CN114906859B - Capacity control type Prussian-like white production method and application - Google Patents
Capacity control type Prussian-like white production method and application Download PDFInfo
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- CN114906859B CN114906859B CN202210631350.2A CN202210631350A CN114906859B CN 114906859 B CN114906859 B CN 114906859B CN 202210631350 A CN202210631350 A CN 202210631350A CN 114906859 B CN114906859 B CN 114906859B
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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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- 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
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- 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
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a capacity control Prussian white production method, which comprises the steps of dissolving divalent manganese salt and electrochemical inert metal water-soluble salt, and then adding a complexing agent and a surfactant to obtain a solution A; dissolving sodium ferrocyanide, and adding sodium salt to obtain solution B; mixing the solution A and the solution B, hermetically aging under inert gas, filtering and drying to obtain the volume-controlled Prussian white. The capacity control type Prussian white is prepared by adopting the production method. The application of the capacity control Prussian white in the sodium ion battery. The beneficial effects are as follows: the capacity release of Prussian white is controlled by electrochemical inert elements, the elements do not generate oxidation-reduction reaction in the electrochemical reaction process to stabilize the structure, the control of the sodium deintercalation amount of the material, namely the control of the electrochemical reaction depth, is realized by the existence of the elements, and the material can be used for sodium ion batteries to effectively improve the stability of the sodium ion batteries.
Description
Technical Field
The invention relates to the technical field of sodium ion battery electrode materials, in particular to a capacity control type Prussian white production method and application.
Background
For batteries, the main parameters that must be considered are: price ($ W h/kg), life (years, cycles) and power (W k/g), which requires raw materials with sufficient availability (low price), sodium batteries are considered for use. Sodium ions and lithium ions have similar chemical properties, belong to alkali metals, are rich in resources, can greatly reduce the cost of the battery, are energy storage media with good application prospects developed in recent years, and are imperative to develop suitable electrode materials of the sodium ion battery.
The development of sodium batteries is limited by the discovery of new positive electrode materials, the radius of sodium ions (0.102 nm) is larger than that of lithium ions (0.076 nm), and the conventional positive electrode materials cannot well meet the requirements of sodium ion batteries on the positive electrode materials, so that we need to find a suitable positive electrode material, wherein advanced positive electrode materials with high specific energy, high rate performance, excellent cycle stability and good safety are still highly desirable.
Sodium ions have larger size and atomic weight than lithium ions, tend to experience greater resistance when diffused in the crystal lattice, although high reversible capacity and sufficient cycle life have been achieved in the current negative electrode materials, such as pyrolytic carbon, alloyed metals and nonmetallic materials, however, in the positive electrode materials, both in terms of capacity and rate capability, the interaction between sodium ions and cyanide ions is weak, so that Prussian blue and its analogues are advantageous on sodium ion battery positive electrode materials, and in addition, layered metal oxides and polyanion compounds tend to be synthesized at high temperatures, and thus are relatively high in large-scale applications, whereas Prussian blue and analogues can be synthesized by simple co-precipitation methods at normal temperature conditions, and are economical, environmentally friendly, and easy to produce on a large scale.
Prussian blue and analogues thereof have the general formula A x M y [B(CN) 6 ]z·PBA·mH 2 O (x, y, z, m=stoichiometric number; A, B =alkali metal; M=transition metal) through the current research situation of Prussian blue and analogues thereof, it can be found that by utilizing the characteristics of the multivalent state and the open framework structure of the Prussian blue analogues, the chemical composition of the Prussian blue analogues can be changed before the integral structure of crystals is not damaged, and the ions can be replaced or inserted to form a multi-element Prussian blue analogue, and different combinations of the types and the numbers of the replaced or inserted elements can effectively adjust the properties of PBA, improve the sodium storage performance of the material, and for the common single-element or binary Prussian blue sodium ion battery positive electrode material, both high capacity and high cycle stability are difficult to be simultaneously considered.
