CN108963269A - A kind of preparation method of process for positive slab lattice of lead-acid accumulator - Google Patents

A kind of preparation method of process for positive slab lattice of lead-acid accumulator Download PDF

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Publication number
CN108963269A
CN108963269A CN201810670472.6A CN201810670472A CN108963269A CN 108963269 A CN108963269 A CN 108963269A CN 201810670472 A CN201810670472 A CN 201810670472A CN 108963269 A CN108963269 A CN 108963269A
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China
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lead
titanium
acid accumulator
preparation
slab lattice
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CN201810670472.6A
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Chinese (zh)
Inventor
毛旭辉
周寿斌
钱帮芬
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JIANGSU HUAFU STORAGE NEW TECHNOLOGY Co Ltd
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JIANGSU HUAFU STORAGE NEW TECHNOLOGY Co Ltd
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Priority to CN201810670472.6A priority Critical patent/CN108963269A/en
Publication of CN108963269A publication Critical patent/CN108963269A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/82—Multi-step processes for manufacturing carriers for lead-acid 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • 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
    • H01M4/68—Selection of materials for use in lead-acid 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
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/80—Porous plates, e.g. sintered carriers
    • H01M4/808—Foamed, spongy materials
    • 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)
  • Materials Engineering (AREA)
  • Composite Materials (AREA)
  • Cell Electrode Carriers And Collectors (AREA)

Abstract

The invention discloses a kind of preparation methods of process for positive slab lattice of lead-acid accumulator, the following steps are included: 1), use titanium foam as raw material, using titanium foam as anode, carry out electrochemical oxidation, so that the titanium on surface is oxidized to+4 valences from 0 valence, obtains the titanium foam of+4 valence of surface；2), the titanium foam for+4 valence of surface for obtaining step 1) carries out electrochemical reduction as cathode, and+4 valence titanium of surface portion is reduced to+trivalent, obtains intermediate materials；3), the intermediate materials for obtaining step 2) carry out carbon thermal reduction, and Surface Creation Magneli phase conductive layer obtains the anode plate grid of lead-acid accumulator.The preparation method of process for positive slab lattice of lead-acid accumulator of the invention can satisfy battery and applied cream, assembly and the requirement during using etc. to intensity, corrosion resistance, electric conductivity etc. using the titanium foam with Magneli conductive layer as anode plate grid.The stable charge/discharge of the titanium foam grid in lead-acid accumulator is good simultaneously, and cycle life is longer, and storing capacity decaying is slow, and better performances, battery possesses higher specific energy.

