CN105552314A - Preparation method of high-reliability bipolar plate for bipolar lead storage battery - Google Patents
Preparation method of high-reliability bipolar plate for bipolar lead storage battery Download PDFInfo
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- CN105552314A CN105552314A CN201510901855.6A CN201510901855A CN105552314A CN 105552314 A CN105552314 A CN 105552314A CN 201510901855 A CN201510901855 A CN 201510901855A CN 105552314 A CN105552314 A CN 105552314A
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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
- H01M4/14—Electrodes for lead-acid accumulators
- H01M4/16—Processes of manufacture
- H01M4/20—Processes of manufacture of pasted electrodes
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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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
- H01M4/662—Alloys
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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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
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- H01M4/667—Composites in the form of layers, e.g. coatings
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/76—Containers for holding the active material, e.g. tubes, capsules
- H01M4/762—Porous or perforated metallic containers
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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
- H01M4/64—Carriers or collectors
- H01M4/82—Multi-step processes for manufacturing carriers for lead-acid accumulators
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/029—Bipolar electrodes
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Abstract
The invention discloses a preparation method of a high-reliability bipolar plate for a bipolar lead storage battery, and relates to the preparation method of the bipolar plate for a bipolar lead storage battery. The problem that a substrate and an active substance cannot be firmly bonded in a conventional bipolar lead storage battery is solved. The preparation method comprises: 1, pre-treatment; 2, titanium plate surface honeycombing; 3, preferred growth of a lead-tin alloy layer through electroplating; and 4, preparation of the high-reliability bipolar plate. The method is applied to preparation of the high-reliability bipolar plate for a bipolar lead storage battery.
Description
Technical field
The present invention relates to the preparation method of the bipolar plates for bipolarity lead accumulator.
Background technology
Bipolarity lead accumulator compared with conventional lead storage cells, specific energy and specific power high, have extended cycle life, and joint lead more than 40%, can realize lead accumulator industry energy-conservation, consumption reduction, reduce discharging, in energy storage and electric automobiles, there is good application prospect.At present, the key issue that bipolarity lead accumulator can not realize industrialization is that in bipolar plates, substrate is combined loosely with active material, causes the poor reliability of bipolar plates, cannot accomplish scale production.
Summary of the invention
The present invention will solve existing bipolarity lead accumulator to be existed substrate and is combined problem loosely with active material, and provides a kind of preparation method of the high reliability bipolar plates for bipolarity lead accumulator.
For a preparation method for the high reliability bipolar plates of bipolarity lead accumulator, specifically carry out according to following steps:
One, preliminary treatment:
Successively oil removing and pickling are carried out to titanium plate, obtains pretreated titanium plate;
Two, titanium plate surface honeycomb:
To scribble the titanium net of ruthenium-oxide for anode, with pretreated titanium plate for negative electrode, then the titanium net anode and pretreated titanium plate cathode that scribble ruthenium-oxide being placed in honeycomb treatment fluid, be 80 DEG C ~ 90 DEG C and current density is 5A/dm in temperature
2~ 20A/dm
2condition under, then process 10s ~ 20s is 80 DEG C ~ 90 DEG C and current density in temperature is 0.5A/dm
2~ 2A/dm
2condition under, process 10min ~ 30min, takes out titanium plate after process, under room temperature, to the titanium plate washed with de-ionized water after process, obtains the honeycomb titanium plate that surface has hydrogenation film to protect;
Described honeycomb treatment fluid by mass percent be 20% ~ 36% hydrochloric acid and promoter form, in described honeycomb treatment fluid, the mass percent of promoter is 5% ~ 20%; Described promoter one or both the mixture that to be oxalic acid and mass percent be in the hydrofluoric acid of 42%;
Three, the layer of lead-tin alloy of preferential growth is electroplated:
The honeycomb titanium plate having hydrogenation film to protect with surface is for negative electrode; with terne metal plate for anode; the honeycomb titanium plate cathode being had on surface hydrogenation film to protect is placed between two panels terne metal plate anode; porous barrier is fixed between the honeycomb titanium plate cathode having hydrogenation film to protect on surface and two panels terne metal plate anode; obtain pending; being placed in Pb-Sn alloy plating bath by pending, be 30 DEG C ~ 40 DEG C and current density is 1A/dm in temperature
2~ 2A/dm
2condition under, plating 20min ~ 4h, obtain surface long have slicker solder must terne metal/titanium/terne metal composite titanium substrate;
Described Pb-Sn alloy plating bath is made up of potassium pyrophosphate, lead（II） ion, divalent tin ion and additive; In described Pb-Sn alloy plating bath, the concentration of potassium pyrophosphate is 0.6mol/L ~ 0.8mol/L; In described Pb-Sn alloy plating bath, the concentration of lead（II） ion is 0.2mol/L ~ 0.4mol/L; In described Pb-Sn alloy plating bath, the concentration of divalent tin ion is 0.005mol/L ~ 0.02mol/L; In described Pb-Sn alloy plating bath, the concentration of additive is 1g/L ~ 5g/L;
Four, high reliability bipolar plates is prepared:
Prepare anode diachylon and cathode lead plaster, then the long terne metal/titanium/terne metal composite titanium substrate side coating anode diachylon having slicker solder palpus on surface, another side coating cathode lead plaster, obtain being coated with cream plate, carry out pickling process again or drench acid treatment, obtain the painting cream plate after acid treatment, first under temperature is 40 DEG C ~ 65 DEG C and humidity is the condition of 50% ~ 100%, to the painting cream plate solidification 24h ~ 48h after acid treatment, then under temperature is 50 DEG C ~ 65 DEG C and humidity is the condition of 30% ~ 50%, solidification 2h ~ 4h, again under temperature is 65 DEG C ~ 70 DEG C and humidity is the condition of 20% ~ 30%, solidification 2h ~ 4h, finally under temperature is 70 DEG C and humidity is the condition of 0%, dry 4h ~ 8h, namely the high reliability bipolar plates for bipolarity lead accumulator is obtained.
