CN106025382A - Preparation method of lead-acid colloid storage battery - Google Patents

Preparation method of lead-acid colloid storage battery Download PDF

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Publication number
CN106025382A
CN106025382A CN201610630161.8A CN201610630161A CN106025382A CN 106025382 A CN106025382 A CN 106025382A CN 201610630161 A CN201610630161 A CN 201610630161A CN 106025382 A CN106025382 A CN 106025382A
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preparation
storage battery
acid colloid
colloid storage
plumbic acid
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CN201610630161.8A
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Chinese (zh)
Inventor
程先清
陈健
刘克宇
徐进
罗旭
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Hubei Runyang New Energy Co Ltd
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Hubei Runyang New Energy Co Ltd
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Priority to CN201610630161.8A priority Critical patent/CN106025382A/en
Publication of CN106025382A publication Critical patent/CN106025382A/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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/06—Lead-acid accumulators
    • H01M10/08—Selection of materials as electrolytes
    • H01M10/10—Immobilising of electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/06—Lead-acid accumulators
    • H01M10/12—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Cell Separators (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention provides a preparation method of a lead-acid colloid storage battery. According to the invention, the partition plate main body is glass fiber, and by adding a hydrophilic material coated hydrophobic fiber, the problem of non-uniform mixing of glass fiber and hydrophobic fiber during slurrying can be solved. In addition, in a drying process, the hydrophilic material decomposes naturally, so that a certain amount of oxygen channels exist in the partition plate. Pole plates adopt tight assembling design, and part of nanoscale gas phase SiO2 can penetrate the partition plate. The electrolyte solution contains gas phase SiO2, and guarantees that the partition plate is in a liquid-rich state during use, and stratification does not occur to the electrolyte solution. At the same time, the partition plate also contains a certain amount of oxygen channels, thus being able to the long-life, high temperature environment and other special use demands of the storage battery.

