CN116314711A - Preparation process of high-density high-conductivity Prussian composite material - Google Patents
Preparation process of high-density high-conductivity Prussian composite material Download PDFInfo
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- CN116314711A CN116314711A CN202310356567.1A CN202310356567A CN116314711A CN 116314711 A CN116314711 A CN 116314711A CN 202310356567 A CN202310356567 A CN 202310356567A CN 116314711 A CN116314711 A CN 116314711A
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- 239000002131 composite material Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical class [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 52
- 239000000243 solution Substances 0.000 claims description 50
- 230000032683 aging Effects 0.000 claims description 38
- 238000003756 stirring Methods 0.000 claims description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 14
- 239000013078 crystal Substances 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 239000008139 complexing agent Substances 0.000 claims description 12
- 239000002244 precipitate Substances 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 239000007921 spray Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 9
- 238000000498 ball milling Methods 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 8
- 230000001681 protective effect Effects 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000000975 co-precipitation Methods 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 238000005469 granulation Methods 0.000 claims description 6
- 230000003179 granulation Effects 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims description 4
- 239000001509 sodium citrate Substances 0.000 claims description 4
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 4
- -1 super P Chemical compound 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 239000006230 acetylene black Substances 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 230000002431 foraging effect Effects 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910021382 natural graphite Inorganic materials 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 231100000252 nontoxic Toxicity 0.000 claims description 2
- 230000003000 nontoxic effect Effects 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 5
- 239000011248 coating agent Substances 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 abstract description 4
- 239000012467 final product Substances 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 238000010924 continuous production Methods 0.000 abstract description 3
- 230000002265 prevention Effects 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 description 16
- 239000006258 conductive agent Substances 0.000 description 6
- 238000004448 titration Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910001415 sodium ion Inorganic materials 0.000 description 4
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 3
- 238000012983 electrochemical energy storage Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000013225 prussian blue Substances 0.000 description 3
- 229960003351 prussian blue Drugs 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- CDUFCUKTJFSWPL-UHFFFAOYSA-L manganese(II) sulfate tetrahydrate Chemical compound O.O.O.O.[Mn+2].[O-]S([O-])(=O)=O CDUFCUKTJFSWPL-UHFFFAOYSA-L 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- JFSUDVTVQZUDOP-UHFFFAOYSA-N tetrasodium;iron(2+);hexacyanide;decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[Na+].[Na+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] JFSUDVTVQZUDOP-UHFFFAOYSA-N 0.000 description 2
- 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 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000009751 slip forming Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- MJEPCYMIBBLUCJ-UHFFFAOYSA-K sodium titanium(4+) phosphate Chemical compound P(=O)([O-])([O-])[O-].[Ti+4].[Na+] MJEPCYMIBBLUCJ-UHFFFAOYSA-K 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C3/00—Cyanogen; Compounds thereof
- C01C3/08—Simple or complex cyanides of metals
-
- 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
- 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
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/01—Particle morphology depicted by an image
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- C01P2006/40—Electric properties
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- 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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a preparation process of a Prussian composite material with high density and high conductivity, which adopts a two-step method to synthesize Prussian blue analogue material to realize in-situ surface coating of the high conductivity material, so that the Prussian composite material with rapid drying, oxidation prevention and controllable morphology can be obtained; the synthesized Prussian composite material is uniform in composition, high in density and conductivity, and high in multiplying power and cycle performance in a thick electrode mode; the final product has obvious advantages in the aspects of conductivity, bulk density and the like, and the Prussian composite material has excellent cycle rate performance; and the process is simple and controllable, and continuous production can be realized.
Description
Technical Field
The invention relates to the field of secondary energy storage batteries, in particular to a preparation process of a Prussian composite material with high density and high conductivity.
