CN116826038A - Prussian blue compound, preparation method and use thereof - Google Patents
Prussian blue compound, preparation method and use thereof Download PDFInfo
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- 239000013225 prussian blue Substances 0.000 title claims abstract description 24
- 229960003351 prussian blue Drugs 0.000 title claims abstract description 24
- -1 Prussian blue compound Chemical class 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 239000011734 sodium Substances 0.000 claims description 43
- 239000002244 precipitate Substances 0.000 claims description 19
- 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 description 17
- 238000000034 method Methods 0.000 claims description 14
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 9
- 229910001415 sodium ion Inorganic materials 0.000 claims description 9
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000011163 secondary particle Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000008139 complexing agent Substances 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 7
- 239000011164 primary particle Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000006230 acetylene black Substances 0.000 claims description 6
- 239000007773 negative electrode material Substances 0.000 claims description 6
- 239000001509 sodium citrate Substances 0.000 claims description 6
- 229910002521 CoMn Inorganic materials 0.000 claims description 5
- 239000007774 positive electrode material Substances 0.000 claims description 5
- 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 5
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 2
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 claims description 2
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 2
- 229910015136 FeMn Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000000661 sodium alginate Substances 0.000 claims description 2
- 235000010413 sodium alginate Nutrition 0.000 claims description 2
- 229940005550 sodium alginate Drugs 0.000 claims description 2
- 239000000176 sodium gluconate Substances 0.000 claims description 2
- 235000012207 sodium gluconate Nutrition 0.000 claims description 2
- 229940005574 sodium gluconate Drugs 0.000 claims description 2
- DZCAZXAJPZCSCU-UHFFFAOYSA-K sodium nitrilotriacetate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CC([O-])=O DZCAZXAJPZCSCU-UHFFFAOYSA-K 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000004378 air conditioning Methods 0.000 claims 2
- 239000000243 solution Substances 0.000 description 54
- 239000000463 material Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
- 238000001000 micrograph Methods 0.000 description 5
- 239000010405 anode material Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000012983 electrochemical energy storage Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 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
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000011149 active 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
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- 229940038773 trisodium citrate Drugs 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—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
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- 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
- H01M2004/027—Negative electrodes
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- Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Toxicology (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a Prussian blue compound, a preparation method and application thereof. In one embodiment, the compound has the formula Na x M[Mn(CN) 6 ] y zH2O, wherein M is Co, ni, mn, cu, or Fe; x is 1-4; y is 0-1; z is 0-6; the compound has a spherical morphology.
Description
Technical Field
The invention relates to the field of battery anode and cathode materials.
Background
The invention relates to the field of sodium ion batteries, the field of battery anode and cathode materials, in particular to Prussian analog Na 2 MnMn(CN) 6 An electrode material and a method for preparing the same.
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, goodenough et al(Y.H.Lu, L.Wang, J.G.Cheng, J.B.Goodenough.Prussian blue: anew framework of electrode materials for sodium bacteria chemical Communications,2012,48 (52): 6544-6546.) A series of Prussian blue analogues KMFe (CN) were synthesized by simple co-precipitation 6 (m= Mn, fe, co, ni, cu, zn, etc.) and studied their performance in organic-based sodium-ion batteries, for which reason the approach of applying prussian blue analogues to sodium-ion batteries was drawn. Patent CN108946765B also mentions a Prussian blue type 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 are based on organic system electrolytes and on Fe (CN) 6 The research of the two-stage voltage platform material of the system has the advantages that the solution depth is low during product synthesis, the single crystal particles of the synthesized product are small, related products cannot be produced stably in batches, and commercial application cannot be performed in a short period on the basis of the current technology. And Prussian blue analogues NaMFe (CN) of the existing system 6 (m= Mn, fe, co, ni, cu, zn, etc.) is by Na 4 Fe(CN) 6 And the sodium hexafluorophosphate is synthesized with Mn, fe, co, ni, cu, zn and other soluble salts through coprecipitation, and is used as a positive electrode, a hard carbon is used as a negative electrode, and the electrolyte is matched with sodium hexafluorophosphate. Whereas the negative electrode material NaM [ Mn (CN) is ignored 6 ](m= Mn, fe, co, ni, cu, zn, etc.), the present invention was developed on NaM [ Mn (CN) based on the advantage of polyvalent state change of Mn itself 6 ]Synthesizing and controlling the mixture to form a spherical shape.
