CN111146408B - Preparation method of iron-nickel battery cathode - Google Patents

Preparation method of iron-nickel battery cathode Download PDF

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CN111146408B
CN111146408B CN202010085854.XA CN202010085854A CN111146408B CN 111146408 B CN111146408 B CN 111146408B CN 202010085854 A CN202010085854 A CN 202010085854A CN 111146408 B CN111146408 B CN 111146408B
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iron
nickel
stannate
nickel battery
negative electrode
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CN111146408A (en
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杨玉锋
徐平
李群杰
李喜歌
彭英长
王晓燕
雷越
刘文昌
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Henan Troily New Energy Technology Co ltd
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Henan Troily New Energy Technology Co ltd
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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
    • H01M4/24—Electrodes for alkaline accumulators
    • H01M4/248—Iron electrodes
    • 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
    • H01M10/24—Alkaline accumulators
    • H01M10/30—Nickel accumulators
    • 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
    • H01M4/24—Electrodes for alkaline accumulators
    • H01M4/26—Processes of manufacture
    • 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
    • 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
    • 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)
  • Battery Electrode And Active Subsutance (AREA)
  • Cell Electrode Carriers And Collectors (AREA)

Abstract

The invention discloses a preparation method of an iron-nickel battery cathode, which comprises the following specific steps: stannate, conductive agent, adhesive, active ferroferric oxide and additive are mixed uniformly to form slurry, and the conductive matrix is subjected to slurry drawing, drying, rolling and cutting to obtain the iron-nickel battery cathode, wherein the stannate is one or more of antimony stannate or bismuth stannate. The cathode of the iron-nickel battery prepared by the invention utilizes the relatively high hydrogen evolution overpotential of tin and the bismuth and antimony with the positive electrode potential to inhibit the hydrogen evolution reaction of the iron cathode during charging, and has the advantages of simple preparation process, no solid waste and wastewater generation, environmental protection, safety and the like.

