CN105428626B - Alkaline capacitor batteries iron electrode and preparation method thereof - Google Patents

Alkaline capacitor batteries iron electrode and preparation method thereof Download PDF

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Publication number
CN105428626B
CN105428626B CN201510962790.6A CN201510962790A CN105428626B CN 105428626 B CN105428626 B CN 105428626B CN 201510962790 A CN201510962790 A CN 201510962790A CN 105428626 B CN105428626 B CN 105428626B
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electrode
iron
electrode material
slurry
ratio surface
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CN105428626A (en
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吴孟强
冯婷婷
刘文龙
文浪
汪东霞
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University of Electronic Science and Technology of China
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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
    • H01M4/362—Composites
    • 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
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/521—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of iron for aqueous cells
    • 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

Abstract

The present invention provides a kind of alkaline super capacitance cell iron electrode, including porous metals collector matrix and electrode material, 85 95wt% of electrode material are electro-chemical activity composite material, 5 15wt% are conductive agent and binder, electro-chemical activity composite material includes electroactive substance and additive, the present invention also provides a kind of preparation methods of alkaline super capacitance cell iron electrode, first electrode material paste is filled by electrode pad slurry automatic assembly line, coating, by drying, precompressed, roll-in, punching press is sliced, fragment, point welding electrode ear, to which iron electrode be made；The ferroelectricity pole strength height of manufacturing method making disclosed by the invention, good electrical property, manufacturing process is simple, consistency is good, of low cost, iron electrode formula disclosed by the invention and manufacturing method are suitable for making the iron cathode of the alkaline secondary cells such as high power capacity, high-power environment-friendly type nickel iron cell, iron/air cell, silver-colored iron cell, to manufacture corresponding superbattery or super capacitance cell.

Description

Alkaline capacitor batteries iron electrode and preparation method thereof
Technical field
The present invention relates to secondary battery technologies, more particularly to the iron electrode composition and system of alkaline super capacitance cell Standby technology, the iron for being applied to make high power capacity, high-power environment-friendly type Ni-Fe battery, iron/air cell, silver-iron cell etc. are negative Pole.
Background technology
Ni-Fe battery is a kind of using the compound of iron or iron as negative electrode active material, and hickelous nydroxide is living as anode Property substance, secondary cell of potassium hydroxide (sodium) aqueous solution as electrolyte.20th century first half leaf, Ni-Fe battery is as power Power supply is widely used in traction locomotive, but with the success of the priority of performance more preferably nickel-cadmium, nickel-hydrogen cell and lithium ion battery Research and development and application, Ni-Fe battery had once been faded out the sight of people.However, there are following significant advantages for Ni-Fe battery：(1) The electrical properties abuses such as iron electrode can bear super-charge super-discharge, long-term electric discharge state is shelved；(2) iron electrode charge and discharge cycles are up to 2000- 4000 cycles, service life was up to 10~25 years；(3) compared to nickel-cadmium cell, the cadmium cathode of lead-acid battery and lead cathode, The pollution to environment is not constituted using iron or ferriferous oxide as the iron electrode of electroactive material；(4) compared to nickel-hydrogen cell with rare earth Hydrogen-bearing alloy electrode based on element, iron electrode cost advantage are fairly obvious.In particular, as environmental protection pressure increasingly increases, people To the pay attention to day by day of green energy resource, Ni-Fe battery as a kind of rising environmentally protective secondary cell again by Due care is arrived.