Has the following advantages:
1. the sphere can greatly increase the bulk density, thereby making up the defect of low theoretical density of Prussian blue material, and being beneficial to improving the electrode load capacity
2. The secondary particle size and the primary particle size of the spherical particles can be adjusted by the process, so that the requirements of different loading amounts and multiplying powers are met
3. The positive electrode and the negative electrode are made of Prussian blue materials, and both are of a three-dimensional open frame structure, so that the rate capability of the battery can be greatly improved
Disclosure of Invention
The invention provides a Prussian blue compound. In one embodiment, the compound has the formula Na x M[Mn(CN) 6 ] y ·zH 2 O, wherein M is Co, ni, mn, cu, or Fe; x is 1-4; y is 0-1; z is 0-6; the compound has a spherical morphology.
The invention provides a preparation method of Prussian blue compounds. In one embodiment, the method comprises the steps of: (a) Preparation of Na 4 M(CN) 6 The solution is formed into a solution A; (b) Mixed MSO 4 The solution and the complexing agent solution form a solution B; (c) Dripping the solution A and the solution B into a reaction kettle together to obtain a precipitate; (d) Drying the precipitate to obtain Na x M[Mn(CN) 6 ] y ·zH 2 O。
The invention also provides an electrode for a sodium ion battery, which comprises the Prussian blue compound.
The invention further provides a battery, which comprises a positive electrode and a negative electrode, and is characterized in that the negative electrode material comprises the Prussian blue compound.
Drawings
Fig. 1 shows a production flow of the prussian blue compound of the present invention.
Fig. 2A shows a prussian analogue electron microscope image of example 1 of the present invention.
Fig. 2B shows the prussian analogue XRD of example 1 of the present invention.
Fig. 2C shows cyclic voltammograms of the prussian analogues of example 1 of the present invention.
FIG. 2D shows the rate capability (positive electrode is Na) of the Prussian analog of example 1 of the present invention 1.87 MnFe(CN) 6 The negative electrode is Na 1.76 MnMn(CN) 6 )。
FIG. 2E shows Prussian analog cycle (1C/1C)/specific capacity/efficiency graph of example 1 of the present invention. Electrochemical performance: positive electrode Na x M n [Fe(CN) 6 ] y ·zH 2 O: SP, ptfe=8:1:1; negative electrode Na x M n [Mn(CN) 6 ] y ·zH 2 O:SP:PTFE＝8:1:1。
Fig. 2F shows a crystal space structure diagram of the prussian analogue of example 1 of the present invention.
Fig. 3 shows a prussian analogue electron microscope image of example 2 of the present invention.
Fig. 4 shows a prussian analogue electron microscope image of example 3 of the present invention.
Detailed Description
The invention provides a Prussian blue compound. In one embodiment, the compound has the formula Na x M[Mn(CN) 6 ] y ·zH 2 O, wherein M is Co, ni, mn, cu, or Fe; x is 1-4; y is 0-1; z is 0-6; the compound has a spherical morphology.
In one embodiment, the Prussian blue compound includes Na 2 MnMn(CN) 6 、Na 2 CoMn(CN) 6 Or Na (or) 2 CuMn(CN) 6 。
In one embodiment, the spherical topography includes the following features: (i) the primary particle size of the spherical morphology is 0.1-10 microns; or (ii) the secondary particle size of the spherical morphology is 5-100 microns.
In one embodiment, the method comprises the steps of: (a) Preparation of Na 4 M(CN) 6 The solution is formed into a solution A; (b) Mixed MSO 4 The solution and the complexing agent solution form a solution B; (b) Dripping the solution A and the solution B into a reaction kettle together to obtain a precipitate; and (d) drying the precipitate to obtain Na x M[Mn(CN) 6 ] y ·zH 2 O。
In one embodiment, the step (a) includes dropping a NaCN solution into the MSO 4 In solution.