Description

Preparation method of iron-nickel battery cathode
Technical Field
The invention belongs to the technical field of iron-nickel secondary battery iron cathode preparation, and particularly relates to a preparation method of an iron-nickel battery cathode.
Background
The currently available square secondary batteries mainly comprise lead-acid batteries and lithium ion batteries, wherein the lead-acid batteries have low specific energy which can only reach 30 to 35Wh/Kg generally, the cycle life is about 300 to 350 times, long charging time is needed, lead is a toxic heavy metal, and the production process and the recovery process cause serious pollution to the environment if the lead is not properly treated, so that the production and the use are limited by countries in the world. The specific energy of the lithium ion battery is relatively high, but the lithium ion battery has a large capacity, is poor in safety performance in a high-voltage use environment, and simultaneously faces a series of problems that the waste lithium ion battery is difficult to recycle, causes environmental pollution and the like. The nickel-hydrogen battery in the alkaline secondary battery uses rare earth and other precious metals, so the use cost is high, and the large-scale popularization and use are difficult; the zinc-nickel secondary battery has higher specific energy and specific power, but zinc dendrite is easy to generate when the zinc cathode material is used, so that the service life of the zinc-nickel secondary battery is shortened, and the problems that the large-capacity battery is difficult to manufacture and the like exist; the iron-nickel secondary battery has long service life, is safe and environment-friendly, but the iron negative electrode of the iron-nickel secondary battery has more negative potential and is easy to separate hydrogen, and the problems of low charging efficiency, easy hydrogen separation and water loss and the like exist. Currently, most of the main research on the iron-nickel secondary battery is focused on the iron negative electrode, the added elements are basically in the form of oxides, particularly, the addition of cobalt element is common, and if more noble metals are used as additives, the inherent advantage of low price of the iron-nickel secondary battery is lost.
Disclosure of Invention
The invention provides a preparation method of an iron-nickel battery cathode capable of effectively improving hydrogen evolution overpotential and charging efficiency by combining the characteristics of an iron-nickel secondary battery. The preparation method has the advantages of simple preparation process, no solid waste or waste water, environmental protection and safety.
The invention adopts the following technical scheme for solving the technical problems, and the preparation method of the iron-nickel battery cathode is characterized by comprising the following specific processes: stannate, conductive agent, adhesive, active ferroferric oxide and additive are mixed uniformly to form slurry, and the conductive matrix is subjected to slurry drawing, drying, rolling and cutting to prepare the iron-nickel battery cathode, wherein the stannate is one or more of antimony stannate or bismuth stannate.
Further limiting, the mass ratio of the stannate, the conductive agent, the adhesive, the active ferroferric oxide and the additive is 1-50.
Further limiting, the mass ratio of the stannate to the conductive agent to the adhesive to the active ferroferric oxide to the additive is 25.
Further defined, the conductive agent is conductive graphite, the binder is 2wt% HPMC (hydroxypropyl methyl cellulose), and the additive is 50wt% SBR (styrene butadiene rubber).
Further, the conductive substrate is a nickel-plated steel strip, a nickel foam, an iron foam or a fiber nickel.
Further limited, the preparation method of the iron-nickel battery cathode is characterized by comprising the following specific steps:
step S1: mixing 25g of stannate, 500g of active ferroferric oxide, 75g of HPMC (hydroxy propyl methyl cellulose) with the concentration of 2wt%, 15g of conductive graphite and 10g of SBR (styrene butadiene rubber) with the concentration of 50wt% with slurry, and carrying out slurry drawing, drying, rolling and cutting by taking a nickel-plated steel strip as a conductive substrate to prepare a negative electrode;
step S2: mixing 500g of cobalt-coated spherical nickel, 15g of cobalt oxide, 100g of CMC with the concentration of 2wt%, 80g of conductive graphite, 4g of yttrium oxide and 10g of PTFE with the concentration of 60wt% to obtain slurry, and carrying out slurry drawing, drying, rolling and cutting by taking a nickel-plated steel strip as a conductive matrix to prepare the anode;
and step S3: adopting a polypropylene diaphragm with the thickness of 0.3 +/-0.2 mm, alternately stacking or winding the positive electrode, the negative electrode and the diaphragm, putting the positive electrode, the negative electrode and the diaphragm into a shell, sealing the shell, adding 6M KOH electrolyte, and assembling the square iron-nickel battery or the cylindrical iron-nickel battery;
the cathode of the iron-nickel battery is beneficial to improving the hydrogen evolution overpotential of the cathode material during charging, so that the charging efficiency of the iron-nickel battery is improved; the passivation phenomenon can be weakened during discharging, and the increase of the internal resistance is prevented, so that the discharging efficiency and the discharging platform of the iron-nickel battery are improved, and the second platform is not provided.
Compared with the prior art, the invention has the following beneficial effects: compared with a battery which singly uses ferroferric oxide or iron powder as a negative electrode, the iron-nickel battery negative electrode prepared by the invention can effectively improve the specific capacity of the iron-nickel battery, reduce the electrode expansion, reduce the gas evolution amount and prolong the service life of the battery. When the negative electrode made of the material is charged, the hydrogen evolution overpotential of the negative electrode material is favorably improved, and the charging efficiency of the battery is further improved; the passivation phenomenon can be weakened during discharging, and the increase of internal resistance is prevented, so that the discharging efficiency and the discharging platform of the battery are improved, and a second platform is not arranged.
Drawings
FIG. 1 shows Sb contained in example 1 2 Sn 2 O 7 And comparing the charge and discharge curves of the cathode and the common cathode.
FIG. 2 shows Bi-containing samples obtained in example 2 2 Sn 2 O 7 And comparing the charge and discharge curves of the cathode and the common cathode.
Detailed Description
The present invention is described in further detail below with reference to examples, but it should not be construed that the scope of the above subject matter of the present invention is limited to the following examples, and that all the technologies realized based on the above subject matter of the present invention belong to the scope of the present invention.
Example 1
1. With Sb 2 Sn 2 O 7 25g of active ferroferric oxide, 500g of HPMC 75g with the concentration of 2wt%, 15g of conductive graphite and 10g of SBR with the concentration of 50wt% are mixed to be slurry, and the cathode is prepared by taking a nickel-plated steel strip as a conductive framework and performing slurry drawing, drying, rolling and cutting.
2. Mixing 500g of cobalt-coated spherical nickel, 15g of cobalt oxide, 100g of CMC with the concentration of 2wt%, 80g of conductive graphite, 4g of yttrium oxide and 10g of PTFE with the concentration of 60wt%, and carrying out slurry drawing, drying, rolling and cutting by taking a nickel-plated steel strip as a conductive framework to prepare the anode.
3. A polypropylene membrane with a thickness of 0.3 ± 0.2mm was used.
4. And (3) alternately stacking or winding the positive electrode, the negative electrode and the diaphragm, putting the positive electrode, the negative electrode and the diaphragm into a shell, sealing the shell, adding 6M KOH electrolyte, and assembling the square iron-nickel battery or the cylindrical iron-nickel battery.
5. After formation, a charge/discharge test was performed.
Example 2
1. With Bi 2 Sn 2 O 7 25g of active ferroferric oxide, 500g of HPMC 75g with the concentration of 2wt%, 15g of conductive graphite and 10g of SBR 10g with the concentration of 50wt% are mixed and subjected to slurry drawing, drying, rolling and cutting by taking a nickel-plated steel strip as a conductive framework to prepare the negative electrode.
2. Mixing 500g of cobalt-coated spherical nickel, 15g of cobalt oxide, 100g of CMC with the concentration of 2wt%, 80g of conductive graphite, 4g of yttrium oxide and 10g of PTFE with the concentration of 60wt%, and carrying out slurry drawing, drying, rolling and cutting by taking a nickel-plated steel strip as a conductive framework to prepare the anode.
3. A polypropylene membrane with a thickness of 0.3 + -0.2 mm is used.
4. And (3) alternately stacking or winding the positive electrode, the negative electrode and the diaphragm, putting the positive electrode, the negative electrode and the diaphragm into a shell, sealing the shell, adding 6M KOH electrolyte, and assembling the square iron-nickel battery or the cylindrical iron-nickel battery.
5. After formation, a charge/discharge test was performed.
The comparison of the charging and discharging curves of the cathode of the iron-nickel battery prepared by the invention with the cathode of the conventional iron-nickel battery shows that the iron-nickel battery containing stannate can effectively reduce the charging voltage, improve the gram volume, improve the formation speed and the discharging platform and reduce the hydrogen evolution amount.
While there have been shown and described the fundamental principles, principal features and advantages of the invention, there are numerous variations and modifications which fall within the scope of the invention as claimed, without departing from the spirit and scope of the invention.