The iron electrode of conventional bag structure has complex manufacturing technology, equipment investment big, and active material utilization is low, high power The shortcomings of rate discharge capability is weaker, and self-discharge rate is high, this leverages the performance boost of Ni-Fe battery, it is difficult to meet great Rong Measure the requirement of energy storage and high-performance dynamic power system.In consideration of it, people have studied the technique that pull pulp type makes iron electrode, to Improve electrode active material utilization rate and large current discharging capability.Patent CN102623710A discloses a kind of Ni-based using foaming The iron electrode of body：By 90-95wt%Fe2O3, the aqueous slurry coating that mixes of 3-8wt% additives, 1-2wt% bonding agents On foaming Ni substrate, by Fe in ammonia atmosphere after drying2O3It is reduced into Fe3O4, to be fabricated to iron electrode, with conventional bag Iron electrode is compared, and electrode active material utilization rate improves 41-47%, and large current discharging capability improves 59-63.5%, is applicable in In the Hawkins cell of high-multiplying power discharge.Patent CN102623712A discloses the ferroelectricity using foaming Ni substrate or the iron-based body that foams Pole：By 85-95wt%Fe3O4, the aqueous slurry that mixes of 1-5wt% additives, 3-7wt% conductive agents, 1-3wt% bonding agents Material is coated on foaming Ni substrate and is made, foam Ni substrate or the foam unique tridimensional network of iron-based body and height Microporous, make active material between collector at a distance from greatly shorten, large current discharging capability improves 50-65.5%, activity Material utilization improves 26-30%.Patent CN102623713A discloses a kind of using chemical after mechanical punching by steel band Band burr steel belt matrix made of nickel plating makes iron electrode：By 85-95wt%Fe3O4, 1-5wt% additives, 3-7wt% it is conductive The aqueous slurry that agent, 1-3wt% bonding agents mix is coated on foaming Ni substrate and is made, unique three-dimensional netted knot Structure, make active material between collector at a distance from greatly shorten, active material utilization improves 14-18.7%, and high current is put Electric energy power improves 45-48%.Accordingly, patent CN102623757A disclose it is a kind of with sintered type nickel electrode be anode, with Ni-Fe battery made of the extremely cathode lamination of ferroelectricity disclosed in patent CN102623713A；Patent CN102623758A is disclosed One kind is with sintered type nickel electrode for anode, with Ni-Fe made of the extremely cathode lamination of ferroelectricity disclosed in patent CN102623712A Battery；Patent CN102623759A discloses one kind with sintered type nickel electrode for anode, with disclosed in patent CN102623710A Ni-Fe battery made of ferroelectricity extremely cathode lamination.Example proves that three of the above Ni-Fe is only battery capacity in existing skill It increases on the basis of art, large current discharging capability has certain enhancing, service life to have certain extension.
In order to improve the electrochemistry capacitance of electroactive material, improve the utilization rate of electroactive material, during the nearly last ten years people A large amount of trial has been carried out in terms of the nanosizing of electroactive material；In order to improve electrode charge transfer rate, battery is increased Charge-discharge velocity, improves the energy density and power density of battery, and common method is that electroactive substance is assembled into height to lead On charge carrier (such as carbon nanotube, carbon nano-fiber, metal nanometer line).(Liu ZL, the Tay SW, Li such as Liu ZL X.2011.Chemical.Communications.47:One kind 12473-12475) is reported with α-Fe2O3/ CNFs is nano combined Object is as cathode, β-Ni (OH)2As the Ni-Fe battery of anode, which shows high charge rate, and preferably cycle is special Property, but by α-Fe2O3It is assembled into that complex process on CNFs, not easy to control, cost is higher, is not suitable for producing in enormous quantities.Wang HL etc. (Wang HL, Liang YY, Gong M, Li YG, Chang W, Mefford T, Zhou JG, Wang J, Regier T, Wei F, Dai H.2012.Nature Communications.3:1921-1926) a kind of Ni-Fe battery reported is to receive Rice Ni (OH)2/ MCNTs nano hybrids are anode, FeOX/ graphene nano hybrid is cathode, and charge-discharge velocity is than tradition Ni-Fe batteries are nearly 1000 times fast, and charging can be completed in 2min, is discharged in 30sec, energy density is up to 120Wh/Kg, power Density is up to 15KW/Kg.The research prepares Ni (OH)2Complex process, the cost of/MCNTs and FeOx/ graphene nano hybrids It is high, it is difficult to heavy industrialization application.
Document report identical with present patent application or patent disclosure situation are not yet found so far.
Invention content
Present invention seek to address that there are active material utilizations is not high, charge efficiency is low, high magnification is put for existing iron electrode The problems such as electrical characteristics are poor, a kind of high power capacity being used for alkaline super capacitance cell of proposition, high power iron electrode and preparation method thereof. The utilization rate of the active ferriferous oxide of the addition of high specific surface carbon effectively enhancing, the super capacitor effect of high specific surface carbon can be carried significantly Rise the output power of iron electrode.