In one embodiment, the step (a) further comprises any one of the following steps: (i) The NaCN solution and the MSO 4 The molar ratio of the solution was 6:1, a step of; (ii) The concentration of the NaCN solution is 1-7mol/L or the MSO 4 The concentration of the solution is 0.1-2mol/L; (iii) The NaCN solution is added into the MSO at a uniform speed of 1-300ml/min 4 A solution; and (iv) said step (a) is performed with continuous stirring.
In one embodiment, said step (b) comprises any one of the following steps: (i) The MSO 4 The concentration of the solution is 0.1-2mol/L; (ii) the concentration of the complexing agent solution is 0.1-2mol/L.
In one embodiment, said step (c) comprises any one of the following steps: (i) The solution A and the solution B are dripped into the reaction kettle together at the speed of 1-300 ml/min; (ii) heating the solution a and the solution B to 20-80 ℃; (iii) stirring the solution a with the solution B.
In one embodiment, step (d) further comprises washing the precipitate with deionized water or washing the precipitate with deionized water followed by methanol prior to drying the precipitate.
In one embodiment, the complexing agent solution comprises one or more of sodium citrate, sodium ethylenediamine tetraacetate, sodium nitrilotriacetate, sodium gluconate, or sodium alginate.
An electrode for a sodium ion battery, comprising the Prussian blue compound of the invention.
In one embodiment, the Prussian blue compound includes Na 2 MnMn(CN) 6 、Na 2 CoMn(CN) 6 、Na 1.87 FeMn(CN) 6 、Na 1.76 MnMn(CN) 6 Or Na (or) 2 CuMn(CN) 6 。
The battery comprises a positive electrode and a negative electrode, and is characterized in that the negative electrode material comprises the Prussian blue compound.
In one embodiment, the positive electrode material of the battery comprises the Prussian blue compound or Na x Mn[Fe(CN) 6 ] y One or more of the following.
In one embodiment, the positive electrode or negative electrode further comprises acetylene black and PTFE, and the ratio of the positive electrode material or negative electrode material, the acetylene black, and the PTFE is (8-9.5): (0.3-1): (0.2-1).
The invention provides a production method of Prussian blue compounds. In one embodiment, the technical solution of the method includes as shown in fig. 1:
1. preparation of solution A (Na 4 Mn(CN) 6 )
2.MSO 4 (m= Mn, fe, co, ni, cu, zn) and trisodium citrate are formulated into a mixed solution B
3. The solution B and the solution A are added into a reaction kettle at the same time according to the metering ratio, and the parameters such as reaction temperature, stirring speed, feeding speed and the like are controlled to generate spherical morphology precipitate Na 2 MMn(CN) 6
4. The pure spherical Na is obtained through filtering, washing and drying 2 MMn(CN) 6
In one embodiment, the technical proposal produces the spherical sodium ion battery material Na 2 MMn(CN) 6 With Mn (CN) 6 4+ The general formula of the Prussian compound is Na x M[Mn(CN) 6 ] y ·zH 2 O, the Prussian anode and cathode materials synthesized by the synthesis method, wherein M is Co, ni, mn, cu, fe.
Example 1
Step 1: and (3) preparing a solution A: 2mol/L of NaCN solution is dripped into 2mol/L of MnSO at a constant speed of 2ml/min in an accurate metering mode 4 The solution is stirred continuously, and the molar ratio is NaCN: mnSO 4 =6: 1, stirring speed 300rpm.
Step 2: and (3) preparing a liquid B: 2mol/L MnSO 4 The solution was mixed with 0.6mol/L sodium citrate.
Step 3: the solution A and the solution B are heated to 60 ℃ and are added into the reaction kettle together at the adding speed of 2ml/min and the stirring speed of 300rpm.
Step 4: after generating the precipitate, washing the precipitate with deionized water and drying to obtain spherical Na 2 MnMn(CN) 6 The primary particle size and the secondary particle size of the powder are respectively 10-20 microns and 50-70 microns (figure 2A: prussian analog electron microscope image), and the large secondary particle size is beneficial to improving the apparent density and tap density of the powder and improving the electrode surface density and the specific energy of a battery.