Description

A kind of preparation method of process for positive slab lattice of lead-acid accumulator
Technical field
The invention belongs to lead-acid accumulator field more particularly to a kind of preparation methods of process for positive slab lattice of lead-acid accumulator.
Background technique
Lead-acid accumulator is since raw material sources are abundant, cheap, function admirable, be current industry, communication, traffic, The most widely used secondary cell of electric system.Compared with other chemical energy storage systems, lead storage battery have power characteristic it is good, Outstanding advantages of cost performance is high, using the easy recovery and reusing and recycling of safe, refuse battery and technology of preparing relative maturity.But at present The energy storage lead storage battery that domestic market uses is in terms of specific energy, the characteristic of heavy-current discharge with alkaline storage battery, lithium power electric There is larger gap in pond etc..The composition of lead-acid accumulator is analyzed it is not difficult to find that the main reason for low specific energy is inert matter lead The dosage of (mainly lead-containing alloy grid) is larger, to increase the quality of lead-acid accumulator.Therefore, lead-containing alloy plate is surrounded The improvement and substitution of grid carry out the research and development of lead storage battery lightweight key technology, by the application of new technology, solve its lead usage amount Greatly, the disadvantages of specific energy is low, cycle life is short can not only be well used as the power supply of electric bicycle and battery-operated motor cycle, and And good effect can be also played on electric car.
Electrode material is the basic element of character for constituting lead-acid accumulator, and influences the core material of performances of the lead-acid battery. Currently, the R&D work in terms of the electrode material of lead-acid accumulator is concentrated mainly on alloy material for slab lattice, grid active material circle Face behavior, active material additive etc., wherein the lightweight of grid material and the improvement of grid/reactive species interface performance are to grind The emphasis studied carefully.
Copper, aluminium, the titanium three dimensional foam material in China all have been carried out industrialization.Copper foamed material is the most mature, and aluminium, titanium The large-scale production of foamed material is in recent years.It all has been able to meet lead from three kinds of foamed materials in production scale and price The demand of battery industry (since the porosity of foamed material is all 80% or more, the dosage of metal is few).By copper, aluminium, titanium bubble Foam material is able to solve as chloride plate grid base material and restricts the light-weighted bottleneck of lead storage battery, increase substantially active matter The utilization rate of matter and the specific energy of battery are that lead storage battery industry should put forth effort the major fields for developing and breaking through.
Therefore, it is necessary to a kind of new process for positive slab lattice of lead-acid accumulator to solve the above problems.
Summary of the invention
For the deficiencies in the prior art, the present invention provides a kind of preparation side of process for positive slab lattice of lead-acid accumulator Method.
The technical solution of the present invention is as follows:
A kind of preparation method of process for positive slab lattice of lead-acid accumulator, comprising the following steps:
1) titanium foam, is used to carry out electrochemical oxidation using titanium foam as anode as raw material, make the titanium on surface from 0 valence + 4 valences are oxidized to, the titanium foam of+4 valence of surface is obtained；
2), the titanium foam for+4 valence of surface for obtaining step 1) carries out electrochemical reduction ,+4 valence of part of the surface as cathode Titanium is reduced to+trivalent, obtains intermediate materials；
3), the intermediate materials for obtaining step 2) carry out carbon thermal reduction, and Surface Creation Magneli phase conductive layer obtains lead The anode plate grid of acid accumulator.
Further, in step 1) preparation method of titanium foam include fiber sintering method, casting, compression-expansion method, Polymeric sponge method, self-propagating high-temperature synthesis and powder sintering.
Further, the porosity of titanium foam described in step 1) is 80%-90%.
Further, using titanium foam as anode in step 1), carry out electrochemical oxidation in electrolyte aqueous solution into Row.
Further, the titanium foam of+4 valence of surface obtained step 1) in step 2) carries out electrochemistry as cathode Reduction carries out in electrolyte aqueous solution.
Further, the current density of electrochemical oxidation is 0.5-10mA/cm in step 1)2, electrochemistry in step 2) The current density of reduction is 0.5-10mA/cm2.Identical current density can be used in oxidation and reduction process, also can be used Different current densities.
Further, the intermediate materials obtained step 2) in step 3) carry out carbon thermal reduction under an inert atmosphere into Row.
Further, inert atmosphere is nitrogen or argon gas.
Further, the temperature of carbon thermal reduction is 500-1000 DEG C in step 3).
Further, the carbon source of carbon thermal reduction is inorganic carbon dust or carbonaceous organic material in step 3).