For achieving the above object, the present invention provides a kind of alkaline super capacitance cell iron electrode, including porous metals The 85-95wt% of collector matrix and electrode material thereon, electrode material is electro-chemical activity composite material, 5-15wt% For conductive agent and binder, the electro-chemical activity composite material includes electroactive substance and additive, electro-chemical activity Substance is the oxide or hydroxide for the iron for accounting for electro-chemical activity composite material 60-90wt%, and additive includes：(1) content For the high-ratio surface carbon dust of electro-chemical activity composite material 5-20wt%, including activated carbon, carbon nanotube, carbon fiber, carbon airsetting One or more in glue, graphene etc., (2) content is the NiO or Ni (OH) of electro-chemical activity composite material 3-10wt%2, (3) content is the metal sulfide of electro-chemical activity composite material 2-10wt%, including FeS, NiS, or also includes Bi2S3；It is described Conductive agent accounts for electrode material 3-10wt%, and bonding agent accounts for electrode material 2-5wt%, and conductive agent includes acetylene carbon black, graphite, sub- oxygen Change titanium it is one or more, bonding agent include PVAC polyvinylalcohol, sodium carboxymethylcellulose CMC, hydroxypropyl cellulose sodium HPMC, One kind or more of polyvinylidene fluoride PVDF, polytetrafluoroethylene PTFE, styrene-butadiene latex SBR, polychloroprene latex CR, phenolic aldehyde latex PF Kind.
It is preferred that there are two types of the space distribution modes of high-ratio surface carbon dust on the electrode：It is dispersed in electrode In material, or the surface coated in electrode.
For achieving the above object, the present invention also provides a kind of preparation sides of the alkaline super capacitance cell iron electrode Method, preparation method when wherein high-ratio surface carbon dust is dispersed in electrode material are：The iron electrode uses nickel foam Or the nickel plated steel strip of punching is filled out first electrode material paste by electrode pad slurry automatic assembly line as matrix It fills, coat, by drying, precompressed, roll-in, punching press slice, fragment, point welding electrode ear, to which iron electrode be made；The first electrode Material paste includes the electroactive substance of above-mentioned weight percentage, high-ratio surface carbon dust, NiO or Ni (OH)2, metal sulphur Compound, conductive agent, binder and make total solid content be 30-40wt% pure water.
It is preferred that the preparation process of the first electrode material paste is as follows：
Step 1：The bonding agent of above-mentioned weight percentage is placed in blender agitator, is stirred after the pure water is added Uniformly；
Step 2：The high-ratio surface carbon dust of above-mentioned weight percentage is added by several times, above-mentioned weight percent is then added and contains The conductive agent of amount adds the NiO or Ni (OH) of above-mentioned weight percentage after stirring 0.5-1h2And metal sulfide, then stir Mix 0.5-1h；
Step 3：The electroactive substance of above-mentioned weight percentage is added by several times, 2-4h is stirred after addition, i.e., Obtain first electrode material paste.
It is preferred that the preparation method specifically comprises the following steps：
Step 1：After nickel foam is depressed into 80% or so of original depth in advance, in the 8-10mm width ranges of one side Tow sides symmetrically paste one layer of High temperature-resistanadhesive adhesive tape, in order to avoid being coated and keeping blank, are convenient for soldering polar ear.Similarly, exist Tow sides in nickel plated steel strip a side 8-10mm width ranges of punching symmetrically paste one layer of High temperature-resistanadhesive adhesive tape；
Step 2：The first electrode material paste of above-mentioned preparation is placed in slurry vessel, allows ready foam in step 1 Nickel or the nickel plated steel strip of punching make slurry uniformly fill, are coated in base band, strike off shaping by slurry vessel；
Step 3：The base band for being coated with slurry is subjected to sectional temperature-controlled drying and processing, drying temperature is controlled in 150 DEG C of ranges Interior, segmentation warm area is：60-100 DEG C, 80-120 DEG C, 100-140 DEG C, 120-150 DEG C, the transmission speed of base band is controlled in 0.5- 2m/min；
Step 4：By the pole plate of drying by precompressed, roll-in, punching press slice, after removing High temperature-resistanadhesive adhesive tape, welding electrode ear is put, from And obtain iron electrode.
