CN109638218A - A method of improving zinc electrode corrosion resistance - Google Patents

A method of improving zinc electrode corrosion resistance Download PDF

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Publication number
CN109638218A
CN109638218A CN201811488948.0A CN201811488948A CN109638218A CN 109638218 A CN109638218 A CN 109638218A CN 201811488948 A CN201811488948 A CN 201811488948A CN 109638218 A CN109638218 A CN 109638218A
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China
Prior art keywords
electrode
zinc electrode
corrosion resistance
zinc
resistance according
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CN201811488948.0A
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Chinese (zh)
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章桥新
王中豪
余金桂
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Wuhan University of Technology WUT
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Wuhan University of Technology WUT
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Priority to CN201811488948.0A priority Critical patent/CN109638218A/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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/045—Electrochemical coating; Electrochemical impregnation
    • H01M4/0452—Electrochemical coating; Electrochemical impregnation from solutions
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a kind of methods for improving zinc electrode corrosion resistance, and using metallic zinc as the matrix of electro-deposition, inorganic inhibitor is added, and electrodeposit reaction is carried out under constant voltage dc source, and deposition obtains doped electrode under room temperature；In electrode process, selects the alkaline electrolyte solution containing a small amount of zinc salt and organic inhibitor is added, stir evenly, be put into doped electrode and be electrochemically reacted.The method of the invention can effective holding capacitor amount, greatly promote the corrosion resistant performance of zinc electrode, reduce hydrogen-separating quantity of the zinc electrode in alkaline electrolyte solution, and reduce the generation of dendrite, extend the storage life of zinc electrode, method preparation is simple and efficient, and can effectively reduce production cost.