1., the present invention surface of preparing honeycomb titanium plate of having hydrogenation film to protect the invention has the beneficial effects as follows:, honeycomb and hydrogenation film concur, and ensure that the bond strength of electroplating lead tin alloy coating and titanium plate; 2., by the long pb-sn alloy plating having slicker solder palpus of plate surface, play " rivet " effect, ensure that the bond strength of lead plaster and composite titanium substrate, active material can be kept in bipolar plates charge and discharge cycles process to be combined with composite base plate firmly; 3., titanium plate has high corrosion-resistant; 4., pb-sn alloy plating can form good thermal interface in lead plaster reaction.Therefore, the bipolar plates that prepared by the present invention has high reliability for bipolarity lead accumulator.
The present invention is used for a kind of preparation method of the high reliability bipolar plates for bipolarity lead accumulator.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of the honeycomb titanium plate that surface prepared by embodiment step 2 has hydrogenation film to protect;
Fig. 2 is XRD collection of illustrative plates and the TiH of the honeycomb titanium plate that surface prepared by embodiment step 2 has hydrogenation film to protect
1.924-PDF22-0983 standard diagram, A is the honeycomb titanium plate that surface prepared by embodiment step 2 has hydrogenation film to protect, and B is TiH
1.924-PDF22-0983;
Fig. 3 is the long scanning electron microscope (SEM) photograph having the terne metal/titanium/terne metal composite titanium substrate of slicker solder palpus in surface prepared by embodiment step 3;
Fig. 4 is the high reliability bipolar plates full face for bipolarity lead accumulator prepared by embodiment step 4;
Fig. 5 is the high reliability bipolar plates side photo for bipolarity lead accumulator prepared by embodiment step 4, and 1 is negative electrode active material, and 2 is positive active material, and 3 is the long terne metal/titanium/terne metal composite titanium substrate having slicker solder palpus in surface;
Fig. 6 is the cyclical stability test result contrast of the bipolarity lead accumulator that embodiment and contrast experiment prepare, and A is the bipolarity lead accumulator that embodiment prepares, and B is the bipolarity lead accumulator that contrast experiment prepares.
Embodiment
Embodiment one: the preparation method of a kind of high reliability bipolar plates for bipolarity lead accumulator described in present embodiment, specifically carry out according to following steps:
One, preliminary treatment:
Successively oil removing and pickling are carried out to titanium plate, obtains pretreated titanium plate;
Two, titanium plate surface honeycomb:
To scribble the titanium net of ruthenium-oxide for anode, with pretreated titanium plate for negative electrode, then the titanium net anode and pretreated titanium plate cathode that scribble ruthenium-oxide being placed in honeycomb treatment fluid, be 80 DEG C ~ 90 DEG C and current density is 5A/dm in temperature
2~ 20A/dm
2condition under, then process 10s ~ 20s is 80 DEG C ~ 90 DEG C and current density in temperature is 0.5A/dm
2~ 2A/dm
2condition under, process 10min ~ 30min, takes out titanium plate after process, under room temperature, to the titanium plate washed with de-ionized water after process, obtains the honeycomb titanium plate that surface has hydrogenation film to protect;
Described honeycomb treatment fluid by mass percent be 20% ~ 36% hydrochloric acid and promoter form, in described honeycomb treatment fluid, the mass percent of promoter is 5% ~ 20%; Described promoter one or both the mixture that to be oxalic acid and mass percent be in the hydrofluoric acid of 42%;
Three, the layer of lead-tin alloy of preferential growth is electroplated:
The honeycomb titanium plate having hydrogenation film to protect with surface is for negative electrode; with terne metal plate for anode; the honeycomb titanium plate cathode being had on surface hydrogenation film to protect is placed between two panels terne metal plate anode; porous barrier is fixed between the honeycomb titanium plate cathode having hydrogenation film to protect on surface and two panels terne metal plate anode; obtain pending; being placed in Pb-Sn alloy plating bath by pending, be 30 DEG C ~ 40 DEG C and current density is 1A/dm in temperature
2~ 2A/dm
2condition under, plating 20min ~ 4h, obtain surface long have slicker solder must terne metal/titanium/terne metal composite titanium substrate;
Described Pb-Sn alloy plating bath is made up of potassium pyrophosphate, lead（II） ion, divalent tin ion and additive; In described Pb-Sn alloy plating bath, the concentration of potassium pyrophosphate is 0.6mol/L ~ 0.8mol/L; In described Pb-Sn alloy plating bath, the concentration of lead（II） ion is 0.2mol/L ~ 0.4mol/L; In described Pb-Sn alloy plating bath, the concentration of divalent tin ion is 0.005mol/L ~ 0.02mol/L; In described Pb-Sn alloy plating bath, the concentration of additive is 1g/L ~ 5g/L;
Four, high reliability bipolar plates is prepared:
Prepare anode diachylon and cathode lead plaster, then the long terne metal/titanium/terne metal composite titanium substrate side coating anode diachylon having slicker solder palpus on surface, another side coating cathode lead plaster, obtain being coated with cream plate, carry out pickling process again or drench acid treatment, obtain the painting cream plate after acid treatment, first under temperature is 40 DEG C ~ 65 DEG C and humidity is the condition of 50% ~ 100%, to the painting cream plate solidification 24h ~ 48h after acid treatment, then under temperature is 50 DEG C ~ 65 DEG C and humidity is the condition of 30% ~ 50%, solidification 2h ~ 4h, again under temperature is 65 DEG C ~ 70 DEG C and humidity is the condition of 20% ~ 30%, solidification 2h ~ 4h, finally under temperature is 70 DEG C and humidity is the condition of 0%, dry 4h ~ 8h, namely the high reliability bipolar plates for bipolarity lead accumulator is obtained.
