CN114906859A - Production method and application of capacity-controlled type Prussian-like white - Google Patents

Production method and application of capacity-controlled type Prussian-like white Download PDF

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CN114906859A
CN114906859A CN202210631350.2A CN202210631350A CN114906859A CN 114906859 A CN114906859 A CN 114906859A CN 202210631350 A CN202210631350 A CN 202210631350A CN 114906859 A CN114906859 A CN 114906859A
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prussian
white
capacity
controlled
sodium
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CN114906859B (en
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韩建涛
徐月
秦道敏
方淳
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Huazhong University of Science and Technology
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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
    • 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
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Inorganic Chemistry (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention relates to a capacity control type Prussian-like white production method, which comprises the steps of dissolving a divalent manganese salt and an electrochemical inert metal water-soluble salt, and adding a complexing agent and a surfactant to obtain a solution A; dissolving sodium ferrocyanide, and adding sodium salt to obtain a solution B; and mixing the solution A and the solution B, sealing and aging under inert gas, filtering and drying to obtain the capacity-controlled type prussian-like white. A capacity-controlled Prussian-like white is prepared by the above production method. An application of capacity control type Prussian-like white in a sodium ion battery. The beneficial effects are that: the capacity release of the Prussian white is controlled by an electrochemical inert element, the element does not generate an oxidation-reduction reaction in the electrochemical reaction process to stabilize the structure, the control of the sodium desorption amount of the material is realized by the existence of the element, namely the electrochemical reaction depth is controlled, and the stability of the sodium ion battery can be effectively improved when the material is used for the sodium ion battery.