Description

A method of improving zinc electrode corrosion resistance
Technical field
The present invention relates to electrochemical device technical fields, refer in particular to a kind of method for improving zinc electrode corrosion resistance.
Background technique
Currently, Zinc material is resourceful, there is excellent chemical property, energy density height, non-environmental-pollution etc. are excellent Performance, is widely used as the cathode material of electrochmical power source, but zinc due to the thermodynamic stability of its own it is relatively poor, relatively hold The phenomenon that being also easy to produce passivation and self-corrosion.
Chinese patent (application publication number CN 101969121A) discloses a kind of improvement zinc electrode charge and discharge circulation life Method.It discloses using calcium zincates as the primary raw material of zinc electrode, addition acetylene black, lead oxide, coats hydrogen-oxygen at bismuth oxide One or more of the four kinds of additives of calcium zincates for changing lanthanum, are made zinc electrode；Wherein every 100g zinc electrode adds acetylene black not More than 1.2g, adds bismuth oxide and be no more than 10g, addition lead oxide is no more than 14g, and the calcium zincates of addition cladding lanthanum hydroxide are not More than 8g.It is described only to prepare zinc electrode by the way that additive appropriate is added, hence it is evident that the specific capacity and charge and discharge for improving zinc electrode are followed Ring number is not related to the stability of zinc electrode and being efficiently modified for corrosion resistance.
Obviously, under the premise of zinc electrode is widely used, the self-corrosion phenomenon that proposition effective ways slow down zinc electrode is especially heavy It wants.
Summary of the invention
The present invention provides a kind of raising zinc electrode corrosion resistant method, by selecting inorganic inhibitor to carry out electro-deposition Method prepares the zinc electrode haveing excellent performance, and is incorporated in alkaline electrolyte and reacts in conjunction with the collaboration of organic inhibitor, can be effective Holding capacitor amount, and the corrosion resistant performance of zinc electrode is greatly promoted, method preparation is simple and efficient, and can effectively reduce production cost.
To achieve the above object, The technical solution adopted by the invention is as follows:
A method of improving zinc electrode corrosion resistance, comprising the following steps: using metallic zinc as the matrix of electro-deposition, add Enter inorganic inhibitor, electrodeposit reaction is carried out under constant voltage dc source, obtains doped electrode under room temperature；In electrode reaction mistake Cheng Zhong selects the alkaline electrolyte solution containing a small amount of zinc salt and organic inhibitor is added, stirs evenly, be put into doped electrode It is electrochemically reacted.
According to above scheme, the inorganic inhibitor is PbCl2And BiCl3Mixture.
According to above scheme, PbCl in the inorganic inhibitor2And BiCl3Mass ratio be 1:1-1:4.
According to above scheme, the organic inhibitor includes neopelex, dodecyl sodium sulfate, benzene And one or more of imidazoles, cetyltrimethylammonium bromide.
According to above scheme, the inorganic inhibitor mass concentration is 0.05-0.07g/L.
According to above scheme, mass fraction of the organic inhibitor in alkaline electrolyte solution is 0.05%- 0.1%.
According to above scheme, the electro-deposition current density is 90-110mA/cm2。
According to above scheme, the room temperature sedimentation time is 25-35 minutes.
The mechanism of action of the invention:
The present invention, which is added in inorganic inhibitor, contains Bi3+、Pb2+The overpotential of hydrogen evolution ratio Zn of ion2+Want high, first in zinc Electrode surface forms substrate, in electric discharge, Bi3+、Pb2+Earlier than Zn2+It is reduced before, the Bi of reduction3+、 Pb2+With Zn2+It is formed To improve the overpotential of hydrogen evolution of zinc electrode the charge efficiency and depth of charge of zinc electrode can be improved, while can in alloy Inhibit charge and discharge cycles and it is wet shelve during hydrogen precipitation, can thus keep capacity and the reduction of zinc electrode Deformation, dendritic growth of zinc electrode etc. occur.
The organic inhibitor being added, organic molecule can be attached to zinc by modes such as chemisorption or physical absorptions Electrode matrix surface layer, organic molecule contain water-wet side and hydrophobic side, during reacting progress, the hydrophobic side of organic molecule It can be adsorbed on around zinc electrode matrix, so that its overpotential of hydrogen evolution increases, the water-wet side of the other end is due to hydration generation water Change shell, so that the free water molecule quantity on matrix periphery reduces, lead to the activity reduction of hydrone, this tunic just Zinc electrode is kept apart with the reactant in solution, so that the corrosion resistance of zinc electrode has obtained very big reinforcement, simultaneously Also related chemical property of the zinc electrode under alkaline environment is improved.
Compared with the prior art, beneficial effects of the present invention:
(1) method that the present invention is added that inorganic inhibitor carries out electro-deposition prepares the zinc electrode haveing excellent performance, and effectively changes The depositional configuration of kind zinc electrode reduces hydrogen-separating quantity of the zinc electrode in alkaline electrolyte solution, and reduces the generation of dendrite, then It cooperates with and is added in conjunction with organic inhibitor, be remarkably improved corrosion resistance of the zinc electrode in alkaline environment, extend the storage of electrode Service life.
(2) present invention is by containing Bi in inorganic inhibitor3+、Pb2+The self discharge of zinc electrode can be effectively suppressed in ion, from And the volumetric properties that zinc electrode can be kept excellent, and improve the charge efficiency and depth of charge of zinc electrode.
(3) this method preparation is simple and efficient, and can effectively reduce production cost.