Description

The preparation method of plumbic acid colloid storage battery
Technical field
The present invention relates to Lead-acid Battery Technology field, particularly relate to the preparation method of a kind of plumbic acid colloid storage battery.
Background technology
Electrolyte dry-out is the key factor that capacity of lead acid battery reduces and service life shortens.
Along with global air temperature warming and the requirement of energy-saving and emission-reduction, it is applied to the battery requirements of high temperature (more than 40 DEG C) environment more Come the biggest, how to ensure that battery and safety are a pendulum difficult problems in face of technological staff.
Colloid battery is primarily present two classes: PVC-SiO in the market2The tubular colloidal battery of dividing plate and common AGM every The colloid battery of plate.
PVC-SiO2The colloid battery of dividing plate is expensive, accounts for the 15% of battery cost, gas phase sio2 content in colloid Reaching 5%～7%, cause battery price high, market share is extremely low；Due to pole group adding without assembling pressure and a large amount of silicon dioxide Entering, the internal resistance of cell is big, is unfavorable for heavy-current discharge；Production typically requires electric discharge acid, adds glue, complex procedures, simultaneously initial stage Sealing reaction efficiency is low, the problem such as later stage thermal runaway, service life are short.
Common AGM colloid battery improves on the basis of valve-regulated lead-acid battery, and difference is in electrolyte to contain Having a small amount of gas phase sio2, belong to and be closely assembled and lean solution battery, silicon dioxide cannot be introduced into dividing plate and pole plate effective site, conventional Life-span on probation and hot environment all cannot meet colloid battery requirement service life.
Summary of the invention
In view of this, the plumbic acid glue that the present invention proposes length in a kind of service life, high temperature resistant, heavy-current discharge performance is excellent Accumulator body and preparation method thereof.
The technical scheme is that and be achieved in that: the invention provides the preparation side of a kind of plumbic acid colloid storage battery Method, described plumbic acid colloid storage battery it include housing, positive plate, dividing plate and the negative pole being arranged in housing and being cascading Plate, also includes the electrolyte being poured in housing, and the preparation of described dividing plate comprises the following steps,
S1, shreds hydrophobic fiber, and at its Surface coating water wetted material；
S2, shreds the ultra-fine fibre glass of average diameter 0.7～1 μm, and obtains with nanometer grade silica, step S1 Material mixing, add serosity, stir, storage slurry, preparation in flakes, is dried, cut-parts, obtains final dividing plate.
On the basis of above technical scheme, it is preferred that in described step S2, hydrophobic fiber consumption accounts for ultra-fine fibre glass Mass percent is 5%～10%, and hydrophobic fiber uses the acid resisting materials such as PP, PE or PVC.It is further preferred that described step In S1, water wetted material is polyethylene terephthalate resinoid, covering amount account for hydrophobic fiber mass percent 8%～ 15%.Further preferred, described water wetted material is polyethylene terephthalate, and in step S2, baking temperature is higher than 110℃。
Basis in above technical scheme, it is preferred that in described step S2, nanometer grade silica consumption accounts for superfine glass Fiber quality percentage ratio is 3%～5%.
Basis in above technical scheme, it is preferred that containing gas phase SiO in described electrolyte2Mass percent be 0.5%～ 1.5%, when accumulator is in open circuit static condition, liquid level of electrolyte is higher than dividing plate top.
Basis in above technical scheme, it is preferred that described positive plate uses grid type plate, and cream raw material includes, oxygen The Hydrocerussitum (Ceruse) of change degree 73%～78%, mass percent be 10%～25% Plumbum preparatium and mass percent be 8%～10% 4BS, and cream maximum temperature controls at 65 DEG C～68 DEG C, solidification temperature is 57 DEG C～65 DEG C.
Basis in above technical scheme, it is preferred that comprise the following steps, carries out layer to positive plate, dividing plate and negative plate Closed assembly is joined, and assembling pressure is at 20kPa～80kPa.
Basis in above technical scheme, it is preferred that also include being melted into step, first charge with 0.01CA electric current 0.5 little Time, improve the electric conductivity of green plate；Secondly use segmentation multistep to be discharged to capacity ＜ 0.05C, 0.12CA～0.20CA constant current to fill Electrically charge, control this step always clean charge volume at 4.8C～5.3C；Then 60%～80% deep discharge is carried out；Finally adopt With first big after small staged electric current, battery abundance electricity, the clean charge volume of this step are controlled at 1.4C～2.0C.
The preparation method of the plumbic acid colloid storage battery of the present invention has the advantages that relative to prior art
(1) diaphragm body of the present invention is glass fibre, by adding the hydrophobic fiber of cladding water wetted material, solves glass Glass fiber and hydrophobic fiber when slurrying can not mixed uniformly problem, in this external dry run, water wetted material natural decomposition, Make dividing plate exists a number of oxygen channel；
(2) pole plate uses and is closely assembled design, nano level gas phase SiO of part2Dividing plate can be penetrated into；
(3) containing gas phase SiO in electrolyte2, and ensureing that in use dividing plate is in liquid rich, electrolyte does not occurs Stratification, there is also a number of oxygen channel simultaneously, can meet accumulator long-life and hot environment etc. special in dividing plate Use demand.
Detailed description of the invention
Below in conjunction with embodiment of the present invention, the technical scheme in the present invention is clearly and completely described, aobvious So, described embodiment is only a part of embodiment of the present invention rather than whole embodiments.Based on the present invention In embodiment, the every other enforcement that those of ordinary skill in the art are obtained under not making creative work premise Mode, broadly falls into the scope of protection of the invention.
