CN107611354A - A kind of preparation method of lead carbon battery anode plate - Google Patents

A kind of preparation method of lead carbon battery anode plate Download PDF

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Publication number
CN107611354A
CN107611354A CN201710933366.8A CN201710933366A CN107611354A CN 107611354 A CN107611354 A CN 107611354A CN 201710933366 A CN201710933366 A CN 201710933366A CN 107611354 A CN107611354 A CN 107611354A
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lead
preparation
carbon battery
constant temperature
air humidity
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CN107611354B (en
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林海波
包金鹏
李洪坤
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Jilin Province Kai Yu Electrochemical Energy Storage Technology Development Co Ltd
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Jilin Province Kai Yu Electrochemical Energy Storage Technology Development Co Ltd
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    • 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 invention discloses the highly controllable lead carbon battery anode additive of a kind of component and crystal formation and its pole plate preparation method, the additive is α/β PbO prepared by constant current electro-deposition2‑SiO2Compound, the pole plate is by lead powder, α/β PbO2‑SiO2, aquadag, chopped fiber composition.As outstanding electrolyte storage medium, silica has certain elastic deformation ability, after lead carbon battery positive pole is added, while it can provide more effecting reaction ions for internal active material, physical buffer effect is provided when pole plate deforms upon, alleviates the phenomenon that lead plaster comes off by Geometrical Bending.And Basal activity material of the brown lead oxide as positive pole, its crystal formation are the deciding factors for influenceing material electrochemical property.The pole plate being made up of the compound of the present invention can significantly improve active material effective rate of utilization and pole plate resistance to corrosion, effectively alleviate the obscission under high magnification partial state of charge, improve battery overall energy density and cycle life.