Description

Production method and application of capacity-controlled type Prussian-like white
Technical Field
The invention relates to the technical field of sodium ion battery electrode materials, in particular to a production method and application of capacity control type Prussian-like white.
Background
For batteries, the main parameters that must be considered are: price ($ W h/kg), life (year, cycles) and power (W k/g), which requires raw materials with sufficient availability (low price), and therefore, sodium batteries are considered. The sodium ion and the lithium ion have similar chemical properties, belong to alkali metals, are rich in resources, and can greatly reduce the cost of the battery.
The development of sodium batteries is limited by the discovery of new cathode materials, the radius of sodium ions (0.102 nm) is larger than that of lithium ions (0.076 nm), and the traditional cathode materials cannot well meet the requirements of sodium ion batteries on the cathode materials, so that a suitable cathode material needs to be found, wherein the advanced cathode material has high specific energy, high rate performance, excellent cycle stability and good safety and is still highly expected by people.
Sodium ions, which have a larger size and atomic weight than lithium ions, tend to experience greater resistance to diffusion in the crystal lattice, although high reversible capacity and sufficient cycle life have been achieved in the negative electrode materials, such as pyrolytic carbon, alloying-type metals, and non-metallic materials, at present, however, in the aspect of positive electrode materials, the positive electrode materials are all deficient in capacity and rate performance, the interaction between sodium ions and cyanide ions is weak, so that Prussian blue and the like have advantages on the positive electrode materials of the sodium-ion batteries, in addition, layered metal oxides and polyanionic compounds tend to require synthesis at high temperatures and are therefore relatively high for large-scale applications, the Prussian blue and the analogues can be synthesized by a simple coprecipitation method at normal temperature, are economical and practical, are environment-friendly and are easy for large-scale production.
The general formula of the Prussian blue and the analogues thereof is A x M y [B(CN) 6 ]z·PBA·mH 2 The fact that O (x, y, z, M is a stoichiometric number; A, B is an alkali metal; and M is a transition metal) is utilized by the current research situation of the Prussian blue and the analogues thereof can be found out that the multivalent state and the open frame of the Prussian blue analogue are utilizedThe characteristics of the frame structure enable the chemical composition of the PBA to be changed before the overall structure of the crystal is not damaged, the PBA can be subjected to ion replacement or insertion to form a multi-element Prussian blue analogue, the properties of the PBA can be effectively adjusted by different combinations of the types and the numbers of elements subjected to replacement or insertion, the sodium storage performance of the PBA is improved, and for a common monobasic or dibasic Prussian blue sodium ion battery positive electrode material, high capacity and high cycle stability are difficult to be considered simultaneously.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a production method and application of capacity control type Prussian-like white, so as to overcome the defects in the prior art.
The technical scheme for solving the technical problems is as follows:
a production method of capacity-controlled type Prussian-like white comprises the following steps:
s100, dissolving a divalent manganese salt and an electrochemical inert metal water-soluble salt, and adding a complexing agent and a surfactant to obtain a solution A;
s200, dissolving sodium ferrocyanide, and adding sodium salt to obtain a solution B;
and S300, mixing the solution A and the solution B, sealing and aging under inert gas, filtering and drying to obtain the capacity-controlled type Prussian-like white.
The beneficial effects of the invention are:
after manganese ions and inert metal ions are mixed in the solution in an atomic scale, a complexing agent is added for coordination in advance, and then the manganese ions and the inert metal ions are reacted with iron cyanide, so that the manganese ions and the inert metal ions are gradually released, and the obtained material has better crystallinity and fewer vacancy defects;
the capacity release of the prussian white is controlled by an electrochemical inert element, and the prussian white is different from the reported prussian blue and prussian white in that a product contains the electrochemical inert element, the element does not undergo a redox reaction in an electrochemical reaction process to stabilize a structure, and the control of the sodium deintercalation amount of a material is realized by the existence of the element, namely the electrochemical reaction depth is controlled, and the material can effectively improve the stability of a sodium ion battery when being used for the sodium ion battery.
On the basis of the technical scheme, the invention can be further improved as follows.
Furthermore, the divalent manganese salt is water-soluble, and the concentration is 10 mmol/L-100 mmol/L.
Adopt above-mentioned further beneficial effect to do: the invention has the advantages of long aging time due to too low concentration, difficult sedimentation, difficult collection and poor appearance of the obtained material due to too high concentration, and the defects can be effectively overcome by limiting the range.
Further, the electrochemically inert metal in the electrochemically inert metal water-soluble salt is nickel, zinc, copper or lanthanide Ce.
Further, the ratio of manganese in the solution A is higher than that of the electrochemically inert metal, and the divalent manganese salt and the electrochemically inert metal water-soluble salt have the same anion. Adopt above-mentioned further beneficial effect to do:
the phenomenon that the content of inert metal is too high to excessively influence the exertion of capacity is avoided, and the optimization of stability is not continuously enhanced;
the divalent manganese salt and the electrochemically inert metal water-soluble salt have the same anion, and the species of the hetero ions can be reduced.
Further, the complexing agent is citric acid, sodium citrate, oxalic acid or EDTA (ethylene diamine tetraacetic acid).
Further, the surfactant is PVP (polyvinylpyrrolidone) or CTAB (cetyltrimethylammonium bromide).
Further, the molar amount of the sodium salt is more than three times of the total amount of the divalent manganese salt and the electrochemically inert metal water-soluble salt.
Adopt above-mentioned further beneficial effect to do: the sodium content of the desired product can be made 2 times the total transition metal by inhibiting hydrolysis of ferricyanide by an excess of sodium.
Further, the aging temperature is below 100 ℃.
Adopt above-mentioned further beneficial effect to do: the aqueous solution is used as a reaction solvent, and water can boil at an excessively high aging temperature to influence the aging process, but the invention can effectively overcome the defects by limiting the range.
Based on the technical scheme, the invention also provides the capacity control type Prussian-like white which is prepared by adopting the production method.
Adopt above-mentioned further beneficial effect to do: the prepared capacity-controlled Prussian-like white has higher structural stability.
Based on the technical scheme, the invention also provides application of the capacity control type Prussian-like white in the positive electrode material of the sodium-ion battery. Adopt above-mentioned further beneficial effect to do: the material is used for the positive electrode material of the sodium-ion battery, and can effectively improve the cycling stability of the sodium-ion battery.
Drawings
FIG. 1 is a diagram showing the morphologies of the products obtained in examples 1, 2 and 3.
FIG. 2 is an XRD pattern of the products obtained in examples 1, 2 and 3.
FIG. 3 shows the results of examples 1, 2 and 3 at 15mA g -1 A charge-discharge curve diagram at a current density of (a).
Detailed Description
The principles and features of this invention are described below in conjunction with the following drawings, which are set forth by way of illustration only and are not intended to limit the scope of the invention.
Example 1
A production method of capacity-controlled type Prussian-like white comprises the following steps:
s100, dissolving 0.8mmol of MnSO4, 0.1mmol of CoSO4,0.1mmol of NiSO4 and 1mmol of citric acid in 100ml of deionized water to obtain a solution A;
s200, dissolving 1mmol of sodium ferrocyanide, 5.85g of NaCl and 0.5g of PVP in 100ml of deionized water to obtain a solution B;
s300, respectively stirring the solution A and the solution B to enable the solutions to be fully dissolved, such as stirring for 30 min;
slowly dripping the solution A into the stirring solution B through a peristaltic pump, stirring for 2 hours after completely dripping, sealing under an inert atmosphere, and then aging at room temperature for 48 hours, wherein the room temperature is usually 25 ℃;
in the actual operation: the solution A can be dripped or directly poured into the solution B, and is determined according to the anion species of the used salt;
after centrifugally collecting the precipitate, washing the precipitate with deionized water for 3 times, and finally washing with absolute ethyl alcohol for one time;
placing the precipitate in a vacuum oven at 80 ℃ for drying for 24 hours to finally obtain a sample;
in this example, the ratio of Mn to Co to Ni is 8:1:1, so the resulting product can be written as: MCN-811.
Example 2
This example differs from example 1 in that: the ratio of Mn, Co and Ni is 6: 2: 2, otherwise unchanged, and is recorded as: MCN-622.
Example 3
This example differs from example 1 in that: the ratio of Mn, Co and Ni is 5: 2: 3, the others are unchanged and are recorded as: MCN-523.
FIG. 1 is a diagram of the morphology of the products obtained in examples 1, 2 and 3, which shows that: with the increase of the content of the inert metal, the appearance of the product is more regular;
FIG. 2 is the XRD pattern of the products obtained in examples 1, 2 and 3, from which it can be seen that: the obtained products have better crystallinity and are all monoclinic phases rich in sodium;
in the experiment, a free-standing method is adopted to manufacture the electrode slice;
active substance: conductive agent: the adhesive is 7:2:1, the conductive agent consists of three-quarter Ketjen black and one-quarter super P, and polyvinylidene fluoride emulsion (PVDF) is used as the adhesive;
fully grinding the materials by using a mortar to obtain electrode slurry, winding the electrode slurry into a sheet, putting the sheet into a vacuum oven at 100 ℃ for drying for more than 12 hours, and then transferring the sheet into a 60-blast oven for drying;
and cutting the membrane into a square electrode slice with the thickness of about 1.5mg, and pressing the square electrode slice on an aluminum net to obtain the working electrode.
FIG. 3 shows the results of examples 1, 2 and 3 at 15mA g -1 The following are shown in the charge-discharge graph at the current density of (1): the discharge capacities were 109.3mAh g, respectively -1 ；127.4mAh g -1 ；103.3mAh g -1 Inert metal addition controls the capacity of the materialThe material can effectively improve the structural stability of the material, has better performance of reversibly extracting and inserting sodium, but can reduce the sodium storage capacity along with the excessive addition of electrochemical inert elements.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.