Further, the time of electrochemical oxidation is 60-120min in step 1), in step 2) electrochemical reduction when Between be 30min-60min.Wherein, when electrochemical oxidation is identical with the electric current of electrochemical reduction, the time of electrochemical reduction is small In the time of electrochemical oxidation.
Inventive principle: titanium foam metal anode plate grid, without lead plate grid material, can be resistant to as lead-acid accumulator product Anode charging oxidative acidic environment, reduces electrode polarization, promotes overpotential for oxygen evolution, extend battery life.Titanium high intensity and Low-density can meet requirement of the pole plate when applying cream, assembly and pole plate depth charge and discharge to grid intensity, be conducive to that grid is inhibited to become Shape, fracture reduce the weight of pole plate, improve the specific energy of battery.Titanium has good corrosion resistance, and lead-acid accumulator can be improved Cycle life.Titanium is that surface can be passivated when it is oxidized anodically in the difficulty in, and generating has semiconductor special Property oxidation titanium film, prevent the electrical contact between titanium and positive active material.
" electrochemical preoxidation-reduction-carbon thermal reduction " treatment process of titanium foam forms one layer on the surface of titanium foam and leads The Magneli oxide phase of electricity, enhancing foamed material improve material as the resistance to of anode plate grid to the binding force of lead, lead oxide The utilization rate of corrosion, inoxidizability and active material.
The utility model has the advantages that the preparation method of process for positive slab lattice of lead-acid accumulator of the invention is with the bubble with Magneli conductive layer Foam titanium can satisfy battery during applying cream, assembly and using etc. to intensity, corrosion resistance, electric conductivity etc. as anode plate grid Requirement.The stable charge/discharge of the titanium foam grid in lead-acid accumulator is good simultaneously, and cycle life is longer, storing capacity Decaying is slow, and better performances, battery possesses higher specific energy.
Detailed description of the invention
Fig. 1 is the brief preparation flow figure of anode plate grid of the present invention.
Fig. 2 be optical photograph in implementations embodiment 1 of the invention before and after titanium foam grid and tradition lead grid coating paste and Quality record.
Fig. 3 is charge-discharge test result in implementation embodiment 2 of the invention.
Specific embodiment
In the following with reference to the drawings and specific embodiments, the present invention is furture elucidated, it should be understood that these embodiments are merely to illustrate It the present invention rather than limits the scope of the invention, after the present invention has been read, those skilled in the art are to of the invention each The modification of kind equivalent form falls within the application range as defined in the appended claims.
It please refers to shown in Fig. 1, Fig. 2 and Fig. 3, the preparation method of process for positive slab lattice of lead-acid accumulator of the invention: anode plate grid Using titanium foam as raw material, first using titanium foam as anode, electrochemical oxidation is carried out, makes the titanium on surface from 0 valence (Ti0) by oxygen Turn to+4 (Ti+4) valence；Later as cathode, electrochemical reduction is carried out, partial-titanium is from+4 valence (Ti+4) it is reduced to+trivalent (Ti+3).Electrochemical preoxidation and reduction carry out in electrolyte aqueous solution.Titanium foam is used as anode to carry out electrochemistry oxygen first Change, carries out electrochemical reduction as cathode later.The current density range that electrochemical preoxidation and reduction process use are as follows: 0.5- 10mA/cm2；Identical current density can be used in oxidation and reduction process, and different current densities also can be used.
Wherein, the time of electrochemical oxidation is 60-120min, and the time of electrochemical reduction is 30min-60min.Wherein, When electrochemical oxidation is identical with the electric current of electrochemical reduction, the time of electrochemical reduction is less than the time of electrochemical oxidation.
Material after electrochemical preoxidation-reduction treatment is subjected to carbon thermal reduction under an inert atmosphere, makes Surface Creation Magneli phase (TixO2x-1) conductive layer.Carbon thermal reduction in the heating furnace that tube furnace and molten salt furnace etc. can provide inert atmosphere into Row.Inert atmosphere is nitrogen or argon gas.Carbon source used in carbon-thermal reduction is inorganic carbon dust or carbonaceous organic material.Carbon-thermal reduction Temperature is 500-1000 degrees Celsius.
The processing for carrying out " electrochemical preoxidation-reduction-carbon thermal reduction " to titanium foam leads its Surface Creation Magneli Electric layer, later as the anode plate grid of lead-acid accumulator.Simplified process is as shown in attached drawing Fig. 1.
