2032 type button sodium ion battery, and a constant current charge and discharge performance test is carried out under the current density of 100mA/g, and the result is detailed as shown in fig. 3 and fig. 4. As can be seen from the data in fig. 3, after 500 continuous cycles, the coulombic efficiency per week is maintained at 99% or more, the capacity retention rate of the battery after 200 cycles is still 90% or more, and the battery still has 75.4% capacity retention rate after 500 cycles, wherein the specific capacity is 82.9 mAh/g; as can be seen from the data in fig. 4, the discharge specific capacities at week 1, week 5, week 10 and week 50 did not substantially decay, and the initial specific capacity reached 110 mAh/g. Therefore, the battery capacity decays slowly and has good cycle stability.
The prepared Prussian blue cathode material is assembled into an organic system CR2032 type button sodium ion battery, constant current charging and discharging performance tests are sequentially carried out at different current densities of 50mA/g, 100mA/g, 200mA/g, 400mA/g, 800mA/g and 1600mA/g, the constant current charging and discharging performance tests are carried out at each current density for 20 weeks, and the results are detailed in figure 5. As can be seen from the data in FIG. 5, the specific capacity is still above 80mAh/g at a high rate current of 1600 mA/g. Therefore, the battery has good rate performance.
The prepared Prussian blue cathode material is assembled into a water system CR2032 type button zinc ion battery, and a constant current charge and discharge performance test is carried out under the current density of 50mA/g, and the result is detailed as shown in figure 6. According to the data in fig. 6, the specific capacity after continuous cycling for 100 weeks is 55.7mAh/g, the capacity retention rate is 66.5%, and the cycle performance is good.
Example 2
Adding 0.25g of 1-butyl-3-methyl imidazolium oxide into 200mL of deionized water, stirring for 20min, adding 2.42g of sodium ferrocyanide, stirring for 20min, adding 2.08g of a 37 wt% hydrochloric acid aqueous solution, and stirring for 3min to obtain a light green mixed solution; putting the light green mixed solution into a glass reaction kettle, putting the glass reaction kettle into a drying oven, reacting at 80 ℃ for 24 hours, then putting the glass reaction kettle at 25 ℃ for aging for 24 hours, then sequentially using deionized water and ethanol to centrifugally clean the mixture obtained after aging, collecting mother liquor for recycling, putting the solid product obtained after cleaning into a freezer at-15 ℃ for freezing for 12 hours until all residual liquid is frozen and frozen, and then putting the frozen solid product into a freezer dryer at-50 ℃ for drying for 48 hours to obtain the Prussian blue cathode material with the low-defect crystal structure.
The prussian blue cathode material prepared in this example was characterized, and the results are as follows:
the XRD spectrum of the Prussian blue anode material prepared in the embodiment accords with the standard card JCPDS52-1907, which indicates that the prepared product is a pure-phase cubic Prussian blue anode material; the sharp peak shape shows that the prepared Prussian blue cathode material has high crystallinity.
According to the characterization result of the SEM image, the prepared prussian blue cathode material was cubic and had a smooth surface.
The prepared Prussian blue anode material is tested by an inductively coupled plasma emission spectrometer (ICP), the number of defects in each molecule of the Prussian blue anode material is 0.09, the Prussian blue anode material belongs to a low-defect crystal structure, and the test results are shown in Table 2 in detail.
TABLE 2
| Example 2 | Na％wt | Fe％wt | C％wt | N％wt | Number of defects per molecule |
| Prussian blue cathode material | 12.78 | 30.36 | 16.22 | 18.92 | 0.09 |
The prepared Prussian blue cathode material is assembled into an organic system CR2032 type button sodium ion battery, constant current charge and discharge performance tests are carried out under the current density of 100mA/g, the continuous cycle lasts for 500 weeks, the coulombic efficiency per week is maintained to be more than 99%, the capacity retention rate of the battery after 200 weeks is still more than 90%, the capacity retention rate after 500 weeks is still 75.6%, and the specific capacity is 80.9mAh/g at the moment, which shows that the battery has slow capacity attenuation and good cycle stability.
Example 3
Adding 0.5g of 1-butyl-3-methyl imidazolium oxide into 200mL of deionized water, stirring for 20min, adding 2.42g of sodium ferrocyanide, stirring for 20min, adding 1.92g of a 37 wt% hydrochloric acid aqueous solution, and stirring for 3min to obtain a light green mixed solution; putting the light green mixed solution into a glass reaction kettle, putting the glass reaction kettle into a drying oven, reacting for 20 hours at 90 ℃, then putting the glass reaction kettle into the drying oven, aging for 36 hours at 15 ℃, then sequentially using deionized water and ethanol to centrifugally clean the mixture obtained after aging, collecting mother liquor for recycling, putting the solid product obtained after cleaning into a freezer at-15 ℃ for freezing for 12 hours until all residual liquid is frozen and frozen, and then putting the frozen solid product into a freezer dryer at-50 ℃ for drying for 48 hours to obtain the Prussian blue cathode material with the low-defect crystal structure.