Claims (10)

1. A production method of capacity-controlled type Prussian-like white is characterized by comprising the following steps:
s100, dissolving a divalent manganese salt and an electrochemical inert metal water-soluble salt, and adding a complexing agent and a surfactant to obtain a solution A;
s200, dissolving sodium ferrocyanide, and adding sodium salt to obtain a solution B;
and S300, mixing the solution A and the solution B, sealing and aging under inert gas, filtering and drying to obtain the capacity-controlled type Prussian-like white.
2. The method for producing capacity-controlled type prussian-like white according to claim 1, wherein: the divalent manganese salt is water-soluble, and the concentration is 10 mmol/L-100 mmol/L.
3. The method for producing capacity-controlled prussian-like white according to claim 1 or 2, wherein: the electrochemical inert metal in the electrochemical inert metal water-soluble salt is nickel, zinc, copper or lanthanide Ce.
4. The method for producing capacity-controlled type Prussian-like white according to claim 1, 2 or 3, wherein: the proportion of manganese in the solution A is higher than that of the electrochemical inert metal, and the anions of the divalent manganese salt and the electrochemical inert metal water-soluble salt are the same.
5. The method for producing capacity-controlled type Prussian-like white according to claim 1, wherein: the complexing agent is citric acid, sodium citrate, oxalic acid or EDTA.
6. The method for producing capacity-controlled type Prussian-like white according to claim 1, wherein: the surfactant is PVP or CTAB.
7. The method for producing capacity-controlled type Prussian-like white according to claim 1, wherein: the molar weight of the sodium salt is more than three times of the total weight of the divalent manganese salt and the electrochemically inert metal water-soluble salt.
8. The method for producing capacity-controlled type Prussian-like white according to claim 1, wherein: the ageing temperature is lower than 100 ℃.
9. A capacity-controlled Prussian-like white characterized by: the product is prepared by the production method of any one of claims 1 to 8.
10. The use of the capacity-controlled Prussian-like white produced by the production method according to any one of claims 1 to 8 or the capacity-controlled Prussian-like white according to claim 9 in a positive electrode material of a sodium-ion battery.
CN202210631350.2A 2022-06-06 2022-06-06 Capacity control type Prussian-like white production method and application Active CN114906859B (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113839032A (en) * 2021-09-15 2021-12-24 杭州思拓瑞吉科技有限公司 Low-cost Prussian white material, and preparation method and application thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113839032A (en) * 2021-09-15 2021-12-24 杭州思拓瑞吉科技有限公司 Low-cost Prussian white material, and preparation method and application thereof

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