Anti-oxidant, the corrosion resistance of anode plate grid directly affect the service life of lead storage battery, so anode plate grid must have Good anti-oxidant and corrosion resistance, H in electrolyte during charge and discharge process can be resisted and shelved2SO4Corrosion；Simultaneously The overpotential for oxygen evolution for needing to have high guarantees the charge-discharge performance and efficiency of battery, reduces the mistake in lead storage battery use process Water makes battery have good maintenance-free performance.The resistance of grid wants small, and the grid of high conductivity can make electric current be easier to edge Grid be distributed to active material, to reduce the internal resistance of battery, play effectively afflux and electric action；And can be with Active material rigid contact, contact surface have it is good wrap up in attached power, prevent falling off for active material；With good mechanical performance and Creep resistance, grid will have some strength, hardness, tensile strength, in order to the manufacture and transport of battery.And Magneli is conductive Titanium foamed material can be enhanced to the binding force of lead, lead oxide in generations of layer, improve material as anode plate grid corrosion resistance, resist The utilization rate of oxidisability and active material, while titanium material itself has good mechanical strength and lower density, Neng Gouji The specific energy of big promotion lead-acid accumulator.
Embodiment 1:
Commercially available titanium foamed material is selected, by wire cutting, forms the titanium foam grid of 15cm*15cm*0.5cm specification.? In using sodium sulphate as the electrolytic cell of electrolyte, using the titanium cystosepiment as anode, Faradaic current is electrolysed in the case where being 50mA 1h is electrolysed 0.5h later using the titanium cystosepiment as cathode under similar circumstances.It takes out, dries later, be placed in tube furnace, Under nitrogen atmosphere (flow velocity of nitrogen is 100ml/min), carbon thermal reduction, tube furnace temperature setting are carried out using commercial activated carbons It is 600 degrees Celsius, reacts 120min, natural cooling, takes out later, and carries out painting cream.Naturally dry after painting cream, uses simultaneously Traditional stereotype grid of same size carry out applying cream and naturally dry.The quality before and after two kinds of anode plate grids painting cream is recorded respectively, such as Shown in attached drawing Fig. 2, it is found that the quality before titanium foam grid coating paste is 25g, and the matter of traditional stereotype grid of same size Amount is then 100g；After applying cream, the quality of titanium foam grid is 160g, and the quality of traditional stereotype grid is 201g.It can be found that Same grid area, titanium foam grid is relative to traditional stereotype grid, and active material has more 35%, while weight is reduced 25%, it can effectively improve the specific energy of lead-acid accumulator.
Embodiment 2:
Selecting commercially available porosity is 80% titanium foamed material, by wire cutting, forms the titanium of 5cm*1cm*0.5cm specification Foam grid.Using the titanium cystosepiment as anode Faradaic current to be electrolysed 1.5h in the case where 30mA in electrolytic cell, later with The titanium cystosepiment is electrolysed 1h as cathode under similar circumstances.It takes out, dries later, be placed in tube furnace, in nitrogen atmosphere Under (flow velocity of nitrogen is 100ml/min), carbon thermal reduction is carried out using active carbon, tube furnace temperature setting is 650 degrees Celsius, instead 120min is answered, later natural cooling, the related electrochemical properties of electrode are characterized by charge-discharge test.Voltage range is 1.75V-2.35V, current density 10mA/g.Just extremely treated titanium foam anode plate grid, cathode are business stereotype, are used Instrument is new prestige charge-discharge test instrument.As a result as shown in attached drawing Fig. 3, when carrying out 200 circulations, as circulation carries out, charge and discharge Electric specific capacity is gradually increased, and shows there is preferable cycle life using titanium foam anode plate grid.
Embodiment 3
Selecting commercially available porosity is 85% titanium foamed material, by wire cutting, forms 20cm*20cm*0.4cm specification Titanium foam grid.Using the titanium cystosepiment as anode Faradaic current to be electrolysed 1h in the case where 40mA in electrolytic cell, later with The titanium cystosepiment is electrolysed 0.6h as cathode under similar circumstances.It takes out, dries later, be placed in tube furnace, in argon atmosphere Under (flow velocity of argon gas is 100ml/min), carbon thermal reduction is carried out using carbon black, tube furnace temperature setting is 600 degrees Celsius, reaction 100min, later natural cooling.It carries out applying cream and battery assembly after taking-up.
Embodiment 4
Using the titanium foamed material that oneself is prepared, using the titanium cystosepiment as anode in electrolytic cell, Faradaic current is 120min is electrolysed in the case where 20mA, later using the titanium cystosepiment as cathode, Faradaic current is electrolysed in the case where being 30mA 60min.It takes out, dries later, be placed in laboratory tube furnace, under argon atmosphere (flow velocity of argon gas is 50ml/min), Carbon thermal reduction is carried out using commercial activated carbons, the thermostat temperature of tube furnace is set as 700 degrees Celsius, and initial temperature is room temperature, rises Warm rate is 10 degrees Celsius per minute, reacts 100min, later natural cooling.It is cooled to after room temperature, closes argon gas valve, It opens tube furnace and takes out titanium cystosepiment, carry out applying cream and laboratory cells assembly later.