The prussian blue cathode material prepared in this example was characterized, and the results are as follows:
the XRD spectrum of the Prussian blue anode material prepared in the embodiment accords with the standard card JCPDS52-1907, which indicates that the prepared product is a pure-phase cubic Prussian blue anode material; the sharp peak shape shows that the prepared Prussian blue cathode material has high crystallinity.
According to the characterization result of the SEM image, the prepared prussian blue cathode material was cubic and had a smooth surface.
The prepared Prussian blue anode material is tested by an inductively coupled plasma emission spectrometer (ICP), the number of defects in each molecule of the Prussian blue anode material is 0.07, the Prussian blue anode material belongs to a low-defect crystal structure, and the test results are shown in Table 3 in detail.
TABLE 3
| Example 3 | Na％wt | Fe％wt | C％wt | N％wt | Number of defects per molecule |
| Prussian blue cathode material | 13.12 | 31.88 | 16.55 | 19.31 | 0.07 |
The prepared Prussian blue cathode material is assembled into a CR2032 type button battery, constant-current charge and discharge performance tests are carried out under the current density of 100mA/g, the continuous circulation lasts for 500 weeks, the coulomb efficiency per week is maintained to be more than 99%, the capacity retention rate of the battery after 200 weeks is still more than 90%, the battery still has the capacity retention rate of 74.2% after 500 weeks, and the specific capacity is 80.5mAh/g at the moment, which shows that the battery has slow capacity attenuation and good circulation stability.
Example 4
Adding 0.4g of 1-butyl-3-methyl imidazolium oxide into 200mL of deionized water, stirring for 20min, adding 2.42g of sodium ferrocyanide, stirring for 20min, adding 1.76g of a 37 wt% hydrochloric acid aqueous solution, and stirring for 3min to obtain a light green mixed solution; putting the light green mixed solution into a glass reaction kettle, putting the glass reaction kettle into a drying oven, reacting for 26h at 75 ℃, then putting the glass reaction kettle into the drying oven, aging for 24h at 25 ℃, then sequentially using deionized water and ethanol to centrifugally clean the mixture obtained after aging, collecting mother liquor for recycling, putting the solid product obtained after cleaning into a freezer at-15 ℃ for freezing for 12h until all residual liquid is frozen and frozen, and then putting the frozen solid product into a freezer dryer at-50 ℃ for drying for 48h to obtain the Prussian blue cathode material with the low-defect crystal structure.
The prussian blue cathode material prepared in this example was characterized, and the results are as follows:
the XRD spectrum of the Prussian blue anode material prepared in the embodiment accords with the standard card JCPDS52-1907, which indicates that the prepared product is a pure-phase cubic Prussian blue anode material; the sharp peak shape shows that the prepared Prussian blue cathode material has high crystallinity.
According to the characterization result of the SEM image, the prepared prussian blue cathode material was cubic and had a smooth surface.
The prepared Prussian blue anode material is tested by an inductively coupled plasma emission spectrometer (ICP), the number of defects in each molecule of the Prussian blue anode material is 0.08, the Prussian blue anode material belongs to a low-defect crystal structure, and the test results are shown in Table 4 in detail.
TABLE 4
| Example 4 | Na％wt | Fe％wt | C％wt | N％wt | Number of defects per molecule |
| Prussian blue cathode material | 12.97 | 31.67 | 16.60 | 19.37 | 0.08 |
The prepared Prussian blue cathode material is assembled into an organic system CR2032 type button sodium ion battery, constant current charge and discharge performance tests are carried out under the current density of 100mA/g, the continuous cycle lasts for 500 weeks, the coulombic efficiency per week is maintained to be more than 99%, the capacity retention rate of the battery after 200 weeks is still more than 90%, the battery still has 74.8% of capacity retention rate after 500 weeks, and the specific capacity is 81.5mAh/g, so that the battery is slow in capacity attenuation and has good cycle stability.