Description

A kind of preparation method of lead carbon battery anode plate
Technical field：
The present invention relates to a kind of lead carbon battery, more particularly to the anode additive and its electrode of a kind of lead carbon battery
Background technology：
With the progressively popularization of electrified equipment, people increasingly increase the demand of energy storage device.Possess closely as one kind The energy storage device of two one-hundred-year histories, lead-acid battery have that cost is low, low-temperature stability is good, the advantage such as safe and reliable.But its energy The shortcomings that density is low, cycle life is short, application is caused to receive restriction.
Lead carbon battery is described as lead-acid battery of future generation, and it is that carbon material is added in lead-acid battery cathode.Due to carbon materials Material is with good electric conductivity, the chemical stability in strong acid environment, the specific surface area far above pure lead, with traditional lead acid batteries To compare, lead carbon battery negative pole sulfation is significantly inhibited, and negative electrode active material effective rate of utilization is significantly improved, Overall cycle life and energy density are substantially strengthened.Lead carbon battery is the state-of-the-art technology in lead-acid battery field, is international new energy The emphasis direction of source energy storage industry, there is wide development space.
As a kind of new lead-acid battery, for lead carbon battery while many advantages are enjoyed, there is also some problems.With The lifting of negative pole performance, both positive and negative polarity matching problem increasingly highlights.Compared with traditional lead acid batteries positive pole, the positive pole-face of lead carbon battery Face higher work potential and more extreme circulation environment, this is just effectively utilized to its anticorrosive exfoliation ability and active material Rate proposes further challenge.Patent CN102931380A discloses a kind of positive electode of lead battery pole plate, and the positive plate includes Anode plate grid and coated on anode plate grid surface made of chopped carbon fiber reinforcing material is mixed into brown lead oxide active matter Matter layer, in battery charge and discharge process, carbon fiber each component is not involved in the electrochemical reaction of battery so that positive plate has high-strength Degree, high-strength bearing capacity and stronger creep resisting ability, are greatly improved between active material and active material and positive plate Adhesion between the small lattice of grid, so that active material is not easy to soften, come off, and then the use longevity of lead-acid accumulator can be improved Life.Patent CN104241641A discloses a kind of positive electode of lead battery lead plaster, and it adds slightly soluble phosphate into formula, makes phosphorus Acid group is sustained during battery use and come out, so both ensure that battery formation process and early stage performance it is unaffected, again The problem of battery is softened using later stage pole plate can be overcome.But in these patents, primary concern is that between active principle Connectivity, and have ignored the influence of the diffusion of the mass transfer inside pole plate.
Silica is a kind of emerging anode additive, its chemical stability under with good concentrated acid, high temperature While, storage degree of the sulfuric acid in pole plate can be improved in immersion process, can be changed in cyclic process by volume Become the pore-size distribution of lifting pole plate, and then improve the active material effective rate of utilization of positive pole and anticorrosive exfoliation ability.Although Silica excellent performance in anode plate, but how silica to be added in electrode makes its advantage be not fully exerted It is the subject matter faced at present.
Compound is a kind of well accepted accumulator plate addition manner.The methods of by chemical deposition, chemical plating, system It is standby go out a variety of compounds such as sheath charcoal, charcoal bag lead, lead charcoal be compound, and then control the ratio and distribution mode of compound, be current The Main way of lead carbon battery.Electrochemical deposition is due to the advantage such as product is highly controllable, energy consumption is low, method is simple, multiple Condensation material receives much concern in preparing.By the method for electro-deposition, α-PbO in positive pole compound can be effectively reconciled2With β-PbO2's Ratio and distribution, and then the energy density and cyclical stability of composite are reconciled, realize the highly controllable of composite.
The content of the invention：
It is an object of the invention to utilize the best electrochemical deposition method of controllability, there is provided a kind of highly controllable, structure α/β-PbO that is stable, being evenly distributed2-SiO2Plus plate assembly.When it is applied to lead carbon battery, positive active material effectively utilizes Rate and resistance to corrosion are remarkably reinforced, and the service life cycle and energy density of high magnification partial state of charge significantly improve.
Therefore, the present invention uses following technical scheme：