Detailed description of the invention
Fig. 1 is that the ZN-Pb-Bi electrode of the embodiment of the present invention 1 impregnates 12 hours SEM in the KOH solution of 1mol/L Figure；
Fig. 2 is the SEM figure that comparative example 1ZN electrode of the present invention impregnates 12 hours in the KOH solution of 1mol/L；
Fig. 3 is the SEM figure that comparative example 2ZN-Pb-Bi electrode of the present invention impregnates 12 hours in the KOH solution of 1mol/L.
Specific embodiment
For a better understanding of the present invention, below with reference to the embodiment content that the present invention is furture elucidated, but it is of the invention Content is not limited solely to the following examples.
Embodiment 1:
Using metallic zinc as the matrix of electro-deposition, the inorganic inhibitor that mass concentration is 0.05g/L is added, it is described inorganic slow Agent is lost by PbCl2And BiCl31:1 in mass ratio configures to obtain, and it is 90mA/cm that current density is carried out under constant voltage dc source2 Electrodeposit reaction, deposit 25 minutes under room temperature, obtain doped electrode；In electrode process, to contain a small amount of zincate 1mol/L KOH electrolyte solution in neopelex is added, the neopelex is in alkaline electrolysis Mass fraction in matter solution is 0.05%, stirs evenly, is put into doped electrode and is electrochemically reacted.
Embodiment 2:
Using metallic zinc as the matrix of electro-deposition, the inorganic inhibitor that mass concentration is 0.06g/L is added, it is described inorganic slow Agent is lost by PbCl2And BiCl31:2 in mass ratio configures to obtain, and it is 100mA/cm that current density is carried out under constant voltage dc source2 Electrodeposit reaction, deposit 30 minutes under room temperature, obtain doped electrode；In electrode process, to contain a small amount of zincate 1mol/L KOH solution in be added dodecyl sodium sulfate and benzimidazole mixed liquor, the dodecyl sodium sulfate and Mass fraction of the mixed liquor of benzimidazole in alkaline electrolyte solution be 0.08%, stir evenly, be put into doped electrode into Row electrochemical reaction.
Embodiment 3:
Using metallic zinc as the matrix of electro-deposition, the inorganic inhibitor that mass concentration is 0.07g/L is added, it is described inorganic slow Agent is lost by PbCl2And BiCl31:4 in mass ratio configures to obtain, and it is 110mA/cm that current density is carried out under constant voltage dc source2 Electrodeposit reaction, deposit 35 minutes under room temperature, obtain doped electrode；In electrode process, to contain a small amount of zincate 1mol/L KOH solution in cetyltrimethylammonium bromide is added, the cetyltrimethylammonium bromide is in alkaline electro Mass fraction in electrolyte solution is 0.1%, stirs evenly, is put into doped electrode and is electrochemically reacted.
Comparative example 1:
Using metallic zinc as zinc electrode, it is added without inorganic inhibitor and carries out electrodeposit reaction, in electrode process, Neopelex, the neopelex is added into the KOH solution of the 1mol/L containing a small amount of zincate Mass fraction in alkaline electrolyte solution is 0.08%, stirs evenly, is put into zinc electrode and is electrochemically reacted
Comparative example 2:
Using metallic zinc as the matrix of electro-deposition, the inorganic inhibitor that mass concentration is 0.06g/L is added, it is described inorganic slow Agent is lost by PbCl2And BiCl31:2 in mass ratio configures to obtain, and it is 100mA/cm that current density is carried out under constant voltage dc source2 Electrodeposit reaction, deposit 30 minutes under room temperature, obtain doped electrode；In electrode process, to contain a small amount of zincate 1mol/L KOH solution as electrolyte solution, be added without organic inhibitor, be directly placed into doped electrode carry out electrochemistry Reaction.
The present invention carries out the test of associated electrical performance to embodiment 1-3 and comparative example 1-2 products obtained therefrom, wherein mixes Miscellaneous zinc electrode and untreated zinc electrode reaction surface are the square that side length is 10mm, and are sealed by epoxy resin Behind and side are added into corresponding electrolyte solution and carry out electrochemical property test, which is by measurement 12 The variation of zinc electrode sample quality in specific solution is calculated the corrosion rate of zinc electrode, corrosion speed in hour Rate calculation formula are as follows:
m1、m2Respectively represent the quality (mg) of corrosion front and back sample；
S representative sample surface area (cm2)；
T represents the time (h) of zinc electrode immersion；
The calculation formula of the inhibition efficiency η of corrosion inhibiter dodecyl sodium sulfate is as follows:
v1Represent corrosion rate of the zinc electrode in the KOH solution without containing organic inhibitor；
v2Represent corrosion rate of the zinc electrode in the KOH of the organic inhibitor containing various concentration.
The corrosion rate and sustained release efficiency of each electrode material of table 1. 1
By upper Biao Ke get, the present invention and the non-electrodeposition process sample of comparative example 1, comparative example 2 are not added at organic inhibitor Reason sample compares, and sample of the present invention is lower than the corrosion rate of comparative example, is sustained efficiency and cycle charge-discharge 100 times The conservation rate of capacitance is above the sample of comparative example processing afterwards, illustrates in same use condition, sample of the present invention Corrosion resistance and capacitance conservation rate are higher, show good cyclical stability.
The above embodiments are only used to illustrate and not limit the technical solutions of the present invention, although above-described embodiment is to the present invention It is described in detail, the related technical personnel of this field are it is understood that can modify to the present invention or replace on an equal basis It changes, but do not depart from any modification of spirit and scope of the invention and part replacement to cover in claim model of the invention In enclosing.