Disclosure of Invention
The invention aims to provide a capacity control type Prussian white production method and application thereof, so as to overcome the defects in the prior art.
The technical scheme for solving the technical problems is as follows:
a method for producing Prussian white with capacity control comprises the following steps:
s100, dissolving divalent manganese salt and electrochemical inert metal water-soluble salt, and then 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, hermetically aging under inert gas, filtering and drying to obtain the capacity-controlled Prussian white.
The beneficial effects of the invention are as follows:
manganese ions and inert metal ions are mixed in an atomic level in a solution, and then complexing agents are added for coordination in advance, and then the manganese ions and the inert metal ions are gradually released after the complexing agents react with iron cyanide, so that the obtained material has better crystallinity and fewer vacancy defects;
the capacity release of Prussian white is controlled by electrochemical inert elements, and the difference between the Prussian white and the Prussian white is that the product contains the electrochemical inert elements, the elements do not generate oxidation-reduction reaction in the electrochemical reaction process to stabilize the structure, the sodium deintercalation amount of the material is controlled by the existence of the elements, namely the electrochemical reaction depth is controlled, and the material is used for a sodium ion battery to effectively improve the stability of the sodium ion battery.
On the basis of the technical scheme, the invention can be improved as follows.
Further, the divalent manganese salt is water-soluble, and the concentration is 10 mmol/L-100 mmol/L.
The adoption of the method has the further beneficial effects that: the aging time is long when the concentration is too low, sedimentation is not easy, collection is difficult, the morphology of the obtained material is poor when the concentration is too high, and the defect can be effectively overcome when the method is limited in the range.
Further, the electrochemically inert metal in the electrochemically inert metal water-soluble salt is nickel, zinc, copper or lanthanide Ce.
Further, the proportion of manganese in solution a is higher than the proportion of electrochemically inert metal, and the anions of the divalent manganese salt and the electrochemically inert metal water-soluble salt are the same. The adoption of the method has the further beneficial effects that:
the excessive influence on the capacity exertion caused by the excessively high content of inert metal is avoided, and the optimization of the stability is not continuously enhanced;
the divalent manganese salt has the same anions as the electrochemically inert metal water-soluble salt, and can reduce the types of hetero ions.
Further, the complexing agent is citric acid, sodium citrate, oxalic acid or EDTA (ethylenediamine 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 the total amount of the divalent manganese salt and the electrochemically inert metal water-soluble salt.
The adoption of the method has the further beneficial effects that: by inhibiting the hydrolysis of ferricyanide with excess sodium, the sodium content of the desired product can be made 2 times the total transition metal.
Further, the aging temperature is lower than 100 ℃.
The adoption of the method has the further beneficial effects that: the water solution is taken as a reaction solvent, water with an excessively high ageing temperature can boil to influence the ageing process, and the invention can effectively overcome the defects when limited in the range.
Based on the technical scheme, the invention also provides the capacity control type Prussian white which is prepared by adopting the production method.
The adoption of the method has the further beneficial effects that: the prepared capacity control Prussian white has higher structural stability.
Based on the technical scheme, the invention also provides application of the capacity control Prussian-like white in a sodium ion battery anode material. The adoption of the method has the further beneficial effects that: 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 graph showing the morphology of the products obtained in examples 1, 2 and 3.
Figure 2 is an XRD pattern of the product obtained in examples 1, 2, 3.
FIG. 3 shows the products obtained in examples 1, 2 and 3 at 15 mA.g -1 Charge-discharge curve graph at current density of (c).
Detailed Description
The principles and features of the present invention are described below with reference to the drawings, the examples are illustrated for the purpose of illustrating the invention and are not to be construed as limiting the scope of the invention.