A kind of preparation method of lead carbon battery anode plate, including at least following steps：
(1)α/β-PbO2-SiO2The preparation of compound
Using the method for galvanostatic deposition, flat board titanium is placed in 0.5-1M lead salts, 0.1-0.2M strong acid, 0.05-0.1M and received Rice SiO2, be platinum electrode to electrode in 0.01-0.05M surface dispersant mixed solutions, depositing current density 10-80mA/ cm2, preferably 50-80mA/cm2, sedimentation time 1-16h, depositing temperature is 20-40 DEG C, preferably 30-40 DEG C.More than control α/β-the PbO with different component and crystal formation is made in condition2-SiO2Compound；
(2) preparation of lead plaster
By 80-95wt% lead powder, 0.1-10wt% α/β-PbO2-SiO2Compound, 1-5wt% aquadag, 1- 5wt% chopped fiber is well mixed to be made active material, and mixed active material is successively slowly added to its gross weight 10- 15wt% water and 4-8wt% sulfuric acid stir into lead plaster；
(3) preparation of lead carbon battery anode plate
Lead plaster prepared by step (2) is coated on metal grid, lead carbon battery anode plate is prepared into after dry solidification.
Lead salt is the one or more in plumbi nitras, lead sulfate, lead chloride, lead perchlorate in the step (1).
Strong acid is the one or more in nitric acid, sulfuric acid, hydrochloric acid, perchloric acid in the step (1).
Surface dispersant is in sodium tripolyphosphate, the own level phosphoric acid of triethyl group, lauryl sodium sulfate in the step (1) One or more, preferably 0.05M.
Step (2) middle short fiber includes the one or more in terylene and acrylic fibers, fibre length 1-40mm.
It is 4-5mol/L, adding speed 1-5mL/s that sulfuric acid concentration is added in the step (2).
It is the step of dry solidification in the step (3)：
1) 55 DEG C, air humidity 95-98%, preferably 98%, constant temperature 1-5h,
2) 60 DEG C, air humidity 90-98%, constant temperature 10-20h
3) 65 DEG C, air humidity 90-98%, constant temperature 25-35h
4) 60 DEG C, air humidity 60-70%, constant temperature 1-5h
5) 70 DEG C, air humidity 20-40%, constant temperature 1-5h.
It is by the method for electrochemical deposition that the brown lead oxide of different crystal forms, silica is compound, based on different lead plasters Composition, the performance of its combination with metal grid, intensity and pole plate product is different, by raw material and structure Analysis, with reference to lot of experiments, pass through above-mentioned specific α/β-PbO2-SiO2Compound, the preparation method of lead plaster and corresponding drying The steps such as solidification, realize the high controllability of material component and distribution, enhancing earth silicon material being well mixed in lead plaster Degree, and then active material effective rate of utilization and pole plate resistance to corrosion are improved, extend battery cycle life, improve discharge and recharge and connect By ability.Lead charcoal battery with this positive plate is in start-stop automobile, solar energy, wind energy energy storage field with more wide Application prospect.
Brief description of the drawings
Fig. 1：Embodiment 1-4 XPS test charts
Fig. 2：The CV test charts of embodiment 1 and blank
Embodiment：
With reference to embodiment, the present invention will be further described：
Embodiment 1：
Using the method for galvanostatic deposition, flat board titanium is placed in 1M lead sulfates, 0.1M sulfuric acid, 0.05M Nano-meter SiO_2s2、 It is platinum electrode to electrode in 0.05M triethyl group hexyl phosphoric acid mixed solutions, depositing current density 10mA/cm2, sedimentation time For 4h, depositing temperature is 25 DEG C, and α/β-PbO is made2-SiO2Compound.
By 85wt% lead powder, 10wt% α/β-PbO2-SiO2Compound, 2.5wt% aquadag, 2.5wt% 40mm terylene is well mixed to be made active material, mixed active material be successively slowly added to its gross weight 12wt% water and 8wt%2mL/s 4.7mol/L sulfuric acid stirs into lead plaster；The lead plaster of preparation is coated on metal grid, dried solid Lead carbon battery anode plate is prepared into after change.Curing schedule is as follows：
1) 55 DEG C, air humidity 98%, constant temperature 2h
2) 60 DEG C, air humidity 95%, constant temperature 10h
3) 65 DEG C, air humidity 90%, constant temperature 26h
4) 60 DEG C, air humidity 65%, constant temperature 3h
5) 70 DEG C, air humidity 30%, constant temperature 3h.
Embodiment 2：
Using the method for galvanostatic deposition, flat board titanium is placed in 1M lead sulfates, 0.1M sulfuric acid, 0.05M Nano-meter SiO_2s2、 It is platinum electrode to electrode in 0.05M triethyl group hexyl phosphoric acid mixed solutions, depositing current density 20mA/cm2, sedimentation time For 4h, depositing temperature is 25 DEG C, and α/β-PbO is made2-SiO2Compound.
By 85wt% lead powder, 10wt% α/β-PbO2-SiO2Compound, 2.5wt% aquadag, 2.5wt% 40mm terylene is well mixed to be made active material, mixed active material be successively slowly added to its gross weight 12wt% water and 8wt%2mL/s 4.7mol/L sulfuric acid stirs into lead plaster；The lead plaster of preparation is coated on metal grid, dried solid Lead carbon battery anode plate is prepared into after change.Curing schedule is as follows：
1) 55 DEG C, air humidity 98%, constant temperature 3h
2) 60 DEG C, air humidity 95%, constant temperature 12h
3) 65 DEG C, air humidity 90%, constant temperature 32h