FIG. 2B is an XRD pattern of the powder obtained, the powder crystallization performance is good, and no impurity peak appears; the obtained Na 2 MnMn(CN) 6 Mixing the powder with acetylene black and PTFE according to the ratio of 8:1:1, coating to prepare a negative electrode plate, and testing CV curves at-1.2-0.6V (vs Ag/AgCl), wherein corresponding oxidation-reduction peaks are shown at-0.8V and 0.2V (vs Ag/AgCl) (figure 2C). By Na 2 MnMn(CN) 6 As the negative electrode, na 2 MnFe(CN) 6 As the positive electrode, respectively mixed with acetylene black and PTFE according to a ratio of 8:1:1, coated to prepare a pole piece, the active material ratio of 1:1, and the specific capacity under different multiplying powers (figure 2D) is tested, it can be seen that when the positive electrode and the negative electrode both adopt Prussian blue analogues, the battery has excellent multiplying power performance, and the specific capacity of 20C is 60% of 0.1C. The efficiency of the battery can reach more than 99.9% after long cycle at 1C, and the capacity retention rate is more than 90% for 5000 times (figure 2E). The crystalline structure of the resulting material is schematically shown in fig. 2F.
Example 2:
step 1: and (3) preparing a solution A: 2mol/L of NaCN solution is dripped into 2mol/L of MnSO at a constant speed of 2ml/min in an accurate metering mode 4 The solution is stirred continuously, and the molar ratio is NaCN: coSO 4 =6: 1, stirring speed 300rpm.
Step 2: and (3) preparing a liquid B: 2mol/L CoSO 4 The solution was mixed with 0.6mol/L sodium citrate.
Step 3: the solution A and the solution B are heated to 40 ℃ and are added into the reaction kettle together at the adding speed of 2ml/min and the stirring speed of 400rpm.
Step 4: after generating the precipitate, washing the precipitate with deionized water and drying to obtain spherical Na 2 CoMn(CN) 6 The material (figure 3: prussian analogue electron microscope image) is suitable for high-power devices by reducing the reaction temperature and improving the stirring rate, wherein the primary particle and the secondary particle of the powder are respectively adjusted to 2 microns and more than ten microns, and the small primary particle diameter and the small secondary particle diameter are beneficial to the reaction kinetics.
Example 3:
1. and (3) preparing a solution A: 2mol/L NaCN solution is dripped into 2mol/L MnSO4 solution at a constant speed of 2ml/min in an accurate metering mode, and stirring is continued, wherein the molar ratio of NaCN: cuSO 4 =6: 1, stirring speed 300rpm.
2、And (3) preparing a liquid B: cuSO at 1mol/L 4 The solution was mixed with 0.6mol/L sodium citrate.
3. The solution A and the solution B are heated to 40 ℃ and are added into the reaction kettle together at the adding speed of 2ml/min and the stirring speed of 400rpm.
4. After generating the precipitate, washing the precipitate with deionized water and drying to obtain spherical Na 2 CuMn(CN) 6 Material (FIG. 4: prussian analog electron microscopy). By reducing the concentration of the reactants, the primary particle size of the powder was increased by 7-8 microns (compared to example 2), while the secondary particle size was unchanged, or tens of microns.
Claims (15)
1. Prussian blue compounds, characterized in that:
i. the chemical formula of the compound is Na x M[Mn(CN) 6 ] y zH2O, wherein M is Co, ni, mn, cu, or Fe; x is 1-4; y is 0-1; z is 0-6;
the compound has a spherical morphology.
2. The Prussian blue-based compound according to claim 1, comprising Na 2 MnMn(CN) 6 、Na 2 CoMn(CN) 6 Or Na (or) 2 CuMn(CN) 6 。
3. Prussian blue based compounds according to claim 1, the spherical morphology comprising the following features:
i. the primary particle size of the spherical morphology is 0.1-10 microns; or (b)
The secondary particle size of the spherical morphology is 5-100 microns.
