CN110867583A - Synthetic method of Prussian blue battery positive electrode active material - Google Patents

Synthetic method of Prussian blue battery positive electrode active material Download PDF

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Publication number
CN110867583A
CN110867583A CN201911101343.6A CN201911101343A CN110867583A CN 110867583 A CN110867583 A CN 110867583A CN 201911101343 A CN201911101343 A CN 201911101343A CN 110867583 A CN110867583 A CN 110867583A
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China
Prior art keywords
dissolving
active material
prussian blue
deionized water
stirring until
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CN201911101343.6A
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Inventor
崔大祥
邓秉浩
张芳
卢玉英
张道明
王亚坤
阳靖峰
解启飞
焦靖华
张放为
王惠亚
赵立敏
周霖
李天昊
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Shanghai National Engineering Research Center for Nanotechnology Co Ltd
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Shanghai National Engineering Research Center for Nanotechnology Co Ltd
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Priority to CN201911101343.6A priority Critical patent/CN110867583A/en
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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
    • 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
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention provides a method for synthesizing a Prussian blue battery anode active material, which is used for improving the battery performance by changing conditions and slowing down the reaction rate to obtain the anode active material with less crystal defects. The complex containing transition metal elements is decomposed under certain conditions to release corresponding transition metal cations, and the transition metal cations and ferrocyanide can generate corresponding Prussian blue materials. The reaction rate can be adjusted by only changing conditions such as temperature, pH value and the like and controlling the decomposition rate of the related complex, and the operation is simple and rapid.