Background
In large scale electrochemical energy storage systems, long life, low cost, environmentally friendly rechargeable batteries are an important direction of development. Among the numerous sodium ion battery anode materials, prussian blue analogues can realize rapid reversible deintercalation of sodium ions due to the unique three-dimensional open frame structure without oxygen crystal lattice, so that the Prussian blue analogues have high specific capacity, long cycle life and excellent multiplying power performance. Meanwhile, the raw materials are rich in resources and low in price, the synthesis process is easy to scale, and the method has great practical application potential.
As early as 2012, in documents Y.H.Lu, L.Wang, J.G.Cheng, J.B.Goodenough.Prussian blue: anew framework of electrode materials for sodium batteries, chemical Communications,2012,48 (52): 6544-6546 (Y.H.Lu, L.Wang, J.G.Cheng, J.B.Goodenough., prussian blue, chemical Communications,2012,48 (52): 6544-6546), goodeugh et al synthesized a series of Prussian blue analogues KMFe (CN) by a simple coprecipitation method 6 (m=mn, fe, co, NI, cu, zn, etc.), and studied their performance in organic-based sodium-ion batteries, for which the approach of applying prussian blue analogues to sodium-ion batteries was drawn. The patent with publication number of CN108946765B also discloses a Prussian blue positive electrode material, a preparation method thereof and an electrochemical energy storage device, and solves the technical difficulty of reducing or even removing the coordinated water content in the material synthesis process, thereby achieving the purpose of obviously improving the performance of the electrochemical energy storage device. Similar studies have often focused on the preparation of materials per se and on the electrolyte systems, however, prussian blue analogues present greater challenges in aqueous electrolytes, such as stability problems of the materials per se and high loading of electrode preparation problems.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation process of a Prussian composite material with high density and high conductivity, wherein a Prussian blue analogue material is synthesized by a two-step method to realize in-situ surface coating of the high conductivity material, so that the high-rate and long-cycle battery performance of the Prussian analogue material in a thick electrode mode under high density is realized.
The technical scheme for achieving the purpose is as follows: a preparation process of a Prussian composite material with high density and high conductivity comprises the following steps:
s1, preparing a Prussian blue analogue by an aqueous solution coprecipitation method, wherein the Prussian blue analogue has a general formula of A x M1[M2(CN) 6 ] y ·zH 2 O, wherein A is one or more of Li, na, K, ca, mg, zn, al, M is one or more of Fe, co, ni, cu, zn, ti, V, cr and Mn, x is more than or equal to 0 and less than or equal to 2, y is more than or equal to 0 and less than or equal to 1, c is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 16, the reaction rate is controlled by controlling the feeding parameters and stirring parameters of the raw materials, and initial crystal nuclei with the grain diameter of 0.1-1 mu M are synthesized; then adjusting the feeding parameters and stirring parameters of the raw materials to control the reaction rate, and growing the secondary nuclei into controllable single crystals with the particle size of 1-15 mu m; then transferring the reaction solution into an aging kettle, standing, and performing filter pressing washing on the suspension in the aging kettle to obtain a precipitate, wherein the precipitate is Prussian blue analogues;
s2, transferring the obtained Prussian blue analogues into a ball mill, adding a solvent for dispersing and stirring uniformly, and then adding composite carbon for ball milling and dispersing; and (3) transferring the composite slurry subjected to ball milling and uniform dispersion into a spray dryer, and performing spray granulation and drying in a nitrogen atmosphere to obtain the spherical Prussian composite material with high density and high conductivity, wherein the particle size of the spherical Prussian composite material is 5-50 mu m.