1., the present embodiment surface of the preparing honeycomb titanium plate that has hydrogenation film to protect the beneficial effect of present embodiment is:, and honeycomb and hydrogenation film concur, and ensure that the bond strength of electroplating lead tin alloy coating and titanium plate; 2., by the long pb-sn alloy plating having slicker solder palpus of plate surface, play " rivet " effect, ensure that the bond strength of lead plaster and composite titanium substrate, active material can be kept in bipolar plates charge and discharge cycles process to be combined with composite base plate firmly; 3., titanium plate has high corrosion-resistant; 4., pb-sn alloy plating can form good thermal interface in lead plaster reaction.Therefore, the bipolar plates that prepared by present embodiment has high reliability for bipolarity lead accumulator.
Embodiment two: present embodiment and embodiment one unlike: the titanium plate thickness described in step one is 0.1mm ~ 0.5mm.Other is identical with embodiment one.
Embodiment three: one of present embodiment and embodiment one or two unlike: the oil removing described in step one and pickling are carried out according to following steps: titanium plate being impregnated in temperature is in the degreasing fluid of 60 DEG C ~ 70 DEG C, dip time is 10min ~ 30min, obtain the titanium plate after oil removing, under room temperature, titanium plate after oil removing be impregnated in pickle, dipping 1min ~ 2min, obtains pretreated titanium plate;
Described degreasing fluid is made up of sodium carbonate, sodium phosphate and sodium metasilicate; In described degreasing fluid, the concentration of sodium carbonate is 35g/L ~ 45g/L; In described degreasing fluid, the concentration of sodium phosphate is 45g/L ~ 55g/L; The concentration of described degreasing fluid mesosilicic acid sodium is 20g/L ~ 30g/L;
Hydrofluoric acid, mass percent that described pickle is 42% by mass percent be 65% red fuming nitric acid (RFNA) and mass percent be 30% hydrogen peroxide form; In described pickle, mass percent is the concentration of the hydrofluoric acid of 42% is 20mL/L ~ 30mL/L; In described pickle, mass percent is the concentration of the red fuming nitric acid (RFNA) of 65% is 20mL/L ~ 40mL/L; In described pickle, mass percent is the concentration of the hydrogen peroxide of 30% is 35mL/L ~ 70mL/L.Other is identical with embodiment one or two.
Embodiment four: one of present embodiment and embodiment one to three unlike: in the terne metal plate described in step 3, Theil indices is 0.5% ~ 5%.Other is identical with embodiment one to three.
Embodiment five: one of present embodiment and embodiment one to four unlike: the porous barrier described in step 3 is the glass mat separator of loose structure or the polypropylene separator of loose structure; Described porous barrier mesopore is through hole, and aperture is 0.5mm ~ 2mm, and porosity is 85% ~ 95%, and the thickness of porous barrier is 2cm ~ 10cm.Other is identical with embodiment one to four.
Embodiment six: one of present embodiment and embodiment one to five unlike: the additive described in step 3 is one or both the mixture in gelatin, phenol and b diammonium disodium edta.Other is identical with embodiment one to five.