Description

Synthetic method of Prussian blue battery positive electrode active material
Technical Field
The invention relates to a method for synthesizing a Prussian blue battery anode active material, in particular to sodium cobalt hexacyanoferrate (Na)2CoFe(CN)6The method of (1).
Technical Field
The lithium ion battery is used as a new energy source and widely applied to the civil and military fields. In order to meet various requirements, such as unmanned aerial vehicles and electric vehicle batteries, high rate performance is required, and therefore, related battery materials are required to be developed. PBs are considered to be a very promising high rate positive electrode material for lithium ion batteries, and a discharge rate of 50C has been proposed in the art.
The common coprecipitation method has high reaction speed and rapid crystal nucleation, so that a large number of structural defects are generated in the crystal, the quality of the battery anode active material is poor, and the performances of the battery such as capacity, multiplying power and the like are influenced. The complex containing transition metal elements is an unstable compound, and can be decomposed under certain conditions to slowly release transition metal cations in the compound. The transition metal cations react with the ferricyanate ions in the solution to generate the Prussian blue material. The reaction rate is greatly reduced compared with the original synthesis method adopting a coprecipitation method, the reaction rate is greatly reduced, the product crystal has sufficient time for nucleation, the crystal defects are reduced, and the quality of the positive active material and the performance of the battery are improved.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to: provides a method for synthesizing a Prussian blue battery positive electrode active material.
The purpose of the invention is realized by the following scheme: a method for synthesizing a Prussian blue battery positive active material is used for improving the battery performance by changing conditions and slowing down the reaction rate to obtain the positive active material with less crystal defects, and comprises the following steps:
(1) dissolving 0-0.02mol of ammonia complex containing transition metals of Ni, Co, Mn, Cu or Fe in 200ml of deionized water, and magnetically stirring until the ammonia complex is dissolved;
(2) 0.02mol of sodium ferrocyanide Na4Fe(CN)6Or potassium ferrocyanide K4Fe(CN)6) Dissolving in 200ml deionized water, and magnetically stirring until dissolving;
(3) mixing the two solutions, and then adding 100ml of hydrochloric acid with the concentration of 0.01 mol/L;
(4) keeping the temperature at 50 ℃, stirring at a high speed for 8h to obtain a solution with dark blue-green color, standing for 3h, extracting precipitates, centrifugally cleaning with clear water and ethanol for three times respectively, and drying in a vacuum oven at 80 ℃ for 3h to obtain a finished product.
According to the properties of various complexes, the complex is decomposed by changing the conditions of temperature, pH value and the like, and corresponding transition metal cations are released to react with ferrocyanide.
The invention reduces the reaction rate of the Prussian blue material by controlling external control modes such as reactant concentration, addition rate and the like, and is improved by controlling the decomposition of a transition metal element complex to generate transition metal cations so as to control the rate of generating precipitates by the reaction. The purpose can be achieved only by controlling the inside of the system, namely controlling the temperature and the pH value. The method is particularly favorable for preparing the ferric ferrocyanide in the Prussian blue material, and sodium ferrocyanide (or potassium ferrocyanide) is a complex compound and can be heated under the acidic condition to obtain the ferric ferrocyanide precipitate. The synthesis method is simple to operate.
Drawings
FIG. 1 shows a schematic view of aIs example Na2CoIIFeII(CN)6SEM image of material.
Detailed Description
The present invention is described in detail by the following specific examples, but the scope of the present invention is not limited to these examples.
Example 1
A method for synthesizing a Prussian blue battery anode active material is characterized in that the conditions are changed, the reaction rate is slowed down, and the obtained anode active material with less crystal defects is used for improving the battery performance and comprises the following steps:
(1) dissolving 0.02mol of cobalt-ammonia complex in 200ml of deionized water, and magnetically stirring until the cobalt-ammonia complex is dissolved;
(2) 0.02mol of sodium ferrocyanide Na4Fe(CN)6Dissolving in 200ml deionized water, and magnetically stirring until dissolving;
(3) mixing the two solutions obtained in the steps (1) and (2), and then adding 100ml of hydrochloric acid with the concentration of 0.01 mol/L;
(4) keeping the temperature at 50 deg.C, stirring at high speed for 8h to turn the solution into dark blue-green, standing for 3h, extracting precipitate, centrifuging and cleaning with clear water and ethanol for three times, and vacuum oven drying at 80 deg.C for 3h to obtain the final product, as shown in FIG. 1, this example is Na2CoIIFeII(CN)6SEM image of material.
Example 2
Compared with the example 1, the method for synthesizing the Prussian blue battery positive electrode active material omits the step (1) and comprises the following steps:
(1) 0.04mol of sodium ferrocyanide Na4Fe(CN)6Dissolving in 200ml deionized water, and magnetically stirring until dissolving;
(2) then 100ml of hydrochloric acid with the concentration of 0.5mol/L is added;
(3) keeping the temperature at 80 ℃, stirring at a high speed for 8h to obtain a solution with dark blue-green color, standing for 3h, extracting precipitates, centrifugally cleaning with clear water and ethanol for three times respectively, and drying in a vacuum oven at 80 ℃ for 3h to obtain a finished product.
Example 3
A method for synthesizing a Prussian blue battery positive electrode active material is similar to that in example 1, and comprises the following steps:
(1) dissolving 0.02mol of cobalt-ammonia complex in 200ml of deionized water, and magnetically stirring until the cobalt-ammonia complex is dissolved;
(2) 0.02mol of potassium ferrocyanide K4Fe(CN)6Dissolving in 200ml deionized water, and magnetically stirring until dissolving;
(3) mixing the two solutions, and then adding 100ml of hydrochloric acid with the concentration of 0.01 mol/L;
(4) keeping the temperature at 50 ℃, stirring at a high speed for 8h to obtain a solution with dark blue-green color, standing for 3h, extracting precipitates, centrifugally cleaning with clear water and ethanol for three times respectively, and drying in a vacuum oven at 80 ℃ for 3h to obtain a finished product.

Claims (5)