Claims (8)

1. a kind of method for improving zinc electrode corrosion resistance, which comprises the steps of:
The preparation of doped electrode: using metallic zinc as the matrix of electro-deposition, inorganic inhibitor is added, in direct current of voltage regulation in step 1) Electrodeposit reaction is carried out under source, deposition obtains doped electrode under room temperature；
Step 2) electrode reaction of doped electrode: is added organic inhibitor to alkaline electrolyte solution, stirs evenly, be put into and mix Strays pole is electrochemically reacted, and obtains electrode finished product.
2. a kind of method for improving zinc electrode corrosion resistance according to claim 1, it is characterised in that: described is inorganic slow Erosion agent is PbCl2And BiCl3Mixture.
3. a kind of method for improving zinc electrode corrosion resistance according to claim 2, it is characterised in that: described is inorganic slow Lose PbCl in agent2And BiCl3Mass ratio be 1:1-1:4.
4. a kind of method for improving zinc electrode corrosion resistance according to claim 1, it is characterised in that: described is organic slow Losing agent includes one of neopelex, dodecyl sodium sulfate, benzimidazole, cetyltrimethylammonium bromide Or it is a variety of.
5. a kind of method for improving zinc electrode corrosion resistance according to claim 1, it is characterised in that: described is inorganic slow The mass concentration for losing agent is 0.05-0.07g/L.
6. a kind of method for improving zinc electrode corrosion resistance according to claim 1, it is characterised in that: described is organic slow Losing mass concentration of the agent in alkaline electrolyte solution is 0.05-0.1g/L.
7. a kind of method for improving zinc electrode corrosion resistance according to claim 1, it is characterised in that: the electro-deposition Current density is 90-110mA/cm2。
8. a kind of method for improving zinc electrode corrosion resistance according to claim 1, it is characterised in that: the room temperature deposition Time is 25-35 minutes.
CN201811488948.0A 2018-12-06 2018-12-06 A method of improving zinc electrode corrosion resistance Pending CN109638218A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114597386A (en) * 2022-02-22 2022-06-07 浙江大学 Zinc metal electrode and preparation method and application thereof

Citations (3)

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Publication number Priority date Publication date Assignee Title
CN102709608A (en) * 2012-07-03 2012-10-03 北京中航长力能源科技有限公司 Mercury-substituted corrosion inhibitor for zinc electrode of alkaline battery
CN103243371A (en) * 2013-05-16 2013-08-14 中国船舶重工集团公司第七二五研究所 Preparation method of zinc anode oxidation film layer
KR20170124791A (en) * 2016-05-03 2017-11-13 경희대학교 산학협력단 Anode material of zinc air cell and method for preparing the same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102709608A (en) * 2012-07-03 2012-10-03 北京中航长力能源科技有限公司 Mercury-substituted corrosion inhibitor for zinc electrode of alkaline battery
CN103243371A (en) * 2013-05-16 2013-08-14 中国船舶重工集团公司第七二五研究所 Preparation method of zinc anode oxidation film layer
KR20170124791A (en) * 2016-05-03 2017-11-13 경희대학교 산학협력단 Anode material of zinc air cell and method for preparing the same

Non-Patent Citations (1)

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Title
周合兵等: "KOH中几种缓蚀剂抑制锌腐蚀的协同作用", 《电源技术》 *

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114597386A (en) * 2022-02-22 2022-06-07 浙江大学 Zinc metal electrode and preparation method and application thereof

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Application publication date: 20190416