Embodiment seven: one of present embodiment and embodiment one to six unlike: prepare anode diachylon and cathode lead plaster in step 4, specifically carry out according to the following steps: 1., take lead powder, red lead and short fiber and mix, under agitation, water is added successively and density is 1.4g/cm
3sulfuric acid solution, obtain anode diachylon;
Described lead powder and the mass ratio of red lead are 100:2; Described lead powder and the mass ratio of short fiber are 100:0.15; Described lead powder and the mass ratio of water are 100:12; Described lead powder and density are 1.4g/cm
3the mass ratio of sulfuric acid solution be 100:8.7;
2., take lead powder, short fiber, barium sulfate, lignin, humic acid and material with carbon element and mix, under agitation, adding water successively and density is 1.4g/cm
3sulfuric acid solution, obtain cathode lead plaster;
Described lead powder and the mass ratio of short fiber are 100:0.08; Described lead powder and the mass ratio of barium sulfate are 100:0.8; Described lead powder and the mass ratio of lignin are 100:0.2; Described lead powder and the mass ratio of humic acid are 100:0.25; Described lead powder and the mass ratio of material with carbon element are 100:(0.25 ~ 1.0); Described lead powder and the mass ratio of water are 100:11; Described lead powder and density are 1.4g/cm
3the mass ratio of sulfuric acid solution be 100:8.5.Other is identical with embodiment one to six.
Embodiment eight: one of present embodiment and embodiment one to seven unlike: step 1. described in short fiber long be 2.5mm ~ 3mm; Step 1. described in short fiber be polyester staple fiber; Step 2. described in short fiber long be 2.5mm ~ 3mm; Step 2. described in short fiber be polyester staple fiber; Step 2. described in lignin be sodium lignin sulfonate; Step 2. described in material with carbon element be one or both mixture in active carbon, carbon black, acetylene black and carbon nano-tube.Other is identical with embodiment one to seven.
Embodiment nine: one of present embodiment and embodiment one to eight, unlike pickling process in step 4, specifically to be carried out: it is 1.1g/cm that painting cream plate be impregnated in density according to the following steps
3sulfuric acid solution in 1s ~ 2s.Other is identical with embodiment one to eight.
Embodiment ten: one of present embodiment and embodiment one to nine unlike: drench acid treatment in step 4, specifically carry out according to the following steps: be 1.1g/cm by density
3sulfuric acid solution to painting cream plate spray 1s ~ 2s.Other is identical with embodiment one to nine.
Following examples are adopted to verify beneficial effect of the present invention:
Embodiment:
The preparation method of a kind of high reliability bipolar plates for bipolarity lead accumulator described in the present embodiment, specifically carries out according to following steps:
One, preliminary treatment:
Successively oil removing and pickling are carried out to the titanium plate that thickness is 0.2mm, obtains pretreated titanium plate;
Two, titanium plate surface honeycomb:
To scribble the titanium net of ruthenium-oxide for anode, with pretreated titanium plate for negative electrode, then the titanium net anode and pretreated titanium plate cathode that scribble ruthenium-oxide being placed in honeycomb treatment fluid, be 90 DEG C and current density is 10A/dm in temperature
2condition under, then process 10s is 90 DEG C and current density in temperature is 1A/dm
2condition under, process 15min, takes out titanium plate after process, under room temperature, to the titanium plate washed with de-ionized water after process, obtains the honeycomb titanium plate that surface has hydrogenation film to protect;
Described honeycomb treatment fluid by mass percent be 20% ~ 36% hydrochloric acid and promoter form, in described honeycomb treatment fluid, the mass percent of promoter is 20%; The mixture of described promoter to be oxalic acid and mass percent the be hydrofluoric acid of 42%; Described oxalic acid and mass percent are the mass ratio of the hydrofluoric acid of 42% is 1:1;
Three, the layer of lead-tin alloy of preferential growth is electroplated:
The honeycomb titanium plate having hydrogenation film to protect with surface is for negative electrode; with terne metal plate for anode; the honeycomb titanium plate cathode being had on surface hydrogenation film to protect is placed between two panels terne metal plate anode; porous barrier is fixed between the honeycomb titanium plate cathode having hydrogenation film to protect on surface and two panels terne metal plate anode; obtain pending; being placed in Pb-Sn alloy plating bath by pending, be 35 DEG C and current density is 1.5A/dm in temperature
2condition under, plating 1h, obtain surface long have slicker solder must terne metal/titanium/terne metal composite titanium substrate;
Described Pb-Sn alloy plating bath is made up of potassium pyrophosphate, lead（II） ion, divalent tin ion and additive; In described Pb-Sn alloy plating bath, the concentration of potassium pyrophosphate is 0.7mol/L; In described Pb-Sn alloy plating bath, the concentration of lead（II） ion is 0.2mol/L; In described Pb-Sn alloy plating bath, the concentration of divalent tin ion is 0.01mol/L; In described Pb-Sn alloy plating bath, the concentration of additive is 2g/L; Described additive is phenol;
Four, high reliability bipolar plates is prepared:
Prepare anode diachylon and cathode lead plaster, then the long terne metal/titanium/terne metal composite titanium substrate side coating anode diachylon having slicker solder palpus on surface, another side coating cathode lead plaster, obtain being coated with cream plate, carry out pickling process again, obtain the painting cream plate after acid treatment, first under temperature is 65 DEG C and humidity is the condition of 95%, to the painting cream plate solidification 24h after acid treatment, then under temperature is 65 DEG C and humidity is the condition of 50%, solidification 2h, again under temperature is 65 DEG C and humidity is the condition of 30%, solidification 2h, finally under temperature is 70 DEG C and humidity is the condition of 0%, dry 4h, namely the high reliability bipolar plates for bipolarity lead accumulator is obtained,
Oil removing described in step one and pickling are carried out according to following steps: titanium plate being impregnated in temperature is in the degreasing fluid of 70 DEG C, and dip time is 20min, obtain the titanium plate after oil removing, under room temperature, impregnated in pickle by the titanium plate after oil removing, dipping 2min, obtains pretreated titanium plate;
Described degreasing fluid is made up of sodium carbonate, sodium phosphate and sodium metasilicate; In described degreasing fluid, the concentration of sodium carbonate is 40g/L; In described degreasing fluid, the concentration of sodium phosphate is 50g/L; The concentration of described degreasing fluid mesosilicic acid sodium is 25g/L;
Hydrofluoric acid, mass percent that described pickle is 42% by mass percent be 65% red fuming nitric acid (RFNA) and mass percent be 30% hydrogen peroxide form; In described pickle, mass percent is the concentration of the hydrofluoric acid of 42% is 20mL/L; In described pickle, mass percent is the concentration of the red fuming nitric acid (RFNA) of 65% is 25mL/L; In described pickle, mass percent is the concentration of the hydrogen peroxide of 30% is 70mL/L;
The Theil indices of the terne metal plate described in step 3 is 1.5%;
Porous barrier described in step 3 is the polypropylene separator of loose structure; Described porous barrier mesopore is through hole, and aperture is 2mm, and porosity is 90%, and the thickness of porous barrier is 5cm;
Prepare anode diachylon and cathode lead plaster in step 4, specifically carry out according to the following steps: 1., take lead powder, red lead and short fiber and mix, under agitation, add water successively and density is 1.4g/cm
3sulfuric acid solution, obtain anode diachylon;
Described lead powder and the mass ratio of red lead are 100:2; Described lead powder and the mass ratio of short fiber are 100:0.15; Described lead powder and the mass ratio of water are 100:12; Described lead powder and density are 1.4g/cm
3the mass ratio of sulfuric acid solution be 100:8.7; Described short fiber is long is 2.5mm ~ 3mm; Described short fiber is polyester staple fiber;
2., take lead powder, short fiber, barium sulfate, lignin, humic acid and material with carbon element and mix, under agitation, adding water successively and density is 1.4g/cm
3sulfuric acid solution, obtain cathode lead plaster;
Described lead powder and the mass ratio of short fiber are 100:0.08; Described lead powder and the mass ratio of barium sulfate are 100:0.8; Described lead powder and the mass ratio of lignin are 100:0.2; Described lead powder and the mass ratio of humic acid are 100:0.25; Described lead powder and the mass ratio of material with carbon element are 100:1.0; Described lead powder and the mass ratio of water are 100:11; Described lead powder and density are 1.4g/cm
3the mass ratio of sulfuric acid solution be 100:8.5; Described short fiber is long is 2.5mm ~ 3mm; Described short fiber is polyester staple fiber; Described lignin is sodium lignin sulfonate; Described material with carbon element is active carbon;
Pickling process in step 4, specifically carries out: it is 1.1g/cm that painting cream plate be impregnated in density according to the following steps
3sulfuric acid solution in 1s ~ 2s.
Contrast experiment:
One, preliminary treatment:
Successively oil removing and pickling are carried out to the titanium plate that thickness is 0.2mm, obtains pretreated titanium plate;
Two, electroplating lead tin alloy layer:
With pretreated titanium plate for negative electrode, with terne metal plate for anode, pretreated titanium plate cathode is placed between two panels terne metal plate anode, obtains pending, being placed in Pb-Sn alloy plating bath by pending, be 35 DEG C and current density is 1.5A/dm in temperature
2condition under, plating 1h, obtain terne metal/titanium/terne metal composite titanium substrate;
Described Pb-Sn alloy plating bath is made up of potassium pyrophosphate, lead（II） ion, divalent tin ion and additive; In described Pb-Sn alloy plating bath, the concentration of potassium pyrophosphate is 0.7mol/L; In described Pb-Sn alloy plating bath, the concentration of lead（II） ion is 0.2mol/L; In described Pb-Sn alloy plating bath, the concentration of divalent tin ion is 0.01mol/L; In described Pb-Sn alloy plating bath, the concentration of additive is 2g/L; Described additive is phenol;
Three, high reliability bipolar plates is prepared:
Prepare anode diachylon and cathode lead plaster, then at terne metal/titanium/terne metal composite titanium substrate side coating anode diachylon, another side coating cathode lead plaster, carry out pickling process again, obtain the painting cream plate after acid treatment, first under temperature is 65 DEG C and humidity is the condition of 95%, to the painting cream plate solidification 24h after acid treatment, then under temperature is 65 DEG C and humidity is the condition of 50%, solidification 2h, again under temperature is 65 DEG C and humidity is the condition of 30%, solidification 2h, finally under temperature is 70 DEG C and humidity is the condition of 0%, dry 4h, namely bipolar plates is obtained,