The preparation process of the Prussian composite material with high density and high conductivity comprises the following steps of:
s11, liquid preparation: preparing an M1 ion solution, an M2 cyanide ion solution and a complexing agent solution, wherein the concentration of the M1 ion solution and the M2 cyanide ion solution is 0-3 mol/L, and the concentration of the complexing agent solution is 0-4 mol/L;
s12, transferring the complexing agent solution into a reaction kettle, introducing inert gas into the reaction kettle as reaction protective atmosphere, wherein the temperature in the reaction kettle is-5-90 ℃, and the stirring speed is 500-1500 r/min; dropwise adding the M1 ionic solution and the M2 cyanide ionic solution into the reaction kettle in two steps, wherein in the first step of feeding, an initial crystal nucleus with the particle size of 0.1-1 mu M is synthesized by controlling the feeding rate of the M1 ionic solution and the M2 cyanide ionic solution and the stirring rate of the reaction kettle, and in the second step of feeding, a controllable monocrystal with the particle size of 1-15 mu M is obtained by controlling the feeding rate of the M1 ionic solution and the M2 cyanide ionic solution and the stirring rate of the reaction kettle;
s13, aging: dripping all the M1 ion solution and the M2 cyanide ion solution, transferring the reaction solution in the reaction kettle into an aging kettle for aging after the reaction is completed, and introducing inert gas into the aging kettle as an aging protective atmosphere, wherein the aging temperature is-5-90 ℃; the aging time is 1-48 h; the ageing and stirring rate is 1-500 r/min;
s14, dehydration: and (3) carrying out filter pressing on the suspension in the ageing kettle through a plate and frame filter press, and washing the materials in the plate and frame of the plate and frame filter press for 1-5 times by adopting a washing solvent to obtain a precipitate, wherein the precipitate is Prussian blue analogues.
In the preparation process of the high-density high-conductivity Prussian composite material, in the step S11, the complexing agent in the complexing agent solution adopts citric acid or sodium citrate;
in the step S12 and the step S13, the inert gas is one or more of nitrogen, argon and helium;
in step S14, the washing solvent is one or more of deionized water, anhydrous ethanol and acetone.
In the preparation process of the high-density high-conductivity Prussian composite material, in the step S2, the composite carbon adopts one or more of artificial graphite, natural graphite, acetylene black, super P, active carbon, graphene, carbon fiber and mesoporous carbon.
In the preparation process of the high-density high-conductivity Prussian composite material, in the step S2, the solvent uses a low-boiling-point nontoxic neutral or reducing solvent.
In the preparation process of the high-density high-conductivity Prussian composite material, in the step S2, the solvent is ethanol or methanol.
The preparation process of the Prussian composite material with high density and high conductivity has the bulk density of 0.6-1.0 g/cm 3 The tap density is 1.0-1.6 g/cm 3 。
The preparation process of the Prussian composite material with high density and high conductivity can obtain the Prussian composite material with rapid drying, oxidation prevention and controllable morphology; the synthesized Prussian composite material is uniform in composition, high in density and conductivity, and high in multiplying power and cycle performance in a thick electrode mode; the final product has obvious advantages in the aspects of conductivity, bulk density and the like, and the Prussian composite material has excellent cycle rate performance; and the process is simple and controllable, and continuous production can be realized.
Drawings
FIG. 1 is an electron microscopic view of the Prussian composite material prepared in example 1;
FIG. 2 is a graph showing the magnification and long-cycle test of the Prussian composite material prepared in example 1;
fig. 3 is an electron microscopic view of the prussian composite material prepared in example 2.