1. A method for synthesizing a Prussian blue battery positive active material is characterized in that the conditions are changed, the reaction rate is slowed down, and the obtained positive active material with less crystal defects is used for improving the battery performance, and comprises the following steps:
(1) dissolving 0-0.02mol of ammonia complex containing transition metals of Ni, Co, Mn, Cu or Fe in 200ml of deionized water, and magnetically stirring until the ammonia complex is dissolved;
(2) 0.02mol of sodium ferrocyanide Na4Fe(CN)6Or potassium ferrocyanide K4Fe(CN)6) Dissolving in 200ml deionized water, and magnetically stirring until dissolving;
(3) mixing the two solutions, and then adding 100ml of hydrochloric acid with the concentration of 0.01 mol/L;
(4) keeping the temperature at 50 ℃, stirring at a high speed for 8h to obtain a solution with dark blue-green color, standing for 3h, extracting precipitates, centrifugally cleaning with clear water and ethanol for three times respectively, and drying in a vacuum oven at 80 ℃ for 3h to obtain a finished product.
2. The method for synthesizing the prussian blue battery cathode active material as claimed in claim 1, wherein the complex is decomposed by changing conditions including temperature and pH according to the properties of each complex, and corresponding transition metal cations are released to react with ferrocyanide.
3. The method for synthesizing the prussian blue battery positive active material according to claim 1 or 2, comprising the steps of:
(1) dissolving 0.02mol of cobalt-ammonia complex in 200ml of deionized water, and magnetically stirring until the cobalt-ammonia complex is dissolved;
(2) 0.02mol of sodium ferrocyanide Na4Fe(CN)6Dissolving in 200ml deionized water, and magnetically stirring until dissolving;
(3) mixing the two solutions obtained in the steps (1) and (2), and then adding 100ml of hydrochloric acid with the concentration of 0.01 mol/L;
(4) keeping the temperature at 50 deg.C, stirring at high speed for 8h to turn the solution into dark blue-green, standing for 3h, extracting precipitate, centrifuging and cleaning with clear water and ethanol for three times, and vacuum oven drying at 80 deg.C for 3h to obtain the final product, as shown in FIG. 1, this example is Na2CoIIFeII(CN)6SEM image of material.
4. The method for synthesizing the prussian blue battery positive active material according to claim 1 or 2, comprising the steps of:
(1) 0.04mol of sodium ferrocyanide Na4Fe(CN)6Dissolving in 200ml deionized water, and magnetically stirring until dissolving;
(2) then 100ml of hydrochloric acid with the concentration of 0.5mol/L is added;
(3) keeping the temperature at 80 ℃, stirring at a high speed for 8h to obtain a solution with dark blue-green color, standing for 3h, extracting precipitates, centrifugally cleaning with clear water and ethanol for three times respectively, and drying in a vacuum oven at 80 ℃ for 3h to obtain a finished product.
5. The method for synthesizing the prussian blue battery positive active material according to claim 1 or 2, comprising the steps of:
(1) dissolving 0.02mol of cobalt-ammonia complex in 200ml of deionized water, and magnetically stirring until the cobalt-ammonia complex is dissolved;
(2) 0.02mol of potassium ferrocyanide K4Fe(CN)6Dissolving in 200ml deionized water, and magnetically stirring until dissolving;
(3) mixing the two solutions, and then adding 100ml of hydrochloric acid with the concentration of 0.01 mol/L;
(4) keeping the temperature at 50 ℃, stirring at a high speed for 8h to obtain a solution with dark blue-green color, standing for 3h, extracting precipitates, centrifugally cleaning with clear water and ethanol for three times respectively, and drying in a vacuum oven at 80 ℃ for 3h to obtain a finished product.
CN201911101343.6A 2019-11-12 2019-11-12 Synthetic method of Prussian blue battery positive electrode active material Pending CN110867583A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112551550A (en) * 2020-12-11 2021-03-26 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of cobalt hexacyanoferrate lithium ion battery positive electrode active material, product and application thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103474659A (en) * 2013-08-23 2013-12-25 中国科学院化学研究所 Preparation method and application of positive pole material of sodium-ion battery
BR102014031926A2 (en) * 2014-12-18 2016-06-21 Univ Estadual Ponta Grossa process for manufacturing electrodes from carbon extracted from zinc / manganese stacks ”.
CN107364875A (en) * 2017-06-22 2017-11-21 全球能源互联网研究院 A kind of method and sodium-ion battery for preparing Prussian blue positive electrode
CN107634220A (en) * 2017-08-04 2018-01-26 上海交通大学 A kind of preparation method of prussian blue energy storage material
CN109698345A (en) * 2017-10-23 2019-04-30 宁德时代新能源科技股份有限公司 Prussian blue positive electrode material, preparation method thereof and electrochemical energy storage device

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103474659A (en) * 2013-08-23 2013-12-25 中国科学院化学研究所 Preparation method and application of positive pole material of sodium-ion battery
BR102014031926A2 (en) * 2014-12-18 2016-06-21 Univ Estadual Ponta Grossa process for manufacturing electrodes from carbon extracted from zinc / manganese stacks ”.
CN107364875A (en) * 2017-06-22 2017-11-21 全球能源互联网研究院 A kind of method and sodium-ion battery for preparing Prussian blue positive electrode
CN107634220A (en) * 2017-08-04 2018-01-26 上海交通大学 A kind of preparation method of prussian blue energy storage material
CN109698345A (en) * 2017-10-23 2019-04-30 宁德时代新能源科技股份有限公司 Prussian blue positive electrode material, preparation method thereof and electrochemical energy storage device

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112551550A (en) * 2020-12-11 2021-03-26 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of cobalt hexacyanoferrate lithium ion battery positive electrode active material, product and application thereof

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