Oil removing described in step one and pickling are carried out according to following steps: titanium plate being impregnated in temperature is in the degreasing fluid of 70 DEG C, and dip time is 20min, obtain the titanium plate after oil removing, under room temperature, impregnated in pickle by the titanium plate after oil removing, dipping 2min, obtains pretreated titanium plate;
Described degreasing fluid is made up of sodium carbonate, sodium phosphate and sodium metasilicate; In described degreasing fluid, the concentration of sodium carbonate is 40g/L; In described degreasing fluid, the concentration of sodium phosphate is 50g/L; The concentration of described degreasing fluid mesosilicic acid sodium is 25g/L;
Hydrofluoric acid, mass percent that described pickle is 42% by mass percent be 65% red fuming nitric acid (RFNA) and mass percent be 30% hydrogen peroxide form; In described pickle, mass percent is the concentration of the hydrofluoric acid of 42% is 20mL/L; In described pickle, mass percent is the concentration of the red fuming nitric acid (RFNA) of 65% is 25mL/L; In described pickle, mass percent is the concentration of the hydrogen peroxide of 30% is 70mL/L;
The Theil indices of the terne metal plate described in step 2 is 1.5%;
Prepare anode diachylon and cathode lead plaster in step 3, specifically carry out according to the following steps: 1., take lead powder, red lead and short fiber and mix, obtaining mixture, under agitation, in mixture, add water successively and density is 1.4g/cm
3sulfuric acid solution, obtain anode diachylon;
Described lead powder and the mass ratio of red lead are 100:2; Described lead powder and the mass ratio of short fiber are 100:0.15; Described lead powder and the mass ratio of water are 100:12; Described lead powder and density are 1.4g/cm
3the mass ratio of sulfuric acid solution be 100:8.7; Described short fiber is long is 2.5mm ~ 3mm; Described short fiber is polyester staple fiber;
2., take lead powder, short fiber, barium sulfate, lignin, humic acid and material with carbon element and mix, obtaining mixture, under agitation, in mixture, adding water successively and density is 1.4g/cm
3sulfuric acid solution, obtain cathode lead plaster;
Described lead powder and the mass ratio of short fiber are 100:0.08; Described lead powder and the mass ratio of barium sulfate are 100:0.8; Described lead powder and the mass ratio of lignin are 100:0.2; Described lead powder and the mass ratio of humic acid are 100:0.25; Described lead powder and the mass ratio of material with carbon element are 100:1.0; Described lead powder and the mass ratio of water are 100:11; Described lead powder and the mass ratio of water are 100:11; Described lead powder and density are 1.4g/cm
3the mass ratio of sulfuric acid solution be 100:8.5; Described short fiber is long is 2.5mm ~ 3mm; Described short fiber is polyester staple fiber; Described lignin is sodium lignin sulfonate; Described material with carbon element is active carbon;
Pickling process in step 3, specifically carries out: it is 1.1g/cm that painting cream plate be impregnated in density according to the following steps
3sulfuric acid solution in 1s ~ 2s.
Fig. 1 is the scanning electron microscope (SEM) photograph of the honeycomb titanium plate that surface prepared by embodiment step 2 has hydrogenation film to protect; As seen from the figure, titanium plate surface defines honeycomb blind hole, diameter about 1 micron, and the degree of depth 1 micron ~ 3 microns, this honeycomb blind hole can increase the bond strength of lead plating tin layers and titanium plate greatly.
Fig. 2 is XRD collection of illustrative plates and the TiH of the honeycomb titanium plate that surface prepared by embodiment step 2 has hydrogenation film to protect
1.924-PDF22-0983 standard diagram, A is the honeycomb titanium plate that surface prepared by embodiment step 2 has hydrogenation film to protect, and B is TiH
1.924-PDF22-0983; As seen from the figure, there is TiH on the titanium plate surface of honeycomb process
1.924thing rete, this rete can prevent the surface of honeycomb titanium plate from being titanium dioxide by the dioxygen oxidation in air or rinse water before electroplating lead tin alloy layer, when fundamentally eliminating Electroplating on Ti, surface film oxide causes the internal factor of the non-constant of binding force of cladding material, during guarantee electroplating lead tin alloy layer, terne metal atom is directly combined with Titanium atom, further increases the bond strength of lead plating tin layers and titanium plate.
Fig. 3 is the long scanning electron microscope (SEM) photograph having the terne metal/titanium/terne metal composite titanium substrate of slicker solder palpus in surface prepared by embodiment step 3; As seen from the figure, the long slicker solder palpus having 5 microns ~ 10 microns in pb-sn alloy plating surface, this slicker solder must play " rivet " effect, play a crucial role with its surperficial bond strength being coated with lead plaster for strengthening composite titanium substrate, can ensure that in charge and discharge cycles process, composite titanium substrate can not be separated with active material, improve the reliability of bipolar plates, thus improve the cyclical stability of bipolarity lead accumulator.
Fig. 4 is the high reliability bipolar plates full face for bipolarity lead accumulator prepared by embodiment step 4; As seen from the figure, be combined well with composite base plate after lead plaster solidification.