Detailed Description
In order to enable those skilled in the art to better understand the technical scheme of the present invention, the following detailed description is provided with reference to the accompanying drawings:
example 1:
referring to fig. 1, in an embodiment of the invention, a preparation process of a high-density high-conductivity Prussian composite material includes the following steps:
s1, preparing a Prussian blue analogue by an aqueous solution coprecipitation method, wherein the Prussian blue analogue specifically comprises the following steps:
s11, liquid preparation: 5mol of sodium ferrocyanide decahydrate is dissolved in 10L of deionized water to obtain M2 cyanide ion solution (precursor solution A); dissolving 5mol of manganous sulfate tetrahydrate in 10L of deionized water to obtain an M1 ion solution (precursor liquid B); dissolving 5mol of sodium citrate in 10L of deionized water to obtain complexing agent solution (precursor liquid C);
s12, transferring the precursor liquid C into a reaction kettle to serve as a base liquid, introducing high-purity nitrogen into the reaction kettle to serve as a reaction protective atmosphere, controlling the flow rate of the nitrogen to be 0.2L/min, controlling the stirring speed of the reaction kettle to be 800r/min, and keeping the temperature of the reaction kettle constant at 60 ℃; then feeding in the first step, adding the precursor solution A and the precursor solution B into a reaction kettle respectively according to a titration rate of 250ml/min, and after the titration reaction is completed and stirring for 20min, synthesizing initial crystal nuclei with the particle size of 0.8-1 mu m; then adjusting the speed and the stirring speed of the reaction kettle to carry out the second feeding, and respectively adding the precursor liquid A and the precursor liquid B into the reaction kettle at the titration speed of 50ml/min, wherein the stirring speed of the reaction kettle is adjusted to 400r/min;
s14, aging: after the reaction is completed, transferring the reaction solution in the reaction kettle into an ageing kettle for ageing, introducing nitrogen into the ageing kettle as an ageing protective atmosphere, wherein the nitrogen flow is 0.5/min, and the ageing temperature is 50 ℃; the aging time is 2 hours; the ageing and stirring rate is 300r/min;
s15, dehydration: filtering the suspension in the ageing kettle by a plate-and-frame filter press, and washing the materials in the plate frame of the plate-and-frame filter press for 2 times by adopting a washing solvent to obtain a precipitate, wherein the precipitate is Prussian blue analogues, and the specific molecular structural formula is Na 2 Mn[Fe(CN) 6 ]·2H 2 O；
S2, transferring the obtained Prussian blue analogues into a ball mill, adding 20L of absolute ethyl alcohol, performing dispersion stirring for 30min until the materials are uniformly stirred, and then adding 500g of composite carbon (conductive agent) for ball milling and dispersing for 30min; transferring the composite slurry with uniform ball milling and dispersion into a spray dryer, and performing spray granulation and drying in nitrogen atmosphere to obtain spherical Prussian composite material (see figure 1 in electron microscope image) with high density and high conductivity, wherein the specific molecular structural formula is Na 2 Mn[Fe(CN) 6 ]·0.4H 2 O。
Referring to fig. 2, the Prussian composite material prepared in example 1 is ground and crushed, 75g of the Prussian composite material is weighed, 5g of dry powder polytetrafluoroethylene is added as a binder, the mixture is further mixed for 30min by a V-type stirrer, the mixed dry powder is crushed and crushed by using air flow to form fiber, fluffy powder is obtained, the powder is added into a feed inlet of a roller press at a speed of 500ml/min, the diameter of rollers is 300mm, a certain roller spacing is set, and the temperature of the rollers is 180 ℃. Rolling and continuously forming a film after powder feeding, controlling the thickness of a film sheet to be 500 mu m, further rolling and compounding the film sheet with carbon-coated aluminum foil after continuously forming the film, and setting the temperature of a compounding roller to 120 ℃ to obtain the positive electrode film compounded with the current collector. The negative electrode adopts sodium titanium phosphate as an active substance and polytetrafluoroethylene as a binder, and is continuously formed into a film by adopting the same proportion and preparation process mode as those of the positive electrode, so as to obtain a negative electrode film. The small monomer battery with 6cm x 6cm is assembled by adopting 1.0mol/L NaClO4 aqueous solution mixed polyethylene glycol as electrolyte and non-woven fabric as a diaphragm. The long cycle test was performed using 3C and the test results are shown in fig. 2. As can be seen from fig. 2, the prussian composite material obtained by the preparation process of the high-density high-conductivity prussian composite material can realize high multiplying power and high cycle performance in a thick electrode mode.