It is preferred that preparation method when high-ratio surface carbon dust is coated in electrode surface includes the following steps：
The iron electrode, as matrix, is given birth to automatically using nickel foam or the nickel plated steel strip of punching by electrode pad slurry Second electrode material paste is filled, coats by producing line, impregnate or spray after drying high-ratio surface carbon pastes, drying, Precompressed, roll-in, punching press slice are to get iron electrode；The second electrode material paste includes the electrification of above-mentioned weight percentage Learn active material, NiO or Ni (OH)2, metal sulfide, partially electronically conductive dose, portion of binder and make total solid content be 30- The pure water of 40wt%；The high-ratio surface carbon pastes include the high-ratio surface carbon dust of above-mentioned weight percentage and remaining Binder and conductive agent and total solid content is made to be the pure water of 20-30wt%, wherein bonding agent and conductive agent are in the second electricity Dosage allocation proportion is (2~4) in pole material paste and high-ratio surface carbon pastes：1.
It is preferred that the preparation process of the second electrode material paste is further：
Step 1：The bonding agent of above-mentioned dosage allocation proportion is placed in blender agitator, the pure water of above-mentioned dosage is added After stir evenly；
Step 2：The electroactive substance of above-mentioned weight percentage is added by several times, stirs 0.5-1h；
Step 3：Then the conductive agent of above-mentioned dosage allocation proportion is added, above-mentioned weight percent is added after stirring 0.5-1h The NiO or Ni (OH) of content2And metal sulfide, 2-4h is stirred for get second electrode material paste.
It is preferred that the preparation process of the high-ratio surface carbon pastes is further：
Step 1：The bonding agent of above-mentioned dosage allocation proportion is placed in blender agitator, the pure water of above-mentioned dosage is added After stir evenly；
Step 2：The high-ratio surface carbon dust of above-mentioned weight percentage is added by several times, above-mentioned dosage allocation proportion is then added Conductive agent, stirring 2-4h to get high-ratio surface carbon pastes.
It is preferred that the method specifically comprises the following steps：
Step 1：After nickel foam is depressed into 80% or so of original depth in advance, in the 8-10mm width ranges of one side Tow sides symmetrically paste one layer of High temperature-resistanadhesive adhesive tape in order to avoid being coated and keeping blank, are convenient for soldering polar ear；Similarly, it is rushing Tow sides in another side 8-10mm width ranges of nickel plated steel strip in hole symmetrically paste one layer of High temperature-resistanadhesive adhesive tape；
Step 2：The second electrode material paste of above-mentioned preparation is placed in slurry vessel, allows ready foam in step 1 Nickel or the nickel plated steel strip of punching make slurry uniformly fill, are coated in base band, strike off shaping by slurry vessel；
Step 3：The base band for being coated with slurry is subjected to sectional temperature-controlled drying and processing, drying temperature is controlled in 150 DEG C of ranges Interior, segmentation warm area is：60-100 DEG C, 80-120 DEG C, 100-140 DEG C, 120-150 DEG C, the transmission speed of base band is controlled in 0.5- 2m/min；
Step 4：By the pole plate dipping of drying or spraying high-ratio surface carbon pastes, drying, precompressed, roll-in, punching press slice, stripping After High temperature-resistanadhesive adhesive tape, welding electrode ear is put, to obtain iron electrode.
Beneficial effects of the present invention are：The utilization rate of the active ferriferous oxide of the addition of high specific surface carbon effectively enhancing, high ratio The super capacitor effect of surface carbon can promote the output power of iron electrode.The ferroelectricity that manufacturing method disclosed by the invention makes is extremely strong Degree height, good electrical property, manufacturing process is simple, consistency is good, of low cost.Iron electrode formula disclosed by the invention and manufacturing method It is suitable for making the alkaline secondary cells such as high power capacity, high-power environment-friendly type Ni-Fe battery, iron/air cell, silver-iron cell Iron cathode, to manufacture corresponding superbattery or super capacitance cell.
Specific implementation mode
Illustrate that embodiments of the present invention, those skilled in the art can be by this specification below by way of specific specific example Disclosed content understands other advantages and effect of the present invention easily.The present invention can also pass through in addition different specific realities The mode of applying is embodied or practiced, the various details in this specification can also be based on different viewpoints with application, without departing from Various modifications or alterations are carried out under the spirit of the present invention.