Fig. 5 is the high reliability bipolar plates side photo for bipolarity lead accumulator prepared by embodiment step 4, and 1 is negative electrode active material, and 2 is positive active material, and 3 is the long terne metal/titanium/terne metal composite titanium substrate having slicker solder palpus in surface; As seen from the figure, positive and negative electrode active material is combined well with composite base plate.
The high reliability bipolar plates for bipolarity lead accumulator utilizing embodiment to prepare, a slice list positive plate and a slice list negative plate assembling 4V bipolarity lead accumulator, fluid injection changes into rear test loop stability;
The bipolar plates utilizing contrast experiment to prepare, a slice list positive plate and a slice list negative plate assembling 4V bipolarity lead accumulator, fluid injection changes into rear test loop stability;
Fig. 6 is the cyclical stability test result contrast of the bipolarity lead accumulator that embodiment and contrast experiment prepare, A is the bipolarity lead accumulator that embodiment prepares, and B is the bipolarity lead accumulator for preparing of contrast experiment; As seen from the figure, the cyclical stability of bipolarity lead accumulator that prepared by embodiment is obviously better than bipolarity lead accumulator prepared by contrast experiment.
Claims (10)
1., for a preparation method for the high reliability bipolar plates of bipolarity lead accumulator, it is characterized in that it carries out according to following steps:
One, preliminary treatment:
Successively oil removing and pickling are carried out to titanium plate, obtains pretreated titanium plate;
Two, titanium plate surface honeycomb:
To scribble the titanium net of ruthenium-oxide for anode, with pretreated titanium plate for negative electrode, then the titanium net anode and pretreated titanium plate cathode that scribble ruthenium-oxide being placed in honeycomb treatment fluid, be 80 DEG C ~ 90 DEG C and current density is 5A/dm in temperature
2~ 20A/dm
2condition under, then process 10s ~ 20s is 80 DEG C ~ 90 DEG C and current density in temperature is 0.5A/dm
2~ 2A/dm
2condition under, process 10min ~ 30min, takes out titanium plate after process, under room temperature, to the titanium plate washed with de-ionized water after process, obtains the honeycomb titanium plate that surface has hydrogenation film to protect;
Described honeycomb treatment fluid by mass percent be 20% ~ 36% hydrochloric acid and promoter form, in described honeycomb treatment fluid, the mass percent of promoter is 5% ~ 20%; Described promoter one or both the mixture that to be oxalic acid and mass percent be in the hydrofluoric acid of 42%;
Three, the layer of lead-tin alloy of preferential growth is electroplated:
The honeycomb titanium plate having hydrogenation film to protect with surface is for negative electrode; with terne metal plate for anode; the honeycomb titanium plate cathode being had on surface hydrogenation film to protect is placed between two panels terne metal plate anode; porous barrier is fixed between the honeycomb titanium plate cathode having hydrogenation film to protect on surface and two panels terne metal plate anode; obtain pending; being placed in Pb-Sn alloy plating bath by pending, be 30 DEG C ~ 40 DEG C and current density is 1A/dm in temperature
2~ 2A/dm
2condition under, plating 20min ~ 4h, obtain surface long have slicker solder must terne metal/titanium/terne metal composite titanium substrate;
Described Pb-Sn alloy plating bath is made up of potassium pyrophosphate, lead（II） ion, divalent tin ion and additive; In described Pb-Sn alloy plating bath, the concentration of potassium pyrophosphate is 0.6mol/L ~ 0.8mol/L; In described Pb-Sn alloy plating bath, the concentration of lead（II） ion is 0.2mol/L ~ 0.4mol/L; In described Pb-Sn alloy plating bath, the concentration of divalent tin ion is 0.005mol/L ~ 0.02mol/L; In described Pb-Sn alloy plating bath, the concentration of additive is 1g/L ~ 5g/L;
Four, high reliability bipolar plates is prepared:
Prepare anode diachylon and cathode lead plaster, then the long terne metal/titanium/terne metal composite titanium substrate side coating anode diachylon having slicker solder palpus on surface, another side coating cathode lead plaster, obtain being coated with cream plate, carry out pickling process again or drench acid treatment, obtain the painting cream plate after acid treatment, first under temperature is 40 DEG C ~ 65 DEG C and humidity is the condition of 50% ~ 100%, to the painting cream plate solidification 24h ~ 48h after acid treatment, then under temperature is 50 DEG C ~ 65 DEG C and humidity is the condition of 30% ~ 50%, solidification 2h ~ 4h, again under temperature is 65 DEG C ~ 70 DEG C and humidity is the condition of 20% ~ 30%, solidification 2h ~ 4h, finally under temperature is 70 DEG C and humidity is the condition of 0%, dry 4h ~ 8h, namely the high reliability bipolar plates for bipolarity lead accumulator is obtained.
2. the preparation method of a kind of high reliability bipolar plates for bipolarity lead accumulator according to claim 1, is characterized in that the titanium plate thickness described in step one is 0.1mm ~ 0.5mm.