Following example use valve controlled sealed lead-acid accumulator 12V100Ah (6GFM100) as experiment sample, difference To the plumbic acid colloid storage battery using the inventive method to prepare and commercially available PVC-SiO2The colloid battery 12V100Ah of dividing plate and general Logical AGM separator cell contrasts.
Embodiment 1
First, dividing plate is prepared.Comprise the following steps,
S1, shreds PP fiber, and in its Surface coating polyethylene terephthalate；
S2, shreds the ultra-fine fibre glass of average diameter 0.7～1 μm, and obtains with nanometer grade silica, step S1 Material mixing, add serosity, stir, storage slurry, preparation in flakes, is dried at 110 DEG C～120 DEG C, cut-parts, obtain finally every Plate.
Secondly, positive plate is prepared.
Include with cream raw material, the Hydrocerussitum (Ceruse) of oxidizability 73%, mass percent be 10% Plumbum preparatium and mass percent be The 4BS of 8%, and cream maximum temperature controls at 65 DEG C～68 DEG C, solidification temperature is 57 DEG C～65 DEG C.Wherein, and cream, prepare plate Grid, are coated with the processes such as cream and use prior art.
Then, electrolyte is prepared.Containing gas phase SiO in described electrolyte2Mass percent is 0.5%, the perfusion of electrolyte Amount is every single lattice 1200ml.Remaining composition of electrolyte uses prior art.
Finally, preparing negative plate, the positive plate obtained, dividing plate and negative plate are carried out stacking assembling, assembling pressure exists 20kPa～80kPa, injects electrolyte, is melted into, and chemical conversion step is as follows: first charge 0.5 hour with 0.01CA electric current；Its Secondary employing segmentation multistep is discharged to capacity ＜ 0.05C, 0.12CA～0.20CA constant-current charge mode and charges, and controls this step the cleanest Charge volume is at 4.8C～5.3C；Then 60%～80% deep discharge is carried out；First big after small staged electric current is finally used to incite somebody to action Battery abundance electricity, the clean charge volume of this step controls at 1.4C～2.0C.
Embodiment 2
First, dividing plate is prepared.Comprise the following steps,
PVC is mixed with silicon dioxide, by calendering, the demoulding, is dried, cuts volume, obtain final dividing plate.
Secondly, positive plate is prepared.
Include with cream raw material, the Hydrocerussitum (Ceruse) of oxidizability 78%, mass percent be 25% Plumbum preparatium and mass percent be The 4BS of 10%, and cream maximum temperature controls at 65 DEG C～68 DEG C, solidification temperature is 57 DEG C～65 DEG C.Wherein, and cream, prepare plate Grid, are coated with the processes such as cream and use prior art.
Then, electrolyte is prepared.Containing gas phase SiO in described electrolyte2Mass percent is 1.5%, the perfusion of electrolyte Amount is every single lattice 1200ml.Remaining composition of electrolyte uses prior art.
Finally, preparing negative plate, the positive plate obtained, dividing plate and negative plate are carried out stacking assembling, assembling pressure exists 10kPa～20kPa, injects electrolyte, is melted into, and chemical conversion step is with embodiment 1.
Embodiment 3
First, dividing plate is prepared.Comprise the following steps,
Glass cotton is soaked in appropriate amount of deionized water, make serosity, adjust pH value, stir, storage slurry, preparation is in blocks, It is dried, cut-parts, obtains final dividing plate.
Secondly, positive plate is prepared.
Include with cream raw material, the Hydrocerussitum (Ceruse) of oxidizability 78%, mass percent be 25% Plumbum preparatium and mass percent be The 4BS of 10%, and cream maximum temperature controls at 65 DEG C～68 DEG C, solidification temperature is 57 DEG C～65 DEG C.Wherein, and cream, prepare plate Grid, are coated with the processes such as cream and use prior art.
Then, electrolyte is prepared.Containing gas phase SiO in described electrolyte2Mass percent is 1.5%, the perfusion of electrolyte Amount is every single lattice 1100ml.Remaining composition of electrolyte uses prior art.
Finally, preparing negative plate, the positive plate obtained, dividing plate and negative plate are carried out stacking assembling, assembling pressure exists 20kPa～80kPa, injects electrolyte, is melted into, and chemical conversion step is with embodiment 1.
Embodiment 4
Preparing the colloid battery 12V100Ah of commercially available common AGM dividing plate, wherein, the groundwater increment of electrolyte is every single lattice 1200ml。
Embodiment 5
Prepare commercially available PVC-SiO2The colloid battery 12V100Ah of dividing plate, wherein, the groundwater increment of electrolyte is every single lattice 1100ml。
Embodiment 6
The AGM dividing plate colloid battery 12V100Ah that preparation improves, wherein, the groundwater increment of electrolyte is every single lattice 1100ml.
Sample Cell to embodiment 1～2,5～6 is analyzed test respectively, obtains following test result.
(1) overcharge gassing rate test.Under the fully charged state of battery, carry out overcharge 1h with 1A, 1.5A, always analyse after 1h Tolerance see table:
(2) cycle life test.Carry out 40%DOD discharge cycles test by GB/T 19638.2-2005, obtain such as following table Shown result:
Sample Cell to embodiment 2～4,6 is analyzed test respectively, obtains following test result.
(1) overcharge gassing rate test.Under the fully charged state of battery, carry out overcharge 1h with 1A, 1.5A, always analyse after 1h Tolerance see table:
(2) cycle life test.Carry out 40%DOD discharge cycles test by GB/T 19638.2-2005, obtain such as following table Shown result:
(3) thermal runaway sensitivity.Test by GB/T 19638.2-2005, obtain result as shown in the table:
From test result it can be seen that improve colloid battery and the PVC-SiO of AGM dividing plate2The colloid battery of dividing plate (is coated with cream Formula pole plate) electric property is close, initial stage gassing rate significantly reduces, production cost only account for its about 70%；Glue with common AGM dividing plate Body battery cost is suitable, all has the biggest difference in lean liquid with electric property under liquid rich.Improve the colloid battery of AGM dividing plate Technological incorporation PVC-SiO2The colloid battery of dividing plate and colloid battery each advantage of common AGM dividing plate, low cost and property Can be excellent, it is especially suitable for hot environment and uses and long-life demand.
The foregoing is only the better embodiment of the present invention, not in order to limit the present invention, all the present invention's Within spirit and principle, any modification, equivalent substitution and improvement etc. made, should be included within the scope of the present invention.