Example 5
Adding 0.5g of 1-butyl-3-methylimidazole dihydrogen phosphate into 200mL of deionized water, stirring for 20min, adding 2.42g of sodium ferrocyanide, stirring for 20min, adding 1.76g of 37 wt% hydrochloric acid aqueous solution, and stirring for 3min to obtain a light green mixed solution; putting the light green mixed solution into a glass reaction kettle, putting the glass reaction kettle into an oven, reacting for 24 hours at 80 ℃, and then aging for 24 hours at 20 ℃; and then, sequentially using deionized water and ethanol to centrifugally clean the mixture obtained after aging, collecting and recycling the mother liquor, placing the solid product obtained after cleaning in a freezer at the temperature of-15 ℃ for freezing for 12h until all residual liquid is frozen and frozen, and then placing the frozen solid product in a freezer dryer at the temperature of-50 ℃ for drying for 48h to obtain the Prussian blue cathode material with the low-defect crystal structure.
The prussian blue cathode material prepared in this example was characterized, and the results are as follows:
the XRD spectrum of the Prussian blue anode material prepared in the embodiment accords with the standard card JCPDS52-1907, which indicates that the prepared product is a pure-phase cubic Prussian blue anode material; the sharp peak shape shows that the prepared Prussian blue cathode material has high crystallinity.
According to the characterization result of the SEM image, the prepared prussian blue cathode material was cubic and had a smooth surface.
The prepared Prussian blue anode material is tested by an inductively coupled plasma emission spectrometer (ICP), the number of defects in each molecule of the Prussian blue anode material is 0.09, the Prussian blue anode material belongs to a low-defect crystal structure, and the test results are shown in Table 5 in detail.
TABLE 5
| Example 5 | Na％wt | Fe％wt | C％wt | N％wt | Number of defects per molecule |
| Prussian blue cathode material | 12.65 | 30.28 | 16.17 | 18.87 | 0.09 |
The prepared Prussian blue cathode material is assembled into an organic system CR2032 type button sodium ion battery, constant current charge and discharge performance tests are carried out under the current density of 100mA/g, the continuous cycle lasts for 500 weeks, the coulombic efficiency per week is maintained to be more than 99%, the capacity retention rate of the battery after 200 weeks is still more than 90%, the capacity retention rate after 500 weeks is still 71.2%, and the specific capacity is 72.5mAh/g at the moment, which shows that the battery has slow capacity attenuation and good cycle stability.
In summary, the above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. A preparation method of a Prussian blue cathode material with a low-defect crystal structure is characterized by comprising the following steps: the steps of the method are as follows,
adding the ionic liquid, the Prussian blue precursor and hydrochloric acid into water, and uniformly mixing to obtain a mixed solution; firstly, transferring the mixed solution to 70-90 ℃ for reaction for 15-30 h, then placing the mixed solution at 5-40 ℃ for aging for 24-72 h, then carrying out solid-liquid separation, and cleaning and drying the collected solid product to obtain the Prussian blue cathode material with the low-defect crystal structure;
in the mixed solution, the concentration of the ionic liquid is 1-3 g/L, the mass ratio of the Prussian blue precursor to the ionic liquid is 4-12: 1, and the concentration of hydrochloric acid is 0.05-0.2 mol/L; the Prussian blue precursor is an iron-based cyanide, and the ionic liquid is 1-butyl-3-methylimidazolium oxide or 1-butyl-3-methylimidazolium dihydrogen phosphate.
2. The method for preparing the Prussian blue cathode material with the low-defect crystal structure according to claim 1, wherein the Prussian blue cathode material with the low-defect crystal structure is characterized in that: the Prussian blue precursor is iron-based cyanide containing sodium.
3. The method for preparing the Prussian blue cathode material with the low-defect crystal structure according to claim 2, wherein the Prussian blue cathode material with the low-defect crystal structure is characterized in that: the Prussian blue precursor is sodium ferrocyanide.
4. The method for preparing the Prussian blue cathode material with the low-defect crystal structure according to claim 1, wherein the Prussian blue cathode material with the low-defect crystal structure is characterized in that: completely dissolving the ionic liquid in water, adding the Prussian blue precursor, dissolving, adding hydrochloric acid, and uniformly mixing to obtain a mixed solution.
5. A positive electrode material for an organic sodium-ion battery, characterized in that: the cathode material is a Prussian blue cathode material with a low-defect crystal structure, which is prepared by the method of claims 1-4.
6. A positive electrode material for an aqueous zinc-ion battery, characterized in that: the cathode material is a Prussian blue cathode material with a low-defect crystal structure, which is prepared by the method of claims 1-4.
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| CN114975913A (en) * | 2022-05-07 | 2022-08-30 | 天能电池集团股份有限公司 | Preparation method and application of core-shell composite nanofiber for preparing zinc ion battery positive electrode material |
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