3. the preparation method of a kind of high reliability bipolar plates for bipolarity lead accumulator according to claim 1, it is characterized in that the oil removing described in step one and pickling are carried out according to following steps: titanium plate being impregnated in temperature is in the degreasing fluid of 60 DEG C ~ 70 DEG C, dip time is 10min ~ 30min, obtain the titanium plate after oil removing, under room temperature, impregnated in pickle by the titanium plate after oil removing, dipping 1min ~ 2min, obtains pretreated titanium plate;
Described degreasing fluid is made up of sodium carbonate, sodium phosphate and sodium metasilicate; In described degreasing fluid, the concentration of sodium carbonate is 35g/L ~ 45g/L; In described degreasing fluid, the concentration of sodium phosphate is 45g/L ~ 55g/L; The concentration of described degreasing fluid mesosilicic acid sodium is 20g/L ~ 30g/L;
Hydrofluoric acid, mass percent that described pickle is 42% by mass percent be 65% red fuming nitric acid (RFNA) and mass percent be 30% hydrogen peroxide form; In described pickle, mass percent is the concentration of the hydrofluoric acid of 42% is 20mL/L ~ 30mL/L; In described pickle, mass percent is the concentration of the red fuming nitric acid (RFNA) of 65% is 20mL/L ~ 40mL/L; In described pickle, mass percent is the concentration of the hydrogen peroxide of 30% is 35mL/L ~ 70mL/L.
4. the preparation method of a kind of high reliability bipolar plates for bipolarity lead accumulator according to claim 1, is characterized in that in the terne metal plate described in step 3, Theil indices is 0.5% ~ 5%.
5. the preparation method of a kind of high reliability bipolar plates for bipolarity lead accumulator according to claim 1, is characterized in that the porous barrier described in step 3 is the glass mat separator of loose structure or the polypropylene separator of loose structure; Described porous barrier mesopore is through hole, and aperture is 0.5mm ~ 2mm, and porosity is 85% ~ 95%, and the thickness of porous barrier is 2cm ~ 10cm.
6. the preparation method of a kind of high reliability bipolar plates for bipolarity lead accumulator according to claim 1, is characterized in that the additive described in step 3 is one or both the mixture in gelatin, phenol and b diammonium disodium edta.
7. the preparation method of a kind of high reliability bipolar plates for bipolarity lead accumulator according to claim 1, it is characterized in that in step 4, preparing anode diachylon and cathode lead plaster, specifically carry out according to the following steps: 1., take lead powder, red lead and short fiber and mix, under agitation, water is added successively and density is 1.4g/cm
3sulfuric acid solution, obtain anode diachylon;
Described lead powder and the mass ratio of red lead are 100:2; Described lead powder and the mass ratio of short fiber are 100:0.15; Described lead powder and the mass ratio of water are 100:12; Described lead powder and density are 1.4g/cm
3the mass ratio of sulfuric acid solution be 100:8.7;
2., take lead powder, short fiber, barium sulfate, lignin, humic acid and material with carbon element and mix, under agitation, adding water successively and density is 1.4g/cm
3sulfuric acid solution, obtain cathode lead plaster;
Described lead powder and the mass ratio of short fiber are 100:0.08; Described lead powder and the mass ratio of barium sulfate are 100:0.8; Described lead powder and the mass ratio of lignin are 100:0.2; Described lead powder and the mass ratio of humic acid are 100:0.25; Described lead powder and the mass ratio of material with carbon element are 100:(0.25 ~ 1.0); Described lead powder and the mass ratio of water are 100:11; Described lead powder and density are 1.4g/cm
3the mass ratio of sulfuric acid solution be 100:8.5.
8. the preparation method of a kind of high reliability bipolar plates for bipolarity lead accumulator according to claim 7, is characterized in that the short fiber length described in step is 1. 2.5mm ~ 3mm; Step 1. described in short fiber be polyester staple fiber; Step 2. described in short fiber long be 2.5mm ~ 3mm; Step 2. described in short fiber be polyester staple fiber; Step 2. described in lignin be sodium lignin sulfonate; Step 2. described in material with carbon element be one or both mixture in active carbon, carbon black, acetylene black and carbon nano-tube.
9. the preparation method of a kind of high reliability bipolar plates for bipolarity lead accumulator according to claim 1, is characterized in that pickling process in step 4, specifically carries out according to the following steps: it is 1.1g/cm that painting cream plate be impregnated in density
3sulfuric acid solution in 1s ~ 2s.
10. the preparation method of a kind of high reliability bipolar plates for bipolarity lead accumulator according to claim 1, is characterized in that drenching acid treatment in step 4, specifically carries out according to the following steps: be 1.1g/cm by density
3sulfuric acid solution to painting cream plate spray 1s ~ 2s.
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| CN106229463A (en) * | 2016-07-29 | 2016-12-14 | 天能电池集团有限公司 | A kind of aquo-lithium ion hybrid battery |
| CN109935787A (en) * | 2019-03-14 | 2019-06-25 | 肇庆中特能科技投资有限公司 | A kind of bipolar plates and preparation method thereof |
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| US5800946A (en) * | 1996-12-06 | 1998-09-01 | Grosvenor; Victor L. | Bipolar lead-acid battery plates |
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| CN109935787A (en) * | 2019-03-14 | 2019-06-25 | 肇庆中特能科技投资有限公司 | A kind of bipolar plates and preparation method thereof |
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