The performance test methods of iron electrode are：(1) with the ferroelectricity of preparation extremely cathode, with 100% excessive sintered nickel Electrode is anode, and calomel electrode tests the battery gram volume of iron electrode as the three-electrode system of reference electrode；(2) with preparation Ferroelectricity extremely cathode is to electrode with Pt nets, and calomel electrode tests the ratio electricity of iron electrode as the three-electrode system of reference electrode Hold.Test electrolyte used is the uniform mixing of the Na2S of KOH, 0.5mol/LLiOH and 2.5g/L for including 5.5mol/L Solution.
The present invention provides a kind of alkaline super capacitance cell iron electrode, including porous metals collector matrix and thereon Electrode material, the 85-95wt% of electrode material is electro-chemical activity composite material, 5-15wt% is conductive agent and binder, institute It includes electroactive substance and additive to state electro-chemical activity composite material, and electroactive substance is to account for electro-chemical activity to answer The oxide or hydroxide of the iron of condensation material 60-90wt%, additive include：(1) content is electro-chemical activity composite material One kind in high-ratio surface carbon dust, including activated carbon, carbon nanotube, carbon fiber, carbon aerogels, graphene of 5-20wt% etc. or A variety of, (2) content is the NiO or Ni (OH) of electro-chemical activity composite material 3-10wt%2, (3) content is multiple for electro-chemical activity The metal sulfide of condensation material 2-10wt%, including FeS, NiS, or also include Bi2S3；The conductive agent accounts for electrode material 3- 10wt%, bonding agent account for electrode material 2-5wt%, conductive agent include acetylene carbon black, graphite, sub- titanium oxide it is one or more, Bonding agent include PVAC polyvinylalcohol, sodium carboxymethylcellulose CMC, hydroxypropyl cellulose sodium HPMC, polyvinylidene fluoride PVDF, Polytetrafluoroethylene PTFE, styrene-butadiene latex SBR, polychloroprene latex CR, phenolic aldehyde latex PF it is one or more.
There are two types of the space distribution modes of high-ratio surface carbon dust on the electrode：It is dispersed in electrode material, or coating On the surface of electrode.
Preparation method when high-ratio surface carbon dust is dispersed in electrode material is：The iron electrode uses nickel foam Or the nickel plated steel strip of punching is filled out first electrode material paste by electrode pad slurry automatic assembly line as matrix It fills, coat, by drying, precompressed, roll-in, punching press slice, fragment, point welding electrode ear, to which iron electrode be made；The first electrode Material paste includes the electroactive substance of above-mentioned weight percentage, high-ratio surface carbon dust, NiO or Ni (OH)2, metal sulphur Compound, conductive agent, binder and make total solid content be 30-40wt% pure water.
The preparation process of the first electrode material paste is as follows：
Step 1：The bonding agent of above-mentioned weight percentage is placed in blender agitator, is stirred after the pure water is added Uniformly；
Step 2：The high-ratio surface carbon dust of above-mentioned weight percentage is added by several times, above-mentioned weight percent is then added and contains The conductive agent of amount adds the NiO or Ni (OH) of above-mentioned weight percentage after stirring 0.5-1h2And metal sulfide, then stir Mix 0.5-1h；
Step 3：The electroactive substance of above-mentioned weight percentage is added by several times, 2-4h is stirred after addition, i.e., Obtain first electrode material paste.
It is preferred that the preparation method specifically comprises the following steps：
Step 1：After nickel foam is depressed into 80% or so of original depth in advance, in the 8-10mm width ranges of one side Tow sides symmetrically paste one layer of High temperature-resistanadhesive adhesive tape, in order to avoid being coated and keeping blank, are convenient for soldering polar ear.Similarly, exist Tow sides in nickel plated steel strip a side 8-10mm width ranges of punching symmetrically paste one layer of High temperature-resistanadhesive adhesive tape；
Step 2：The first electrode material paste of above-mentioned preparation is placed in slurry vessel, allows ready foam in step 1 Nickel or the nickel plated steel strip of punching make slurry uniformly fill, are coated in base band, strike off shaping by slurry vessel；
Step 3：The base band for being coated with slurry is subjected to sectional temperature-controlled drying and processing, drying temperature is controlled in 150 DEG C of ranges Interior, segmentation warm area is：60-100 DEG C, 80-120 DEG C, 100-140 DEG C, 120-150 DEG C, the transmission speed of base band is controlled in 0.5- 2m/min；
Step 4：By the pole plate of drying by precompressed, roll-in, punching press slice, after removing High temperature-resistanadhesive adhesive tape, welding electrode ear is put, from And obtain iron electrode.