Example 2:
referring to fig. 3, in an embodiment of the present invention, a process for preparing a high-density high-conductivity Prussian composite material includes the following steps:
s1, preparing a Prussian blue analogue by an aqueous solution coprecipitation method, wherein the Prussian blue analogue specifically comprises the following steps:
s11, liquid preparation: 5mol of sodium ferrocyanide decahydrate is dissolved in 10L of deionized water to obtain M2 cyanide ion solution (precursor solution A); dissolving 5mol of manganous sulfate tetrahydrate in 10L of deionized water to obtain an M1 ion solution (precursor liquid B); dissolving 5mol of sodium citrate in 10L of deionized water to obtain complexing agent solution (precursor liquid C);
s12, transferring the precursor liquid C into a reaction kettle to serve as a base liquid, introducing high-purity nitrogen into the reaction kettle to serve as a reaction protective atmosphere, controlling the flow rate of the nitrogen to be 0.2L/min, controlling the stirring speed of the reaction kettle to be 1000r/min, and keeping the temperature of the reaction kettle constant at 60 ℃; then feeding in the first step, adding the precursor solution A and the precursor solution B into a reaction kettle respectively according to a titration rate of 250ml/min, and after the titration reaction is completed and stirring for 20min, synthesizing initial crystal nuclei with the particle size of 0.4-0.8 mu m; then adjusting the speed and the stirring speed of the reaction kettle to carry out the second feeding, and respectively adding the precursor liquid A and the precursor liquid B into the reaction kettle at the titration speed of 100ml/min, wherein the stirring speed of the reaction kettle is adjusted to 600r/min;
s14, aging: after the reaction is completed, transferring the reaction solution in the reaction kettle into an ageing kettle for ageing, introducing nitrogen into the ageing kettle as an ageing protective atmosphere, wherein the nitrogen flow is 0.5/min, and the ageing temperature is 50 ℃; the aging time is 2 hours; the ageing and stirring rate is 300r/min;
s15, dehydration: filtering the suspension in the ageing kettle by a plate-and-frame filter press, and washing the materials in the plate frame of the plate-and-frame filter press for 2 times by adopting a washing solvent to obtain a precipitate, wherein the precipitate is Prussian blue analogues, and the specific molecular structural formula is Na 2 Mn[Fe(CN) 6 ]·2H 2 O；
S2, transferring the obtained Prussian blue analogues into a ball mill, adding 20L of absolute ethyl alcohol (solvent) for dispersion and stirring for 30min until the mixture is uniformly stirred, and then adding 500g of composite carbon (conductive agent) for ball milling and dispersing for 30min; transferring the composite slurry with uniform ball milling and dispersion into a spray dryer, and performing spray granulation and drying in nitrogen atmosphere to obtain spherical Prussian composite material (see figure 3 in electron microscope image) with high density and high conductivity, wherein the specific molecular structural formula is Na 2 Mn[Fe(CN) 6 ]·0.4H 2 O。
According to the preparation process of the high-density high-conductivity Prussian composite material, the initial crystal nucleus with the size of 0.1-1 mu m is synthesized by controlling the input amount of raw materials with different concentrations, the parameters are adjusted, the secondary crystal nucleus is grown to a controllable single crystal with the particle size of 1-15 mu m, and the crystal form defect of the Prussian blue analogue can be reduced from the intrinsic property of the material. Filtering and washing the single-crystal Prussian blue analog, transferring to a dispersing machine, adding a solvent and a conductive agent, and dispersing at high speed; the liquid phase high-speed dispersion is used for coating the conductive agent, is essentially different from the mechanical mixing of the conductive agent in the later stage, and can be used for remarkably solving the problem of poor conductivity of Prussian blue analogues. The uniformly mixed Prussian composite material slurry is subjected to spray granulation drying under nitrogen or inert atmosphere, the process can be used for rapidly drying, oxidation prevention is realized, and the particle size of the Prussian composite material is controllable to be 5-50 mu m and high in density.