Claims (9)

1. a preparation method for plumbic acid colloid storage battery, described plumbic acid colloid storage battery it include housing, be arranged in housing And positive plate, dividing plate and the negative plate being cascading, also include the electrolyte being poured in housing, it is characterised in that: institute The preparation stating dividing plate comprises the following steps,
S1, shreds hydrophobic fiber, and at its Surface coating water wetted material；
S2, shreds the ultra-fine fibre glass of average diameter 0.7～1 μm, and the material obtained with nanometer grade silica, step S1 Material mixing, adds serosity, stirs, storage slurry, and preparation in flakes, is dried, cut-parts, obtains final dividing plate.
2. the preparation method of plumbic acid colloid storage battery as claimed in claim 1, it is characterised in that: in described step S2, hydrophobic is fine It is 5%～10% that Wesy's amount accounts for ultra-fine fibre glass mass percent, and hydrophobic fiber uses PP, PE or PVC.
3. the preparation method of plumbic acid colloid storage battery as claimed in claim 2, it is characterised in that: hydrophilic material in described step S1 Material is polyethylene terephthalate resinoid, and covering amount accounts for the 8%～15% of hydrophobic fiber mass percent.
4. the preparation method of plumbic acid colloid storage battery as claimed in claim 3, it is characterised in that: described water wetted material is for poly-right PET, in step S2, baking temperature is higher than 110 DEG C.
5. the preparation method of plumbic acid colloid storage battery as claimed in claim 1, it is characterised in that: nanoscale in described step S2 It is 3%～5% that silica content accounts for ultra-fine fibre glass mass percent.
6. the preparation method of plumbic acid colloid storage battery as claimed in claim 1, it is characterised in that: containing gas phase in described electrolyte SiO2Mass percent is 0.5%～1.5%, and when accumulator is in open circuit static condition, liquid level of electrolyte is higher than dividing plate top.
7. the preparation method of plumbic acid colloid storage battery as claimed in claim 1, it is characterised in that: described positive plate uses and is coated with cream Formula pole plate, and cream raw material includes, the Hydrocerussitum (Ceruse) of oxidizability 73%～78%, mass percent are Plumbum preparatium and the matter of 10%～25% Amount percentage ratio is the 4BS of 8%～10%, and cream maximum temperature controls at 65 DEG C～68 DEG C, and solidification temperature is 57 DEG C～65 DEG C.
8. the preparation method of plumbic acid colloid storage battery as claimed in claim 1, it is characterised in that: comprise the following steps, align Pole plate, dividing plate and negative plate carry out stacking assembling, and assembling pressure is at 20kPa～80kPa.
9. the preparation method of plumbic acid colloid storage battery as claimed in claim 1, it is characterised in that: also include being melted into step, first First charge 0.5 hour with 0.01CA electric current；Secondly segmentation multistep is used to be discharged to capacity ＜ 0.05C, 0.12CA～0.20CA permanent Current charge mode is charged, and controls this step always clean charge volume at 4.8C～5.3C；Then 60%～80% deep discharge is carried out；? Battery abundance electricity, the clean charge volume of this step are controlled at 1.4C～2.0C by the first big after small staged electric current of rear employing.
CN201610630161.8A 2016-08-03 2016-08-03 Preparation method of lead-acid colloid storage battery Pending CN106025382A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106654129A (en) * 2017-02-24 2017-05-10 营口中捷仕达隔板有限公司 Start-stop automobile battery separator and preparation method thereof
CN106910871A (en) * 2017-02-14 2017-06-30 山东超威磁窑电源有限公司 A kind of manufacturing process for improving lead-acid battery cycle performance and environment-friendly type pole plate
CN114050328A (en) * 2021-11-17 2022-02-15 骆驼集团华中蓄电池有限公司 Preparation method of SLI parking air conditioner battery