Example 1
A method for producing Prussian white with capacity control comprises the following steps:
s100, dissolving 0.8 mmole of MnSO4,0.1 mmole of CoSO4,0.1 mmole of NiSO4 and 1 mmole of citric acid in 100ml of deionized water to obtain a solution A;
s200, 1mmol of sodium ferrocyanide, 5.85g of NaCl and 0.5g of PVP are dissolved in 100ml of deionized water to obtain a solution B;
s300, respectively stirring the solution A and the solution B to enable the solution A and the solution B to be fully dissolved, for example, stirring for 30min;
slowly dripping the solution A into the stirring solution B by a peristaltic pump, stirring for 2 hours after the solution A is completely dripped, sealing under inert atmosphere, and aging for 48 hours at room temperature, wherein the room temperature is usually 25 ℃;
in actual operation: the solution A can be added dropwise or directly into the solution B, and is determined according to the anion type of the salt used;
after centrifugally collecting the precipitate, washing the precipitate with deionized water for 3 times, and finally washing the precipitate with absolute ethyl alcohol once;
placing the precipitate in a vacuum oven at 80 ℃ for drying for 24 hours to finally obtain a sample;
in this example, the Mn to Co to Ni ratio is 8:1:1, so the resulting product can be described as: MCN-811.
Example 2
This embodiment differs from embodiment 1 in that: mn, co and Ni are in a proportion of 6:2:2, the others are unchanged, and are marked as: MCN-622.
Example 3
This embodiment differs from embodiment 1 in that: mn, co and Ni are in a proportion of 5:2:3, the others are unchanged, and are marked as: MCN-523.
Fig. 1 is a graph showing the morphology of the products obtained in examples 1, 2 and 3, in that order, and it can be seen from the graph: with the increase of the content of inert metal, the morphology of the product is more regular;
fig. 2 shows XRD patterns 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 material: conductive agent: the binder is 7:2:1, the conductive agent consists of three quarters of ketjen black and one quarter of super P, and the binder is polyvinylidene fluoride emulsion (PVDF);
fully grinding the materials by using a mortar to obtain electrode slurry, winding the electrode slurry into sheets, drying the sheets in a vacuum oven at 100 ℃ for more than 12 hours, and then transferring the sheets into a 60-blast oven for drying;
and shearing the membrane to obtain a square electrode slice with the concentration of about 1.5mg, and pressing the square electrode slice on an aluminum net to obtain the working electrode.
FIG. 3 shows the products obtained in examples 1, 2 and 3 at 15 mA.g -1 The charge-discharge curve at the current density of (3) is shown by the graph: discharge capacities were 109.3mAh g, respectively -1 ；127.4mAh g -1 ；103.3mAh g -1 The capacity of the material is controlled by adding inert metal, the structural stability of the material can be effectively improved, the material has better reversible sodium intercalation and deintercalation performance, but the sodium storage capacity can be reduced along with excessive addition of electrochemical inert elements.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.
Claims (3)
1. The capacity control type Prussian white production method is characterized by comprising the following steps of:
s100, 0.6mmolMnSO 4 、0.2mmolCoSO 4 、0.2mmolNiSO 4 1mmol of citric acid is dissolved in 100ml deionized water to obtain solution A;
s200, 1mmol of sodium ferrocyanide, 5.85g of NaCl and 0.5g of PVP are dissolved in 100ml of deionized water to obtain a solution B;
s300, respectively stirring the solution A and the solution B to be fully dissolved, slowly dripping the solution A into the stirring solution B through a peristaltic pump, stirring for 2 hours after the solution A is completely dripped, sealing under inert atmosphere, aging for 48 hours at room temperature, centrifugally collecting the precipitate, washing the precipitate with deionized water for 3 times, and finally washing the precipitate with absolute ethyl alcohol for 1 time; and (3) placing the precipitate in a vacuum oven at 80 ℃ for drying for 24 hours to obtain the capacity-controlled Prussian white.
2. A capacity control type Prussian white, characterized in that: is produced by the production method as claimed in claim 1.
3. Use of the capacity-controlled Prussian-like white according to claim 2 in a positive electrode material of a sodium ion battery.
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| 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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| 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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