Claims (10)

1. a kind of preparation method of process for positive slab lattice of lead-acid accumulator, it is characterised in that: the following steps are included:
1) titanium foam, is used to carry out electrochemical oxidation using titanium foam as anode as raw material, make the titanium on surface from 0 valence by oxygen + 4 valences are turned to, the titanium foam of+4 valence of surface is obtained；
2), the titanium foam for+4 valence of surface for obtaining step 1) carries out electrochemical reduction ,+4 valence titanium quilt of part of the surface as cathode It is reduced to+trivalent, obtains intermediate materials；
3), the intermediate materials for obtaining step 2) carry out carbon thermal reduction, and Surface Creation Magneli phase conductive layer obtains plumbic acid storage The anode plate grid of battery.
2. the preparation method of process for positive slab lattice of lead-acid accumulator according to claim 1, it is characterised in that: foam in step 1) The preparation method of titanium includes fiber sintering method, casting, compression-expansion method, Polymeric sponge method, self-propagating high-temperature synthesis And powder sintering.
3. the preparation method of process for positive slab lattice of lead-acid accumulator according to claim 1, it is characterised in that: described in step 1) The porosity of titanium foam is 80%-90%.
4. the preparation method of process for positive slab lattice of lead-acid accumulator according to claim 1, it is characterised in that: will bubble in step 1) Foam titanium carries out electrochemical oxidation and carries out in electrolyte aqueous solution as anode.
5. the preparation method of process for positive slab lattice of lead-acid accumulator according to claim 1, it is characterised in that: will step in step 2) The titanium foam of rapid+4 valence of surface 1) obtained carries out electrochemical reduction and carries out in electrolyte aqueous solution as cathode.
6. the preparation method of process for positive slab lattice of lead-acid accumulator according to claim 1, it is characterised in that: electrochemical in step 1) The current density for learning oxidation is 0.5-10mA/cm2, the current density of electrochemical reduction is 0.5-10mA/cm in step 2)2。
7. the preparation method of process for positive slab lattice of lead-acid accumulator according to claim 1, it is characterised in that: will step in step 3) The rapid intermediate materials 2) obtained carry out carbon thermal reduction and carry out under an inert atmosphere.
8. the preparation method of process for positive slab lattice of lead-acid accumulator according to claim 7, it is characterised in that: inert atmosphere is nitrogen Gas or argon gas.
9. the preparation method of process for positive slab lattice of lead-acid accumulator according to claim 1, it is characterised in that: carbon heat in step 3) The temperature of reduction is 500-1000 DEG C.
10. the preparation method of process for positive slab lattice of lead-acid accumulator according to claim 1, it is characterised in that: carbon in step 3) The carbon source of thermal reduction is inorganic carbon dust or carbonaceous organic material.
CN201810670472.6A 2018-06-26 2018-06-26 A kind of preparation method of process for positive slab lattice of lead-acid accumulator Pending CN108963269A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1988224A (en) * 2006-12-29 2007-06-27 徐宏力 Titanium base foam lead positive and negative electrode plate grating material for lead acid accumulator and its producing method
US20080193850A1 (en) * 2005-04-27 2008-08-14 Atraverda Limited Electrode and Manufacturing Methods
CN103515579A (en) * 2012-06-21 2014-01-15 中国人民解放军63971部队 Negative plate of lead storage battery
CN103510041A (en) * 2012-06-21 2014-01-15 中国人民解放军63971部队 Preparation method for titanium-based grid
CN103614587A (en) * 2013-12-05 2014-03-05 北京师范大学 Cell-shaped foam titanium of spherical hole structure

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080193850A1 (en) * 2005-04-27 2008-08-14 Atraverda Limited Electrode and Manufacturing Methods
CN1988224A (en) * 2006-12-29 2007-06-27 徐宏力 Titanium base foam lead positive and negative electrode plate grating material for lead acid accumulator and its producing method
CN103515579A (en) * 2012-06-21 2014-01-15 中国人民解放军63971部队 Negative plate of lead storage battery
CN103510041A (en) * 2012-06-21 2014-01-15 中国人民解放军63971部队 Preparation method for titanium-based grid
CN103614587A (en) * 2013-12-05 2014-03-05 北京师范大学 Cell-shaped foam titanium of spherical hole structure

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