Preparation method when high-ratio surface carbon dust is coated in electrode surface includes the following steps：
The iron electrode, as matrix, is given birth to automatically using nickel foam or the nickel plated steel strip of punching by electrode pad slurry Second electrode material paste is filled, coats by producing line, impregnate or spray after drying high-ratio surface carbon pastes, drying, Precompressed, roll-in, punching press slice are to get iron electrode；The second electrode material paste includes the electrification of above-mentioned weight percentage Learn active material, NiO or Ni (OH)2, metal sulfide, partially electronically conductive dose, portion of binder and make total solid content be 30- The pure water of 40wt%；The high-ratio surface carbon pastes include the high-ratio surface carbon dust of above-mentioned weight percentage and remaining Binder and conductive agent and total solid content is made to be the pure water of 20-30wt%, wherein bonding agent and conductive agent are in the second electricity Dosage allocation proportion is (2~4) in pole material paste and high-ratio surface carbon pastes：1.
The preparation process of the second electrode material paste is further：
Step 1：The bonding agent of above-mentioned dosage allocation proportion is placed in blender agitator, the pure water of above-mentioned dosage is added After stir evenly；
Step 2：The electroactive substance of above-mentioned weight percentage is added by several times, stirs 0.5-1h；
Step 3：Then the conductive agent of above-mentioned dosage allocation proportion is added, above-mentioned weight percent is added after stirring 0.5-1h The NiO or Ni (OH) of content2And metal sulfide, 2-4h is stirred for get second electrode material paste.
The preparation process of the high-ratio surface carbon pastes is further：
Step 1：The bonding agent of above-mentioned dosage allocation proportion is placed in blender agitator, the pure water of above-mentioned dosage is added After stir evenly；
Step 2：The high-ratio surface carbon dust of above-mentioned weight percentage is added by several times, above-mentioned dosage allocation proportion is then added Conductive agent, stirring 2-4h to get high-ratio surface carbon pastes.
Further, the method specifically comprises the following steps：
Step 1：After nickel foam is depressed into 80% or so of original depth in advance, in the 8-10mm width ranges of one side Tow sides symmetrically paste one layer of High temperature-resistanadhesive adhesive tape in order to avoid being coated and keeping blank, are convenient for soldering polar ear；Similarly, it is rushing Tow sides in another side 8-10mm width ranges of nickel plated steel strip in hole symmetrically paste one layer of High temperature-resistanadhesive adhesive tape；
Step 2：The second electrode material paste of above-mentioned preparation is placed in slurry vessel, allows ready foam in step 1 Nickel or the nickel plated steel strip of punching make slurry uniformly fill, are coated in base band, strike off shaping by slurry vessel；
Step 3：The base band for being coated with slurry is subjected to sectional temperature-controlled drying and processing, drying temperature is controlled in 150 DEG C of ranges Interior, segmentation warm area is：60-100 DEG C, 80-120 DEG C, 100-140 DEG C, 120-150 DEG C, the transmission speed of base band is controlled in 0.5- 2m/min；
Step 4：By the pole plate dipping of drying or spraying high-ratio surface carbon pastes, drying, precompressed, roll-in, punching press slice, stripping After High temperature-resistanadhesive adhesive tape, welding electrode ear is put, to obtain iron electrode.
The electrode performance that the specific formula of each embodiment and test obtain see the table below.
Embodiment
The specific formula and test performance (accounting for electrode material wt%) of 1 each embodiment of table
From data above it can be concluded that the present invention passes through the height to adding certain content in iron electrode material Specific surface carbon material can improve the cell performance specific capacity of iron cathode, while iron electrode being made to have higher capacitive character specific capacitance, So as to realize capacitor batteries electrode that capacitance and battery " interior and formula " combine so that iron cathode make Ni-Fe, iron-air, The batteries such as silver-iron have battery high energy metric density and super capacitor high power density.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe The personage for knowing this technology can all carry out modifications and changes to above-described embodiment without violating the spirit and scope of the present invention.Cause This, all those of ordinary skill in the art are completed without departing from the spirit and technical ideas disclosed in the present invention All equivalent modifications or change, should by the present invention claim be covered.