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JPH0729560A (en) * 1993-07-12 1995-01-31 Nippon Sheet Glass Co Ltd Separator for sealed lead-acid battery
JP2002313305A (en) * 2001-04-18 2002-10-25 Nippon Sheet Glass Co Ltd Separator for use in lead acid battery and lead acid battery using it
CN101246968A (en) * 2007-07-30 2008-08-20 华南师范大学 Nano-gas-phase SiO2 colloid electrolytic solution and its preparing method and colloid accumulator
CN101697370A (en) * 2009-10-22 2010-04-21 山东义和诚实业集团有限公司 Novel lead-acid storage battery clapboard and preparation method thereof
CN102610802A (en) * 2012-03-22 2012-07-25 株洲冶炼集团股份有限公司 Lead-acid storage battery and anode material thereof
CN103094516A (en) * 2013-01-23 2013-05-08 华南师范大学 Composite reinforced colloid storage battery separator and preparation method thereof

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JPH0729560A (en) * 1993-07-12 1995-01-31 Nippon Sheet Glass Co Ltd Separator for sealed lead-acid battery
JP2002313305A (en) * 2001-04-18 2002-10-25 Nippon Sheet Glass Co Ltd Separator for use in lead acid battery and lead acid battery using it
CN101246968A (en) * 2007-07-30 2008-08-20 华南师范大学 Nano-gas-phase SiO2 colloid electrolytic solution and its preparing method and colloid accumulator
CN101697370A (en) * 2009-10-22 2010-04-21 山东义和诚实业集团有限公司 Novel lead-acid storage battery clapboard and preparation method thereof
CN102610802A (en) * 2012-03-22 2012-07-25 株洲冶炼集团股份有限公司 Lead-acid storage battery and anode material thereof
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106910871A (en) * 2017-02-14 2017-06-30 山东超威磁窑电源有限公司 A kind of manufacturing process for improving lead-acid battery cycle performance and environment-friendly type pole plate
CN106654129A (en) * 2017-02-24 2017-05-10 营口中捷仕达隔板有限公司 Start-stop automobile battery separator and preparation method thereof
CN114050328A (en) * 2021-11-17 2022-02-15 骆驼集团华中蓄电池有限公司 Preparation method of SLI parking air conditioner battery
CN114050328B (en) * 2021-11-17 2024-05-17 骆驼集团华中蓄电池有限公司 Preparation method of SLI parking air conditioner battery

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