4) 60 DEG C, air humidity 60%, constant temperature 3h
5) 70 DEG C, air humidity 30%, constant temperature 3h
Embodiment 3：
Using the method for galvanostatic deposition, flat board titanium is placed in 1M lead sulfates, 0.1M sulfuric acid, 0.05M Nano-meter SiO_2s2、 It is platinum electrode to electrode in 0.05M triethyl group hexyl phosphoric acid mixed solutions, depositing current density 50mA/cm2, sedimentation time For 4h, depositing temperature is 30 DEG C, and α/β-PbO is made2-SiO2Compound.
By 85wt% lead powder, 10wt% α/β-PbO2-SiO2Compound, 2.5wt% aquadag, 2.5wt% 40mm terylene is well mixed to be made active material, mixed active material be successively slowly added to its gross weight 12wt% water and 8wt%2mL/s 4.7mol/L sulfuric acid stirs into lead plaster；The lead plaster of preparation is coated on metal grid, dried solid Lead carbon battery anode plate is prepared into after change.Curing schedule is as follows：
1) 55 DEG C, air humidity 98%, constant temperature 4h
2) 60 DEG C, air humidity 98%, constant temperature 10h
3) 65 DEG C, air humidity 98%, constant temperature 32h
4) 60 DEG C, air humidity 70%, constant temperature 3h
5) 70 DEG C, air humidity 30%, constant temperature 3h
Embodiment 4：
Using the method for galvanostatic deposition, flat board titanium is placed in 1M lead sulfates, 0.1M sulfuric acid, 0.05M Nano-meter SiO_2s2、 It is platinum electrode to electrode in the own level phosphoric acid mixed solution of 0.05M triethyl groups, depositing current density 80mA/cm2, sedimentation time For 4h, depositing temperature is 35 DEG C, and α/β-PbO is made2-SiO2Compound.
By 85wt% lead powder, 10wt% α/β-PbO2-SiO2Compound, 2.5wt% aquadag, 2.5wt% 40mm terylene is well mixed to be made active material, mixed active material be successively slowly added to its gross weight 12wt% water and 8wt%2mL/s 4.7mol/L sulfuric acid stirs into lead plaster；The lead plaster of preparation is coated on metal grid, dried solid Lead carbon battery anode plate is prepared into after change.Curing schedule is as follows：
1) 55 DEG C, air humidity 98%, constant temperature 5h
2) 60 DEG C, air humidity 98%, constant temperature 15h
3) 65 DEG C, air humidity 98%, constant temperature 32h
4) 60 DEG C, air humidity 70%, constant temperature 3h
5) 70 DEG C, air humidity 30%, constant temperature 3h
Embodiment 1-4 is subjected to XRD analysis test, as shown in Figure 1, it can be seen that with the change of current density, dioxy The crystal formation for changing lead is gradually changed, and β-PbO are mainly generated under low current density2, and α-PbO under high current density2Content Gradually increase, therefore can be determined that current density is the major control factors of crystal formation.By the sample obtained by embodiment 1 and equally Under the conditions of undope silica sample carry out CV tests, as shown in Fig. 2 can substantially observe peak height increase and peak The shortening of spacing.The increase of peak height represents the raising of active material effective rate of utilization, shows to be stored in the electrolysis of silica In material internal redox reaction can occur for liquid, there is provided more avtive spots.And it is peak-to-peak away from diminution represent it is faster Faraday's reaction speed, mainly due to the reaction deformation of electrode, the silica as ion transmission channel can be with for this Active ion more timely is provided for reaction site, improves ion-diffusibility.
By the anode plate prepared by embodiment 1-4 and lead carbon battery negative plates, AGM barrier films, 4.7M electrolyte sulfuric acids 6Ah pregnant solution type batteries are assembled into, lead carbon battery is made by being internalized into.By the lead carbon electricity of above-mentioned addition embodiment 1-4 additives Pond carries out HRPSoC tests in accordance with the following steps：
(1) it is discharged to 30%Soc:0.5C (3A) constant current, discharge 1.4h；
(2) HRPSoC is circulated：
A. charge：1C (6A), 2.4V constant-current constant-voltage chargings 60s；
B. discharge：0.45C (2.7A) constant-current discharge 59s, then 3C (18A) constant-current discharges 1s；
C. HRPSoC circulations are repeated until voltage is less than 1.75V.Record cycle life；
Test result is as shown in the table, it can be seen that has benefited from the electrolyte storage ability and geometric deformation of silica Ability, the tension stress resistance to corrosion of electrode are significantly improved, and battery has good under high magnification partial state of charge Cycle life.On the other hand, the crystal formation of brown lead oxide significantly affects the life-span of electrode, by controlling brown lead oxide crystal formation to control Prepared material performance just has feasibility.
Finally it should be noted that：The above embodiments are merely illustrative of the technical scheme of the present invention and are not intended to be limiting thereof, to the greatest extent The present invention is described in detail with reference to above-described embodiment for pipe, those of ordinary skills in the art should understand that：Still The embodiment of the present invention can be modified or equivalent substitution, and without departing from any of spirit and scope of the invention Modification or equivalent substitution, it all should cover among scope of the presently claimed invention.