Claims (7)

1. a kind of alkalinity super capacitance cell iron electrode, it is characterised in that：Including porous metals collector matrix and thereon Electrode material, the 85-95wt% of electrode material is electro-chemical activity composite material, 5-15wt% is conductive agent and binder, institute It includes electroactive substance and additive to state electro-chemical activity composite material, and electroactive substance is to account for electro-chemical activity to answer The oxide or hydroxide of the iron of condensation material 60-90wt%, additive include：(1) content is electro-chemical activity composite material One kind in high-ratio surface carbon dust, including activated carbon, carbon nanotube, carbon fiber, carbon aerogels, graphene of 5-20wt% etc. or A variety of, (2) content is the NiO or Ni (OH) of electro-chemical activity composite material 3-10wt%2, (3) content is multiple for electro-chemical activity The metal sulfide of condensation material 2-10wt%, including FeS and two kinds of NiS, or including FeS and NiS and Bi2S3Three kinds；The conduction Agent accounts for electrode material 3-10wt%, and bonding agent accounts for electrode material 2-5wt%, and conductive agent includes acetylene carbon black, graphite, sub- titanium oxide It is one or more, bonding agent includes PVAC polyvinylalcohol, sodium carboxymethylcellulose CMC, hydroxypropyl cellulose sodium HPMC, poly- inclined Difluoroethylene PVDF, polytetrafluoroethylene PTFE, styrene-butadiene latex SBR, polychloroprene latex CR, phenolic aldehyde latex PF it is one or more；
There are two types of the space distribution modes of high-ratio surface carbon dust on the electrode：It is dispersed in electrode material, or coated in electricity The surface of pole；
Preparation method when high-ratio surface carbon dust is dispersed in electrode material is：The iron electrode uses nickel foam or punching First electrode material paste is filled as matrix, by electrode pad slurry automatic assembly line, applies by the nickel plated steel strip in hole It covers, by drying, precompressed, roll-in, punching press slice, fragment, point welding electrode ear, to which iron electrode be made；The first electrode material Slurry includes the electroactive substance of above-mentioned weight percentage, high-ratio surface carbon dust, NiO or Ni (OH)2, metal vulcanization Object, conductive agent, binder and make total solid content be 30-40wt% pure water.
2. alkalinity super capacitance cell iron electrode according to claim 1, it is characterised in that：The first electrode material slurry The preparation process of material is as follows：
Step 1：The bonding agent of above-mentioned weight percentage is placed in blender agitator, is stirred after the pure water is added It is even；
Step 2：The high-ratio surface carbon dust of above-mentioned weight percentage is added by several times, above-mentioned weight percentage is then added Conductive agent adds the NiO or Ni (OH) of above-mentioned weight percentage after stirring 0.5-1h2And metal sulfide, it is stirred for 0.5-1h；
Step 3：The electroactive substance of above-mentioned weight percentage is added by several times, 2-4h is stirred after addition to get the One electrode material slurry.
3. alkalinity super capacitance cell iron electrode according to claim 1, it is characterised in that：High-ratio surface carbon dust uniformly divides Preparation method when being dispersed in electrode material specifically comprises the following steps：
Step 1：It is positive and negative in the 8-10mm width ranges of one side after nickel foam is depressed into 80% or so of original depth in advance One layer of High temperature-resistanadhesive adhesive tape is symmetrically pasted on two sides, similarly, in nickel plated steel strip a side 8-10mm width ranges of punching Tow sides symmetrically paste one layer of High temperature-resistanadhesive adhesive tape；
Step 2：The first electrode material paste of above-mentioned preparation is placed in slurry vessel, allow in step 1 ready nickel foam or The nickel plated steel strip of punching makes slurry uniformly fill, is coated in base band, strike off shaping by slurry vessel；
Step 3：The base band for being coated with slurry is subjected to sectional temperature-controlled drying and processing, drying temperature controls within the scope of 150 DEG C, point Duan Wenqu is：60-100 DEG C, 80-120 DEG C, 100-140 DEG C, 120-150 DEG C, the transmission speed of base band is controlled in 0.5-2m/ min；
Step 4：By the pole plate of drying by precompressed, roll-in, punching press slice, after removing High temperature-resistanadhesive adhesive tape, welding electrode ear is put, to obtain Obtain iron electrode.