Claims (5)

1. A preparation method of an iron-nickel battery cathode is characterized by comprising the following specific steps: uniformly mixing stannate, a conductive agent, an adhesive, ferroferric oxide and an additive to form slurry, and carrying out slurry drawing, drying, rolling and cutting on a conductive substrate to obtain the iron-nickel battery negative electrode, wherein the stannate is antimony stannate, the adhesive is 2wt% of HPMC, the additive is 50wt% of SBR, and the feeding mass ratio of the stannate, the conductive agent, the adhesive, the ferroferric oxide to the additive is (1-50).
2. The method for preparing an iron-nickel battery negative electrode according to claim 1, characterized in that: the mass ratio of the stannate to the conductive agent to the adhesive to the ferroferric oxide to the additive is 25.
3. The method for preparing an iron-nickel battery negative electrode according to claim 1, characterized in that: the conductive agent is conductive graphite.
4. The method for preparing an iron-nickel battery negative electrode according to claim 1, characterized in that: the conductive substrate is a nickel-plated steel strip, foamed nickel, foamed iron or fiber nickel.
5. A preparation method of an iron-nickel battery is characterized by comprising the following specific steps:
step S1: mixing 25g of stannate, 500g of active ferroferric oxide, 75g of HPMC (hydroxy propyl methyl cellulose) with the concentration of 2wt%, 15g of conductive graphite and 10g of SBR (styrene butadiene rubber) with the concentration of 50wt% with slurry, and carrying out slurry drawing, drying, rolling and cutting by taking a nickel-plated steel strip as a conductive matrix to prepare a negative electrode, wherein the stannate is antimony stannate;
step S2: mixing 500g of cobalt-coated spherical nickel, 15g of cobalt oxide, 100g of CMC with the concentration of 2wt%, 80g of conductive graphite, 4g of yttrium oxide and 10g of PTFE with the concentration of 60wt% with slurry, and carrying out slurry drawing, drying, rolling and cutting by taking a nickel-plated steel strip as a conductive matrix to prepare a positive electrode;
and step S3: adopting a polypropylene diaphragm with the thickness of 0.3 +/-0.2 mm, alternately stacking or winding the positive electrode, the negative electrode and the diaphragm, putting the positive electrode, the negative electrode and the diaphragm into a shell, sealing the shell, adding 6M KOH electrolyte, and assembling the square iron-nickel battery or the cylindrical iron-nickel battery;
the cathode of the iron-nickel battery is beneficial to improving the hydrogen evolution overpotential of the cathode material during charging, so that the charging efficiency of the iron-nickel battery is improved; the passivation phenomenon can be weakened during discharging, and the increase of the internal resistance is prevented, so that the discharging efficiency and the discharging platform of the iron-nickel battery are improved, and the second platform is not provided.
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