Claims (9)

  1. A kind of 1. preparation method of lead carbon battery anode plate, it is characterised in that：Including at least following steps：
    (1)α/β-PbO2-SiO2The preparation of compound
    Using the method for galvanostatic deposition, flat board titanium is placed in 0.5-1M lead salts, 0.1-0.2M strong acid, 0.05-0.1M nanometers SiO2, be platinum electrode to electrode in 0.01-0.05M surface dispersant mixed solutions, depositing current density 10-80mA/cm2, Sedimentation time is 1-16h, and depositing temperature is 20-40 DEG C.By control conditions above be made the α with different component and crystal formation/ β-PbO2-SiO2Compound；The surface dispersant is in sodium tripolyphosphate, triethyl group hexyl phosphoric acid, lauryl sodium sulfate It is one or more of；
    (2) preparation of lead plaster
    By about 80-95wt% lead powder, 0.1-10wt% α/β-PbO2-SiO2Compound, 1-5wt% aquadag, 1- 5wt% chopped fiber is well mixed to be made active material, and mixed active material is successively slowly added to its gross weight 10- 15wt% water and 4-8wt% sulfuric acid stir into lead plaster；
    (3) preparation of negative plate of lead-carbon battery
    Lead plaster prepared by step (2) is coated on metal grid, lead carbon battery anode plate is prepared into after dry solidification.
  2. 2. according to a kind of preparation method of lead carbon battery anode plate described in claim 1, it is characterised in that：The step (1) lead salt is the one or more in plumbi nitras, lead sulfate, lead chloride, lead perchlorate in.
  3. 3. according to a kind of preparation method of lead carbon battery anode plate described in claim 1, it is characterised in that：The step (1) strong acid is the one or more in nitric acid, sulfuric acid, hydrochloric acid, perchloric acid in.
  4. 4. according to a kind of preparation method of lead carbon battery anode plate described in claim 1, it is characterised in that：The step (1) surface dispersant is triethyl group hexyl phosphoric acid in.
  5. 5. according to a kind of preparation method of lead carbon battery anode plate described in claim 1, it is characterised in that：Deposition current Density is 50-80mA/cm2, depositing temperature is 30-40 DEG C.
  6. 6. according to a kind of preparation method of lead carbon battery anode plate described in claim 1, it is characterised in that：The step (2) middle short fiber includes the one or more in terylene and acrylic fibers, fibre length 1-40mm.
  7. 7. according to a kind of preparation method of lead carbon battery anode plate described in claim 1, it is characterised in that：The step (2) it is 4-5mol/L, adding speed 1-5mL/s that sulfuric acid concentration is added in.
  8. 8. according to a kind of preparation method of lead carbon battery anode plate described in claim 1, it is characterised in that：The step (3) it is the step of dry solidification in：
    1) 55 DEG C, air humidity 95-98%, constant temperature 1-5h,
    2) 60 DEG C, air humidity 90-98%, constant temperature 10-20h,
    3) 65 DEG C, air humidity 90-98%, constant temperature 25-35h,
    4) 60 DEG C, air humidity 60-70%, constant temperature 1-5h,
    5) 70 DEG C, air humidity 20-40%, constant temperature 1-5h.
  9. 9. according to a kind of preparation method of lead carbon battery anode plate described in claim 8, it is characterised in that：The step (3) it is the step of dry solidification in：
    1) 55 DEG C, air humidity 98%, constant temperature 2h,
    2) 60 DEG C, air humidity 98%, constant temperature 10h,
    3) 65 DEG C, air humidity 98%, constant temperature 32h,
    4) 60 DEG C, air humidity 70%, constant temperature 3h,
    5) 70 DEG C, air humidity 30%, constant temperature 3h.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108428891A (en) * 2018-04-11 2018-08-21 河南超威电源有限公司 A kind of novel high-capacity lead-acid accumulator anode diachylon and preparation method thereof
CN111627718A (en) * 2020-06-09 2020-09-04 吉林大学 Preparation method of lead-carbon supercapacitor positive electrode
CN113394408A (en) * 2021-06-17 2021-09-14 昆明高聚科技有限公司 Long-life light composite positive grid and preparation method thereof, and positive electrode plate and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009235521A (en) * 2008-03-27 2009-10-15 Niigata Univ Ozone generating electrode
CN102280626A (en) * 2010-06-13 2011-12-14 宝山钢铁股份有限公司 Composite lead dioxide electrode plate and manufacturing method thereof
CN102646832A (en) * 2012-05-10 2012-08-22 山东瑞宇蓄电池有限公司 Lead plaster composition for manufacturing positive plate of lead-acid storage battery, positive plate of lead-acid storage battery and lead-acid storage battery
WO2016084858A1 (en) * 2014-11-27 2016-06-02 日立化成株式会社 Lead storage cell

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009235521A (en) * 2008-03-27 2009-10-15 Niigata Univ Ozone generating electrode
CN102280626A (en) * 2010-06-13 2011-12-14 宝山钢铁股份有限公司 Composite lead dioxide electrode plate and manufacturing method thereof
CN102646832A (en) * 2012-05-10 2012-08-22 山东瑞宇蓄电池有限公司 Lead plaster composition for manufacturing positive plate of lead-acid storage battery, positive plate of lead-acid storage battery and lead-acid storage battery
WO2016084858A1 (en) * 2014-11-27 2016-06-02 日立化成株式会社 Lead storage cell

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108428891A (en) * 2018-04-11 2018-08-21 河南超威电源有限公司 A kind of novel high-capacity lead-acid accumulator anode diachylon and preparation method thereof
CN111627718A (en) * 2020-06-09 2020-09-04 吉林大学 Preparation method of lead-carbon supercapacitor positive electrode
CN113394408A (en) * 2021-06-17 2021-09-14 昆明高聚科技有限公司 Long-life light composite positive grid and preparation method thereof, and positive electrode plate and preparation method thereof

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