4. alkalinity super capacitance cell iron electrode according to claim 1, it is characterised in that：High-ratio surface carbon dust is coated in Preparation method when electrode surface includes the following steps：
The iron electrode, as matrix, passes through electrode pad slurry automatic assembly line using nickel foam or the nickel plated steel strip of punching Second electrode material paste is filled, is coated, impregnate or spray after drying high-ratio surface carbon pastes, drying, precompressed, Roll-in, punching press slice are to get iron electrode；The second electrode material paste includes the electro-chemical activity of above-mentioned weight percentage Substance, NiO or Ni (OH)2, metal sulfide, partially electronically conductive dose, portion of binder and make total solid content be 30-40wt% Pure water；The high-ratio surface carbon pastes include the high-ratio surface carbon dust of above-mentioned weight percentage and remaining binder With conductive agent and make total solid content be 20-30wt% pure water, wherein bonding agent and conductive agent are in second electrode material Dosage allocation proportion is (2~4) in slurry and high-ratio surface carbon pastes：1.
5. alkalinity super capacitance cell iron electrode according to claim 4, it is characterised in that：The second electrode material slurry The preparation process of material is further：
Step 1：The bonding agent of above-mentioned dosage allocation proportion is placed in blender agitator, is stirred after the pure water of above-mentioned dosage is added It mixes uniformly；
Step 2：The electroactive substance of above-mentioned weight percentage is added by several times, stirs 0.5-1h；
Step 3：Then the conductive agent of above-mentioned dosage allocation proportion is added, above-mentioned weight percentage is added after stirring 0.5-1h NiO or Ni (OH)2And metal sulfide, 2-4h is stirred for get second electrode material paste.
6. alkalinity super capacitance cell iron electrode according to claim 4, it is characterised in that：The high-ratio surface carbon pastes Preparation process be further：
Step 1：The bonding agent of above-mentioned dosage allocation proportion is placed in blender agitator, is stirred after the pure water of above-mentioned dosage is added It mixes uniformly；
Step 2：The high-ratio surface carbon dust of above-mentioned weight percentage is added by several times, leading for above-mentioned dosage allocation proportion is then added Electric agent, 2-4h is to get high-ratio surface carbon pastes for stirring.
7. alkalinity super capacitance cell iron electrode according to claim 4, it is characterised in that high-ratio surface carbon dust is coated in Preparation method when electrode surface specifically comprises the following steps：
Step 1：It is positive and negative in the 8-10mm width ranges of one side after nickel foam is depressed into 80% or so of original depth in advance Symmetrically paste one layer of High temperature-resistanadhesive adhesive tape in two sides；Similarly, in another side 8-10mm width ranges of the nickel plated steel strip of punching Tow sides symmetrically paste one layer of High temperature-resistanadhesive adhesive tape；
Step 2：The second electrode material paste of above-mentioned preparation is placed in slurry vessel, allow in step 1 ready nickel foam or The nickel plated steel strip of punching makes slurry uniformly fill, is coated in base band, strike off shaping by slurry vessel；
Step 3：The base band for being coated with slurry is subjected to sectional temperature-controlled drying and processing, drying temperature controls within the scope of 150 DEG C, point Duan Wenqu is：60-100 DEG C, 80-120 DEG C, 100-140 DEG C, 120-150 DEG C, the transmission speed of base band is controlled in 0.5-2m/ min；
Step 4：The pole plate dipping of drying or spraying high-ratio surface carbon pastes, drying, precompressed, roll-in, punching press slice, stripping is resistance to After high temperature gummed tape, welding electrode ear is put, to obtain iron electrode.
CN201510962790.6A 2015-12-18 2015-12-18 Alkaline capacitor batteries iron electrode and preparation method thereof Expired - Fee Related CN105428626B (en)

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CN108777234B (en) * 2018-05-25 2021-02-05 深圳探影生物科技有限公司 Graphite fiber electrode coated with activated carbon and supercapacitor prepared from graphite fiber electrode
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