4. A process for preparing the prussian blue compound of claim 1, comprising the steps of:
a. preparation of Na 4 M(CN) 6 The solution is formed into a solution A;
b. mixed MSO 4 The solution and the complexing agent solution form a solution B;
c. dripping the solution A and the solution B into a reaction kettle together to obtain a precipitate; a kind of electronic device with high-pressure air-conditioning system
d. Drying the precipitate to obtain Na x M[Mn(CN) 6 ] y ·zH 2 O。
5. The method of claim 4, wherein step (a) comprises dropping a NaCN solution into the MSO 4 In solution.
6. The method of claim 5, said step (a) further comprising any one of the following steps:
i. the NaCN solution and the MSO 4 The molar ratio of the solution was 6:1, a step of;
the NaCN solution has a concentration of 1-7mol/L or the MSO 4 The concentration of the solution is 0.1-2mol/L;
the NaCN solution is dropped into the MSO at a uniform rate of 1-300ml/min 4 A solution; a kind of electronic device with high-pressure air-conditioning system
The step (a) is carried out with continuous stirring.
7. The method of claim 4, said step (b) comprising any one of the following steps:
i. the MSO 4 The concentration of the solution is 0.1-2mol/L;
the concentration of the complexing agent solution is 0.1-2mol/L.
8. The method of claim 4, said step (c) comprising any one of the following steps:
i. the solution A and the solution B are dripped into the reaction kettle together at the speed of 1-300 ml/min;
heating the solution A and the solution B to 20-80 ℃;
stirring the solution a and the solution B.
9. The method of claim 4, said step (d) further comprising washing said precipitate with deionized water or washing said precipitate with deionized water followed by methanol prior to drying said precipitate.
10. The method of claim 4, wherein the complexing agent solution comprises one or more of sodium citrate, sodium ethylenediamine tetraacetate, sodium nitrilotriacetate, sodium gluconate, or sodium alginate.
11. An electrode for a sodium ion battery, the electrode comprising the prussian blue based compound of claim 1.
12. The electrode of claim 11, the prussian blue-based compound comprising Na 2 MnMn(CN) 6 、Na 2 CoMn(CN) 6 、Na 1.87 FeMn(CN) 6 、Na 1.76 MnMn(CN) 6 Or Na (or) 2 CuMn(CN) 6 。
13. A battery comprising a positive electrode and a negative electrode, characterized in that the negative electrode material comprises the prussian blue compound according to claim 1.
14. The battery according to claim 13, wherein the positive electrode material of the battery comprises the Prussian blue compound, na, and the like according to claim 1 x Mn[Fe(CN) 6 ] y One or more of the following.
15. The battery according to any one of claims 13 or 14, the positive electrode or negative electrode further comprising acetylene black and PTFE, the ratio of the positive electrode material or negative electrode material, the acetylene black, and the PTFE being (8-9.5): (0.3-1): (0.2-1).
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| WO2021168600A1 (en) * | 2020-02-24 | 2021-09-02 | 辽宁星空钠电电池有限公司 | Prussian blue sodium ion battery positive electrode material having low moisture content, preparation method therefor, and sodium ion battery |
| WO2022121570A1 (en) * | 2020-12-08 | 2022-06-16 | 宁德时代新能源科技股份有限公司 | Prussian blue transition metal cyanide, preparation method therefor, and positive electrode pole piece, secondary battery, battery module, battery pack, and apparatus related to prussian blue transition metal cyanide |
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| WO2021168600A1 (en) * | 2020-02-24 | 2021-09-02 | 辽宁星空钠电电池有限公司 | Prussian blue sodium ion battery positive electrode material having low moisture content, preparation method therefor, and sodium ion battery |
| WO2022121570A1 (en) * | 2020-12-08 | 2022-06-16 | 宁德时代新能源科技股份有限公司 | Prussian blue transition metal cyanide, preparation method therefor, and positive electrode pole piece, secondary battery, battery module, battery pack, and apparatus related to prussian blue transition metal cyanide |
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