According to the preparation process of the high-density high-conductivity Prussian composite material, in the step of preparing the Prussian blue analogues by the aqueous solution coprecipitation method, the liquid phase nucleates and grows nuclei, and the grain size can be accurately controlled by controlling the feeding concentration and the reaction time; in the step S2, a solvent and a conductive agent are added into the Prussian blue analogues and mixed in a ball milling mode, so that uniform coating is achieved, and the water content in the active material is reduced; and then, spray granulation and quick drying are carried out, so that the grain size and morphology of the final product are accurately controlled.
In conclusion, the preparation process of the high-density high-conductivity Prussian composite material can obtain the Prussian composite material which is quick to dry, prevents oxidation and is controllable in appearance; the synthesized Prussian composite material is uniform in composition, high in density and conductivity, and high in multiplying power and cycle performance in a thick electrode mode; the final product has obvious advantages in the aspects of conductivity, bulk density and the like, and the Prussian composite material has excellent cycle rate performance; and the process is simple and controllable, and continuous production can be realized.
It will be appreciated by persons skilled in the art that the above embodiments are provided for illustration only and not for limitation of the invention, and that variations and modifications of the above described embodiments are intended to fall within the scope of the claims of the invention as long as they fall within the true spirit of the invention.
Claims (7)
1. The preparation process of the Prussian composite material with high density and high conductivity is characterized by comprising the following steps of:
s1, preparing a Prussian blue analogue by an aqueous solution coprecipitation method, wherein the Prussian blue analogue has a general formula of A x M1[M2(CN) 6 ] y ·zH 2 O, wherein A is one or more of Li, na, K, ca, mg, zn, al, M is one or more of Fe, co, ni, cu, zn, ti, V, cr and Mn, x is more than or equal to 0 and less than or equal to 2, y is more than or equal to 0 and less than or equal to 1, c is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 16, the reaction rate is controlled by controlling the feeding parameters and stirring parameters of the raw materials, and the synthetic particle size is 0.1-1 mu MAn initial crystal nucleus; then adjusting the feeding parameters and stirring parameters of the raw materials to control the reaction rate, and growing the secondary nuclei into controllable single crystals with the particle size of 1-15 mu m; then transferring the reaction solution into an aging kettle, standing, and performing filter pressing washing on the suspension in the aging kettle to obtain a precipitate, wherein the precipitate is Prussian blue analogues;
s2, transferring the obtained Prussian blue analogues into a ball mill, adding a solvent for dispersing and stirring uniformly, and then adding composite carbon for ball milling and dispersing; and (3) transferring the composite slurry subjected to ball milling and uniform dispersion into a spray dryer, and performing spray granulation and drying in a nitrogen atmosphere to obtain the spherical Prussian composite material with high density and high conductivity, wherein the particle size of the spherical Prussian composite material is 5-50 mu m.
2. The process for preparing the high-density high-conductivity Prussian composite material according to claim 1, wherein the step S1 is characterized by preparing the Prussian blue analogues by an aqueous solution coprecipitation method, and specifically comprises the following steps:
s11, liquid preparation: preparing an M1 ion solution, an M2 cyanide ion solution and a complexing agent solution, wherein the concentration of the M1 ion solution and the M2 cyanide ion solution is 0-3 mol/L, and the concentration of the complexing agent solution is 0-4 mol/L;
s12, transferring the complexing agent solution into a reaction kettle, introducing inert gas into the reaction kettle as reaction protective atmosphere, wherein the temperature in the reaction kettle is-5-90 ℃, and the stirring speed is 500-1500 r/min; dropwise adding the M1 ionic solution and the M2 cyanide ionic solution into the reaction kettle in two steps, wherein in the first step of feeding, an initial crystal nucleus with the particle size of 0.1-1 mu M is synthesized by controlling the feeding rate of the M1 ionic solution and the M2 cyanide ionic solution and the stirring rate of the reaction kettle, and in the second step of feeding, a controllable monocrystal with the particle size of 1-15 mu M is obtained by controlling the feeding rate of the M1 ionic solution and the M2 cyanide ionic solution and the stirring rate of the reaction kettle;
s13, aging: dripping all the M1 ion solution and the M2 cyanide ion solution, transferring the reaction solution in the reaction kettle into an aging kettle for aging after the reaction is completed, and introducing inert gas into the aging kettle as an aging protective atmosphere, wherein the aging temperature is-5-90 ℃; the aging time is 1-48 h; the ageing and stirring rate is 1-500 r/min;
s14, dehydration: and (3) carrying out filter pressing on the suspension in the ageing kettle through a plate and frame filter press, and washing the materials in the plate and frame of the plate and frame filter press for 1-5 times by adopting a washing solvent to obtain a precipitate, wherein the precipitate is Prussian blue analogues.
3. The process for preparing a high-density and high-conductivity Prussian composite according to claim 2, wherein in step S11, the complexing agent in the complexing agent solution is citric acid or sodium citrate;
in the step S12 and the step S13, the inert gas is one or more of nitrogen, argon and helium;
in step S14, the washing solvent is one or more of deionized water, anhydrous ethanol and acetone.
4. The process for preparing the high-density and high-conductivity Prussian composite material according to claim 1, wherein in the step S2, the composite carbon is one or more of artificial graphite, natural graphite, acetylene black, super P, activated carbon, graphene, carbon fiber and mesoporous carbon.
5. The process for preparing a high-density and high-conductivity Prussian composite according to claim 1, wherein in the step S2, the solvent is a low-boiling non-toxic neutral or reducing solvent.
6. The process for preparing a high-density and high-conductivity Prussian composite according to claim 5, wherein in step S2, ethanol or methanol is used as the solvent.
7. The process for preparing the high-density and high-conductivity Prussian composite material according to claim 1, wherein the Prussian composite material has a bulk density of 0.6-1.0 g/cm 3 The tap density is 1.0-1.6 g/cm 3 。
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| CN110492077A (en) * | 2019-08-23 | 2019-11-22 | 河南工学院 | A kind of ferrocyanide carbon composite anode material and preparation method thereof, kalium ion battery, sodium-ion battery |
| CN112259730A (en) * | 2020-12-08 | 2021-01-22 | 江苏时代新能源科技有限公司 | Prussian blue transition metal cyanide, preparation method thereof, and related positive electrode plate, secondary battery, battery pack and device |
| CN115650253A (en) * | 2022-11-03 | 2023-01-31 | 湖南长远锂科新能源有限公司 | Spherical-like single crystal Prussian white positive electrode material, preparation method thereof and sodium ion battery |
| CN115911380A (en) * | 2022-11-24 | 2023-04-04 | 远景动力技术(江苏)有限公司 | Positive electrode material, preparation method of positive electrode material, positive electrode piece and sodium-ion battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110492077A (en) * | 2019-08-23 | 2019-11-22 | 河南工学院 | A kind of ferrocyanide carbon composite anode material and preparation method thereof, kalium ion battery, sodium-ion battery |
| CN112259730A (en) * | 2020-12-08 | 2021-01-22 | 江苏时代新能源科技有限公司 | Prussian blue transition metal cyanide, preparation method thereof, and related positive electrode plate, secondary battery, battery pack and device |
| CN115650253A (en) * | 2022-11-03 | 2023-01-31 | 湖南长远锂科新能源有限公司 | Spherical-like single crystal Prussian white positive electrode material, preparation method thereof and sodium ion battery |
| CN115911380A (en) * | 2022-11-24 | 2023-04-04 | 远景动力技术(江苏)有限公司 | Positive electrode material, preparation method of positive electrode material, positive electrode piece and sodium-ion battery |
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